Synthesis of Ag/Cu decorated 3D self-assembled nanowire TiO2 Photocatalyst for Hydrogen Production: A Promising Pathway towards Sustainable Energy Generation

Synthesis of Ag/Cu decorated 3D self-assembled nanowire TiO2 Photocatalyst for Hydrogen Production: A Promising Pathway towards Sustainable Energy Generation | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Synthesis of Ag/Cu decorated 3D self-assembled nanowire TiO2 Photocatalyst for Hydrogen Production: A Promising Pathway towards Sustainable Energy Generation Sachin Wadhai, Pragati Thakur This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4503595/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 11 Oct, 2024 Read the published version in Environmental Science and Pollution Research → Version 1 posted 5 You are reading this latest preprint version Abstract Here synthesis and characterization of TiO 2 with different morphologies along with the cost-effective bimetallic decoration on optimized 3D self-assembled nanowire TiO 2 (NWT) photocatalyst (Ag/Cu-NWT) with overwhelming hydrogen production rate is reported. All the photocatalysts were well characterised by different characterization techniques. Initially, the effect of morphology change obtained by changing the NaOH concentration has been studied for TiO 2 . Morphology obtained at 10 M NaOH solution i.e., NWT (678 μmol/g) showed better hydrogen production than morphology obtained at 5M (410 μmol/g), 15M (210 μmol/g) and 20M (160 μmol/g) NaOH solutions. Further with the aim to achieve comparable or better activity low cost photocatalyst as compared to Pt-TiO 2 system, NWT was decorated with various Cu percentages and then with minimal percentage of Ag on optimized Cu-NWT photocatalyst. The observed trend for photocatalytic hydrogen production has been found to be P25 TiO 2 < NWT < 1.0Cu-NWT < 0.5Pt-NWT ≤ 0.1Ag/1.0Cu-NWT. The marked increase by a factor of 103 in hydrogen production for the optimized bimetallic 0.1Ag/1.0Cu-NWT (10,184 μmol/g) photocatalyst compared to P25 TiO 2 (99 μmol/g), nearly threefold increment in hydrogen production than optimized 1.0 Cu-NWT (3,907 μmol/g) photocatalyst and comparable hydrogen production as compared to 0.5Pt-NWT (10,050 μmol/g) may be attributed to the successful synthesis of a highly porous NWT morphology, which offers large surface area, increased light absorption combined with the synergistic effects of surface plasmon resonance (SPR) and the Schottky barrier for H + reduction to H 2 gas. The optimization of TiO 2 morphology and inexpensive bimetallic decoration strategy opens up promising opportunities for the development of cost-effective photocatalysts in the realm of energy and environment. Photocatalytic hydrogen production titania photocatalysis morphological study SPR effect nanowire Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Highlights Synthesis of Ag/Cu-NWT photocatalysts for photocatalytic H 2 production. 3D hierarchical TiO 2 showed 2-fold surface area and 7-fold HER activity than P25. Cost effective co-metallic decoration was better choice over costly Pt system. Schottky junction, SPR and synergetic effect of Ag and Cu improved H 2 production. 1. Introduction Entire world is looking for a sustainable and alternative clean energy source in anticipation to the future high energy demand and to mitigate the issues of global warming and climate change (Ni et al. 2007 ; Navarro Yerga et al. 2009 ). The environmentally friendly nature of hydrogen as a green fuel, along with its comparable potential to fossil fuels when generated through the photocatalytic water splitting techniques has created significant interest in recent years in research community thereby presenting a feasible approach for its facile production using renewable and virtually inexhaustible solar energy. (Navarro et al. 2009 ; Melo and Silva 2011; Jafari et al. 2016 ; Baykara 2018 ). Although TiO 2 is a benchmark photocatalyst among various semiconductors due to its magnificent properties viz. chemical inertness, environmental compatibility, low cost, photoactivity, and excellent photostability, it has critical limitations of fast electron/hole recombination and limited photoconversion efficiency (Riegel and Bolton 1995 ; Ni et al. 2007 ; Amano et al. 2016 ). Therefore, it is indispensable to map out strategic approach for the betterment of TiO 2 in terms of its impediments to make it a powerful tool for technology transfer. The very first simplest approach could be a suitable morphology frame up resulting in high surface area and improved light absorption as compared to commercially available P25 TiO 2 (Amano et al. 2016 ). Thus to design the desired photocatalyst with favourable crystal structure and morphology for improved photoconversion efficiency has become crucial important (Bhatt and Lee 2017 ; Clarizia et al. 2017 ). The solvent and the reaction time are the key factors in determining the morphologies and dimensions of the anatase TiO 2 nanostructures (Padmanabhan et al. 2020 ). Das et al. demonstrated the tunability of the structures, sizes, and morphologies of anatase TiO 2 products by manipulating the reaction temperature and time, as well as utilizing mixed solvents with varying compositions (Das et al. 2008 ). Alshehri et al. investigated the photocatalytic reformation of methanol to hydrogen using PtOx (2.0 wt.%) deposited TiO 2 anatase with nanoparticles, nanotubes, and nanofibers morphology. Many researchers have reported that TiO 2 anatase nanotubes exhibit exceptional photocatalytic activity (Alshehri and Narasimharao 2020 ). A 3D Pt/TiO 2 architecture composed of numerous 1D TiO 2 nanowires was synthesized by Li et al. using a one-pot solvothermal method, with a photocatalytic hydrogen production rate of 13.33 mmol h − 1 g − 1 . This excellent performance can be attributed to the cumulative effects of the unique TiO 2 architecture, allowing enhanced light absorption depths along with the presence of noble metal decoration (Li et al. 2015a ). Recently literature also reports the decoration of bimetallic nanoparticles to improve the photocatalytic activity of TiO 2 (Zielińska-Jurek 2014 ). Liu et al. have provided a comprehensive review of various bimetallic cocatalyst systems, including bi-noble and non-noble metal cocatalysts, plasmonic and non-plasmonic bimetallic cocatalysts, among others, for photocatalytic hydrogen production from water. The review aimed to underscore the synergetic effects within bimetallic systems and elucidate the impact of factors such as elemental composition, overall metal loading, structure, particle size, and more (Liu et al. 2021 ). Decorating semiconductor photocatalysts with cocatalysts has been emerged as a potent strategy to mitigate the recombination of photo-excited electron-hole pairs, minimize overpotential for redox reactions, enhance visible light absorption, suppress reverse reactions, and ultimately improve the overall efficiency of photocatalysis (Zhang et al. 2014 ; Gao et al. 2017 ; She et al. 2020 ). Although noble metallic or noble bi-metallic cocatalyst systems such as Pt/Au (Shuang et al. 2016 ; Grabowska et al. 2016 ; Gołąbiewska et al. 2017 ), Pd/Au (Xin et al. 2015 ; Zhang et al. 2015b ; Han et al. 2015 ; She et al. 2020 ), etc show high performance but their towering costs and inadequate reserves restrict their applications for large scale commercialization in future. Thus, one of the efficacious strategies would be to use a combination of noble metal with a low-cost and abundantly available non-noble transition metals, such as Ni (Tian et al. 2015 ), Co (Iwasaki et al. 2000 ; Sadanandam et al. 2013 ), Cu (Zhang et al. 2015a ; Mani et al. 2024 ; Zou et al. 2024 ) and Sn (Gao et al. 2019 ) as cocatalysts without compromising with the performance for hydrogen production. The current emphasis on cost-effective and highly efficient noble and non-noble metal bimetallic cocatalyst systems, as opposed to monometallic cocatalysts, underscores the remarkable synergetic effects that can significantly enhance catalytic activity and stability (Mani et al. 2024 ; Li et al. 2024 ; Yadav et al. 2024 ; Ramírez et al. 2024 ; 2024 ). Wang et al. and Reddy et al. have reported comparable bimetallic systems, namely hydrogenated Ag-Cu-modified P25 TiO 2 and Cu/Ag quantum dots on TiO 2 nanotubes, demonstrating hydrogen production rates of 1.16 mmol h − 1 g − 1 and 56,167 µmol h − 1 g − 1 (Reddy et al. 2017 ; Wang et al. 2022 ) respectively Through a comprehensive literature survey, it has been noted that no detailed study has been conducted to substantiate the morphological optimization along with plasmonic noble-non noble bimetallic cocatalyst decoration of TiO 2 for cost-effective and enhanced photocatalytic hydrogen production. Thus, at this point, it would be highly intriguing to explore the advantages offered by both aspects i.e. TiO 2 morphology optimization for improved light harvesting and high surface area and further decoration of bimetallic nanoparticles on the TiO 2 surface. Decoration of noble metal Pt has been studied extensively due to its fascinating co-catalyst attributes (Li et al. 2015a ; Denisov et al. 2019 )(Mani et al. 2024 ). But Pt decoration ends up with higher cost issues. Therefore, decoration of inexpensive non-noble metal Cu along with low-cost noble metal Ag with their individual properties of visible light harvesting ability along with an excellent electron sink capacity and surface plasmon resonance (SPR) effect respectively for improved solar photocatalytic hydrogen production would be an interesting piece of research. In view of this, firstly, we have performed a detailed investigation on the synthesis and characterization of different morphologies of TiO 2 by solvothermal method and checked for their photocatalytic hydrogen production capacity. NWT like morphology of TiO 2 was found to be the best as compared to other obtained morphologies with a remarkable photocatalytic hydrogen production activity (678 µmol/g) which was nearly 7-fold better than benchmark P25 TiO 2 (99 µmol/g). NWT was further decorated with popular co-catalyst Pt for improved hydrogen production. In the later part, non-noble metal Cu decoration and its percentage optimization on NWT (Cu-NWT) was carried out with further co-decoration of minimal quantity of plasmonic noble metal Ag (Ag/Cu-NWT) for improved hydrogen production activity comparable with Pt-NWT with an added advantage of cost effectivity. The proposed mechanism outlined at the end emphasizes the highly porous morphology of NWT, which enhances light absorption through repeated light reflection and refraction. This, combined with increased charge transfer and separation, the surface plasmon resonance (SPR) effect from Ag nanoparticles, and the electron sink capability of Cu, collectively contributes to the improvement in photocatalytic hydrogen production. 2. Experimental 2.1. Materials Titanium tetraisopropoxide (Ti {OCH(CH 3 ) 2 } 4 ) and Hexachloroplatinic acid (H 2 PtCl 6 ) were purchased from Sigma Aldrich; Hydrochloric acid (HCl) and Methanol (CH 3 OH) were purchased from SDFCL; Sodium hydroxide (NaOH), Ethylene glycol (CH 2 -OH) 2 , Copper sulphate (CuSO 4 .H 2 O) were purchased from Merck; Silver nitrate (AgNO 3 ) was purchased from Thermo Fisher Scientific India Pvt. Ltd. All chemicals used are of analytical reagents grade (AR). The chemicals were utilized as it is, without undergoing additional purification procedures. 2.2. Synthesis of catalyst materials In the typical process, 0.2M TTIP (Titanium tetraisopropoxide) in 50 mL ethylene glycol was taken in a round bottom flask and was stirred for 2 h. 50 mL of 10M NaOH was then added slowly to this TTIP solution and stirred for 3 h to get a clear solution. The reaction mixture was then put in an autoclave for 16 h at 200 ºC. Then the precipitate was washed with 0.2M HCl and distilled water several times and then was kept in a vacuum oven overnight at 80 ºC. The product was then calcined for 2 h at 500 ºC which gave white powder of Nanowire TiO 2 (NWT) as demonstrated in Fig. 1 (Li et al. 2015b ). Different morphologies of TiO 2 were obtained as a function of NaOH concentration (ranging from 5–20M) and labelled as TiO 2 at 5M NaOH (TiO 2 @5M), TiO 2 at 10M NaOH (NWT), TiO 2 at 15M NaOH (TiO 2 @15M) and TiO 2 at 20M NaOH (TiO 2 @20M). All these samples were further investigated for their improved photocatalytic hydrogen production capacity over P25 TiO 2 . The obtained data was then taken into consideration to correlate the relationship between the morphology and photocatalytic hydrogen production capacity. For the preparation of 0.1Ag/1.0Cu-NWT, as prepared and optimized 1.0 Cu-NWT photocatalyst (supporting information) was further decorated with a minimal quantity of 0.1% Ag, for which silver nitrate (AgNO 3 ) was used as a precursor. The typical synthesis of Ag decorated 1.0Cu-NWT (labelled as 0.1Ag/1.0Cu-NWT) was carried out by mixing 0.095 mL of 0.02 M AgNO 3 solution with 200 mg of 1.0Cu-NWT in 10% methanol solution. Subsequently, the mixture was subjected to UV light irradiation for 3 h, followed by washing with distilled water and drying at 60°C to obtain the desired product. Pt decorated NWT (Pt-NWT) and its percentage variation also prepared by using the photo-deposition method as mentioned in supplementary information (Reddy et al. 2017 ; Shinde et al. 2018a ). 2.3. Photocatalytic hydrogen production setup All the photocatalytic hydrogen production reactions were checked in simulated solar light. In the standard experimental procedure, a 10% methanol solution (100 mL) was placed in a 200 mL quartz reactor with a top loading port. Here, methanol has been used as hole scavenger as it is relatively stable compound under various experimental conditions. Further it is inexpensive and widely available which makes it a cost-effective choice for large-scale experiments, unlike some other sacrificial agents which can be more expensive or difficult to source in large quantities. (Guzman et al. 2013 ; Schneider and Bahnemann 2013 ). Due to all these reasons 10% methanol solution was the best choice. To this 100mL solution, 40 mg of catalyst was added. The quartz reactor was then packed with a rubber cork and nitrogen gas was purged into it for 10 minutes to remove the other gases present in the free space of the quartz reactor as well as dissolved in the reaction solution. The quartz reactor was then mounted in front of 1000 W Xenon lamp irradiation which is a case similar to solar irradiation. At specific time intervals, samples were extracted and the amount of generated hydrogen gas was determined using offline Shimadzu GC-2014 gas chromatography (GC) equipped with a thermal conductivity detector (TCD) and a molecular sieve/5A column. The measurement was performed at 70°C utilizing N 2 as the carrier gas (Shinde et al. 2018b ). Recyclability test of optimized photocatalyst was carried out upto 5 cycles to check the stability and reusability of the photocatalyst. After completion of the first cycle, the quartz reactor was dismounted, rubber cork was removed and kept as it is overnight under ambient conditions by covering it with aluminium foil. In the second cycle, the same solution was employed and purged with N 2 gas to preserve a neutral environment within the reactor. The solution was then exposed to solar simulated light for 4 h. This procedure was repeated for the subsequent three cycles, and the hydrogen production was quantified using GC. 2.4. Characterization of the photocatalysts The prepared photocatalysts underwent various characterization techniques. X-ray diffraction (XRD) analysis was performed using a Rigaku Ultima IV instrument with Cu K alpha radiation, scanning at a rate of 10 o /min and a sampling width of 0.02 o to determine the crystallographic information. Fourier Transform Infrared Spectra (FTIR) in the mid-IR region (400 to 4000 cm-1) were recorded using a Bruker Tensor 37 instrument. UV-visible absorption spectra (DRS) were obtained using a Shimadzu 1800 UV-visible spectrophotometer. X-ray photoelectron spectroscopy (XPS) analysis was employed using PHI 5000 Versa Probe III equipment and Al Kα radiation as the excitation source to ascertain the oxidation state of the photocatalyst. Scanning Electron Microscopy (SEM) images were acquired using a Quanta FEG 450 instrument, along with Energy Dispersive X-ray (EDX) analysis. Raman Spectroscopy was conducted on a micro-Raman spectrometer Lab RAM ARAMIS, Horiba Jobin-Yvon instrument, specifically for carbon photocatalysts characterization. Transmission Electron Microscopy (TEM) images were captured using a JEOL JEM F200, Tokyo instrument. The BET method, employing a Quantachrome Auto sorbiQ instrument, was utilized to measure porosity and surface area. The quantity of evolved hydrogen gas was measured using a Gas Chromatography (GC) Shimadzu GC 2014 equipped with a TCD detector, and a PORAPAK Q column (length 2.0 m, ID 3.13 mm) was employed (Wadhai et al. 2021 ). 3. Results and discussion 3.1. Catalyst characterization X-ray diffraction (XRD) analysis was conducted to investigate the crystalline structure of the photocatalysts, including NWT, Pt-NWT, Cu-NWT, and Ag/Cu-NWT (Fig. 2 a and S1). The XRD pattern of NWT revealed a highly crystalline anatase structure with dominant peaks at 2θ = 25.3 ◦ , 37.9 ◦ , 48 ◦ , and 54.9 ◦ corresponding to the (101), (004), (200), and (211) planes, respectively, as indicated by the JCPDS Card No. 21-1272 (Zhu et al. 2021 ). Figure 2 a shows the XRD patterns of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT photocatalysts. For all these four photocatalysts the major peaks observed were of the anatase phase of TiO 2 . There was no peak of Pt, Cu or Ag found in the XRD pattern because of the very small quantity of these metals in the metal-decorated NWT photocatalysts. All the optimized photocatalysts also showed the characteristic peak at 2θ = 25.3 ◦ , 37.9 ◦ , 48 ◦ and 54.9 ◦ corresponding to (101), (004), (200) and (211) planes respectively which not only confirms the formation of high crystallinity but also pure compound. The intensity of the reflections related to the TiO 2 anatase phase decreased following the deposition of metals, suggesting that the presence of an additional crystalline phase had modified the crystalline structure of TiO 2 (Alshehri and Narasimharao 2020 ). High crystallinity and co-presence of Ag and Cu on NWT photocatalysts are responsible for enhanced light harvesting capacity and ultimately the photocatalytic hydrogen production. Fig. S1 a shows the XRD pattern of NWT and Pt-NWT (0.2Pt-NWT, 0.4Pt-NWT, 0.5Pt-NWT, 0.6Pt-NWT, 0.8Pt-NWT and 1.0Pt-NWT) photocatalysts and Fig. S1 b shows the XRD of Cu-NWT (0.5Cu-NWT, 0.75Cu-NWT, 1.0Cu-NWT, 1.5Cu-NWT and 2.0Cu-NWT) photocatalysts. The XRD pattern of all Pt-NWT and Cu-NWT photocatalysts retained the peak of bare NWT and no other peak or impurity was observed. Raman measurements for all four samples i.e., NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT were carried out. Figure 2 b exhibits the Raman spectroscopy analysis, elucidating the characterization of the Ti-O-Ti network structure of NWT materials within the wavenumber range of 100–900 cm − 1 . Notably, the well-established anatase peaks at 142, 393, 511, and 635 cm − 1 are distinctly observed. In the case of NWT, these four pronounced peaks at 142, 393, 511, and 635 cm − 1 correspond to the vibration modes of Eg, B1g, A1g, and Eg, respectively, aligning with the TiO 2 anatase phase. The Eg peak arises predominantly from the symmetric stretching vibration of the O–Ti–O linkages in TiO 2 , whereas the B1g peak corresponds to the symmetric bending vibration of O–Ti–O and the A1g peak is attributed to the antisymmetric bending vibration of the O–Ti–O linkage (Balachandran and Eror 1982 ; Melvin et al. 2015 ). In the case of Pt-NWT, Cu-NWT, and Ag/Cu-NWT, no distinct separate peak was observed. However, a slight shift towards lower wavenumbers and broadening of the peak were noted compared to bare NWT. This phenomenon can be attributed to the strong electronic interaction between the metals and the surface of NWT (Fan et al. 2014 ). Thus, Ag and Cu decoration improves the crystal structure of anatase TiO 2 . The phase of NWT was retained even after the metal decoration. These findings are consistent with the XRD data mentioned earlier. Fig. S2 shows the FTIR spectra of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT photocatalysts. The FTIR spectra manifest prominent and comprehensive peaks, signifying the existence of diverse functional groups within the materials. Notably, a slight dip around 3360 cm − 1 and 1643 cm − 1 can be attributed to the stretching and bending vibrations of adsorbed molecules and surface hydroxyls on TiO 2 particles, respectively (Li et al. 2016 ; Chougala et al. 2017 ). The intense peak at 485 cm − 1 is assigned to the Ti-O stretching band which is the characteristic peak of TiO 2 (Zhang et al. 2014 ). There is no significant peak-shift or extra peak observed in optimized metal decorated NWT photocatalysts because of a very small percentage of metal present in it and/or can be mainly attributed to the metal loading effect. The optical and electronic properties of materials have been characterized by using Diffuse Reflectance Spectroscopy (DRS). To gain insights into the optical absorbance of the optimized photocatalysts, namely NWT, 0.5Pt-NWT, 1.0Cu-NWT, and 0.1Ag/1.0Cu-NWT, Fig. 2 c presents the UV-visible diffuse reflectance spectroscopy (DRS) data. The strong absorption bands around 380 nm, attributed to the intrinsic absorption of TiO 2 , are thought to result from the excitation of O2p electrons to the Ti3d level (Xu et al. 2010 ; Zhang et al. 2015b ). Absorption edges of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT are around 390 nm, 408 nm, 420 nm and 435 nm respectively. The DR spectra of the modified NWT is noteworthy for exhibiting a significant shift in the absorption transition towards longer wavelengths (400 nm < λ < 435 nm). The extended visible light absorption of 0.1Ag/1.0Cu-NWT among all photocatalysts is due to the plasmonic resonance and light harvesting capacity of Ag and Cu respectively which shows absorption above 400 nm (Wang et al. 2022 ). The absorption of 0.5Pt-NWT and 1.0Cu-NWT was found to be significantly lower compared to 0.1Ag/1.0Cu-NWT, which could be attributed to the lower sensitivity of Pt and Cu to visible light absorption relative to Ag. Ultimately co-decoration of both Ag and Cu on NWT is found to be responsible for improved photocatalytic hydrogen production. Optical band gap studies have been carried out using Tauc Plot (Fig. S9), observed that the absorption shifts are consistent with a reduction in the optical band gap energies, mirroring the trends observed in the absorption spectra. Notably, Ag/Cu-NWT (3.06 eV) exhibits a significantly lower band gap energy compared to bare NWT (3.27 eV), Pt-NWT (3.20 eV), and Cu-NWT (3.15 eV). The reduction in band gap energy in Ag/Cu-NWT is likely due to the synergistic effect of silver and copper decoration, which enhances charge carrier separation and facilitates better light absorption in the visible region, thereby narrowing the band gap (Scarisoreanu et al. 2020 ). While Pt-NWT and Cu-NWT also exhibit some degree of band gap narrowing, they are not as effective as the Ag/Cu combination. Platinum, although excellent for enhancing photocatalytic activity, is costly and does not significantly affect light absorption in the visible range. Copper alone provides some enhancement in visible light absorption, but it is the addition of silver that amplifies the effect due to the plasmonic resonance (Zhu et al. 2019 ; Scarisoreanu et al. 2020 ; Liu et al. 2022 ). To gain insight into the growth process of the NWT structure, we monitored the growth steps of the samples using SEM at various NaOH concentrations. Fig. S3 shows the SEM images of synthesised TiO 2 at different NaOH concentrations at the same magnification i.e., at 1µm. Irregular morphology of TiO 2 (TiO 2 @5M) was observed with 5M NaOH solution in the synthesis method. Well-organized 3D spheres made up of nanowire TiO 2 (NWT) morphology was obtained with 10M NaOH solution. The rod like (TiO 2 @15M) and scale like (TiO 2 @20M) morphologies of TiO 2 were obtained when 15M and 20M NaOH solution was used in the synthesis method. It is obvious from the above data that the NaOH concentration in the reaction mixture plays crucial role in morphology elucidation. It can also be inferred that the morphology of the product can be controlled by the choice of solvent (Lu et al. 2021 ). Solvent provides sufficient space to grow the titanium oxide into nano-wire ball like morphology. The observed variations in morphologies can be attributed to the polarity and coordinating ability of the co-solvent, which significantly affects the solubility, reactivity, and diffusion behaviour of the reactants, thereby influencing the structural and morphological characteristics of the final products (Das et al. 2008 ; Lu et al. 2021 ). The optimized NWT morphology not only enhanced light harvesting ability due to its unique nanowire ball like structure but also improved its surface area due to high porosity for enhanced photocatalytic hydrogen production. The efficient 0.1Ag/1.0Cu-NWT photocatalyst's microscopic nature was first characterized by SEM (Fig. 3 a-c), and then by low-resolution transmission electron microscopy (LRTEM) and high-resolution transmission electron microscopy (HRTEM) (Fig. 3 d-h). Uniformly dispersed ball like structure made up of nanowire is shown in Fig. 3 a having diameter of nanowire as 10–20 nm and the whole NWT structure is around 3–4 µm as confirmed by SEM images (Fig. S4). Figure 3 d-h shows LRTEM and HRTEM images of optimized 0.1Ag/1.0Cu-NWT photocatalyst. The lattice fringes observed in the HRTEM image (Fig. 3 g-h) of 0.1Ag/1.0Cu-NWT correspond to the (111) plane of Ag (d = 0.24 nm) (Li et al. 2017 ), (111) plane of Cu (d = 0.211 nm) (Kainthla et al. 2018 ) and (101) plane of anatase TiO 2 (d-space value of 0.326 nm) (Reddy et al. 2017 ). These results provide clear evidence of homogeneously dispersed Ag and Cu in their metallic forms on the NWT surface, indicating a close association between them. The crystalline quality of the 0.1Ag/1.0Cu-NWT photocatalyst was further demonstrated by the Selected Area Diffraction (SAED) pattern shown in Fig. 3 i, which reveals a well-defined diffraction pattern with a lattice spacing of 0.326 nm, matching the (101) plane of anatase TiO 2 . SAED pattern of the TiO 2 nanowires reveal their single crystallinity and conclude the growth of the single-crystal TiO 2 nanowire/nanorod along the [0 0 1] direction (Sun et al. 2013 ). Corresponding LR and HRTEM along with SAED pattern for 0.5Pt-NWT and 1.0Cu-NWT photocatalysts are shown in Fig. S5a-d and S5e-h respectively. Figure 4 presents the elemental mapping and TEM-EDAX analysis to visualize the distribution of elements and determine the atomic percentage of each element across the 0.1Ag/1.0Cu-NWT photocatalyst. Figure 4 a-f shows elemental mapping of 0.1Ag/1.0Cu-NWT photocatalyst depicting the homogeneous dispersion of elements throughout the sample. Figure 4 g shows TEM-EDAX spectra of 0.1Ag/1.0Cu-NWT photocatalyst which confirms the presence of 0.13% Ag, 6.72%Cu, 53.56% O and 39.58% Ti atomic percentages. Cu atomic percentage has been found to be higher than the actual percentage of synthesized 1%Cu-NWT which might be due to the copper gride used for the sample analysis. Overall observation confirmed the presence of Ag and Cu in the 0.1Ag/1.0Cu-NWT photocatalyst. The impressive organization of nanowires in TiO 2 serves as a driving force for our in-depth examination for its Brunauer–Emmett–Teller (BET) surface area and pore volume. Consequently, we conducted an investigation onto the N 2 sorption isotherm and corresponding BET surface area plot of both P25 TiO 2 and NWT, aiming to validate the superior photocatalytic performance of NWT compared to P25 TiO 2 (as shown in Fig. S6). TiO 2 being the main photocatalyst which would contribute to the photocatalytic efficiency majorly due to its surface area and other properties, therefore BET surface area, pore volume, and pore size diameter of the P25 and NWT has been reported in Table 1 . Metal decoration or co-decoration did not contribute much to the surface area. As expected, the BET surface area of NWT (123 m 2 g − 1 ) was found to be significantly higher than that of P25 TiO 2 (52.90 m 2 g − 1 ). The well-organized porous morphology of NWT exhibits a 2.5 times greater surface area than P25 TiO 2 , leading to improved light harvesting ability through repeated reflection and refraction. Additionally, the increased surface area provides more active reaction sites and facilitates mass transfer, allowing for efficient transport of reactant and product molecules. Table 1 BET surface area, pore volume and pore size diameter values of the P25 TiO 2 , and NWT samples. Sample BET surface area (m 2 /g) Pore volume (cm 3 /g) Pore size diameter (nm) P25 52.90 0.354 25.94 NWT 123.00 0.636 16.20 Since 0.1Ag/1.0Cu-NWT display high crystallinity and well optical response ability, it is very necessary to investigate its surface compositions and electronic status, X-ray photoelectron spectroscopy (XPS) analysis was also performed. Figure 5 a illustrates the survey spectrum of the 0.1Ag/1.0Cu-NWT photocatalyst, revealing the presence of elements Ti, O, Cu, and Ag. Figure 5 b shows the peaks corresponding to Ti 2p at 458.80 eV and 464.55 eV, and 530.23 eV and observed data of O1s peak (Fig. 5 c ) includes one major peak at 530.23 eV and small shoulder also appeared at 532.22 eV corresponding to the binding energies of O1s, which was attributed to O 1s electron binding energy for TiO 2 and the H–O from the absorbed H 2 O on their surface respectively (Erdem et al. 2001 ; Kruse and Chenakin 2011 ; Zhu et al. 2017 ). The Ti 2p region displays an asymmetric peak at 458.80 eV and 464.55 eV, corresponding to the binding energies of Ti 2p 3/2 and Ti 2p 1/2 , respectively (Erdem et al. 2001 ; Su et al. 2013 ). The binding energy values at 367.85 and 373.82 eV refers to Ag 3d 5/2 and Ag 3d 3/2 , respectively (Fan et al. 2014 ). This observation confirms the presence of metallic silver (Ag⁰) in the sample. The peaks at 932.75 and 952.56 eV are identified as Cu 2p 3/2 and Cu 2p 1/2 , respectively, indicating the presence of Cu in reduced form (Cu⁰) (Zhang et al. 2015a ; Reddy et al. 2017 ). High resolution spectra of Cu 2p and Ag 3d serving as proof of Cu and Ag in their metallic states. The XPS spectra of 0.5Pt-NWT photocatalyst is depicted in Fig. S8, and the presence of Platinum species was confirmed through deconvolution of Pt 4f peak into two components, Pt 4f 7/2 and Pt 4f 5/2 , at binding energies 68.97 and 72.52 eV, respectively (Fig. S8d) (Shinde et al. 2018b ; Sravani et al. 2020 ). 3.2. Photocatalytic hydrogen production A series of methodical experiments on photocatalytic hydrogen production were conducted, employing simulated solar light irradiation, and utilizing methanol as a sacrificial agent across all the prepared photocatalysts. A comparison was made with commercially available P25 TiO 2 . P25 TiO 2 , being the widely recognized benchmark photocatalyst in commercial use, is the preferred starting point for further development and modifications aimed at overcoming its limitations. The objective is to augment the efficiency while maintaining the cost-effectiveness of both the photocatalyst and the experimental configuration for solar-driven photocatalytic hydrogen generation. Thus, motivated by this idea, focused attempts were made to obtain and optimize the morphology of synthesized TiO 2 which would deliver much more superior results as compared to commercially available P25 TiO 2 in terms of efficiency. Thus initially, the effect of morphology of TiO 2 on the hydrogen production capacity was studied. Moreover, the optimized morphology was further improved by decorating it with noble metal Pt, non-noble metal Cu, and a combination of non-noble Cu and a minimal amount of noble metal Ag to further enhance hydrogen production. The trend observed for photocatalytic hydrogen production, as depicted in Fig. 6 a, is as follows: P25 TiO 2 < NWT < Cu-NWT < Pt-NWT ≤ Ag/Cu-NWT. Optimized low-cost 0.1Ag/1.0Cu-NWT (10,184 µmol/g) photocatalyst showed the highest hydrogen production as compared to all P25 TiO 2 , NWT, Cu-NWT photocatalysts and at par hydrogen production with 0.5Pt-NWT (10,050 µmol/g) photocatalyst. Morphology obtained by using 10 M NaOH concentration i.e., NWT showed a dramatic increment in hydrogen production than other morphologies obtained at 5 M, 15 M and 20 M respectively (Fig. 6 b). In comparison to the commercially available P25 TiO 2 (99 µmol/g), NWT exhibited a remarkable nearly 7-fold increase in hydrogen production capacity (678 µmol/g). This significant improvement in photocatalytic efficiency can be attributed to the favourable morphology achieved through the specific arrangement of atoms. This morphology enhances the absorption of light energy (as shown in Fig. 2 d and S7) and facilitates mass transfer through the increased specific surface area (see BET explanation). To achieve the highest possible activity, NWT was modified by decorating with the popular noble metal Pt since Pt has more work function as well as better reduction potential than other noble metals. Various % Pt-NWT photocatalysts were synthesized and checked for photocatalytic hydrogen production. Optimized 0.5Pt-NWT (10,050 µmol/g ) showed a better increment in hydrogen production than other Pt percentages. 0.2 to 0.5 percentage of Pt with NWT i.e., 0.2Pt-NWT, 0.3Pt-NWT, 0.4Pt-NWT and 0.5Pt-NWT shows gradual increment in hydrogen production (Fig. 6 c). The photocatalytic performance of nanowire-tethered (NWT) materials decreases when the Pt content exceeds 0.5%, a result of the light-blocking and scattering effects caused by the accumulation of Pt on the NWT surface (Sun et al. 2012 ; Lee and Chang 2019 ). However, the optimized 0.5Pt-NWT exhibited significantly enhanced hydrogen production, reaching nearly a 15-fold increase compared to NWT (678 µmol/g) and a remarkable 102-fold increase compared to P25 (99 µmol/g). The reason behind the betterment is the Pt decoration on NWT which reduces the electron hole recombination and increases the absorption of light energy (Fig. 2 b-c and 7 ). Further, as Pt-TiO 2 , is a very exhaustively studied system due to the very high work function of Pt to reduce H + to H 2 for enhanced efficiency, it is always a challenge to work out a system or photocatalyst which would be a cost-effective alternative to beat Pt-TiO 2 . Therefore, the study was further directed to modify the optimized NWT photocatalyst with bimetallic non-noble metal Cu and low-cost noble metal Ag to explore and exploit their very fascinating properties of SPR effect and extended solar light absorption for improved hydrogen production activity at par with Pt-TiO 2 systems. Firstly, TiO2 decoration with varying Cu concentration in the range of 0.5 to 2% has been studied. 1% Cu-NWT was found to show excellent improvement in hydrogen production sample among other concentrations; however these results were still lower than the Pt-NWT system. In this attempt, initially, NWT was decorated with an inexpensive non-noble metal Cu with its percentage varying from 0.5 to 2%. (Fig. 6 d). The increasing hydrogen production trend was observed from 0.5%to1.0%, and on further increase in Cu % the trend was found to decrease. The optimized 1.0Cu-NWT photocatalyst (3,907 µmol/g) demonstrated a substantial increase in hydrogen production, achieving nearly 6-fold improvement compared to NWT (678 µmol/g) and a remarkable 40-fold increase compared to P25 TiO 2 (99 µmol/g). This enhancement in hydrogen production is due to the presence of Cu which absorbs plasmon-induced irradiation to generate hot electrons which are partly ejected to CB of TiO 2 overcoming the Schottky barrier and separating the photogenerated charge carriers significantly (Zhang et al. 2015a ; Kumaravel et al. 2019 ). Further, optimized 1.0Cu-NWT was decorated with a minimal quantity of Ag to improve the efficiency of the photocatalyst and to get comparable results at par with Pt-NWT photocatalyst. A very small quantity of Ag i.e., 0.1% Ag was decorated on an optimized 1.0Cu-NWT photocatalyst which resulted in a dramatic increment in photocatalytic hydrogen production capacity as compared to Cu-NWT, NWT as well as P25 TiO 2 . 0.1Ag/1.0Cu-NWT (10,184 µmol/g ) photocatalyst showed almost 2.6-fold increment in hydrogen production than 1.0Cu-NWT (3,907 µmol/g) photocatalyst. This improvement also showed comparable hydrogen production as of optimized 0.5Pt-NWT (10,050 µmol/g) photocatalyst (Fig. 6 a). The main reason for choosing 0.1%Ag on 1.0 Cu-NWT system was to highlight that even the very small amount viz. 0.1% of Ag along with 1.0Cu-NWT will be sufficient to replace the 0.5Pt-NWT. It is indeed interesting to study the effect of variable concentration of Ag with 1.0 Cu-NWT system for further enhancement in hydrogen production. The detail study and optimization of variable metal concentrations and combinations of different metals will surely replace the Pt in future for cost-effective catalysts for cheap hydrogen production. The remarkable photocatalytic performance exhibited by the 0.1Ag/1.0Cu-NWT photocatalyst can be attributed to several key factors. Firstly, its unique morphology and bimetallic decoration play a crucial role. These features enable enhanced absorption of visible light, resulting in more efficient utilization of solar energy. Additionally, the modified structure of the photocatalyst leads to an increased surface area, providing more active sites for the photocatalytic reaction. Moreover, the bimetallic decoration facilitates accelerated charge transfer processes, enhancing the overall efficiency of the photocatalyst. Lastly, the presence of silver and copper on the nanowires effectively suppresses the recombination of photogenerated electron-hole pairs, leading to an extended lifetime of the charge carriers and further enhancing the photocatalytic performance. These attributes ultimately result in excellent photocatalytic hydrogen production, as explained in the mechanism section. To evaluate the reusability of the optimized 0.1Ag/1.0Cu-NWT photocatalyst, cyclic experiments were performed under identical experimental conditions. As depicted in Fig. 6 e, the amount of hydrogen production remained consistent throughout the five cycles. This observation indicates that the photocatalyst maintained its activity without any noticeable decrease, demonstrating its remarkable stability. 3.3. Mechanism of photoinduced charge transfer in Ag/Cu-NWT The results obtained indicate that the 0.1Ag/1.0Cu-NWT photocatalyst possesses remarkable photocatalytic hydrogen production ability under simulated solar light irradiation. In order to elucidate the mechanism responsible for enhanced photocatalytic hydrogen production, a plausible charge transfer pathway is proposed and visually illustrated in Fig. 7 . The achieved nanowire ball-like morphology of the photocatalyst through the use of 10M NaOH resulted in a significant improvement in hydrogen production. This enhancement can be attributed to the unique structure of the photocatalyst, which plays a vital role in efficiently harnessing light energy through repeated reflection and refraction from the light source. This ball-like arrangement of nanowires also has been found to improve the porosity and surface area of the photocatalyst which ultimately facilitates more reaction sites and mass transfer. The 2.5 times improved BET surface area and UV-visible DRS (Fig. 2 d) spectral data of NWT clearly demonstrates probable reasons for 7-fold improved photocatalytic hydrogen production as compared to P25 TiO 2 . To achieve the highest possible activity at par or better than Pt-TiO 2 with an added advantage of cost effectivity, the NWT was decorated with non-noble metal Cu and a minimal quantity of noble metal Ag. 0.1Ag/1.0Cu-NWT. The unique structure of this photocatalyst exhibited superior hydrogen production compared to all other prepared photocatalysts, and similar hydrogen production to that of 0.5Pt-NWT. This can be attributed to the proposed charge transfer mechanism, where upon light irradiation, electrons are excited from the valence band to the conduction band of NWT, and hot electrons are continuously supplied to the conduction band of TiO 2 due to the collective oscillation of conduction band electrons of decorated Ag nanoparticles. The surface plasmon resonance (SPR) effect of the decorated Ag nanoparticles enhances the absorption of visible light, resulting in more photoelectrons being available in the conduction band of NWT. (Nyamukamba et al. 2017 ). Further, these photoexcited electrons are captured by Cu which acts as an electron sink for the effective H + to H 2 reduction reaction. Thus, Cu decoration not only acts as a co-catalyst but also plays an important role in charge separation (Reddy et al. 2017 ; Wang et al. 2022 ). The VB holes are trapped by methanol which acts as a hole scavenger or used for the oxidation process of H 2 O (Denisov et al. 2019 ). Hence, notwithstanding the significance of the SPR effect, the catalytic activity of co-metallic decorated Ag and Cu on NWT exerts a more influential effect by mitigating electron-hole recombination and promoting the charge transfer rate. In conclusion, the combination of the tailored morphology of TiO 2 (NWT) and the co-metallic decoration (Ag/Cu-NWT) bestows exceptional characteristics upon the photocatalyst. These features encompass amplified light absorption in the visible spectrum, augmented surface area, expedited efficiency in charge transfer, and subdued recombination of photogenerated electron-hole pairs. Collectively, these factors contribute to the remarkable photocatalytic hydrogen production achieved by the catalyst. 4. Conclusions We have successfully synthesized NWT using the solvothermal method, as well as Pt-NWT, Cu-NWT, and Ag/Cu-NWT using the photo-deposition method. These photocatalysts have been thoroughly characterized using various techniques including XRD, FTIR, Raman, UV-visible DRS, BET, SEM, LRTEM-HRTEM, and XPS. TiO 2 with different morphologies were obtained at different NaOH concentrations as confirmed by the SEM analysis. 3D self-assembled nanowire TiO 2 (NWT) morphology was found to have greater potential to absorb more light energy due to its structure and higher surface area thereby providing more active sites for improved photocatalytic hydrogen production than other morphologies. Further, NWT was successfully decorated with traditional noble metal Pt, non-noble metal Cu and a bimetallic combination of Ag/Cu respectively to compare their efficiencies. The deposition of Cu and Ag particles on NWT with homogeneous dispersion of these elements throughout 0.1Ag/1.0Cu-NWT photocatalyst has been confirmed by elemental mapping, TEM-EDAX and XPS analysis. The analysis of optical properties of the 0.1Ag/1.0Cu-NWT photocatalyst has unveiled its remarkable light absorption capabilities, primarily attributed to the surface plasmon resonance (SPR) effect induced by the presence of Ag and Cu. The finely structured morphology, along with the cooperative influences of bimetallic Ag and Cu embellishment on the surface of nanowire-TiO 2 (NWT) materials, facilitates augmented absorption of visible light and expanded surface area of the photocatalyst. Consequently, these factors engender heightened efficacy in charge transfer and inhibition of recombination of electron-hole pairs generated through photon absorption. The cumulative outcome is an outstanding level of activity in the process of photocatalytic hydrogen production. Importantly, this study emphasizes the facile fabrication of a cost-effective Ag/Cu-NWT solar photocatalyst as a viable alternative to the widely recognized Pt-TiO 2 system, while maintaining high photocatalytic hydrogen production capacity. Declarations Acknowledgements SW is thankful to UGC (Grant No.2061610320), New Delhi for Junior Research Fellowship and to P. E. S. Modern College of Engineering, Pune. PT is thankful to the Board of Research in Nuclear Sciences (BRNS) (Grant No. 2013/37C/52/BRNS/2464 Dated December 4, 2013), UGC-DAE Consortium for Scientific Research, University Grants Commission (Grant No. CSIR–IC–/MSRSR-15/CSR- 223/2017–18/1304) and UPE (II) grant under UGC, for financial support. The authors express their gratitude to the Central Instrumentation Facility (CIF) at the Department of Chemistry and the Department of Physics of Savitribai Phule Pune University, Pune, India for providing characterization facilities. The authors would like to express their gratitude to the National Chemical Laboratory (NCL), Pune, for granting access to the HRTEM characterization facility. Acknowledgements SW is thankful to UGC (Grant No.2061610320), New Delhi for Junior Research Fellowship and to P. E. S. Modern College of Engineering, Pune. PT is thankful to the Board of Research in Nuclear Sciences (BRNS) (Grant No. 2013/37C/52/BRNS/2464 Dated December 4, 2013), UGC-DAE Consortium for Scientific Research, University Grants Commission (Grant No. CSIR–IC–/MSRSR-15/CSR- 223/2017–18/1304) and UPE (II) grant under UGC, for financial support. The authors express their gratitude to the Central Instrumentation Facility (CIF) at the Department of Chemistry and the Department of Physics of Savitribai Phule Pune University, Pune, India for providing characterization facilities. The authors would like to express their gratitude to the National Chemical Laboratory (NCL), Pune, for granting access to the HRTEM characterization facility. Data availability: The data can be requested from the authors. Ethical approval: Not applicable. Consent to participate: Not applicable. Consent to publish: Not applicable. Authors contributions: SW was involved in designing the methodology, material synthesis, conducting experiments, and original manuscript preparation. PT was involved in conceptualizing the research, providing the resources, guidance, reviewing, revising, and editing the manuscript, and supervising the research work. Funding: SW is thankful to UGC (Grant No.2061610320), New Delhi for Junior Research Fellowship. PT is thankful to the Board of Research in Nuclear Sciences (BRNS) (Grant No. 2013/37C/52/BRNS/2464 Dated December 4, 2013) and UGC-DAE Consortium for Scientific Research for financial support. Competing interests: The authors declare no competing interests. References Alshehri A, Narasimharao K (2020) PtOx-TiO2 anatase nanomaterials for photocatalytic reformation of methanol to hydrogen: effect of TiO2 morphology. J Mater Res Technol 9:14907–14921. https://doi.org/10.1016/j.jmrt.2020.10.087 Amano F, Nakata M, Yamamoto A, Tanaka T (2016) Rutile titanium dioxide prepared by hydrogen reduction of Degussa P25 for highly efficient photocatalytic hydrogen evolution. Catal Sci Technol 6:5693–5699. https://doi.org/10.1039/C6CY00296J Balachandran U, Eror NG (1982) Raman spectra of titanium dioxide. J Solid State Chem 42:276–282. https://doi.org/10.1016/0022-4596(82)90006-8 Baykara SZ (2018) Hydrogen: A brief overview on its sources, production and environmental impact. Int J Hydrogen Energy 43:10605–10614. https://doi.org/10.1016/j.ijhydene.2018.02.022 Bhatt MD, Lee JS (2017) Nanomaterials for photocatalytic hydrogen production: from theoretical perspectives. RSC Adv 7:34875–34885. https://doi.org/10.1039/C7RA03435K Chougala LS, Yatnatti MS, Linganagoudar RK, et al (2017) A simple approach on synthesis of TiO2 nanoparticles and its application in dye sensitized solar cells. J Nano- Electron Phys 9:2–7. https://doi.org/10.21272/jnep.9(4).04005 Clarizia L, Russo D, Di Somma I, et al (2017) Hydrogen Generation through Solar Photocatalytic Processes: A Review of the Configuration and the Properties of Effective Metal-Based Semiconductor Nanomaterials. Energies 10:1624. https://doi.org/10.3390/en10101624 Das K, Panda SK, Chaudhuri S (2008) Solvent-controlled synthesis of TiO2 1D nanostructures: Growth mechanism and characterization. J Cryst Growth 310:3792–3799. https://doi.org/10.1016/j.jcrysgro.2008.05.039 Denisov N, Yoo J, Schmuki P (2019) Effect of different hole scavengers on the photoelectrochemical properties and photocatalytic hydrogen evolution performance of pristine and Pt-decorated TiO2 nanotubes. Electrochim Acta 319:61–71. https://doi.org/10.1016/j.electacta.2019.06.173 Erdem B, Hunsicker RA, Simmons GW, et al (2001) XPS and FTIR Surface Characterization of TiO 2 Particles Used in Polymer Encapsulation. Langmuir 17:2664–2669. https://doi.org/10.1021/la0015213 Fan X, Fan J, Hu X, et al (2014) Preparation and characterization of Ag deposited and Fe doped TiO2 nanotube arrays for photocatalytic hydrogen production by water splitting. Ceram Int 40:15907–15917. https://doi.org/10.1016/j.ceramint.2014.07.119 Gao D, Wu X, Wang P, et al (2019) Simultaneous Realization of Direct Photoinduced Deposition and Improved H 2 -Evolution Performance of Sn-Nanoparticle-Modified TiO 2 Photocatalyst. ACS Sustain Chem Eng 7:10084–10094. https://doi.org/10.1021/acssuschemeng.9b01516 Gao H, Zhang P, Zhao J, et al (2017) Plasmon enhancement on photocatalytic hydrogen production over the Z-scheme photosynthetic heterojunction system. Appl Catal B Environ 210:297–305. https://doi.org/10.1016/j.apcatb.2017.03.050 Gołąbiewska A, Lisowski W, Jarek M, et al (2017) The effect of metals content on the photocatalytic activity of TiO2 modified by Pt/Au bimetallic nanoparticles prepared by sol-gel method. Mol Catal 442:154–163. https://doi.org/10.1016/j.mcat.2017.09.004 Grabowska E, Marchelek M, Klimczuk T, et al (2016) Preparation, characterization and photocatalytic activity of TiO 2 microspheres decorated by bimetallic nanoparticles. J Mol Catal A Chem 424:241–253. https://doi.org/10.1016/j.molcata.2016.09.004 Guzman F, Chuang SSC, Yang C (2013) Role of Methanol Sacrificing Reagent in the Photocatalytic Evolution of Hydrogen. Ind Eng Chem Res 52:61–65. https://doi.org/10.1021/ie301177s Han C, Wu L, Ge L, et al (2015) AuPd bimetallic nanoparticles decorated graphitic carbon nitride for highly efficient reduction of water to H2 under visible light irradiation. Carbon N Y 92:31–40. https://doi.org/10.1016/j.carbon.2015.02.070 Iwasaki M, Hara M, Kawada H, et al (2000) Cobalt Ion-Doped TiO2 Photocatalyst Response to Visible Light. J Colloid Interface Sci 224:202–204. https://doi.org/10.1006/jcis.1999.6694 Jafari T, Moharreri E, Amin A, et al (2016) Photocatalytic Water Splitting—The Untamed Dream: A Review of Recent Advances. Molecules 21:900. https://doi.org/10.3390/molecules21070900 Kainthla I, Gurram VRB, Bhanushali JT, et al (2018) In Situ Generation of Cu0 Supported on TiO2 Aerogel as a Catalyst for the Vapour Phase Hydrogenation of Nitrobenzene to Aniline. Catal Letters 148:2891–2900. https://doi.org/10.1007/s10562-018-2481-6 Kruse N, Chenakin S (2011) XPS characterization of Au/TiO2 catalysts: Binding energy assessment and irradiation effects. Appl Catal A Gen 391:367–376. https://doi.org/10.1016/j.apcata.2010.05.039 Kumaravel V, Mathew S, Bartlett J, Pillai SC (2019) Photocatalytic hydrogen production using metal doped TiO2: A review of recent advances. Appl Catal B Environ 244:1021–1064. https://doi.org/10.1016/j.apcatb.2018.11.080 Lee SL, Chang C-J (2019) Recent Progress on Metal Sulfide Composite Nanomaterials for Photocatalytic Hydrogen Production. Catalysts 9:457. https://doi.org/10.3390/catal9050457 Li H, Yu H, Sun L, et al (2015a) A self-assembled 3D Pt/TiO 2 architecture for high-performance photocatalytic hydrogen production. Nanoscale 7:1610–1615. https://doi.org/10.1039/C4NR06310D Li H, Yu H, Sun L, et al (2015b) A self-assembled 3D Pt/TiO 2 architecture for high-performance photocatalytic hydrogen production. Nanoscale 7:1610–1615. https://doi.org/10.1039/C4NR06310D Li R, Gao T, Wang Y, et al (2024) Engineering of bimetallic Au–Pd alloyed particles on nitrogen defects riched g-C3N4 for efficient photocatalytic hydrogen production. Int J Hydrogen Energy 63:1116–1127. https://doi.org/10.1016/J.IJHYDENE.2024.03.113 Li S, Hu J, Yang Y, et al (2017) Ag/nano-TiO2 composite compact film for enhanced performance of perovskite solar cells based on carbon counter electrodes. Appl Phys A Mater Sci Process 123:1–9. https://doi.org/10.1007/s00339-017-1240-7 Li Z, Jiang G, Zhang Z, et al (2016) Phosphorus-doped g-C3N4 nanosheets coated with square flake-like TiO2: Synthesis, characterization and photocatalytic performance in visible light. J Mol Catal A Chem 425:340–348. https://doi.org/10.1016/j.molcata.2016.10.020 Liu M, Kang Q, Xie Z, et al (2022) Heterostructure nanocomposite with local surface plasmon resonance effect enhanced photocatalytic activity-a critical review. J Phys D Appl Phys 55:043002. https://doi.org/10.1088/1361-6463/ac2cac Liu Y, Sun Z, Hu YH (2021) Bimetallic cocatalysts for photocatalytic hydrogen production from water. Chem Eng J 409:128250. https://doi.org/10.1016/j.cej.2020.128250 Lu X, Li M, Hoang S, et al (2021) Solvent effects on the heterogeneous growth of TiO2 nanostructure arrays by solvothermal synthesis. Catal Today 360:275–283. https://doi.org/10.1016/j.cattod.2020.02.044 Mani SS, Rajendran S, Arun PS, et al (2024) Bimetallic and plasmonic Ag and Cu integrated TiO 2 thin films for enhanced solar hydrogen production in direct sunlight. Energy Adv 3:829–840. https://doi.org/10.1039/D4YA00056K Melo M de O, Silva LA (2011) Photocatalytic production of hydrogen: an innovative use for biomass derivatives. J Braz Chem Soc 22:1399–1406. https://doi.org/10.1590/S0103-50532011000800002 Melvin AA, Illath K, Das T, et al (2015) M-Au/TiO2 (M = Ag, Pd, and Pt) nanophotocatalyst for overall solar water splitting: role of interfaces. Nanoscale 7:13477–88. https://doi.org/10.1039/c5nr03735b Navarro RM, del Valle F, Villoria de la Mano JA, et al (2009) Photocatalytic Water Splitting Under Visible Light. In: Advances in Chemical Engineering. pp 111–143 Navarro Yerga RM, Alvarez Galván MC, del Valle F, et al (2009) Water splitting on semiconductor catalysts under visible-light irradiation. ChemSusChem 2:471–85. https://doi.org/10.1002/cssc.200900018 Ni M, Leung MKH, Leung DYC, Sumathy K (2007) A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renew Sustain Energy Rev 11:401–425. https://doi.org/10.1016/j.rser.2005.01.009 Nyamukamba P, Tichagwa L, Ngila JC, Petrik L (2017) Plasmonic metal decorated titanium dioxide thin films for enhanced photodegradation of organic contaminants. J Photochem Photobiol A Chem 343:85–95. https://doi.org/10.1016/j.jphotochem.2017.04.014 Padmanabhan NT, Ganguly P, Pillai SC, John H (2020) Morphology engineered spatial charge separation in superhydrophilic TiO2/graphene hybrids for hydrogen production. Mater Today Energy 17:100447. https://doi.org/10.1016/j.mtener.2020.100447 Ramírez O, Lopéz-Frances A, Baldoví HG, et al (2024) Hydrogel composites based on chitosan and CuAuTiO2 photocatalysts for hydrogen production under simulated sunlight irradiation. Int J Biol Macromol 273:132898. https://doi.org/10.1016/J.IJBIOMAC.2024.132898 Reddy NL, Kumar S, Krishnan V, et al (2017) Multifunctional Cu/Ag quantum dots on TiO 2 nanotubes as highly efficient photocatalysts for enhanced solar hydrogen evolution. J Catal 350:226–239. https://doi.org/10.1016/j.jcat.2017.02.032 Riegel G, Bolton JR (1995) Photocatalytic Efficiency Variability in TiO2 Particles. J Phys Chem 99:4215–4224. https://doi.org/10.1021/j100012a050 Sadanandam G, Lalitha K, Kumari VD, et al (2013) Cobalt doped TiO2: A stable and efficient photocatalyst for continuous hydrogen production from glycerol: Water mixtures under solar light irradiation. Int J Hydrogen Energy 38:9655–9664. https://doi.org/10.1016/j.ijhydene.2013.05.116 Scarisoreanu M, Ilie AG, Goncearenco E, et al (2020) Ag, Au and Pt decorated TiO2 biocompatible nanospheres for UV & vis photocatalytic water treatment. Appl Surf Sci 509:145217. https://doi.org/10.1016/j.apsusc.2019.145217 Schneider J, Bahnemann DW (2013) Undesired Role of Sacrificial Reagents in Photocatalysis. J Phys Chem Lett 4:3479–3483. https://doi.org/10.1021/jz4018199 She P, Qin J, Rao H, et al (2020) Spatially separated bimetallic cocatalysts on hollow-structured TiO 2 for photocatalytic hydrogen generation. Mater Chem Front 4:1671–1678. https://doi.org/10.1039/D0QM00042F Shinde Y, Wadhai S, Ponkshe A, et al (2018a) Decoration of Pt on the metal free RGO-TiO 2 composite photocatalyst for the enhanced photocatalytic hydrogen evolution and photocatalytic degradation of pharmaceutical pollutant β blocker. Int J Hydrogen Energy 43:4015–4027. https://doi.org/10.1016/j.ijhydene.2017.10.089 Shinde Y, Wadhai S, Ponkshe A, et al (2018b) Decoration of Pt on the metal free RGO-TiO 2 composite photocatalyst for the enhanced photocatalytic hydrogen evolution and photocatalytic degradation of pharmaceutical pollutant β blocker. Int J Hydrogen Energy 43:4015–4027. https://doi.org/10.1016/j.ijhydene.2017.10.089 Shuang S, Lv R, Xie Z, Zhang Z (2016) Surface plasmon enhanced photocatalysis of Au/Pt-decorated TiO2 nanopillar arrays. Sci Rep 6:1–8. https://doi.org/10.1038/srep26670 Sravani B, Chandrashekar Y, Sri Chandana P, et al (2020) Bimetallic PtCu-decorated reduced graphene oxide (RGO)-TiO2 nanocomposite for efficient oxygen reduction reaction. Synth Met 266:116433. https://doi.org/10.1016/j.synthmet.2020.116433 Su F, Wang T, Lv R, et al (2013) Dendritic Au/TiO2 nanorod arrays for visible-light driven photoelectrochemical water splitting. Nanoscale 5:9001. https://doi.org/10.1039/c3nr02766j Sun F, Qiao X, Tan F, et al (2012) One-step microwave synthesis of Ag/ZnO nanocomposites with enhanced photocatalytic performance. J Mater Sci 47:7262–7268. https://doi.org/10.1007/s10853-012-6676-8 Sun X, Sun Q, Zhang Q, et al (2013) Significant effects of reaction temperature on morphology, crystallinity, and photoelectrical properties of rutile TiO 2 nanorod array films. J Phys D Appl Phys 46:095102. https://doi.org/10.1088/0022-3727/46/9/095102 Tian H, Kang S-Z, Li X, et al (2015) Fabrication of an efficient noble metal-free TiO2-based photocatalytic system using Cu–Ni bimetallic deposit as an active center of H2 evolution from water. Sol Energy Mater Sol Cells 134:309–317. https://doi.org/10.1016/j.solmat.2014.12.016 Wadhai S, Jadhav Y, Thakur P (2021) Synthesis of metal-free phosphorus doped graphitic carbon nitride-P25 (TiO2) composite: Characterization, cyclic voltammetry and photocatalytic hydrogen evolution. Sol Energy Mater Sol Cells 223:110958. https://doi.org/10.1016/j.solmat.2021.110958 Wang T-T, Yang Y-T, Lim S-C, et al (2022) Hydrogenation engineering of bimetallic Ag–Cu-modified-titania photocatalysts for production of hydrogen. Catal Today 388–389:79–86. https://doi.org/10.1016/j.cattod.2020.11.012 Xin Y, Wu L, Ge L, et al (2015) Gold–palladium bimetallic nanoalloy decorated ultrathin 2D TiO 2 nanosheets as efficient photocatalysts with high hydrogen evolution activity. J Mater Chem A 3:8659–8666. https://doi.org/10.1039/C5TA00759C Xu S, Ng J, Zhang X, et al (2010) Fabrication and comparison of highly efficient Cu incorporated TiO2 photocatalyst for hydrogen generation from water. Int J Hydrogen Energy 35:5254–5261. https://doi.org/10.1016/j.ijhydene.2010.02.129 Yadav S, Jilani A, Sachan S, et al (2024) Highly Efficient Visible-Light-Driven Photocatalysis of Rose Bengal Dye and Hydrogen Production Using Ag@Cu/TiO2 Ternary Nanocomposites. Chemistry (Easton) 6:489–505. https://doi.org/10.3390/chemistry6030028 Zhang S, Peng B, Yang S, et al (2015a) Non-noble metal copper nanoparticles-decorated TiO 2 nanotube arrays with plasmon-enhanced photocatalytic hydrogen evolution under visible light. Int J Hydrogen Energy 40:303–310. https://doi.org/10.1016/j.ijhydene.2014.10.122 Zhang Z, Cao S-W, Liao Y, Xue C (2015b) Selective photocatalytic decomposition of formic acid over AuPd nanoparticle-decorated TiO 2 nanofibers toward high-yield hydrogen production. Appl Catal B Environ 162:204–209. https://doi.org/10.1016/j.apcatb.2014.06.055 Zhang Z, Li A, Cao S-W, et al (2014) Direct evidence of plasmon enhancement on photocatalytic hydrogen generation over Au/Pt-decorated TiO 2 nanofibers. Nanoscale 6:5217–5222. https://doi.org/10.1039/C3NR06562F Zhu L, Lu Q, Lv L, et al (2017) Ligand-free rutile and anatase TiO 2 nanocrystals as electron extraction layers for high performance inverted polymer solar cells. RSC Adv 7:20084–20092. https://doi.org/10.1039/C7RA00134G Zhu X, Wen G, Liu H, et al (2019) One-step hydrothermal synthesis and characterization of Cu-doped TiO2 nanoparticles/nanobucks/nanorods with enhanced photocatalytic performance under simulated solar light. J Mater Sci Mater Electron 30:13826–13834. https://doi.org/10.1007/s10854-019-01766-3 Zhu X, Zhou Q, Xia Y, et al (2021) Preparation and characterization of Cu-doped TiO2 nanomaterials with anatase/rutile/brookite triphasic structure and their photocatalytic activity. J Mater Sci Mater Electron 32:21511–21524. https://doi.org/10.1007/s10854-021-06660-5 Zielińska-Jurek A (2014) Progress, Challenge, and Perspective of Bimetallic TiO 2 -Based Photocatalysts. J Nanomater 2014:1–17. https://doi.org/10.1155/2014/208920 Zou H, Tong Y, Feng Y, et al (2024) Cu Atomic Subnanoclusters on TiO 2 for Photocatalytic Hydrogen Evolution. ACS Appl Nano Mater 7:11680–11689. https://doi.org/10.1021/acsanm.4c01277 (2024) Ni-Pt nanoparticle decorated, C, N-doped titania microparticles with low band gap energy as an efficient catalyst for hydrogen generation from hydrous hydrazine. Colloids Surfaces A Physicochem Eng Asp 135143. https://doi.org/10.1016/J.COLSURFA.2024.135143 Supplementary Files AgCuNWTSupportingdatafile20.09.2024Revised.docx floatimage1.jpeg Graphical Abstract Cite Share Download PDF Status: Published Journal Publication published 11 Oct, 2024 Read the published version in Environmental Science and Pollution Research → Version 1 posted Editorial decision: Accept 02 Oct, 2024 Reviewers agreed at journal 23 Sep, 2024 Reviewers invited by journal 23 Sep, 2024 Editor invited by journal 23 Sep, 2024 First submitted to journal 20 Sep, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4503595","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":357649466,"identity":"ec6e5956-5537-40e8-95f0-b5f6ff2a7ea1","order_by":0,"name":"Sachin Wadhai","email":"","orcid":"","institution":"Savitribai Phule Pune University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Sachin","middleName":"","lastName":"Wadhai","suffix":""},{"id":357649467,"identity":"5b73332d-e3ca-4fc8-aac7-b0f210e5de67","order_by":1,"name":"Pragati Thakur","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0002-0923-2276","institution":"Savitribai Phule Pune University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Pragati","middleName":"","lastName":"Thakur","suffix":""}],"badges":[],"createdAt":"2024-05-30 14:12:09","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4503595/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4503595/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11356-024-35238-x","type":"published","date":"2024-10-11T15:57:04+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":65251516,"identity":"ed4a778c-2cd8-4d0c-ab67-b2236e8ab006","added_by":"auto","created_at":"2024-09-25 09:00:12","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":139444,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of the synthesis procedure of nanowire TiO\u003csub\u003e2\u003c/sub\u003e (NWT) with different steps involved.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/b365def9a5a8a30b0df9b21e.png"},{"id":65251789,"identity":"23183828-d334-4034-8131-84eeb77387ea","added_by":"auto","created_at":"2024-09-25 09:08:12","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":285774,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Powder XRD pattern recorded on NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/Cu-NWT photocatalysts, (b) Raman spectra recorded on NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/Cu-NWT photocatalysts, (c) UV-visible DRS spectra of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/Cu-NWT photocatalysts, (d) UV-visible DRS spectra of P25 TiO\u003csub\u003e2\u003c/sub\u003e, TiO\u003csub\u003e2\u003c/sub\u003e@5M, NWT and TiO\u003csub\u003e2\u003c/sub\u003e@15M photocatalysts.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/e0b0e400aa0e15c608e72c04.png"},{"id":65251796,"identity":"57a32bfc-db00-4023-a423-bae3ad488098","added_by":"auto","created_at":"2024-09-25 09:08:13","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":616219,"visible":true,"origin":"","legend":"\u003cp\u003e(a-c) SEM images, (d-f) LRTEM images, (g-h) HRTEM images and (i) SAED pattern of optimized 0.1Ag/1.0Cu-NWT photocatalyst.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/2e302fda31feff4a8173c0fd.png"},{"id":65252832,"identity":"435185ab-12af-482f-be05-1fcb1d48b71c","added_by":"auto","created_at":"2024-09-25 09:16:12","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":769013,"visible":true,"origin":"","legend":"\u003cp\u003e(a-f) Elemental mapping and (g) TEM-EDAX of optimized 0.1Ag/1.0Cu-NWT photocatalyst.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/74183284aa036821454f0e92.png"},{"id":65254027,"identity":"d66dc77f-f90b-40c1-bf90-39db1e0f618a","added_by":"auto","created_at":"2024-09-25 09:24:15","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":348470,"visible":true,"origin":"","legend":"\u003cp\u003eXPS spectra of 0.1Ag/1.0Cu-NWT (a) survey spectrum and high-resolution spectra of (b) Ti 2p, (c) O 1s, (d) Cu 2p, and (e) Ag 3d.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/06ea6c120f81cdd0b542bdf4.png"},{"id":65252833,"identity":"62b8bbda-0b10-4bc2-b54f-84b632928d0c","added_by":"auto","created_at":"2024-09-25 09:16:13","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":329748,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Amount of H\u003csub\u003e2\u003c/sub\u003e evolved by P25 TiO\u003csub\u003e2\u003c/sub\u003e, NWT, 1.0Cu-NWT, 0.5Pt-NWT and 0.1Ag/1.0Cu-NWT photocatalysts, (b) amount of H\u003csub\u003e2\u003c/sub\u003e evolved by P25, TiO\u003csub\u003e2\u003c/sub\u003e@5M, NWT, TiO\u003csub\u003e2\u003c/sub\u003e@15M and TiO\u003csub\u003e2\u003c/sub\u003e@20M photocatalysts, (c) amount of H\u003csub\u003e2\u003c/sub\u003e evolved by NWT, 0.2Pt-NWT, 0.4Pt-NWT, 0.5Pt-NWT, 0.6Pt-NWT and 0.8Pt-NWT photocatalysts, (d) amount of H\u003csub\u003e2\u003c/sub\u003e evolved by NWT, 0.5Cu-NWT, 0.75Cu-NWT, 1.0Cu-NWT, 1.5Cu-NWT and 2.0Cu-NWT photocatalysts and (e) Cyclic reusability of 0.1Ag/1.0Cu-NWT photocatalyst.\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/ffa00240434f18336d55dea2.png"},{"id":65251793,"identity":"973a6e92-f8e4-4da1-8ae3-3df6eafd7220","added_by":"auto","created_at":"2024-09-25 09:08:12","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":608594,"visible":true,"origin":"","legend":"\u003cp\u003eMechanism of optimized 0.1Ag/1.0Cu-NWT photocatalyst.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/445ede0d001b558b9c35b51f.png"},{"id":66597057,"identity":"7a5e0ee1-16eb-42b9-ae7f-a071d148ae07","added_by":"auto","created_at":"2024-10-14 16:06:23","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3795765,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/cca14ff2-c7e8-43dd-868f-907c02ad0eb8.pdf"},{"id":65251509,"identity":"265211b0-6a7a-4c85-9f68-f3ce86fb72fc","added_by":"auto","created_at":"2024-09-25 09:00:12","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1132382,"visible":true,"origin":"","legend":"","description":"","filename":"AgCuNWTSupportingdatafile20.09.2024Revised.docx","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/25b3c685c91dfc9518fdc03b.docx"},{"id":65251513,"identity":"799eee8b-51bc-4267-868d-2ac73ee90ac8","added_by":"auto","created_at":"2024-09-25 09:00:12","extension":"jpeg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":664742,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical Abstract\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4503595/v1/4476ce9754e897656d2746cc.jpeg"}],"financialInterests":"","formattedTitle":"Synthesis of Ag/Cu decorated 3D self-assembled nanowire TiO2 Photocatalyst for Hydrogen Production: A Promising Pathway towards Sustainable Energy Generation","fulltext":[{"header":"Highlights","content":"\u003col\u003e\n \u003cli\u003eSynthesis of Ag/Cu-NWT photocatalysts for photocatalytic H\u003csub\u003e2\u003c/sub\u003e production.\u003c/li\u003e\n \u003cli\u003e3D hierarchical TiO\u003csub\u003e2\u003c/sub\u003e showed 2-fold surface area and 7-fold HER activity than P25.\u003c/li\u003e\n \u003cli\u003eCost effective co-metallic decoration was better choice over costly Pt system.\u003c/li\u003e\n \u003cli\u003eSchottky junction, SPR and synergetic effect of Ag and Cu improved H\u003csub\u003e2\u003c/sub\u003e production.\u003c/li\u003e\n\u003c/ol\u003e\n"},{"header":"1. Introduction","content":"\u003cp\u003eEntire world is looking for a sustainable and alternative clean energy source in anticipation to the future high energy demand and to mitigate the issues of global warming and climate change (Ni et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Navarro Yerga et al. \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). The environmentally friendly nature of hydrogen as a green fuel, along with its comparable potential to fossil fuels when generated through the photocatalytic water splitting techniques has created significant interest in recent years in research community thereby presenting a feasible approach for its facile production using renewable and virtually inexhaustible solar energy. (Navarro et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Melo and Silva 2011; Jafari et al. \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Baykara \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Although TiO\u003csub\u003e2\u003c/sub\u003e is a benchmark photocatalyst among various semiconductors due to its magnificent properties viz. chemical inertness, environmental compatibility, low cost, photoactivity, and excellent photostability, it has critical limitations of fast electron/hole recombination and limited photoconversion efficiency (Riegel and Bolton \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e1995\u003c/span\u003e; Ni et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Amano et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Therefore, it is indispensable to map out strategic approach for the betterment of TiO\u003csub\u003e2\u003c/sub\u003e in terms of its impediments to make it a powerful tool for technology transfer. The very first simplest approach could be a suitable morphology frame up resulting in high surface area and improved light absorption as compared to commercially available P25 TiO\u003csub\u003e2\u003c/sub\u003e (Amano et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Thus to design the desired photocatalyst with favourable crystal structure and morphology for improved photoconversion efficiency has become crucial important (Bhatt and Lee \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Clarizia et al. \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The solvent and the reaction time are the key factors in determining the morphologies and dimensions of the anatase TiO\u003csub\u003e2\u003c/sub\u003e nanostructures (Padmanabhan et al. \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Das et al. demonstrated the tunability of the structures, sizes, and morphologies of anatase TiO\u003csub\u003e2\u003c/sub\u003e products by manipulating the reaction temperature and time, as well as utilizing mixed solvents with varying compositions (Das et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). Alshehri et al. investigated the photocatalytic reformation of methanol to hydrogen using PtOx (2.0 wt.%) deposited TiO\u003csub\u003e2\u003c/sub\u003e anatase with nanoparticles, nanotubes, and nanofibers morphology. Many researchers have reported that TiO\u003csub\u003e2\u003c/sub\u003e anatase nanotubes exhibit exceptional photocatalytic activity (Alshehri and Narasimharao \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). A 3D Pt/TiO\u003csub\u003e2\u003c/sub\u003e architecture composed of numerous 1D TiO\u003csub\u003e2\u003c/sub\u003e nanowires was synthesized by Li et al. using a one-pot solvothermal method, with a photocatalytic hydrogen production rate of 13.33 mmol h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. This excellent performance can be attributed to the cumulative effects of the unique TiO\u003csub\u003e2\u003c/sub\u003e architecture, allowing enhanced light absorption depths along with the presence of noble metal decoration (Li et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2015a\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eRecently literature also reports the decoration of bimetallic nanoparticles to improve the photocatalytic activity of TiO\u003csub\u003e2\u003c/sub\u003e (Zielińska-Jurek \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). Liu et al. have provided a comprehensive review of various bimetallic cocatalyst systems, including bi-noble and non-noble metal cocatalysts, plasmonic and non-plasmonic bimetallic cocatalysts, among others, for photocatalytic hydrogen production from water. The review aimed to underscore the synergetic effects within bimetallic systems and elucidate the impact of factors such as elemental composition, overall metal loading, structure, particle size, and more (Liu et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Decorating semiconductor photocatalysts with cocatalysts has been emerged as a potent strategy to mitigate the recombination of photo-excited electron-hole pairs, minimize overpotential for redox reactions, enhance visible light absorption, suppress reverse reactions, and ultimately improve the overall efficiency of photocatalysis (Zhang et al. \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Gao et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; She et al. \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2020\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eAlthough noble metallic or noble bi-metallic cocatalyst systems such as Pt/Au (Shuang et al. \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Grabowska et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Gołąbiewska et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), Pd/Au (Xin et al. \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2015b\u003c/span\u003e; Han et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; She et al. \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), etc show high performance but their towering costs and inadequate reserves restrict their applications for large scale commercialization in future. Thus, one of the efficacious strategies would be to use a combination of noble metal with a low-cost and abundantly available non-noble transition metals, such as Ni (Tian et al. \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), Co (Iwasaki et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2000\u003c/span\u003e; Sadanandam et al. \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2013\u003c/span\u003e), Cu (Zhang et al. \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2015a\u003c/span\u003e; Mani et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Zou et al. \u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) and Sn (Gao et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) as cocatalysts without compromising with the performance for hydrogen production. The current emphasis on cost-effective and highly efficient noble and non-noble metal bimetallic cocatalyst systems, as opposed to monometallic cocatalysts, underscores the remarkable synergetic effects that can significantly enhance catalytic activity and stability (Mani et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Li et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Yadav et al. \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Ram\u0026iacute;rez et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). Wang et al. and Reddy et al. have reported comparable bimetallic systems, namely hydrogenated Ag-Cu-modified P25 TiO\u003csub\u003e2\u003c/sub\u003e and Cu/Ag quantum dots on TiO\u003csub\u003e2\u003c/sub\u003e nanotubes, demonstrating hydrogen production rates of 1.16 mmol h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 56,167 \u0026micro;mol h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Reddy et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2022\u003c/span\u003e) respectively\u003c/p\u003e \u003cp\u003eThrough a comprehensive literature survey, it has been noted that no detailed study has been conducted to substantiate the morphological optimization along with plasmonic noble-non noble bimetallic cocatalyst decoration of TiO\u003csub\u003e2\u003c/sub\u003e for cost-effective and enhanced photocatalytic hydrogen production. Thus, at this point, it would be highly intriguing to explore the advantages offered by both aspects i.e. TiO\u003csub\u003e2\u003c/sub\u003e morphology optimization for improved light harvesting and high surface area and further decoration of bimetallic nanoparticles on the TiO\u003csub\u003e2\u003c/sub\u003e surface. Decoration of noble metal Pt has been studied extensively due to its fascinating co-catalyst attributes (Li et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2015a\u003c/span\u003e; Denisov et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2019\u003c/span\u003e)(Mani et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). But Pt decoration ends up with higher cost issues. Therefore, decoration of inexpensive non-noble metal Cu along with low-cost noble metal Ag with their individual properties of visible light harvesting ability along with an excellent electron sink capacity and surface plasmon resonance (SPR) effect respectively for improved solar photocatalytic hydrogen production would be an interesting piece of research.\u003c/p\u003e \u003cp\u003eIn view of this, firstly, we have performed a detailed investigation on the synthesis and characterization of different morphologies of TiO\u003csub\u003e2\u003c/sub\u003e by solvothermal method and checked for their photocatalytic hydrogen production capacity. NWT like morphology of TiO\u003csub\u003e2\u003c/sub\u003e was found to be the best as compared to other obtained morphologies with a remarkable photocatalytic hydrogen production activity (678 \u0026micro;mol/g) which was nearly 7-fold better than benchmark P25 TiO\u003csub\u003e2\u003c/sub\u003e (99 \u0026micro;mol/g). NWT was further decorated with popular co-catalyst Pt for improved hydrogen production. In the later part, non-noble metal Cu decoration and its percentage optimization on NWT (Cu-NWT) was carried out with further co-decoration of minimal quantity of plasmonic noble metal Ag (Ag/Cu-NWT) for improved hydrogen production activity comparable with Pt-NWT with an added advantage of cost effectivity. The proposed mechanism outlined at the end emphasizes the highly porous morphology of NWT, which enhances light absorption through repeated light reflection and refraction. This, combined with increased charge transfer and separation, the surface plasmon resonance (SPR) effect from Ag nanoparticles, and the electron sink capability of Cu, collectively contributes to the improvement in photocatalytic hydrogen production.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials\u003c/h2\u003e \u003cp\u003eTitanium tetraisopropoxide (Ti {OCH(CH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e}\u003csub\u003e4\u003c/sub\u003e) and Hexachloroplatinic acid (H\u003csub\u003e2\u003c/sub\u003ePtCl\u003csub\u003e6\u003c/sub\u003e) were purchased from Sigma Aldrich; Hydrochloric acid (HCl) and Methanol (CH\u003csub\u003e3\u003c/sub\u003eOH) were purchased from SDFCL; Sodium hydroxide (NaOH), Ethylene glycol (CH\u003csub\u003e2\u003c/sub\u003e-OH)\u003csub\u003e2\u003c/sub\u003e, Copper sulphate (CuSO\u003csub\u003e4\u003c/sub\u003e.H\u003csub\u003e2\u003c/sub\u003eO) were purchased from Merck; Silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e) was purchased from Thermo Fisher Scientific India Pvt. Ltd. All chemicals used are of analytical reagents grade (AR). The chemicals were utilized as it is, without undergoing additional purification procedures.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Synthesis of catalyst materials\u003c/h2\u003e \u003cp\u003eIn the typical process, 0.2M TTIP (Titanium tetraisopropoxide) in 50 mL ethylene glycol was taken in a round bottom flask and was stirred for 2 h. 50 mL of 10M NaOH was then added slowly to this TTIP solution and stirred for 3 h to get a clear solution. The reaction mixture was then put in an autoclave for 16 h at 200 \u0026ordm;C. Then the precipitate was washed with 0.2M HCl and distilled water several times and then was kept in a vacuum oven overnight at 80 \u0026ordm;C. The product was then calcined for 2 h at 500 \u0026ordm;C which gave white powder of Nanowire TiO\u003csub\u003e2\u003c/sub\u003e (NWT) as demonstrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e (Li et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2015b\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eDifferent morphologies of TiO\u003csub\u003e2\u003c/sub\u003e were obtained as a function of NaOH concentration (ranging from 5\u0026ndash;20M) and labelled as TiO\u003csub\u003e2\u003c/sub\u003e at 5M NaOH (TiO\u003csub\u003e2\u003c/sub\u003e@5M), TiO\u003csub\u003e2\u003c/sub\u003e at 10M NaOH (NWT), TiO\u003csub\u003e2\u003c/sub\u003e at 15M NaOH (TiO\u003csub\u003e2\u003c/sub\u003e@15M) and TiO\u003csub\u003e2\u003c/sub\u003e at 20M NaOH (TiO\u003csub\u003e2\u003c/sub\u003e@20M). All these samples were further investigated for their improved photocatalytic hydrogen production capacity over P25 TiO\u003csub\u003e2\u003c/sub\u003e. The obtained data was then taken into consideration to correlate the relationship between the morphology and photocatalytic hydrogen production capacity.\u003c/p\u003e \u003cp\u003eFor the preparation of 0.1Ag/1.0Cu-NWT, as prepared and optimized 1.0 Cu-NWT photocatalyst (supporting information) was further decorated with a minimal quantity of 0.1% Ag, for which silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e) was used as a precursor. The typical synthesis of Ag decorated 1.0Cu-NWT (labelled as 0.1Ag/1.0Cu-NWT) was carried out by mixing 0.095 mL of 0.02 M AgNO\u003csub\u003e3\u003c/sub\u003e solution with 200 mg of 1.0Cu-NWT in 10% methanol solution. Subsequently, the mixture was subjected to UV light irradiation for 3 h, followed by washing with distilled water and drying at 60\u0026deg;C to obtain the desired product. Pt decorated NWT (Pt-NWT) and its percentage variation also prepared by using the photo-deposition method as mentioned in supplementary information (Reddy et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Shinde et al. \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2018a\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Photocatalytic hydrogen production setup\u003c/h2\u003e \u003cp\u003eAll the photocatalytic hydrogen production reactions were checked in simulated solar light. In the standard experimental procedure, a 10% methanol solution (100 mL) was placed in a 200 mL quartz reactor with a top loading port. Here, methanol has been used as hole scavenger as it is relatively stable compound under various experimental conditions. Further it is inexpensive and widely available which makes it a cost-effective choice for large-scale experiments, unlike some other sacrificial agents which can be more expensive or difficult to source in large quantities. (Guzman et al. \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Schneider and Bahnemann \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Due to all these reasons 10% methanol solution was the best choice. To this 100mL solution, 40 mg of catalyst was added. The quartz reactor was then packed with a rubber cork and nitrogen gas was purged into it for 10 minutes to remove the other gases present in the free space of the quartz reactor as well as dissolved in the reaction solution. The quartz reactor was then mounted in front of 1000 W Xenon lamp irradiation which is a case similar to solar irradiation. At specific time intervals, samples were extracted and the amount of generated hydrogen gas was determined using offline Shimadzu GC-2014 gas chromatography (GC) equipped with a thermal conductivity detector (TCD) and a molecular sieve/5A column. The measurement was performed at 70\u0026deg;C utilizing N\u003csub\u003e2\u003c/sub\u003e as the carrier gas (Shinde et al. \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2018b\u003c/span\u003e). Recyclability test of optimized photocatalyst was carried out upto 5 cycles to check the stability and reusability of the photocatalyst. After completion of the first cycle, the quartz reactor was dismounted, rubber cork was removed and kept as it is overnight under ambient conditions by covering it with aluminium foil. In the second cycle, the same solution was employed and purged with N\u003csub\u003e2\u003c/sub\u003e gas to preserve a neutral environment within the reactor. The solution was then exposed to solar simulated light for 4 h. This procedure was repeated for the subsequent three cycles, and the hydrogen production was quantified using GC.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Characterization of the photocatalysts\u003c/h2\u003e \u003cp\u003eThe prepared photocatalysts underwent various characterization techniques. X-ray diffraction (XRD) analysis was performed using a Rigaku Ultima IV instrument with Cu K alpha radiation, scanning at a rate of 10\u003csup\u003eo\u003c/sup\u003e/min and a sampling width of 0.02\u003csup\u003eo\u003c/sup\u003e to determine the crystallographic information. Fourier Transform Infrared Spectra (FTIR) in the mid-IR region (400 to 4000 cm-1) were recorded using a Bruker Tensor 37 instrument. UV-visible absorption spectra (DRS) were obtained using a Shimadzu 1800 UV-visible spectrophotometer. X-ray photoelectron spectroscopy (XPS) analysis was employed using PHI 5000 Versa Probe III equipment and Al Kα radiation as the excitation source to ascertain the oxidation state of the photocatalyst. Scanning Electron Microscopy (SEM) images were acquired using a Quanta FEG 450 instrument, along with Energy Dispersive X-ray (EDX) analysis. Raman Spectroscopy was conducted on a micro-Raman spectrometer Lab RAM ARAMIS, Horiba Jobin-Yvon instrument, specifically for carbon photocatalysts characterization. Transmission Electron Microscopy (TEM) images were captured using a JEOL JEM F200, Tokyo instrument. The BET method, employing a Quantachrome Auto sorbiQ instrument, was utilized to measure porosity and surface area. The quantity of evolved hydrogen gas was measured using a Gas Chromatography (GC) Shimadzu GC 2014 equipped with a TCD detector, and a PORAPAK Q column (length 2.0 m, ID 3.13 mm) was employed (Wadhai et al. \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Catalyst characterization\u003c/h2\u003e \u003cp\u003eX-ray diffraction (XRD) analysis was conducted to investigate the crystalline structure of the photocatalysts, including NWT, Pt-NWT, Cu-NWT, and Ag/Cu-NWT (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea and S1). The XRD pattern of NWT revealed a highly crystalline anatase structure with dominant peaks at 2θ\u0026thinsp;=\u0026thinsp;25.3\u003csup\u003e◦\u003c/sup\u003e, 37.9\u003csup\u003e◦\u003c/sup\u003e, 48\u003csup\u003e◦\u003c/sup\u003e, and 54.9\u003csup\u003e◦\u003c/sup\u003e corresponding to the (101), (004), (200), and (211) planes, respectively, as indicated by the JCPDS Card No. 21-1272 (Zhu et al. \u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea shows the XRD patterns of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT photocatalysts. For all these four photocatalysts the major peaks observed were of the anatase phase of TiO\u003csub\u003e2\u003c/sub\u003e. There was no peak of Pt, Cu or Ag found in the XRD pattern because of the very small quantity of these metals in the metal-decorated NWT photocatalysts. All the optimized photocatalysts also showed the characteristic peak at 2θ\u0026thinsp;=\u0026thinsp;25.3\u003csup\u003e◦\u003c/sup\u003e, 37.9\u003csup\u003e◦\u003c/sup\u003e, 48\u003csup\u003e◦\u003c/sup\u003e and 54.9\u003csup\u003e◦\u003c/sup\u003e corresponding to (101), (004), (200) and (211) planes respectively which not only confirms the formation of high crystallinity but also pure compound. The intensity of the reflections related to the TiO\u003csub\u003e2\u003c/sub\u003e anatase phase decreased following the deposition of metals, suggesting that the presence of an additional crystalline phase had modified the crystalline structure of TiO\u003csub\u003e2\u003c/sub\u003e (Alshehri and Narasimharao \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). High crystallinity and co-presence of Ag and Cu on NWT photocatalysts are responsible for enhanced light harvesting capacity and ultimately the photocatalytic hydrogen production. Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003ea shows the XRD pattern of NWT and Pt-NWT (0.2Pt-NWT, 0.4Pt-NWT, 0.5Pt-NWT, 0.6Pt-NWT, 0.8Pt-NWT and 1.0Pt-NWT) photocatalysts and Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003eb shows the XRD of Cu-NWT (0.5Cu-NWT, 0.75Cu-NWT, 1.0Cu-NWT, 1.5Cu-NWT and 2.0Cu-NWT) photocatalysts. The XRD pattern of all Pt-NWT and Cu-NWT photocatalysts retained the peak of bare NWT and no other peak or impurity was observed.\u003c/p\u003e \u003cp\u003eRaman measurements for all four samples i.e., NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT were carried out. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb exhibits the Raman spectroscopy analysis, elucidating the characterization of the Ti-O-Ti network structure of NWT materials within the wavenumber range of 100\u0026ndash;900 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Notably, the well-established anatase peaks at 142, 393, 511, and 635 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are distinctly observed. In the case of NWT, these four pronounced peaks at 142, 393, 511, and 635 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e correspond to the vibration modes of Eg, B1g, A1g, and Eg, respectively, aligning with the TiO\u003csub\u003e2\u003c/sub\u003e anatase phase. The Eg peak arises predominantly from the symmetric stretching vibration of the O\u0026ndash;Ti\u0026ndash;O linkages in TiO\u003csub\u003e2\u003c/sub\u003e, whereas the B1g peak corresponds to the symmetric bending vibration of O\u0026ndash;Ti\u0026ndash;O and the A1g peak is attributed to the antisymmetric bending vibration of the O\u0026ndash;Ti\u0026ndash;O linkage (Balachandran and Eror \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e1982\u003c/span\u003e; Melvin et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). In the case of Pt-NWT, Cu-NWT, and Ag/Cu-NWT, no distinct separate peak was observed. However, a slight shift towards lower wavenumbers and broadening of the peak were noted compared to bare NWT. This phenomenon can be attributed to the strong electronic interaction between the metals and the surface of NWT (Fan et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). Thus, Ag and Cu decoration improves the crystal structure of anatase TiO\u003csub\u003e2\u003c/sub\u003e. The phase of NWT was retained even after the metal decoration. These findings are consistent with the XRD data mentioned earlier. Fig. S2 shows the FTIR spectra of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT photocatalysts. The FTIR spectra manifest prominent and comprehensive peaks, signifying the existence of diverse functional groups within the materials. Notably, a slight dip around 3360 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1643 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e can be attributed to the stretching and bending vibrations of adsorbed molecules and surface hydroxyls on TiO\u003csub\u003e2\u003c/sub\u003e particles, respectively (Li et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Chougala et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The intense peak at 485 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is assigned to the Ti-O stretching band which is the characteristic peak of TiO\u003csub\u003e2\u003c/sub\u003e (Zhang et al. \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). There is no significant peak-shift or extra peak observed in optimized metal decorated NWT photocatalysts because of a very small percentage of metal present in it and/or can be mainly attributed to the metal loading effect.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe optical and electronic properties of materials have been characterized by using Diffuse Reflectance Spectroscopy (DRS). To gain insights into the optical absorbance of the optimized photocatalysts, namely NWT, 0.5Pt-NWT, 1.0Cu-NWT, and 0.1Ag/1.0Cu-NWT, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec presents the UV-visible diffuse reflectance spectroscopy (DRS) data. The strong absorption bands around 380 nm, attributed to the intrinsic absorption of TiO\u003csub\u003e2\u003c/sub\u003e, are thought to result from the excitation of O2p electrons to the Ti3d level (Xu et al. \u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2015b\u003c/span\u003e). Absorption edges of NWT, 0.5Pt-NWT, 1.0Cu-NWT and 0.1Ag/1.0Cu-NWT are around 390 nm, 408 nm, 420 nm and 435 nm respectively. The DR spectra of the modified NWT is noteworthy for exhibiting a significant shift in the absorption transition towards longer wavelengths (400 nm\u0026thinsp;\u0026lt;\u0026thinsp;λ\u0026thinsp;\u0026lt;\u0026thinsp;435 nm). The extended visible light absorption of 0.1Ag/1.0Cu-NWT among all photocatalysts is due to the plasmonic resonance and light harvesting capacity of Ag and Cu respectively which shows absorption above 400 nm (Wang et al. \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The absorption of 0.5Pt-NWT and 1.0Cu-NWT was found to be significantly lower compared to 0.1Ag/1.0Cu-NWT, which could be attributed to the lower sensitivity of Pt and Cu to visible light absorption relative to Ag. Ultimately co-decoration of both Ag and Cu on NWT is found to be responsible for improved photocatalytic hydrogen production. Optical band gap studies have been carried out using Tauc Plot (Fig. S9), observed that the absorption shifts are consistent with a reduction in the optical band gap energies, mirroring the trends observed in the absorption spectra. Notably, Ag/Cu-NWT (3.06 eV) exhibits a significantly lower band gap energy compared to bare NWT (3.27 eV), Pt-NWT (3.20 eV), and Cu-NWT (3.15 eV). The reduction in band gap energy in Ag/Cu-NWT is likely due to the synergistic effect of silver and copper decoration, which enhances charge carrier separation and facilitates better light absorption in the visible region, thereby narrowing the band gap (Scarisoreanu et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). While Pt-NWT and Cu-NWT also exhibit some degree of band gap narrowing, they are not as effective as the Ag/Cu combination. Platinum, although excellent for enhancing photocatalytic activity, is costly and does not significantly affect light absorption in the visible range. Copper alone provides some enhancement in visible light absorption, but it is the addition of silver that amplifies the effect due to the plasmonic resonance (Zhu et al. \u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Scarisoreanu et al. \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Liu et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eTo gain insight into the growth process of the NWT structure, we monitored the growth steps of the samples using SEM at various NaOH concentrations. Fig. S3 shows the SEM images of synthesised TiO\u003csub\u003e2\u003c/sub\u003e at different NaOH concentrations at the same magnification i.e., at 1\u0026micro;m. Irregular morphology of TiO\u003csub\u003e2\u003c/sub\u003e (TiO\u003csub\u003e2\u003c/sub\u003e@5M) was observed with 5M NaOH solution in the synthesis method. Well-organized 3D spheres made up of nanowire TiO\u003csub\u003e2\u003c/sub\u003e (NWT) morphology was obtained with 10M NaOH solution. The rod like (TiO\u003csub\u003e2\u003c/sub\u003e@15M) and scale like (TiO\u003csub\u003e2\u003c/sub\u003e@20M) morphologies of TiO\u003csub\u003e2\u003c/sub\u003e were obtained when 15M and 20M NaOH solution was used in the synthesis method. It is obvious from the above data that the NaOH concentration in the reaction mixture plays crucial role in morphology elucidation. It can also be inferred that the morphology of the product can be controlled by the choice of solvent (Lu et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Solvent provides sufficient space to grow the titanium oxide into nano-wire ball like morphology. The observed variations in morphologies can be attributed to the polarity and coordinating ability of the co-solvent, which significantly affects the solubility, reactivity, and diffusion behaviour of the reactants, thereby influencing the structural and morphological characteristics of the final products (Das et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Lu et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). The optimized NWT morphology not only enhanced light harvesting ability due to its unique nanowire ball like structure but also improved its surface area due to high porosity for enhanced photocatalytic hydrogen production.\u003c/p\u003e \u003cp\u003eThe efficient 0.1Ag/1.0Cu-NWT photocatalyst's microscopic nature was first characterized by SEM (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea-c), and then by low-resolution transmission electron microscopy (LRTEM) and high-resolution transmission electron microscopy (HRTEM) (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed-h). Uniformly dispersed ball like structure made up of nanowire is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea having diameter of nanowire as 10\u0026ndash;20 nm and the whole NWT structure is around 3\u0026ndash;4 \u0026micro;m as confirmed by SEM images (Fig. S4). Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed-h shows LRTEM and HRTEM images of optimized 0.1Ag/1.0Cu-NWT photocatalyst. The lattice fringes observed in the HRTEM image (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg-h) of 0.1Ag/1.0Cu-NWT correspond to the (111) plane of Ag (d\u0026thinsp;=\u0026thinsp;0.24 nm) (Li et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), (111) plane of Cu (d\u0026thinsp;=\u0026thinsp;0.211 nm) (Kainthla et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2018\u003c/span\u003e) and (101) plane of anatase TiO\u003csub\u003e2\u003c/sub\u003e (d-space value of 0.326 nm) (Reddy et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). These results provide clear evidence of homogeneously dispersed Ag and Cu in their metallic forms on the NWT surface, indicating a close association between them. The crystalline quality of the 0.1Ag/1.0Cu-NWT photocatalyst was further demonstrated by the Selected Area Diffraction (SAED) pattern shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ei, which reveals a well-defined diffraction pattern with a lattice spacing of 0.326 nm, matching the (101) plane of anatase TiO\u003csub\u003e2\u003c/sub\u003e. SAED pattern of the TiO\u003csub\u003e2\u003c/sub\u003e nanowires reveal their single crystallinity and conclude the growth of the single-crystal TiO\u003csub\u003e2\u003c/sub\u003e nanowire/nanorod along the [0 0 1] direction (Sun et al. \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Corresponding LR and HRTEM along with SAED pattern for 0.5Pt-NWT and 1.0Cu-NWT photocatalysts are shown in Fig. S5a-d and S5e-h respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e presents the elemental mapping and TEM-EDAX analysis to visualize the distribution of elements and determine the atomic percentage of each element across the 0.1Ag/1.0Cu-NWT photocatalyst. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea-f shows elemental mapping of 0.1Ag/1.0Cu-NWT photocatalyst depicting the homogeneous dispersion of elements throughout the sample. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg shows TEM-EDAX spectra of 0.1Ag/1.0Cu-NWT photocatalyst which confirms the presence of 0.13% Ag, 6.72%Cu, 53.56% O and 39.58% Ti atomic percentages. Cu atomic percentage has been found to be higher than the actual percentage of synthesized 1%Cu-NWT which might be due to the copper gride used for the sample analysis. Overall observation confirmed the presence of Ag and Cu in the 0.1Ag/1.0Cu-NWT photocatalyst.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe impressive organization of nanowires in TiO\u003csub\u003e2\u003c/sub\u003e serves as a driving force for our in-depth examination for its Brunauer\u0026ndash;Emmett\u0026ndash;Teller (BET) surface area and pore volume. Consequently, we conducted an investigation onto the N\u003csub\u003e2\u003c/sub\u003e sorption isotherm and corresponding BET surface area plot of both P25 TiO\u003csub\u003e2\u003c/sub\u003e and NWT, aiming to validate the superior photocatalytic performance of NWT compared to P25 TiO\u003csub\u003e2\u003c/sub\u003e (as shown in Fig. S6). TiO\u003csub\u003e2\u003c/sub\u003e being the main photocatalyst which would contribute to the photocatalytic efficiency majorly due to its surface area and other properties, therefore BET surface area, pore volume, and pore size diameter of the P25 and NWT has been reported in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Metal decoration or co-decoration did not contribute much to the surface area. As expected, the BET surface area of NWT (123 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) was found to be significantly higher than that of P25 TiO\u003csub\u003e2\u003c/sub\u003e (52.90 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). The well-organized porous morphology of NWT exhibits a 2.5 times greater surface area than P25 TiO\u003csub\u003e2\u003c/sub\u003e, leading to improved light harvesting ability through repeated reflection and refraction. Additionally, the increased surface area provides more active reaction sites and facilitates mass transfer, allowing for efficient transport of reactant and product molecules.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eBET surface area, pore volume and pore size diameter values of the P25 TiO\u003csub\u003e2\u003c/sub\u003e, and NWT samples.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eBET surface area\u003c/p\u003e \u003cp\u003e(m\u003csup\u003e2\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003ePore volume\u003c/p\u003e \u003cp\u003e(cm\u003csup\u003e3\u003c/sup\u003e/g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ePore size diameter\u003c/p\u003e \u003cp\u003e(nm)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eP25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e52.90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.354\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e25.94\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNWT\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e123.00\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.636\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e16.20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSince 0.1Ag/1.0Cu-NWT display high crystallinity and well optical response ability, it is very necessary to investigate its surface compositions and electronic status, X-ray photoelectron spectroscopy (XPS) analysis was also performed. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea illustrates the survey spectrum of the 0.1Ag/1.0Cu-NWT photocatalyst, revealing the presence of elements Ti, O, Cu, and Ag. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb shows the peaks corresponding to Ti 2p at 458.80 eV and 464.55 eV, and 530.23 eV and observed data of O1s peak (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec ) includes one major peak at 530.23 eV and small shoulder also appeared at 532.22 eV corresponding to the binding energies of O1s, which was attributed to O 1s electron binding energy for TiO\u003csub\u003e2\u003c/sub\u003e and the H\u0026ndash;O from the absorbed H\u003csub\u003e2\u003c/sub\u003eO on their surface respectively (Erdem et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Kruse and Chenakin \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Zhu et al. \u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The Ti 2p region displays an asymmetric peak at 458.80 eV and 464.55 eV, corresponding to the binding energies of Ti 2p\u003csub\u003e3/2\u003c/sub\u003e and Ti 2p\u003csub\u003e1/2\u003c/sub\u003e, respectively (Erdem et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Su et al. \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). The binding energy values at 367.85 and 373.82 eV refers to Ag 3d\u003csub\u003e5/2\u003c/sub\u003e and Ag 3d\u003csub\u003e3/2\u003c/sub\u003e, respectively (Fan et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). This observation confirms the presence of metallic silver (Ag⁰) in the sample. The peaks at 932.75 and 952.56 eV are identified as Cu 2p\u003csub\u003e3/2\u003c/sub\u003e and Cu 2p\u003csub\u003e1/2\u003c/sub\u003e, respectively, indicating the presence of Cu in reduced form (Cu⁰) (Zhang et al. \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2015a\u003c/span\u003e; Reddy et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). High resolution spectra of Cu 2p and Ag 3d serving as proof of Cu and Ag in their metallic states. The XPS spectra of 0.5Pt-NWT photocatalyst is depicted in Fig. S8, and the presence of Platinum species was confirmed through deconvolution of Pt 4f peak into two components, Pt 4f\u003csub\u003e7/2\u003c/sub\u003e and Pt 4f\u003csub\u003e5/2\u003c/sub\u003e, at binding energies 68.97 and 72.52 eV, respectively (Fig. S8d) (Shinde et al. \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2018b\u003c/span\u003e; Sravani et al. \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2020\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Photocatalytic hydrogen production\u003c/h2\u003e \u003cp\u003eA series of methodical experiments on photocatalytic hydrogen production were conducted, employing simulated solar light irradiation, and utilizing methanol as a sacrificial agent across all the prepared photocatalysts. A comparison was made with commercially available P25 TiO\u003csub\u003e2\u003c/sub\u003e. P25 TiO\u003csub\u003e2\u003c/sub\u003e, being the widely recognized benchmark photocatalyst in commercial use, is the preferred starting point for further development and modifications aimed at overcoming its limitations. The objective is to augment the efficiency while maintaining the cost-effectiveness of both the photocatalyst and the experimental configuration for solar-driven photocatalytic hydrogen generation. Thus, motivated by this idea, focused attempts were made to obtain and optimize the morphology of synthesized TiO\u003csub\u003e2\u003c/sub\u003e which would deliver much more superior results as compared to commercially available P25 TiO\u003csub\u003e2\u003c/sub\u003e in terms of efficiency.\u003c/p\u003e \u003cp\u003eThus initially, the effect of morphology of TiO\u003csub\u003e2\u003c/sub\u003e on the hydrogen production capacity was studied. Moreover, the optimized morphology was further improved by decorating it with noble metal Pt, non-noble metal Cu, and a combination of non-noble Cu and a minimal amount of noble metal Ag to further enhance hydrogen production. The trend observed for photocatalytic hydrogen production, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea, is as follows: P25 TiO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;\u0026lt;\u0026thinsp;NWT\u0026thinsp;\u0026lt;\u0026thinsp;Cu-NWT\u0026thinsp;\u0026lt;\u0026thinsp;Pt-NWT\u0026thinsp;\u0026le;\u0026thinsp;Ag/Cu-NWT. Optimized low-cost 0.1Ag/1.0Cu-NWT (10,184 \u0026micro;mol/g) photocatalyst showed the highest hydrogen production as compared to all P25 TiO\u003csub\u003e2\u003c/sub\u003e, NWT, Cu-NWT photocatalysts and at par hydrogen production with 0.5Pt-NWT (10,050 \u0026micro;mol/g) photocatalyst.\u003c/p\u003e \u003cp\u003eMorphology obtained by using 10 M NaOH concentration i.e., NWT showed a dramatic increment in hydrogen production than other morphologies obtained at 5 M, 15 M and 20 M respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb). In comparison to the commercially available P25 TiO\u003csub\u003e2\u003c/sub\u003e (99 \u0026micro;mol/g), NWT exhibited a remarkable nearly 7-fold increase in hydrogen production capacity (678 \u0026micro;mol/g). This significant improvement in photocatalytic efficiency can be attributed to the favourable morphology achieved through the specific arrangement of atoms. This morphology enhances the absorption of light energy (as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed and S7) and facilitates mass transfer through the increased specific surface area (see BET explanation).\u003c/p\u003e \u003cp\u003eTo achieve the highest possible activity, NWT was modified by decorating with the popular noble metal Pt since Pt has more work function as well as better reduction potential than other noble metals. Various % Pt-NWT photocatalysts were synthesized and checked for photocatalytic hydrogen production. Optimized 0.5Pt-NWT (10,050 \u0026micro;mol/g\u003cb\u003e)\u003c/b\u003e showed a better increment in hydrogen production than other Pt percentages. 0.2 to 0.5 percentage of Pt with NWT i.e., 0.2Pt-NWT, 0.3Pt-NWT, 0.4Pt-NWT and 0.5Pt-NWT shows gradual increment in hydrogen production (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec). The photocatalytic performance of nanowire-tethered (NWT) materials decreases when the Pt content exceeds 0.5%, a result of the light-blocking and scattering effects caused by the accumulation of Pt on the NWT surface (Sun et al. \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Lee and Chang \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). However, the optimized 0.5Pt-NWT exhibited significantly enhanced hydrogen production, reaching nearly a 15-fold increase compared to NWT (678 \u0026micro;mol/g) and a remarkable 102-fold increase compared to P25 (99 \u0026micro;mol/g). The reason behind the betterment is the Pt decoration on NWT which reduces the electron hole recombination and increases the absorption of light energy (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb-c and \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eFurther, as Pt-TiO\u003csub\u003e2\u003c/sub\u003e, is a very exhaustively studied system due to the very high work function of Pt to reduce H\u003csup\u003e+\u003c/sup\u003e to H\u003csub\u003e2\u003c/sub\u003e for enhanced efficiency, it is always a challenge to work out a system or photocatalyst which would be a cost-effective alternative to beat Pt-TiO\u003csub\u003e2\u003c/sub\u003e. Therefore, the study was further directed to modify the optimized NWT photocatalyst with bimetallic non-noble metal Cu and low-cost noble metal Ag to explore and exploit their very fascinating properties of SPR effect and extended solar light absorption for improved hydrogen production activity at par with Pt-TiO\u003csub\u003e2\u003c/sub\u003e systems.\u003c/p\u003e \u003cp\u003eFirstly, TiO2 decoration with varying Cu concentration in the range of 0.5 to 2% has been studied. 1% Cu-NWT was found to show excellent improvement in hydrogen production sample among other concentrations; however these results were still lower than the Pt-NWT system.\u003c/p\u003e \u003cp\u003eIn this attempt, initially, NWT was decorated with an inexpensive non-noble metal Cu with its percentage varying from 0.5 to 2%. (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed). The increasing hydrogen production trend was observed from 0.5%to1.0%, and on further increase in Cu % the trend was found to decrease. The optimized 1.0Cu-NWT photocatalyst (3,907 \u0026micro;mol/g) demonstrated a substantial increase in hydrogen production, achieving nearly 6-fold improvement compared to NWT (678 \u0026micro;mol/g) and a remarkable 40-fold increase compared to P25 TiO\u003csub\u003e2\u003c/sub\u003e (99 \u0026micro;mol/g). This enhancement in hydrogen production is due to the presence of Cu which absorbs plasmon-induced irradiation to generate hot electrons which are partly ejected to CB of TiO\u003csub\u003e2\u003c/sub\u003e overcoming the Schottky barrier and separating the photogenerated charge carriers significantly (Zhang et al. \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2015a\u003c/span\u003e; Kumaravel et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2019\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eFurther, optimized 1.0Cu-NWT was decorated with a minimal quantity of Ag to improve the efficiency of the photocatalyst and to get comparable results at par with Pt-NWT photocatalyst. A very small quantity of Ag i.e., 0.1% Ag was decorated on an optimized 1.0Cu-NWT photocatalyst which resulted in a dramatic increment in photocatalytic hydrogen production capacity as compared to Cu-NWT, NWT as well as P25 TiO\u003csub\u003e2\u003c/sub\u003e. 0.1Ag/1.0Cu-NWT (10,184 \u0026micro;mol/g\u003cb\u003e)\u003c/b\u003e photocatalyst showed almost 2.6-fold increment in hydrogen production than 1.0Cu-NWT (3,907 \u0026micro;mol/g) photocatalyst.\u003c/p\u003e \u003cp\u003eThis improvement also showed comparable hydrogen production as of optimized 0.5Pt-NWT (10,050 \u0026micro;mol/g) photocatalyst (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). The main reason for choosing 0.1%Ag on 1.0 Cu-NWT system was to highlight that even the very small amount viz. 0.1% of Ag along with 1.0Cu-NWT will be sufficient to replace the 0.5Pt-NWT. It is indeed interesting to study the effect of variable concentration of Ag with 1.0 Cu-NWT system for further enhancement in hydrogen production. The detail study and optimization of variable metal concentrations and combinations of different metals will surely replace the Pt in future for cost-effective catalysts for cheap hydrogen production. The remarkable photocatalytic performance exhibited by the 0.1Ag/1.0Cu-NWT photocatalyst can be attributed to several key factors. Firstly, its unique morphology and bimetallic decoration play a crucial role. These features enable enhanced absorption of visible light, resulting in more efficient utilization of solar energy. Additionally, the modified structure of the photocatalyst leads to an increased surface area, providing more active sites for the photocatalytic reaction. Moreover, the bimetallic decoration facilitates accelerated charge transfer processes, enhancing the overall efficiency of the photocatalyst. Lastly, the presence of silver and copper on the nanowires effectively suppresses the recombination of photogenerated electron-hole pairs, leading to an extended lifetime of the charge carriers and further enhancing the photocatalytic performance. These attributes ultimately result in excellent photocatalytic hydrogen production, as explained in the mechanism section.\u003c/p\u003e \u003cp\u003eTo evaluate the reusability of the optimized 0.1Ag/1.0Cu-NWT photocatalyst, cyclic experiments were performed under identical experimental conditions. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee, the amount of hydrogen production remained consistent throughout the five cycles. This observation indicates that the photocatalyst maintained its activity without any noticeable decrease, demonstrating its remarkable stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Mechanism of photoinduced charge transfer in Ag/Cu-NWT\u003c/h2\u003e \u003cp\u003eThe results obtained indicate that the 0.1Ag/1.0Cu-NWT photocatalyst possesses remarkable photocatalytic hydrogen production ability under simulated solar light irradiation. In order to elucidate the mechanism responsible for enhanced photocatalytic hydrogen production, a plausible charge transfer pathway is proposed and visually illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe achieved nanowire ball-like morphology of the photocatalyst through the use of 10M NaOH resulted in a significant improvement in hydrogen production. This enhancement can be attributed to the unique structure of the photocatalyst, which plays a vital role in efficiently harnessing light energy through repeated reflection and refraction from the light source. This ball-like arrangement of nanowires also has been found to improve the porosity and surface area of the photocatalyst which ultimately facilitates more reaction sites and mass transfer. The 2.5 times improved BET surface area and UV-visible DRS (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed) spectral data of NWT clearly demonstrates probable reasons for 7-fold improved photocatalytic hydrogen production as compared to P25 TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eTo achieve the highest possible activity at par or better than Pt-TiO\u003csub\u003e2\u003c/sub\u003e with an added advantage of cost effectivity, the NWT was decorated with non-noble metal Cu and a minimal quantity of noble metal Ag. 0.1Ag/1.0Cu-NWT. The unique structure of this photocatalyst exhibited superior hydrogen production compared to all other prepared photocatalysts, and similar hydrogen production to that of 0.5Pt-NWT. This can be attributed to the proposed charge transfer mechanism, where upon light irradiation, electrons are excited from the valence band to the conduction band of NWT, and hot electrons are continuously supplied to the conduction band of TiO\u003csub\u003e2\u003c/sub\u003e due to the collective oscillation of conduction band electrons of decorated Ag nanoparticles. The surface plasmon resonance (SPR) effect of the decorated Ag nanoparticles enhances the absorption of visible light, resulting in more photoelectrons being available in the conduction band of NWT. (Nyamukamba et al. \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Further, these photoexcited electrons are captured by Cu which acts as an electron sink for the effective H\u003csup\u003e+\u003c/sup\u003e to H\u003csub\u003e2\u003c/sub\u003e reduction reaction. Thus, Cu decoration not only acts as a co-catalyst but also plays an important role in charge separation (Reddy et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The VB holes are trapped by methanol which acts as a hole scavenger or used for the oxidation process of H\u003csub\u003e2\u003c/sub\u003eO (Denisov et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Hence, notwithstanding the significance of the SPR effect, the catalytic activity of co-metallic decorated Ag and Cu on NWT exerts a more influential effect by mitigating electron-hole recombination and promoting the charge transfer rate. In conclusion, the combination of the tailored morphology of TiO\u003csub\u003e2\u003c/sub\u003e (NWT) and the co-metallic decoration (Ag/Cu-NWT) bestows exceptional characteristics upon the photocatalyst. These features encompass amplified light absorption in the visible spectrum, augmented surface area, expedited efficiency in charge transfer, and subdued recombination of photogenerated electron-hole pairs. Collectively, these factors contribute to the remarkable photocatalytic hydrogen production achieved by the catalyst.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eWe have successfully synthesized NWT using the solvothermal method, as well as Pt-NWT, Cu-NWT, and Ag/Cu-NWT using the photo-deposition method. These photocatalysts have been thoroughly characterized using various techniques including XRD, FTIR, Raman, UV-visible DRS, BET, SEM, LRTEM-HRTEM, and XPS. TiO\u003csub\u003e2\u003c/sub\u003e with different morphologies were obtained at different NaOH concentrations as confirmed by the SEM analysis. 3D self-assembled nanowire TiO\u003csub\u003e2\u003c/sub\u003e (NWT) morphology was found to have greater potential to absorb more light energy due to its structure and higher surface area thereby providing more active sites for improved photocatalytic hydrogen production than other morphologies. Further, NWT was successfully decorated with traditional noble metal Pt, non-noble metal Cu and a bimetallic combination of Ag/Cu respectively to compare their efficiencies. The deposition of Cu and Ag particles on NWT with homogeneous dispersion of these elements throughout 0.1Ag/1.0Cu-NWT photocatalyst has been confirmed by elemental mapping, TEM-EDAX and XPS analysis. The analysis of optical properties of the 0.1Ag/1.0Cu-NWT photocatalyst has unveiled its remarkable light absorption capabilities, primarily attributed to the surface plasmon resonance (SPR) effect induced by the presence of Ag and Cu. The finely structured morphology, along with the cooperative influences of bimetallic Ag and Cu embellishment on the surface of nanowire-TiO\u003csub\u003e2\u003c/sub\u003e (NWT) materials, facilitates augmented absorption of visible light and expanded surface area of the photocatalyst. Consequently, these factors engender heightened efficacy in charge transfer and inhibition of recombination of electron-hole pairs generated through photon absorption. The cumulative outcome is an outstanding level of activity in the process of photocatalytic hydrogen production. Importantly, this study emphasizes the facile fabrication of a cost-effective Ag/Cu-NWT solar photocatalyst as a viable alternative to the widely recognized Pt-TiO\u003csub\u003e2\u003c/sub\u003e system, while maintaining high photocatalytic hydrogen production capacity.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSW is thankful to UGC (Grant No.2061610320), New Delhi for Junior Research Fellowship and to P. E. S. Modern College of Engineering, Pune. PT is thankful to the Board of Research in Nuclear Sciences (BRNS) (Grant No. 2013/37C/52/BRNS/2464 Dated December 4, 2013), UGC-DAE Consortium for Scientific Research, University Grants Commission (Grant No. CSIR\u0026ndash;IC\u0026ndash;/MSRSR-15/CSR- 223/2017\u0026ndash;18/1304) and UPE (II) grant under UGC, for financial support. The authors express their gratitude to the Central Instrumentation Facility (CIF) at the Department of Chemistry and the Department of Physics of Savitribai Phule Pune University, Pune, India for providing characterization facilities. The authors would like to express their gratitude to the National Chemical Laboratory (NCL), Pune, for granting access to the HRTEM characterization facility.\u003c/p\u003e\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSW is thankful to UGC (Grant No.2061610320), New Delhi for Junior Research Fellowship and to P. E. S. Modern College of Engineering, Pune. PT is thankful to the Board of Research in Nuclear Sciences (BRNS) (Grant No. 2013/37C/52/BRNS/2464 Dated December 4, 2013), UGC-DAE Consortium for Scientific Research, University Grants Commission (Grant No. CSIR\u0026ndash;IC\u0026ndash;/MSRSR-15/CSR- 223/2017\u0026ndash;18/1304) and UPE (II) grant under UGC, for financial support. The authors express their gratitude to the Central Instrumentation Facility (CIF) at the Department of Chemistry and the Department of Physics of Savitribai Phule Pune University, Pune, India for providing characterization facilities. The authors would like to express their gratitude to the National Chemical Laboratory (NCL), Pune, for granting access to the HRTEM characterization facility.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cstrong\u003eData availability:\u003c/strong\u003e\u0026nbsp; The data can be requested from the authors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical approval:\u003c/strong\u003e Not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to participate:\u003c/strong\u003e Not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to publish:\u003c/strong\u003e Not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors contributions:\u0026nbsp;\u003c/strong\u003eSW was involved in designing the methodology, material synthesis, conducting experiments, and original manuscript preparation.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003ePT was involved in conceptualizing the research, providing the resources, guidance, reviewing, revising, and editing the manuscript, and supervising the research work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding:\u003c/strong\u003e SW is thankful to UGC (Grant No.2061610320), New Delhi for Junior Research Fellowship. PT is thankful to the Board of Research in Nuclear Sciences (BRNS) (Grant No. 2013/37C/52/BRNS/2464 Dated December 4, 2013) and UGC-DAE Consortium for Scientific Research for financial support.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests:\u003c/strong\u003e The authors declare no competing interests.\u003c/p\u003e\n"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eAlshehri A, Narasimharao K (2020) PtOx-TiO2 anatase nanomaterials for photocatalytic reformation of methanol to hydrogen: effect of TiO2 morphology. J Mater Res Technol 9:14907\u0026ndash;14921. https://doi.org/10.1016/j.jmrt.2020.10.087\u003c/li\u003e\n \u003cli\u003eAmano F, Nakata M, Yamamoto A, Tanaka T (2016) Rutile titanium dioxide prepared by hydrogen reduction of Degussa P25 for highly efficient photocatalytic hydrogen evolution. Catal Sci Technol 6:5693\u0026ndash;5699. https://doi.org/10.1039/C6CY00296J\u003c/li\u003e\n \u003cli\u003eBalachandran U, Eror NG (1982) Raman spectra of titanium dioxide. J Solid State Chem 42:276\u0026ndash;282. https://doi.org/10.1016/0022-4596(82)90006-8\u003c/li\u003e\n \u003cli\u003eBaykara SZ (2018) Hydrogen: A brief overview on its sources, production and environmental impact. Int J Hydrogen Energy 43:10605\u0026ndash;10614. https://doi.org/10.1016/j.ijhydene.2018.02.022\u003c/li\u003e\n \u003cli\u003eBhatt MD, Lee JS (2017) Nanomaterials for photocatalytic hydrogen production: from theoretical perspectives. RSC Adv 7:34875\u0026ndash;34885. https://doi.org/10.1039/C7RA03435K\u003c/li\u003e\n \u003cli\u003eChougala LS, Yatnatti MS, Linganagoudar RK, et al (2017) A simple approach on synthesis of TiO2 nanoparticles and its application in dye sensitized solar cells. J Nano- Electron Phys 9:2\u0026ndash;7. https://doi.org/10.21272/jnep.9(4).04005\u003c/li\u003e\n \u003cli\u003eClarizia L, Russo D, Di Somma I, et al (2017) Hydrogen Generation through Solar Photocatalytic Processes: A Review of the Configuration and the Properties of Effective Metal-Based Semiconductor Nanomaterials. Energies 10:1624. https://doi.org/10.3390/en10101624\u003c/li\u003e\n \u003cli\u003eDas K, Panda SK, Chaudhuri S (2008) Solvent-controlled synthesis of TiO2 1D nanostructures: Growth mechanism and characterization. J Cryst Growth 310:3792\u0026ndash;3799. https://doi.org/10.1016/j.jcrysgro.2008.05.039\u003c/li\u003e\n \u003cli\u003eDenisov N, Yoo J, Schmuki P (2019) Effect of different hole scavengers on the photoelectrochemical properties and photocatalytic hydrogen evolution performance of pristine and Pt-decorated TiO2 nanotubes. Electrochim Acta 319:61\u0026ndash;71. https://doi.org/10.1016/j.electacta.2019.06.173\u003c/li\u003e\n \u003cli\u003eErdem B, Hunsicker RA, Simmons GW, et al (2001) XPS and FTIR Surface Characterization of TiO 2 Particles Used in Polymer Encapsulation. Langmuir 17:2664\u0026ndash;2669. https://doi.org/10.1021/la0015213\u003c/li\u003e\n \u003cli\u003eFan X, Fan J, Hu X, et al (2014) Preparation and characterization of Ag deposited and Fe doped TiO2 nanotube arrays for photocatalytic hydrogen production by water splitting. Ceram Int 40:15907\u0026ndash;15917. https://doi.org/10.1016/j.ceramint.2014.07.119\u003c/li\u003e\n \u003cli\u003eGao D, Wu X, Wang P, et al (2019) Simultaneous Realization of Direct Photoinduced Deposition and Improved H 2 -Evolution Performance of Sn-Nanoparticle-Modified TiO 2 Photocatalyst. ACS Sustain Chem Eng 7:10084\u0026ndash;10094. https://doi.org/10.1021/acssuschemeng.9b01516\u003c/li\u003e\n \u003cli\u003eGao H, Zhang P, Zhao J, et al (2017) Plasmon enhancement on photocatalytic hydrogen production over the Z-scheme photosynthetic heterojunction system. Appl Catal B Environ 210:297\u0026ndash;305. https://doi.org/10.1016/j.apcatb.2017.03.050\u003c/li\u003e\n \u003cli\u003eGołąbiewska A, Lisowski W, Jarek M, et al (2017) The effect of metals content on the photocatalytic activity of TiO2 modified by Pt/Au bimetallic nanoparticles prepared by sol-gel method. Mol Catal 442:154\u0026ndash;163. https://doi.org/10.1016/j.mcat.2017.09.004\u003c/li\u003e\n \u003cli\u003eGrabowska E, Marchelek M, Klimczuk T, et al (2016) Preparation, characterization and photocatalytic activity of TiO 2 microspheres decorated by bimetallic nanoparticles. J Mol Catal A Chem 424:241\u0026ndash;253. https://doi.org/10.1016/j.molcata.2016.09.004\u003c/li\u003e\n \u003cli\u003eGuzman F, Chuang SSC, Yang C (2013) Role of Methanol Sacrificing Reagent in the Photocatalytic Evolution of Hydrogen. Ind Eng Chem Res 52:61\u0026ndash;65. https://doi.org/10.1021/ie301177s\u003c/li\u003e\n \u003cli\u003eHan C, Wu L, Ge L, et al (2015) AuPd bimetallic nanoparticles decorated graphitic carbon nitride for highly efficient reduction of water to H2 under visible light irradiation. Carbon N Y 92:31\u0026ndash;40. https://doi.org/10.1016/j.carbon.2015.02.070\u003c/li\u003e\n \u003cli\u003eIwasaki M, Hara M, Kawada H, et al (2000) Cobalt Ion-Doped TiO2 Photocatalyst Response to Visible Light. J Colloid Interface Sci 224:202\u0026ndash;204. https://doi.org/10.1006/jcis.1999.6694\u003c/li\u003e\n \u003cli\u003eJafari T, Moharreri E, Amin A, et al (2016) Photocatalytic Water Splitting\u0026mdash;The Untamed Dream: A Review of Recent Advances. Molecules 21:900. https://doi.org/10.3390/molecules21070900\u003c/li\u003e\n \u003cli\u003eKainthla I, Gurram VRB, Bhanushali JT, et al (2018) In Situ Generation of Cu0 Supported on TiO2 Aerogel as a Catalyst for the Vapour Phase Hydrogenation of Nitrobenzene to Aniline. Catal Letters 148:2891\u0026ndash;2900. https://doi.org/10.1007/s10562-018-2481-6\u003c/li\u003e\n \u003cli\u003eKruse N, Chenakin S (2011) XPS characterization of Au/TiO2 catalysts: Binding energy assessment and irradiation effects. Appl Catal A Gen 391:367\u0026ndash;376. https://doi.org/10.1016/j.apcata.2010.05.039\u003c/li\u003e\n \u003cli\u003eKumaravel V, Mathew S, Bartlett J, Pillai SC (2019) Photocatalytic hydrogen production using metal doped TiO2: A review of recent advances. Appl Catal B Environ 244:1021\u0026ndash;1064. https://doi.org/10.1016/j.apcatb.2018.11.080\u003c/li\u003e\n \u003cli\u003eLee SL, Chang C-J (2019) Recent Progress on Metal Sulfide Composite Nanomaterials for Photocatalytic Hydrogen Production. Catalysts 9:457. https://doi.org/10.3390/catal9050457\u003c/li\u003e\n \u003cli\u003eLi H, Yu H, Sun L, et al (2015a) A self-assembled 3D Pt/TiO 2 architecture for high-performance photocatalytic hydrogen production. Nanoscale 7:1610\u0026ndash;1615. https://doi.org/10.1039/C4NR06310D\u003c/li\u003e\n \u003cli\u003eLi H, Yu H, Sun L, et al (2015b) A self-assembled 3D Pt/TiO 2 architecture for high-performance photocatalytic hydrogen production. Nanoscale 7:1610\u0026ndash;1615. https://doi.org/10.1039/C4NR06310D\u003c/li\u003e\n \u003cli\u003eLi R, Gao T, Wang Y, et al (2024) Engineering of bimetallic Au\u0026ndash;Pd alloyed particles on nitrogen defects riched g-C3N4 for efficient photocatalytic hydrogen production. Int J Hydrogen Energy 63:1116\u0026ndash;1127. https://doi.org/10.1016/J.IJHYDENE.2024.03.113\u003c/li\u003e\n \u003cli\u003eLi S, Hu J, Yang Y, et al (2017) Ag/nano-TiO2 composite compact film for enhanced performance of perovskite solar cells based on carbon counter electrodes. Appl Phys A Mater Sci Process 123:1\u0026ndash;9. https://doi.org/10.1007/s00339-017-1240-7\u003c/li\u003e\n \u003cli\u003eLi Z, Jiang G, Zhang Z, et al (2016) Phosphorus-doped g-C3N4 nanosheets coated with square flake-like TiO2: Synthesis, characterization and photocatalytic performance in visible light. J Mol Catal A Chem 425:340\u0026ndash;348. https://doi.org/10.1016/j.molcata.2016.10.020\u003c/li\u003e\n \u003cli\u003eLiu M, Kang Q, Xie Z, et al (2022) Heterostructure nanocomposite with local surface plasmon resonance effect enhanced photocatalytic activity-a critical review. J Phys D Appl Phys 55:043002. https://doi.org/10.1088/1361-6463/ac2cac\u003c/li\u003e\n \u003cli\u003eLiu Y, Sun Z, Hu YH (2021) Bimetallic cocatalysts for photocatalytic hydrogen production from water. Chem Eng J 409:128250. https://doi.org/10.1016/j.cej.2020.128250\u003c/li\u003e\n \u003cli\u003eLu X, Li M, Hoang S, et al (2021) Solvent effects on the heterogeneous growth of TiO2 nanostructure arrays by solvothermal synthesis. Catal Today 360:275\u0026ndash;283. https://doi.org/10.1016/j.cattod.2020.02.044\u003c/li\u003e\n \u003cli\u003eMani SS, Rajendran S, Arun PS, et al (2024) Bimetallic and plasmonic Ag and Cu integrated TiO 2 thin films for enhanced solar hydrogen production in direct sunlight. Energy Adv 3:829\u0026ndash;840. https://doi.org/10.1039/D4YA00056K\u003c/li\u003e\n \u003cli\u003eMelo M de O, Silva LA (2011) Photocatalytic production of hydrogen: an innovative use for biomass derivatives. J Braz Chem Soc 22:1399\u0026ndash;1406. https://doi.org/10.1590/S0103-50532011000800002\u003c/li\u003e\n \u003cli\u003eMelvin AA, Illath K, Das T, et al (2015) M-Au/TiO2 (M = Ag, Pd, and Pt) nanophotocatalyst for overall solar water splitting: role of interfaces. Nanoscale 7:13477\u0026ndash;88. https://doi.org/10.1039/c5nr03735b\u003c/li\u003e\n \u003cli\u003eNavarro RM, del Valle F, Villoria de la Mano JA, et al (2009) Photocatalytic Water Splitting Under Visible Light. In: Advances in Chemical Engineering. pp 111\u0026ndash;143\u003c/li\u003e\n \u003cli\u003eNavarro Yerga RM, Alvarez Galv\u0026aacute;n MC, del Valle F, et al (2009) Water splitting on semiconductor catalysts under visible-light irradiation. ChemSusChem 2:471\u0026ndash;85. https://doi.org/10.1002/cssc.200900018\u003c/li\u003e\n \u003cli\u003eNi M, Leung MKH, Leung DYC, Sumathy K (2007) A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renew Sustain Energy Rev 11:401\u0026ndash;425. https://doi.org/10.1016/j.rser.2005.01.009\u003c/li\u003e\n \u003cli\u003eNyamukamba P, Tichagwa L, Ngila JC, Petrik L (2017) Plasmonic metal decorated titanium dioxide thin films for enhanced photodegradation of organic contaminants. J Photochem Photobiol A Chem 343:85\u0026ndash;95. https://doi.org/10.1016/j.jphotochem.2017.04.014\u003c/li\u003e\n \u003cli\u003ePadmanabhan NT, Ganguly P, Pillai SC, John H (2020) Morphology engineered spatial charge separation in superhydrophilic TiO2/graphene hybrids for hydrogen production. Mater Today Energy 17:100447. https://doi.org/10.1016/j.mtener.2020.100447\u003c/li\u003e\n \u003cli\u003eRam\u0026iacute;rez O, Lop\u0026eacute;z-Frances A, Baldov\u0026iacute; HG, et al (2024) Hydrogel composites based on chitosan and CuAuTiO2 photocatalysts for hydrogen production under simulated sunlight irradiation. Int J Biol Macromol 273:132898. https://doi.org/10.1016/J.IJBIOMAC.2024.132898\u003c/li\u003e\n \u003cli\u003eReddy NL, Kumar S, Krishnan V, et al (2017) Multifunctional Cu/Ag quantum dots on TiO 2 nanotubes as highly efficient photocatalysts for enhanced solar hydrogen evolution. J Catal 350:226\u0026ndash;239. https://doi.org/10.1016/j.jcat.2017.02.032\u003c/li\u003e\n \u003cli\u003eRiegel G, Bolton JR (1995) Photocatalytic Efficiency Variability in TiO2 Particles. J Phys Chem 99:4215\u0026ndash;4224. https://doi.org/10.1021/j100012a050\u003c/li\u003e\n \u003cli\u003eSadanandam G, Lalitha K, Kumari VD, et al (2013) Cobalt doped TiO2: A stable and efficient photocatalyst for continuous hydrogen production from glycerol: Water mixtures under solar light irradiation. Int J Hydrogen Energy 38:9655\u0026ndash;9664. https://doi.org/10.1016/j.ijhydene.2013.05.116\u003c/li\u003e\n \u003cli\u003eScarisoreanu M, Ilie AG, Goncearenco E, et al (2020) Ag, Au and Pt decorated TiO2 biocompatible nanospheres for UV \u0026amp;amp; vis photocatalytic water treatment. Appl Surf Sci 509:145217. https://doi.org/10.1016/j.apsusc.2019.145217\u003c/li\u003e\n \u003cli\u003eSchneider J, Bahnemann DW (2013) Undesired Role of Sacrificial Reagents in Photocatalysis. J Phys Chem Lett 4:3479\u0026ndash;3483. https://doi.org/10.1021/jz4018199\u003c/li\u003e\n \u003cli\u003eShe P, Qin J, Rao H, et al (2020) Spatially separated bimetallic cocatalysts on hollow-structured TiO 2 for photocatalytic hydrogen generation. Mater Chem Front 4:1671\u0026ndash;1678. https://doi.org/10.1039/D0QM00042F\u003c/li\u003e\n \u003cli\u003eShinde Y, Wadhai S, Ponkshe A, et al (2018a) Decoration of Pt on the metal free RGO-TiO 2 composite photocatalyst for the enhanced photocatalytic hydrogen evolution and photocatalytic degradation of pharmaceutical pollutant \u0026beta; blocker. Int J Hydrogen Energy 43:4015\u0026ndash;4027. https://doi.org/10.1016/j.ijhydene.2017.10.089\u003c/li\u003e\n \u003cli\u003eShinde Y, Wadhai S, Ponkshe A, et al (2018b) Decoration of Pt on the metal free RGO-TiO 2 composite photocatalyst for the enhanced photocatalytic hydrogen evolution and photocatalytic degradation of pharmaceutical pollutant \u0026beta; blocker. Int J Hydrogen Energy 43:4015\u0026ndash;4027. https://doi.org/10.1016/j.ijhydene.2017.10.089\u003c/li\u003e\n \u003cli\u003eShuang S, Lv R, Xie Z, Zhang Z (2016) Surface plasmon enhanced photocatalysis of Au/Pt-decorated TiO2 nanopillar arrays. Sci Rep 6:1\u0026ndash;8. https://doi.org/10.1038/srep26670\u003c/li\u003e\n \u003cli\u003eSravani B, Chandrashekar Y, Sri Chandana P, et al (2020) Bimetallic PtCu-decorated reduced graphene oxide (RGO)-TiO2 nanocomposite for efficient oxygen reduction reaction. Synth Met 266:116433. https://doi.org/10.1016/j.synthmet.2020.116433\u003c/li\u003e\n \u003cli\u003eSu F, Wang T, Lv R, et al (2013) Dendritic Au/TiO2 nanorod arrays for visible-light driven photoelectrochemical water splitting. Nanoscale 5:9001. https://doi.org/10.1039/c3nr02766j\u003c/li\u003e\n \u003cli\u003eSun F, Qiao X, Tan F, et al (2012) One-step microwave synthesis of Ag/ZnO nanocomposites with enhanced photocatalytic performance. J Mater Sci 47:7262\u0026ndash;7268. https://doi.org/10.1007/s10853-012-6676-8\u003c/li\u003e\n \u003cli\u003eSun X, Sun Q, Zhang Q, et al (2013) Significant effects of reaction temperature on morphology, crystallinity, and photoelectrical properties of rutile TiO 2 nanorod array films. J Phys D Appl Phys 46:095102. https://doi.org/10.1088/0022-3727/46/9/095102\u003c/li\u003e\n \u003cli\u003eTian H, Kang S-Z, Li X, et al (2015) Fabrication of an efficient noble metal-free TiO2-based photocatalytic system using Cu\u0026ndash;Ni bimetallic deposit as an active center of H2 evolution from water. Sol Energy Mater Sol Cells 134:309\u0026ndash;317. https://doi.org/10.1016/j.solmat.2014.12.016\u003c/li\u003e\n \u003cli\u003eWadhai S, Jadhav Y, Thakur P (2021) Synthesis of metal-free phosphorus doped graphitic carbon nitride-P25 (TiO2) composite: Characterization, cyclic voltammetry and photocatalytic hydrogen evolution. Sol Energy Mater Sol Cells 223:110958. https://doi.org/10.1016/j.solmat.2021.110958\u003c/li\u003e\n \u003cli\u003eWang T-T, Yang Y-T, Lim S-C, et al (2022) Hydrogenation engineering of bimetallic Ag\u0026ndash;Cu-modified-titania photocatalysts for production of hydrogen. Catal Today 388\u0026ndash;389:79\u0026ndash;86. https://doi.org/10.1016/j.cattod.2020.11.012\u003c/li\u003e\n \u003cli\u003eXin Y, Wu L, Ge L, et al (2015) Gold\u0026ndash;palladium bimetallic nanoalloy decorated ultrathin 2D TiO 2 nanosheets as efficient photocatalysts with high hydrogen evolution activity. J Mater Chem A 3:8659\u0026ndash;8666. https://doi.org/10.1039/C5TA00759C\u003c/li\u003e\n \u003cli\u003eXu S, Ng J, Zhang X, et al (2010) Fabrication and comparison of highly efficient Cu incorporated TiO2 photocatalyst for hydrogen generation from water. Int J Hydrogen Energy 35:5254\u0026ndash;5261. https://doi.org/10.1016/j.ijhydene.2010.02.129\u003c/li\u003e\n \u003cli\u003eYadav S, Jilani A, Sachan S, et al (2024) Highly Efficient Visible-Light-Driven Photocatalysis of Rose Bengal Dye and Hydrogen Production Using Ag@Cu/TiO2 Ternary Nanocomposites. Chemistry (Easton) 6:489\u0026ndash;505. https://doi.org/10.3390/chemistry6030028\u003c/li\u003e\n \u003cli\u003eZhang S, Peng B, Yang S, et al (2015a) Non-noble metal copper nanoparticles-decorated TiO 2 nanotube arrays with plasmon-enhanced photocatalytic hydrogen evolution under visible light. Int J Hydrogen Energy 40:303\u0026ndash;310. https://doi.org/10.1016/j.ijhydene.2014.10.122\u003c/li\u003e\n \u003cli\u003eZhang Z, Cao S-W, Liao Y, Xue C (2015b) Selective photocatalytic decomposition of formic acid over AuPd nanoparticle-decorated TiO 2 nanofibers toward high-yield hydrogen production. Appl Catal B Environ 162:204\u0026ndash;209. https://doi.org/10.1016/j.apcatb.2014.06.055\u003c/li\u003e\n \u003cli\u003eZhang Z, Li A, Cao S-W, et al (2014) Direct evidence of plasmon enhancement on photocatalytic hydrogen generation over Au/Pt-decorated TiO 2 nanofibers. Nanoscale 6:5217\u0026ndash;5222. https://doi.org/10.1039/C3NR06562F\u003c/li\u003e\n \u003cli\u003eZhu L, Lu Q, Lv L, et al (2017) Ligand-free rutile and anatase TiO 2 nanocrystals as electron extraction layers for high performance inverted polymer solar cells. RSC Adv 7:20084\u0026ndash;20092. https://doi.org/10.1039/C7RA00134G\u003c/li\u003e\n \u003cli\u003eZhu X, Wen G, Liu H, et al (2019) One-step hydrothermal synthesis and characterization of Cu-doped TiO2 nanoparticles/nanobucks/nanorods with enhanced photocatalytic performance under simulated solar light. J Mater Sci Mater Electron 30:13826\u0026ndash;13834. https://doi.org/10.1007/s10854-019-01766-3\u003c/li\u003e\n \u003cli\u003eZhu X, Zhou Q, Xia Y, et al (2021) Preparation and characterization of Cu-doped TiO2 nanomaterials with anatase/rutile/brookite triphasic structure and their photocatalytic activity. J Mater Sci Mater Electron 32:21511\u0026ndash;21524. https://doi.org/10.1007/s10854-021-06660-5\u003c/li\u003e\n \u003cli\u003eZielińska-Jurek A (2014) Progress, Challenge, and Perspective of Bimetallic TiO 2 -Based Photocatalysts. J Nanomater 2014:1\u0026ndash;17. https://doi.org/10.1155/2014/208920\u003c/li\u003e\n \u003cli\u003eZou H, Tong Y, Feng Y, et al (2024) Cu Atomic Subnanoclusters on TiO 2 for Photocatalytic Hydrogen Evolution. ACS Appl Nano Mater 7:11680\u0026ndash;11689. https://doi.org/10.1021/acsanm.4c01277\u003c/li\u003e\n \u003cli\u003e(2024) Ni-Pt nanoparticle decorated, C, N-doped titania microparticles with low band gap energy as an efficient catalyst for hydrogen generation from hydrous hydrazine. Colloids Surfaces A Physicochem Eng Asp 135143. https://doi.org/10.1016/J.COLSURFA.2024.135143\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Photocatalytic hydrogen production, titania, photocatalysis, morphological study, SPR effect, nanowire","lastPublishedDoi":"10.21203/rs.3.rs-4503595/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4503595/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eHere synthesis and characterization of TiO\u003csub\u003e2\u003c/sub\u003e with different morphologies along with the cost-effective bimetallic decoration on optimized 3D self-assembled nanowire TiO\u003csub\u003e2\u003c/sub\u003e (NWT) photocatalyst (Ag/Cu-NWT) with overwhelming hydrogen production rate is reported. All the photocatalysts were well characterised by different characterization techniques. Initially, the effect of morphology change obtained by changing the NaOH concentration has been studied for TiO\u003csub\u003e2\u003c/sub\u003e. Morphology obtained at 10 M NaOH solution i.e., NWT (678 μmol/g) showed better hydrogen production than morphology obtained at 5M (410 μmol/g), 15M (210 μmol/g) and 20M (160 μmol/g) NaOH solutions. Further with the aim to achieve comparable or better activity low cost photocatalyst as compared to Pt-TiO\u003csub\u003e2\u003c/sub\u003e system, NWT was decorated with various Cu percentages and then with minimal percentage of Ag on optimized Cu-NWT photocatalyst. The observed trend for photocatalytic hydrogen production has been found to be P25 TiO\u003csub\u003e2\u003c/sub\u003e \u0026lt; NWT \u0026lt; 1.0Cu-NWT \u0026lt; 0.5Pt-NWT ≤ 0.1Ag/1.0Cu-NWT. The marked increase by a factor of 103 in hydrogen production for the optimized bimetallic 0.1Ag/1.0Cu-NWT (10,184 μmol/g) photocatalyst compared to P25 TiO\u003csub\u003e2\u003c/sub\u003e (99 μmol/g), nearly threefold increment in hydrogen production than optimized 1.0 Cu-NWT (3,907 μmol/g) photocatalyst and comparable hydrogen production as compared to 0.5Pt-NWT (10,050 μmol/g) may be attributed to the successful synthesis of a highly porous NWT morphology, which offers large surface area, increased light absorption combined with the synergistic effects of surface plasmon resonance (SPR) and the Schottky barrier for H\u003csup\u003e+\u003c/sup\u003e reduction to H\u003csub\u003e2\u003c/sub\u003e gas. The optimization of TiO\u003csub\u003e2\u003c/sub\u003e morphology and inexpensive bimetallic decoration strategy opens up promising opportunities for the development of cost-effective photocatalysts in the realm of energy and environment.\u003c/p\u003e","manuscriptTitle":"Synthesis of Ag/Cu decorated 3D self-assembled nanowire TiO2 Photocatalyst for Hydrogen Production: A Promising Pathway towards Sustainable Energy Generation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-09-25 09:00:07","doi":"10.21203/rs.3.rs-4503595/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Accept","date":"2024-10-02T13:11:28+00:00","index":"","fulltext":""},{"type":"reviewerAgreed","content":"","date":"2024-09-23T04:49:05+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-09-23T04:38:27+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Environmental Science and Pollution Research","date":"2024-09-23T04:08:40+00:00","index":"","fulltext":""},{"type":"submitted","content":"Environmental Science and Pollution Research","date":"2024-09-20T09:51:09+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"environmental-science-and-pollution-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"espr","sideBox":"Learn more about [Environmental Science and Pollution Research](https://www.springer.com/journal/11356)","snPcode":"11356","submissionUrl":"https://submission.nature.com/new-submission/11356/3","title":"Environmental Science and Pollution Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"f20506c3-f0cb-42fa-8f74-c240426cf3f2","owner":[],"postedDate":"September 25th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-10-14T15:59:22+00:00","versionOfRecord":{"articleIdentity":"rs-4503595","link":"https://doi.org/10.1007/s11356-024-35238-x","journal":{"identity":"environmental-science-and-pollution-research","isVorOnly":false,"title":"Environmental Science and Pollution Research"},"publishedOn":"2024-10-11 15:57:04","publishedOnDateReadable":"October 11th, 2024"},"versionCreatedAt":"2024-09-25 09:00:07","video":"","vorDoi":"10.1007/s11356-024-35238-x","vorDoiUrl":"https://doi.org/10.1007/s11356-024-35238-x","workflowStages":[]},"version":"v1","identity":"rs-4503595","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4503595","identity":"rs-4503595","version":["v1"]},"buildId":"rHA-KDH7Qsr4HCuvH75dn","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}