Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction

Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction | 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 Article Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction Sheng-Liang Zhong, Jing Gao, Chaochao Tao, Tang Jianqiang, Lei Wang, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5991362/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The pursuit of clean and sustainable energy sources has intensified the research focus on water electrolysis, particularly the oxygen evolution reaction (OER), which serves as a pivotal step in hydrogen generation. However, the development of efficient and cost-effective OER catalysts remains a major bottleneck hindering the widespread adoption of water electrolysis technology. In this work, utilizing vermiculite (VMT), an abundant and environmentally friendly clay mineral, was employed as the precursor to obtain SiO 2 (V-SiO 2 ). We have successfully synthesized a novel phosphate-modified layered nickel silicate Ni 3 Si 2 O 5 (OH) 4 (NiSi-P) derived from the VMT through a combination of hydrothermal and vapor deposition method. Electrochemical evaluations in 1.0 M KOH revealed that NiSi-P exhibited remarkable OER performance, achieving a low overpotential of 334 mV at 10 mA·cm -2 , significantly outperforming unmodified nickel silicate (NiSi, 564 mV). This improvement is attributed to the unique structural features and surface chemistry of NiSi-P, which facilitate efficient charge transfer and protonation/deprotonation during the catalytic process. This study provided an idea for the application of low-cost silicate materials in electrocatalytic water splitting in OER. Earth and environmental sciences/Environmental sciences/Environmental impact Earth and environmental sciences/Environmental social sciences/Environmental impact Vermiculite Nickel silicate Phosphorus modification Oxygen evolution reaction Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction The relentless depletion of fossil fuels, a cornerstone of modern energy consumption, has given rise to pressing ecological concerns, including global warming and land degradation, underscoring the urgency to identify and adopt clean, renewable energy sources as viable alternatives. [ 1 – 3 ] Hydrogen energy is considered as a rational alternative to fossil fuels due to its high energy density and conversion efficiency, Among the various methods to produce hydrogen, electrocatalytic water splitting stands out as a sustainable and environmentally friendly approach. [ 4 , 5 ] Noble metal catalysts such as ruthenium and iridium have shown excellent oxygen evolution reaction (OER) activity, but their high cost and scarcity have severely limited their large-scale applications [ 6 ] . Consequently, the scientific community has shifted its focus towards the development of cost-effective, highly active, and stable OER electrocatalysts derived from abundant, earth-abundant elements. [ 7 – 9 ] Transition metal silicates have attracted widespread attention due to their abundant silicon content, low cost, stable tetrahedral framework, and excellent chemical properties. [ 10 , 11 ] For instance, Zhang et al. assembled hybrid supercapacitor devices from C/FeSi anode and CoNiSi cathode materials derived from natural bamboo leaves, which have excellent electrochemical energy storage performance [ 12 ] . Mu et al. designed FeO x -modified Co 2 SiO 4, exhibiting excellent OER properties. [ 13 ] Compared with energy storage technology, there are fewer studies to explore its application in OER. Transition metal silicates served as OER electrocatalysts mainly face problems such as poor conductivity and few active sites. [ 14 ] Therefore, a series of studies have been devoted to improving their electrocatalytic OER. For example, Qiu's group used a simple sol-gel method to combine the carbon nanotubes as a carrier with nickel-cobalt silicate, and the synthesized catalyst not only has high structural stability, but also has good conductivity and exhibits enhanced OER activity, and the optimized material requires a low overpotential of 440 mV to provide a current density of 10 mA·cm − 2 . [ 15 ] In addition, their group has also prepared phosphate-modified basic nickel-cobalt silicate, which regulates the electronic structure of basic cobalt silicate through phosphate, increases the number of reactive sites, and reduces the energy barrier of the OER reaction. It exhibited an overpotential of 394 mV at 10 mA cm − 2 in 0.1 M KOH. [ 16 ] In addition, layered transition metal silicates are similar in structure to layered double hdrotalcite. So Mal et al. designed that Fe-modified Co 3 Si 2 O 5 (OH) 4 exhibited an overpotential of 297 mV at 10 mA·cm − 2 , much lower than Co 3 Si 2 O 5 (OH) 4 . [ 17 ] Zhang et al. then studied Ni 3 Si 2 O 5 (OH) 4 with different Fe content, and the bimetallic catalyst (Ni, Fe) 3 Si 2 O 5 (OH) 4 showed a low overpotential of 286 mV and long-term stability at room temperature for 24 h. [ 18 ] Therefore, it is of great significance to develop and prepare new low-cost transition metal-based electrocatalytic OER by morphology manipulation and improvement of electronic structure. As the most abundant and environmentally friendly clay mineral on the earth, vermiculite (VMT), a two-dimensional material, has good cationic, adsorption and swelling properties due to the magnesium aluminium iron silicate containing a layered structure of water molecules which has attracted the attention of many scholars. [ 19 – 21 ] For instance, by using modified VMT, Meng et al. created a two-dimensional layered porous silica material (EXVTM-SiO 2 ). The bimetallic NiCu/EXVTM-SiO 2 catalyst demonstrated stable and strong catalytic activity for CO 2 conversion. [ 22 ] Meanwhile, Wang prepared mesoporous silica nanosheets (SiNSs) with a large surface area (764 m 2 g − 1 ) using 2 M HCl acid-activated VMT. [ 23 ] So two-dimensional nanosheet SiO 2 materials with high content can be prepared by modifying VMT. Compared with other silicon-containing raw materials for the preparation of transition metal silicates, the preparation of VMT is considered to be a sustainable and simple way. [ 24 ] In addition, some elements (Mg, Al, Fe, etc.) of VMT will be doped with the target product, resulting in heteroatom doping or defect effects, thereby enhancing the catalytic performance. Such as Fe-MOF particles grown in the surface of VMT nanosheets prepared by Yang et al. though a solvothermal method exhibited well catalytic activity in the degradation of RMB due to the synergistic effect between the Fe-based metal-organic framework (Fe-MOF) and VNs and the presence of ferric iron in VMT. [ 25 ] Although there have been various studies on VMT composite materials in other fields, as we know, the application of OER about silicate prepared from VMT has not yet been reported. In this work, we embarked on the development of an innovative NiSi-P via a multifaceted approach. Originating from a silicon source procured from VMT, the foundation of NiSi was laid through a meticulous hydrothermal synthesis route involving nickel chloride hexahydrate. Subsequently, a low-temperature phosphating treatment was executed, transforming the pristine NiSi into the advanced NiSi-P electrocatalyst. Notably, this electrocatalyst exhibited a remarkable performance in alkaline media, specifically attaining an overpotential of merely 334 mV at 10 mA·cm − 2 in 1 M KOH solution, showing a substantial improvement over its unmodified NiSi counterpart. This breakthrough not only underscores the potential of phosphate modification in enhancing the electrocatalytic activity for OER but also opens new avenues for the strategic design of silicate-based materials in the realm of electrochemical catalysis. Results and Discussion The synthesis and formation process of NiSi-P were shown in Fig. 1, involving acid-treatment, hydrothermal, and thermal phosphorization steps. The results of chemical composition analysis of VMT and modified VMT were shown in Table S1. From the table the expanded VMT mainly contains SiO 2 , MgO, Al 2 O 3 , Fe 2 O 3 , CaO. Then VMT is treated with 2 M HCl can obtain a high content of SiO 2 . Hydrothermal treatment of the mixed solution containing NiCl 2 ·6H 2 O and V-SiO 2 resulted in the growth of Ni 3 Si 2 O 5 (OH) 4 (NiSi) nanosheets. Finally, the NiSi-P was further prepared by phosphorision at 325 ℃ in a nitrogen atmosphere by using NiSi as the precursor, and Na 2 H 2 PO 2 as the phosphorus source. FESEM and TEM were used to analyze the microscopic morphology and structure of the prepared catalysts. Figure S1 displayed the SEM images of VMT, V-SiO 2 , NiSi and NiSi-P-325, reflecting that both the raw vermiculite and the SiO 2 prepared from VMT exhibit lamellar structures, while NiSi and phosphate NiSi are composed of nanosheets. The FESEM images of Fig. 2(a-b) clearly showed that the nanosheets in NiSi-P, further indicating that Phosphating treatment did not affect its morphology. Then the TEM images in Figs. 2(c-e) found some residual precursor VMT nanosheets, and the edge layer thickness of the nanosheets is approximately between 1–5 nm, demonstrating that SiO 2 in VMT has been successfully introduced into the bulk phase of layered nickel silicate as a silicon source. Notably, the HRTEM in Fig. 2(f) revealed the interlayer spacing of the nanosheets is about 0.244 nm, and 0.263 nm, which mainly correspond to the (202) and (200) crystal planes of Ni 3 Si 2 O 5 (OH) 4 , which is consistent with previous reports. [26] Moreover, P species cannot be found in the HRTEM, so we need to use other methods to determine whether the phosphorus modification is successful. In order to determine the presence of phosphorus in the product, EDS and EDS mapping tests were carried out. The EDS spectrum in Figure S2 revealed the presence of Mg, Al, Fe, Ni, O, Si and Mg, Al, Fe, Ni, O, Si, P elemental signals in NiSi and NiSi-P. Obviously, the small content of Mg, Al and Fe elements origin from the VMT. The element mapping image was displayed in Fig. 2(g), which exhibits the Ni, Co, O, Si, and P elements uniformly distributed in the nanosheets without any element segregation, confirming the successfully doping of P into NiSi. Figure 3a and Figure S3 presented the XRD patterns of VMT, NiSi, NiSi-P, and V-SiO 2 , which were applied to investigate their composition and structure. The SiO 2 obtained from VMT (Figure S3) displayed a diffraction peak at 2θ of about 26°,which can be indexed to the standard patterns of SiO 2 (JCPDS file no. 70-1522). [27] Moreover, it can be observed that the diffraction peaks of NiSi and NiSi-P at 33.8°, and 60.3°, which corresponds to the 1:1 layered nickel silicate (Ni 3 Si 2 O 5 (OH) 4 , JCPD 49-1859), and the diffraction peak at 2θ of 26° assigned to incompletely reacted silica. [28] After the phosphidation, no diffraction peak shifts and P species was observed in NiSi-P-325, indicating that low-temperature phosphating did not destroy the structure of the original substance, and the phosphate is only modified on its surface and does not enter the crystal lattice. [16] The relationship between NiSi and NiSi-P-325 can be further analyzed by FTIR, as shown in Figure S4, The spectrum contains the bonds around 3410 cm -1 , corresponding to the O-H bonds. [29] Notably, the vibrations of Si-O and Ni-O bonds appear at 1000 cm -1 and 668 cm -1 , proving the formation of NiSi. [30, 31] Besides, The observed peak at around 1160 cm -1 corresponds to the vibration of P-O, indicating the presence of phosphate in NiSi-P-325. [32] X-ray photoelectron spectroscopy (XPS) further analyzed the electronic state and conditions of the NiSi and NiSi-P-325. In Fig. 3b, full-scan survey showed that the coexistence of Si, O, and Ni elements in both catalysts, but P only exists in NiSi-P-325, reflecting that P is effectively doped in NiSi. Figure 3c proposed the high-resolution Ni 2p XPS spectrum, with peaks at binding energies of approximately 856.1 eV and 873.6 eV for NiSi and two satellite peaks, confirming the presence of Ni 2+ species. [33] After phosphate introduction, the corresponding Ni 2p peak in the NiSi-P-325 sample exhibited a positive shift, reflecting a slight change in the local electronic structure of NiSi due to phosphate incorporation. Meanwhile, the high-resolution Si 2p XPS (Fig. 3d) of NiSi and NiSi-P-325 fit well at binding energies of 104 and 101.9 eV, due to the presence of Si-O and M-O bonds. [34, 35] The high-resolution O1s XPS spectra in NCS (Fig. 3e) are well deconvoluted at 530.2 and 531.68 eV at binding energies into two peaks, assigned to metal-oxygen bonds and Si − O bonds in NiSi, respectively. [36] In addition, in NCS-P, there is also a fitting peak at 533.1 eV, showing the presence of P-O bonds in phosphate. [37] P 2p XPS was detected in NiSi-P-325 at high resolution (Fig. 3f), at 134.0 eV by a pronounced large peak, corresponding to phosphorus in the oxidation state in PO 4 3- , and it corroborates with the results of FTIR tests. The XPS results showed that P element existed in the form of phosphate, and the phosphate surface modification improved the electronic structure of NiSi, which was conducive to the occurrence of OER. In order to investigate the effect of different phosphating temperatures on OER performance, Figs. 4a and 4c showed the polarization curves of NiSi and NiSi-P measured in 1.0 M KOH solution. The overpotential (η) required for NiSi-P-325 at a current density of 10 mA·cm − 2 is approximately 334 mV, which is superior to NiSi-P-300 (357 mV) and NiSi-P-350 (381 mV). Compared to undoped NiSi (564 mV), η 10 is reduced by 230 mV. These results indicated that phosphate modification can help to change the electronic structure of the product, thereby achieving efficient electrocatalytic OER activity. By comparison, in Figure S5 we synthesized several catalysts with different ratios of Ni (0.07 g, 0.14 g, 0.21 g) and named Ni 1 , Ni 2 , Ni 3 , after phosphating at 325°C, and Ni 1 exhibited the best OER activity. Then, Figure S6 displayed the LSV curves of NiSi-P-325 prepared from VMT treated with different concentrations of hydrochloric acid treatments, which discovers that the higher the concentration of hydrochloric acid, the worse the OER performance. Moreover, recently reported catalysts were shown in Table S2; the target catalyst exhibited good electrocatalytic performance in 1 M KOH. Therefore, this result confirmed that the addition of phosphate and the multi-metal effect in VMT can significantly improve the OER activity of NiSi. [25] The Tafel slope can also further reflect the kinetics of the OER electrocatalyst. As shown in Fig. 4c, the Tafel slope of the NiSi-P-325 sample is minimal (66.5 mV dec − 1 ), which is much smaller than that of NiSi (149.2 mV dec − 1 ), assuming that the reaction kinetics of the NiSi-P-325 catalyst are much faster. In addition, the performance of OER is also related to the charge transfer resistance (Rct), so conducted electrochemical impedance testing and fitted the obtained Nyquist plot with an Rs - (Rct//CPE) equivalent circuit. The Rct of NiSi-P-325 is the smallest (Fig. 4d), at 36 Ω, while the Rct of NiSi, NiSi-P-300, and NiSi-P-350 are 144, 54, and 60 Ω, respectively. The impedance data further indicates that NiSi-P-325 has the fastest charge transfer rate and catalytic kinetics. In addition, due to the similarity in morphology between NCS-P samples, the electrochemical double-layer capacitance (C dl ) was used to estimate the electrochemically active surface area (ECSA), as C dl is linearly proportional to ECSA. As shown in Fig. 4f, the linear plot obtained from the CV (Figure S7 Supplementary materials) collected from the Faraday region yielded C dl (Fig. 4e). Notably, The C dl value of NiSi-P-325 was 1.09 mF·cm − 2 , which is about 2.5 times that of NiSi (0.38 mF·cm − 2 ). NiSi-P-325 still exhibited better OER activity than NiSi. Finally, the OER stability of NiSi-P-325 was also tested at 10 mA·cm − 2 , as shown in Fig. 4f. NCS-P-325 showed no significant increase in potential after continuous operation for 24000 seconds, indicating that NiSi-P-325 maintained good catalytic activity based on its unique structure and added phosphate. These results demonstrated that phosphorus-modified basic nickel silicate derivated from VMT could produce more active sites and achieve a high OER activity. Finally, the NiSi-P material after OER was tested by FESEM, TEM and EDS mapping. As can be seen from Figure S8, the morphology of NiSi-P after the OER is similar to that before alkali treatment, showing a similar layered structure of nanosheets, except for some ambiguity, which may be the main reason for the addition of binder in the preparation of catalyst inks. At the same time, EDS mapping showed that there was a small amount of overflow of P element after the reaction, and the elements Ni、Si、O were present in the overall structure of the catalyst, which was consistent with the EDS mapping before the reaction. XPS was used to further investigate the electronic states of NiSi-P before and after OER. For Ni 2p, the 2p 3/2 peak at 856.5 eV with a negative shift of 0.5 eV after OER (Figure S9(a)). These negative shifts confirmed the P doping and electronic interactions of the NiSi-P. From the Si 2p in Figure S9(b), the peaks without any shift in NiSi-P before and after OER. These results indicated that Si is served as a structure of NiSi-P. For the P 2p in Figure S9(c), the intensity of the peaks is significantly reduced after OER, indicating that the phosphate of the surface modification can be spilled during OER. Based on these dates, further confirmed the efficient modification of phosphate promoted the transfer of electrons in NiSi-P. Conclusion In summary, a phosphate-modified nickel silica nanosheet with significant oxygen evolution activity toward water spliting was successfully prepared by hydrothermal synthesis and vapor deposition. Through the cross-linked silicate nanosheets, the heteroatom effect of VMT, and the synergistic effect of P species, NiSi-P exhibited lower overpotentials (334 mV) at 10 mA·cm -2 , smaller Tafel slopes (66.5 mV dec -1 ) and relatively stable durability to OER. And the high oxidation nickel species promoted the surface reconstitution of the NCS-P, The NiSi-P prepared in this study served as a low-cost and sustainable electrochemical water-splitting electrocatalyst, providing a new approach to the design of silicates in electrocatalysis. Methods 1. Preparation of silica from the VMT 2 g of VMT (150 molybdenum) was dispersed in 80 mL of HCl aqueous solution (2 M), and the suspension was magnetically stirred at 50 °C water bath for 8 h, The suspension was then separated by suction filtration and washed with deionized water and ethanol several times until the pH of the filtrate reached 6.8. Subsequently, the obtained solid was dried in a vacuum drying oven at 60 °C for 12 h. The final product after grinding was labeled as V-SiO 2 nanosheets. 2. Preparation of NiSi-P NiSi-P was synthesized by using VMT derived SiO 2 as a silicon source. Typically, 0.4239 g of NiCl 2 ·6H 2 O was add to 4 mL of water and stirred for 20 min. Then, 0.14 g of SiO 2 (the molar ratio of metal to silicon was 4:5) and 4 mL of NH 3 ·H 2 O (25wt%) were sequentially added to the above mixture. After 30 min, the mixture solution was transferred into a 40 mL Teflon-lined stainless steel autoclave and heated at 180 °C for 24 h. When the solution has cooled down to room temperature naturally, the green powder was centrifuged and washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 60 °C for 24 h. For further phosphating, 0.01 g green powder and 0.30 g of NaH 2 PO 2 ·H 2 O were paced in the downstream and upstream of the tube furnace, respectively. Subsequently, it was heated at different calcination temperatures for 2 h at a heating rate of 5 °C min -1 in N 2 atmosphere. The final products are labelled as NiSi-P-X (x indicates the phosphating temperature). The NiSi-P-325 showed the best OER performance, so, the NiSi-P notation refers to NiSi-P-325. Declarations Acknowledgements This study was financially supported by the Thousand Talents Plan of Jiangxi Province (jxsq2023201068) and the National Natural Science Foundation of China (22065016, 22265013, 22061020) and National Key R&D Program of China (2022YFA1203200). Conflicts of Interest There are no conflicts to declare. References Beniya A (2019) Higashi Towards dense single-atom catalysts for future automotive applications. Nat Catal 2:590–602 Yang Q, Jiang Y, Zhuo H, Mitchell EM (2023) Yu. Recent progress of metal single-atom catalysts for energy applications. Nano Energy 111:108404 Li D, Shao X, Umair MM, Hou F, Li S, Tang Y, Cao L et al (2024) Superhydrophilic cobalt-doped NiFe LDH graphite felt with enriched oxygen vacancy as an efficient oxygen evolution electrocatalyst in alkaline media. J Hydrog Energy 80:11–21 Lin X, Liu J, Qiu X, Liu B, Wang X, Chen L et al (2023) Ru-FeNi Alloy Heterojunctions on Lignin-derived Carbon as Bifunctional Electrocatalysts for Efficient Overall Water Splitting. Angewandte Chemie-International Ed Angew Chem Int Ed 135:e202306333 Wang X, Yang Q, Singh S, Borrmann H, Hasse V, Yi C et al (2024) Topological semimetals with intrinsic chirality as spin-controlling electrocatalysts for the oxygen evolution reaction. Nat. Energy 1–9 Zhang D et al (2024) Optimal Electrocatalyst Design Strategies for Acidic Oxygen Evolution. Adv Sci 2401975 Jiang F, Li Y (2024) Pan Design Principles of Single-Atom Catalysts for Oxygen Evolution Reaction: From Targeted Structures to Active Sites. Adv Mater 36:2306309 Retuerto M, Pascual L, Torrero J, Salam MA, Tolosana-Moranchel Á, Gianolio D et al (2022) Highly active and stable OER electrocatalysts derived from Sr 2 MIrO 6 for proton exchange membrane water electrolyzers. Nat Commun 13:7935 Zhang H, Xu H, Wang L, Ouyang C, Liang H, Zhong S (2023) A Metal–Organic Frameworks Derived 1T-MoS 2 with Expanded Layer Spacing for Enhanced Electrocatalytic Hydrogen Evolution. Small 19:2205736 He T, Bruening M, Espinosa M, Agapie T (2024) Novel Silicate Platform as Weakly-Coordinating Anions for Diverse Organometallic and Electrochemical Applications. Angew Chem Int Ed e202417136 Chen X, Zhou S, Zhang X, Chen S, Wang L, Zhang C et al (2024) Research progress on the preparation of transition metal-modified zeolite catalysts and their catalytic performance for the purification of engine exhausts. J Mater Chem 12:16293–16328 Zhang Y, Wang C, Chen X, Dong X, Meng C, Huang C (2021) Bamboo leaves as sustainable sources for the preparation of amorphous carbon/iron silicate anode and nickel–cobalt silicate cathode materials for hybrid Supercapacitors. ACS Appl Energy Mater 4:9328–9340 Mu Y, Zhang Y, Pei X, Dong X, Kou Z, Cui M (2022) Dispersed FeO nanoparticles decorated with Co 2 SiO 4 hollow spheres for enhanced oxygen evolution reaction. J Adv Colloid Interface Sci 611:235–245 Anantharaj S, Aravindan V (2020) Developments and perspectives in 3D transition-metal‐based electrocatalysts for neutral and near‐neutral water electrolysis. Adv Energy Mater 10:1902666 Qiu C, Jiang J (2015) Ai When Layered Nickel–Cobalt Silicate Hydroxide Nanosheets Meet Carbon Nanotubes: A Synergetic Coaxial Nanocable Structure for Enhanced Electrocatalytic Water Oxidation. ACS Appl Mater Interfaces 8:945–951 Qiu C, Ai L (2018) Jiang Layered Phosphate-Incorporated Nickel–Cobalt Hydrosilicates for Highly Efficient Oxygen Evolution Electrocatalysis. ACS Sustain Chem Eng 6:4492–4498 Zhu J, Xia L, Yang W, Yu R, Zhang W, Luo W et al (2022) Activating inert sites in cobalt silicate hydroxides for oxygen evolution through atomically doping. Energy Environ Mater 5:655–661 Zhang J, Li Z, Bai G, Wang Q, Zhang J, Wang W et al (2023) Nickel-iron layered silicate nanomembrane as efficient electrocatalyst for oxygen evolution reaction in alkaline media. Fuel 332 Plachá P, Kovář J, Vaněk M, Mikeska K, Škrlová O, Dutko et al (2020) Adsorption of nerve agent simulants onto vermiculite structure: Experiments and modelling. J Hazard Mater 382:121001 Ma L, Huang H, Feng W, Chen L, Xia L, Yu Y et al (2022) 2D Catalytic, Chemodynamic, and Ferroptotic Vermiculite Nanomedicine. Adv Funct Mater 32:2208220 Ji X, Ge L, Liu C, Tang Z, Xiao Y, Chen W et al (2021) Capturing functional two-dimensional nanosheets from sandwich-structure vermiculite for cancer theranostics. Nat Commun 12:1124 Meng Z (2021) Wang The effect of different promoters (La 2 O 3 , CeO 2 , and ZrO 2 ) on the catalytic activity of the modified vermiculite-based bimetallic NiCu/EXVTM-SiO 2 catalyst in methane dry reforming. ACS omega 6:29651–29658 Wang L, Wang X, Yin& J (2016) Wang Insights into the physicochemical characteristics from vermiculite to silica nanosheets. Appl Clay Sci 132–133:17–23 Kozhevnikov IV, Chibiryaev AM (2021) Martyanov One-pot synthesis of TMOS from SiO 2 -enriched minerals and supercritical MeOH in a flow reactor. Chem Eng J 426:131871 Yang H, Guo J, Chu L, Huang Z, Liu Z, Wang L et al (2023) Self-assembly of Fe-MOF on vermiculite nanosheets with enhanced catalytic activity. Appl Clay Sci 245:107138 Wang Q, Zhang Y, Jiang H (2018) Hu& C. Meng. In situ generated Ni 3 Si 2 O 5 (OH) 4 on mesoporous heteroatom-enriched carbon derived from natural bamboo leaves for high-performance supercapacitors. ACS Appl Energy 1:3396–3409 Yu Y, Movick WJ, Obata K, Yoshida S (2024) Takanabe Mn-Na 2 WO 4 /SiO 2 -tridymite with improved stability and selectivity for high-pressure oxidative coupling of methane. Chem Eng J 500:156938 Rong Q, Long L-L, Zhang X, Huang Y-X (2015) Yu Layered cobalt nickel silicate hollow spheres as a highly-stable supercapacitor material. Appl Energy 153:63–69 Ananias D, Rainho JP, Ferreira A, Lopes M, Morais CM, Rocha J et al (2002) Synthesis and characterization of Er (III) and Y (III) sodium silicates: Na 3 ErSi 3 O 9 , a new infrared emitter. Chem Mater 14:1767–1772 Kim P, Jones SC, Hotchkiss PJ, Haddock JN, Kippelen B, Marder SR et al (2007) Phosphonic acid-modified barium titanate polymer nanocomposites with high permittivity and dielectric strength. Adv Mater 19:1001–1005 Zhang Y, Wang C, Dong X, Jiang H, Hu T, Meng C et al (2021) Alkali etching metal silicates derived from bamboo leaves with enhanced electrochemical properties for solid-state hybrid supercapacitors. Chem Eng J 417:127964 Austeria M, Dao HT, Mai M (2023) Kim Dual-phase cobalt phosphide/phosphate hybrid interactions via iridium nanocluster interfacial engineering toward efficient overall seawater splitting. Appl Catal 327:122467 Du M, Shang J, Mao (2017) Song Hierarchical MoP/Ni 2 P heterostructures on nickel foam for efficient water splitting. J Mater Chem 5:15940–15949 Kong D, Zhang M, Xiao Y, Hu J, Zhao W, Han L et al (2019) Insights into the structural evolution and Li/O loss in high-Ni layered oxide cathodes. Nano Energy 59:327–335 Johnson AM (2023) Johnson Thermally Robust yet Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)‐Like Materials Based on Si – O Bonds. Angew Chem Int Ed 135:e202315085 Hu R, Xiao J, Wang T, Chen G, Chen L, Tian X (2020) Engineering of phosphate-functionalized biochars with highly developed surface area and porosity for efficient and selective extraction of uranium. Chem Eng J 379:122388 Fan J, Wang L, Xiang X, Liu Y, Shi N, Lin Y et al (2024) Porous Flower-Like Nanoarchitectures Derived from Nickel Phosphide Nanocrystals Anchored on Amorphous Vanadium Phosphate Nanosheet Nanohybrids for Superior Overall Water Splitting. Small Methods 8:2301279 Additional Declarations There is NO Competing Interest. Supplementary Files SupplementaryInformation.docx Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction Cite Share Download PDF Status: Posted Version 1 posted 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-5991362","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":415487549,"identity":"82d0bdd4-29ca-479a-944d-e47ba2b5eccf","order_by":0,"name":"Sheng-Liang Zhong","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2klEQVRIiWNgGAWjYDACdgY2ECXH2ADmMhOhhRmixZh0LYkNMC5BIN/M/uzBxx216c0zco9JMFRYJzawnz2AV4vBYYZ0w5lnjuc29pxLk2A4k57YwJOXgF8LM8Mxad62Y7mN7T1mEoxthxMbJHgMCDiMsQ2kJZ2xmQeo5R8RWhgOM7MBtdQkMIJtaSBCi8FhNjbJmW0HDBt7zhhbJBxLN27jySHgsPb2ZxIf2+rkDWfkGN74UGMt289+hoDDoM5jMGwAUglAzEaMeiCoY5AnUuUoGAWjYBSMQAAA2C4/Oxu4aXoAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-6660-6465","institution":"Jiangxi Normal University","correspondingAuthor":true,"prefix":"","firstName":"Sheng-Liang","middleName":"","lastName":"Zhong","suffix":""},{"id":415487550,"identity":"c5ba6ecc-00e2-4aba-8c7e-a5758480634c","order_by":1,"name":"Jing Gao","email":"","orcid":"","institution":"Jiangxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Jing","middleName":"","lastName":"Gao","suffix":""},{"id":415487551,"identity":"bbb1d721-d920-454e-9aa5-51a4463be037","order_by":2,"name":"Chaochao Tao","email":"","orcid":"","institution":"Jiangxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Chaochao","middleName":"","lastName":"Tao","suffix":""},{"id":415487552,"identity":"986f2b4c-45e5-46b7-87c2-42442bdadfcb","order_by":3,"name":"Tang Jianqiang","email":"","orcid":"","institution":"Jiangxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Tang","middleName":"","lastName":"Jianqiang","suffix":""},{"id":415487553,"identity":"19da8670-13d5-4af2-ab94-28cd565fbd10","order_by":4,"name":"Lei Wang","email":"","orcid":"","institution":"Jiangxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Lei","middleName":"","lastName":"Wang","suffix":""},{"id":415487554,"identity":"56818f88-361a-440c-b9dc-4973dd0db751","order_by":5,"name":"Hang Zhang","email":"","orcid":"","institution":"Jiangxi Normal University","correspondingAuthor":false,"prefix":"","firstName":"Hang","middleName":"","lastName":"Zhang","suffix":""}],"badges":[],"createdAt":"2025-02-09 08:40:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5991362/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5991362/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":79177696,"identity":"a3808176-695e-402c-93cc-a02d2d811298","added_by":"auto","created_at":"2025-03-25 10:06:17","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":42773,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic illustration of the formation of NiSi-P.\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5991362/v1/f7d789edd6c6183068a778f8.jpg"},{"id":79176244,"identity":"db35ca70-2f73-43c4-817c-1b5f9215fc9d","added_by":"auto","created_at":"2025-03-25 09:58:17","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":150440,"visible":true,"origin":"","legend":"\u003cp\u003eFESEM (a,b), TEM (c,d,e), HRTEM (f), elemental mapping images of the NiSi-P (g).\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5991362/v1/5aada53fac04d49dab2849fe.jpg"},{"id":79176252,"identity":"f3020338-7cae-47fc-a707-24d1a6617167","added_by":"auto","created_at":"2025-03-25 09:58:17","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":130658,"visible":true,"origin":"","legend":"","description":"","filename":"3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5991362/v1/b18e8bffcd86d4da7a531628.jpg"},{"id":79179316,"identity":"8fcc7156-7799-4b82-bca9-518b698ae4cd","added_by":"auto","created_at":"2025-03-25 10:14:17","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":143427,"visible":true,"origin":"","legend":"\u003cp\u003e(a) LSV polarization curves, (b) Tafel plots, (c) comparison of overpotential at 10 mA\u003csup\u003e.\u003c/sup\u003ecm\u003csup\u003e-2\u003c/sup\u003e, (d) Nyquist EIS plots, C\u003csub\u003edl \u003c/sub\u003ecalculation of different catalysts. (f) chronopotentiometry curve of NiSi and NiSi-P at 10 mA·cm\u003csup\u003e-2\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5991362/v1/e90fc2476563eb755f37d477.jpg"},{"id":79181001,"identity":"e61f5950-5aa1-4530-9a79-540150e52e18","added_by":"auto","created_at":"2025-03-25 10:30:19","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":923529,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5991362/v1/bde6c39b-1d73-4a7a-b670-f6c22a845902.pdf"},{"id":79176257,"identity":"4e1f474a-ca11-4ff3-88cf-2295e17be4c6","added_by":"auto","created_at":"2025-03-25 09:58:17","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3016491,"visible":true,"origin":"","legend":"Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction","description":"","filename":"SupplementaryInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-5991362/v1/d92652e2855ab4ac360f9c8c.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe relentless depletion of fossil fuels, a cornerstone of modern energy consumption, has given rise to pressing ecological concerns, including global warming and land degradation, underscoring the urgency to identify and adopt clean, renewable energy sources as viable alternatives.\u003csup\u003e[\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]\u003c/sup\u003e Hydrogen energy is considered as a rational alternative to fossil fuels due to its high energy density and conversion efficiency, Among the various methods to produce hydrogen, electrocatalytic water splitting stands out as a sustainable and environmentally friendly approach.\u003csup\u003e[\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]\u003c/sup\u003e Noble metal catalysts such as ruthenium and iridium have shown excellent oxygen evolution reaction (OER) activity, but their high cost and scarcity have severely limited their large-scale applications\u003csup\u003e[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]\u003c/sup\u003e. Consequently, the scientific community has shifted its focus towards the development of cost-effective, highly active, and stable OER electrocatalysts derived from abundant, earth-abundant elements.\u003csup\u003e[\u003cspan additionalcitationids=\"CR8\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eTransition metal silicates have attracted widespread attention due to their abundant silicon content, low cost, stable tetrahedral framework, and excellent chemical properties.\u003csup\u003e[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]\u003c/sup\u003e For instance, Zhang et al. assembled hybrid supercapacitor devices from C/FeSi anode and CoNiSi cathode materials derived from natural bamboo leaves, which have excellent electrochemical energy storage performance\u003csup\u003e[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]\u003c/sup\u003e. Mu et al. designed FeO\u003csub\u003ex\u003c/sub\u003e-modified Co\u003csub\u003e2\u003c/sub\u003eSiO\u003csub\u003e4,\u003c/sub\u003e exhibiting excellent OER properties.\u003csup\u003e[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]\u003c/sup\u003e Compared with energy storage technology, there are fewer studies to explore its application in OER. Transition metal silicates served as OER electrocatalysts mainly face problems such as poor conductivity and few active sites.\u003csup\u003e[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]\u003c/sup\u003e Therefore, a series of studies have been devoted to improving their electrocatalytic OER. For example, Qiu's group used a simple sol-gel method to combine the carbon nanotubes as a carrier with nickel-cobalt silicate, and the synthesized catalyst not only has high structural stability, but also has good conductivity and exhibits enhanced OER activity, and the optimized material requires a low overpotential of 440 mV to provide a current density of 10 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e.\u003csup\u003e[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]\u003c/sup\u003e In addition, their group has also prepared phosphate-modified basic nickel-cobalt silicate, which regulates the electronic structure of basic cobalt silicate through phosphate, increases the number of reactive sites, and reduces the energy barrier of the OER reaction. It exhibited an overpotential of 394 mV at 10 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e in 0.1 M KOH.\u003csup\u003e[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]\u003c/sup\u003e In addition, layered transition metal silicates are similar in structure to layered double hdrotalcite. So Mal et al. designed that Fe-modified Co\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e exhibited an overpotential of 297 mV at 10 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, much lower than Co\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e.\u003csup\u003e[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e Zhang et al. then studied Ni\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e with different Fe content, and the bimetallic catalyst (Ni, Fe)\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e showed a low overpotential of 286 mV and long-term stability at room temperature for 24 h.\u003csup\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]\u003c/sup\u003e Therefore, it is of great significance to develop and prepare new low-cost transition metal-based electrocatalytic OER by morphology manipulation and improvement of electronic structure.\u003c/p\u003e \u003cp\u003eAs the most abundant and environmentally friendly clay mineral on the earth, vermiculite (VMT), a two-dimensional material, has good cationic, adsorption and swelling properties due to the magnesium aluminium iron silicate containing a layered structure of water molecules which has attracted the attention of many scholars.\u003csup\u003e[\u003cspan additionalcitationids=\"CR20\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/sup\u003e For instance, by using modified VMT, Meng et al. created a two-dimensional layered porous silica material (EXVTM-SiO\u003csub\u003e2\u003c/sub\u003e). The bimetallic NiCu/EXVTM-SiO\u003csub\u003e2\u003c/sub\u003e catalyst demonstrated stable and strong catalytic activity for CO\u003csub\u003e2\u003c/sub\u003e conversion.\u003csup\u003e[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e Meanwhile, Wang prepared mesoporous silica nanosheets (SiNSs) with a large surface area (764 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) using 2 M HCl acid-activated VMT.\u003csup\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/sup\u003e So two-dimensional nanosheet SiO\u003csub\u003e2\u003c/sub\u003e materials with high content can be prepared by modifying VMT. Compared with other silicon-containing raw materials for the preparation of transition metal silicates, the preparation of VMT is considered to be a sustainable and simple way.\u003csup\u003e[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e In addition, some elements (Mg, Al, Fe, etc.) of VMT will be doped with the target product, resulting in heteroatom doping or defect effects, thereby enhancing the catalytic performance. Such as Fe-MOF particles grown in the surface of VMT nanosheets prepared by Yang et al. though a solvothermal method exhibited well catalytic activity in the degradation of RMB due to the synergistic effect between the Fe-based metal-organic framework (Fe-MOF) and VNs and the presence of ferric iron in VMT.\u003csup\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e Although there have been various studies on VMT composite materials in other fields, as we know, the application of OER about silicate prepared from VMT has not yet been reported.\u003c/p\u003e \u003cp\u003eIn this work, we embarked on the development of an innovative NiSi-P via a multifaceted approach. Originating from a silicon source procured from VMT, the foundation of NiSi was laid through a meticulous hydrothermal synthesis route involving nickel chloride hexahydrate. Subsequently, a low-temperature phosphating treatment was executed, transforming the pristine NiSi into the advanced NiSi-P electrocatalyst. Notably, this electrocatalyst exhibited a remarkable performance in alkaline media, specifically attaining an overpotential of merely 334 mV at 10 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e in 1 M KOH solution, showing a substantial improvement over its unmodified NiSi counterpart. This breakthrough not only underscores the potential of phosphate modification in enhancing the electrocatalytic activity for OER but also opens new avenues for the strategic design of silicate-based materials in the realm of electrochemical catalysis.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eThe synthesis and formation process of NiSi-P were shown in Fig.\u0026nbsp;1, involving acid-treatment, hydrothermal, and thermal phosphorization steps. The results of chemical composition analysis of VMT and modified VMT were shown in Table S1. From the table the expanded VMT mainly contains SiO\u003csub\u003e2\u003c/sub\u003e, MgO, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, CaO. Then VMT is treated with 2 M HCl can obtain a high content of SiO\u003csub\u003e2\u003c/sub\u003e. Hydrothermal treatment of the mixed solution containing NiCl\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO and V-SiO\u003csub\u003e2\u003c/sub\u003e resulted in the growth of Ni\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e (NiSi) nanosheets. Finally, the NiSi-P was further prepared by phosphorision at 325 ℃ in a nitrogen atmosphere by using NiSi as the precursor, and Na\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003ePO\u003csub\u003e2\u003c/sub\u003e as the phosphorus source.\u003c/p\u003e\n\u003cp\u003eFESEM and TEM were used to analyze the microscopic morphology and structure of the prepared catalysts. Figure S1 displayed the SEM images of VMT, V-SiO\u003csub\u003e2\u003c/sub\u003e, NiSi and NiSi-P-325, reflecting that both the raw vermiculite and the SiO\u003csub\u003e2\u003c/sub\u003e prepared from VMT exhibit lamellar structures, while NiSi and phosphate NiSi are composed of nanosheets. The FESEM images of Fig.\u0026nbsp;2(a-b) clearly showed that the nanosheets in NiSi-P, further indicating that Phosphating treatment did not affect its morphology. Then the TEM images in Figs.\u0026nbsp;2(c-e) found some residual precursor VMT nanosheets, and the edge layer thickness of the nanosheets is approximately between 1\u0026ndash;5 nm, demonstrating that SiO\u003csub\u003e2\u003c/sub\u003e in VMT has been successfully introduced into the bulk phase of layered nickel silicate as a silicon source. Notably, the HRTEM in Fig.\u0026nbsp;2(f) revealed the interlayer spacing of the nanosheets is about 0.244 nm, and 0.263 nm, which mainly correspond to the (202) and (200) crystal planes of Ni\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e, which is consistent with previous reports.\u003csup\u003e[26]\u003c/sup\u003e Moreover, P species cannot be found in the HRTEM, so we need to use other methods to determine whether the phosphorus modification is successful. In order to determine the presence of phosphorus in the product, EDS and EDS mapping tests were carried out. The EDS spectrum in Figure S2 revealed the presence of Mg, Al, Fe, Ni, O, Si and Mg, Al, Fe, Ni, O, Si, P elemental signals in NiSi and NiSi-P. Obviously, the small content of Mg, Al and Fe elements origin from the VMT. The element mapping image was displayed in Fig.\u0026nbsp;2(g), which exhibits the Ni, Co, O, Si, and P elements uniformly distributed in the nanosheets without any element segregation, confirming the successfully doping of P into NiSi.\u003c/p\u003e\n\u003cp\u003eFigure 3a and Figure S3 presented the XRD patterns of VMT, NiSi, NiSi-P, and V-SiO\u003csub\u003e2\u003c/sub\u003e, which were applied to investigate their composition and structure. The SiO\u003csub\u003e2\u003c/sub\u003e obtained from VMT (Figure S3) displayed a diffraction peak at 2\u0026theta; of about 26\u0026deg;,which can be indexed to the standard patterns of SiO\u003csub\u003e2\u003c/sub\u003e (JCPDS file no. 70-1522).\u003csup\u003e[27]\u003c/sup\u003e Moreover, it can be observed that the diffraction peaks of NiSi and NiSi-P at 33.8\u0026deg;, and 60.3\u0026deg;, which corresponds to the 1:1 layered nickel silicate (Ni\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e, JCPD 49-1859), and the diffraction peak at 2\u0026theta; of 26\u0026deg; assigned to incompletely reacted silica.\u003csup\u003e[28]\u003c/sup\u003e After the phosphidation, no diffraction peak shifts and P species was observed in NiSi-P-325, indicating that low-temperature phosphating did not destroy the structure of the original substance, and the phosphate is only modified on its surface and does not enter the crystal lattice.\u003csup\u003e[16]\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eThe relationship between NiSi and NiSi-P-325 can be further analyzed by FTIR, as shown in Figure S4, The spectrum contains the bonds around 3410 cm\u003csup\u003e-1\u003c/sup\u003e, corresponding to the O-H bonds.\u003csup\u003e[29]\u003c/sup\u003e Notably, the vibrations of Si-O and Ni-O bonds appear at 1000 cm\u003csup\u003e-1\u003c/sup\u003e and 668 cm\u003csup\u003e-1\u003c/sup\u003e, proving the formation of NiSi.\u003csup\u003e[30, 31]\u003c/sup\u003e Besides, The observed peak at around 1160 cm\u003csup\u003e-1\u003c/sup\u003e corresponds to the vibration of P-O, indicating the presence of phosphate in NiSi-P-325.\u003csup\u003e[32]\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eX-ray photoelectron spectroscopy (XPS) further analyzed the electronic state and conditions of the NiSi and NiSi-P-325. In Fig.\u0026nbsp;3b, full-scan survey showed that the coexistence of Si, O, and Ni elements in both catalysts, but P only exists in NiSi-P-325, reflecting that P is effectively doped in NiSi. Figure\u0026nbsp;3c proposed the high-resolution Ni 2p XPS spectrum, with peaks at binding energies of approximately 856.1 eV and 873.6 eV for NiSi and two satellite peaks, confirming the presence of Ni\u003csup\u003e2+\u003c/sup\u003e species.\u003csup\u003e[33]\u003c/sup\u003e After phosphate introduction, the corresponding Ni 2p peak in the NiSi-P-325 sample exhibited a positive shift, reflecting a slight change in the local electronic structure of NiSi due to phosphate incorporation. Meanwhile, the high-resolution Si 2p XPS (Fig. 3d) of NiSi and NiSi-P-325 fit well at binding energies of 104 and 101.9 eV, due to the presence of Si-O and M-O bonds.\u003csup\u003e[34, 35]\u003c/sup\u003e The high-resolution O1s XPS spectra in NCS (Fig. 3e) are well deconvoluted at 530.2 and 531.68 eV at binding energies into two peaks, assigned to metal-oxygen bonds and Si\u0026thinsp;\u0026minus;\u0026thinsp;O bonds in NiSi, respectively.\u003csup\u003e[36]\u003c/sup\u003e In addition, in NCS-P, there is also a fitting peak at 533.1 eV, showing the presence of P-O bonds in phosphate.\u003csup\u003e[37]\u003c/sup\u003e P 2p XPS was detected in NiSi-P-325 at high resolution (Fig. 3f), at 134.0 eV by a pronounced large peak, corresponding to phosphorus in the oxidation state in PO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e3-\u003c/sup\u003e, and it corroborates with the results of FTIR tests. The XPS results showed that P element existed in the form of phosphate, and the phosphate surface modification improved the electronic structure of NiSi, which was conducive to the occurrence of OER.\u003c/p\u003e\n\u003cp\u003eIn order to investigate the effect of different phosphating temperatures on OER performance, Figs.\u0026nbsp;4a and 4c showed the polarization curves of NiSi and NiSi-P measured in 1.0 M KOH solution. The overpotential (\u0026eta;) required for NiSi-P-325 at a current density of 10 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e is approximately 334 mV, which is superior to NiSi-P-300 (357 mV) and NiSi-P-350 (381 mV). Compared to undoped NiSi (564 mV), \u0026eta;\u003csub\u003e10\u003c/sub\u003e is reduced by 230 mV. These results indicated that phosphate modification can help to change the electronic structure of the product, thereby achieving efficient electrocatalytic OER activity. By comparison, in Figure S5 we synthesized several catalysts with different ratios of Ni (0.07 g, 0.14 g, 0.21 g) and named Ni\u003csub\u003e1\u003c/sub\u003e, Ni\u003csub\u003e2\u003c/sub\u003e, Ni\u003csub\u003e3\u003c/sub\u003e, after phosphating at 325\u0026deg;C, and Ni\u003csub\u003e1\u003c/sub\u003e exhibited the best OER activity. Then, Figure S6 displayed the LSV curves of NiSi-P-325 prepared from VMT treated with different concentrations of hydrochloric acid treatments, which discovers that the higher the concentration of hydrochloric acid, the worse the OER performance. Moreover, recently reported catalysts were shown in Table S2; the target catalyst exhibited good electrocatalytic performance in 1 M KOH. Therefore, this result confirmed that the addition of phosphate and the multi-metal effect in VMT can significantly improve the OER activity of NiSi.\u003csup\u003e[25]\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eThe Tafel slope can also further reflect the kinetics of the OER electrocatalyst. As shown in Fig.\u0026nbsp;4c, the Tafel slope of the NiSi-P-325 sample is minimal (66.5 mV dec\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), which is much smaller than that of NiSi (149.2 mV dec\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), assuming that the reaction kinetics of the NiSi-P-325 catalyst are much faster. In addition, the performance of OER is also related to the charge transfer resistance (Rct), so conducted electrochemical impedance testing and fitted the obtained Nyquist plot with an Rs - (Rct//CPE) equivalent circuit. The Rct of NiSi-P-325 is the smallest (Fig.\u0026nbsp;4d), at 36 Ω, while the Rct of NiSi, NiSi-P-300, and NiSi-P-350 are 144, 54, and 60 Ω, respectively. The impedance data further indicates that NiSi-P-325 has the fastest charge transfer rate and catalytic kinetics.\u003c/p\u003e\n\u003cp\u003eIn addition, due to the similarity in morphology between NCS-P samples, the electrochemical double-layer capacitance (C\u003csub\u003edl\u003c/sub\u003e) was used to estimate the electrochemically active surface area (ECSA), as C\u003csub\u003edl\u003c/sub\u003e is linearly proportional to ECSA. As shown in Fig.\u0026nbsp;4f, the linear plot obtained from the CV (Figure S7 Supplementary materials) collected from the Faraday region yielded C\u003csub\u003edl\u003c/sub\u003e (Fig.\u0026nbsp;4e). Notably, The C\u003csub\u003edl\u003c/sub\u003e value of NiSi-P-325 was 1.09 mF\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, which is about 2.5 times that of NiSi (0.38 mF\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e). NiSi-P-325 still exhibited better OER activity than NiSi. Finally, the OER stability of NiSi-P-325 was also tested at 10 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, as shown in Fig.\u0026nbsp;4f. NCS-P-325 showed no significant increase in potential after continuous operation for 24000 seconds, indicating that NiSi-P-325 maintained good catalytic activity based on its unique structure and added phosphate. These results demonstrated that phosphorus-modified basic nickel silicate derivated from VMT could produce more active sites and achieve a high OER activity.\u003c/p\u003e\n\u003cp\u003eFinally, the NiSi-P material after OER was tested by FESEM, TEM and EDS mapping. As can be seen from Figure S8, the morphology of NiSi-P after the OER is similar to that before alkali treatment, showing a similar layered structure of nanosheets, except for some ambiguity, which may be the main reason for the addition of binder in the preparation of catalyst inks. At the same time, EDS mapping showed that there was a small amount of overflow of P element after the reaction, and the elements Ni、Si、O were present in the overall structure of the catalyst, which was consistent with the EDS mapping before the reaction. XPS was used to further investigate the electronic states of NiSi-P before and after OER. For Ni 2p, the 2p\u003csub\u003e3/2\u003c/sub\u003e peak at 856.5 eV with a negative shift of 0.5 eV after OER (Figure S9(a)). These negative shifts confirmed the P doping and electronic interactions of the NiSi-P. From the Si 2p in Figure S9(b), the peaks without any shift in NiSi-P before and after OER. These results indicated that Si is served as a structure of NiSi-P. For the P 2p in Figure S9(c), the intensity of the peaks is significantly reduced after OER, indicating that the phosphate of the surface modification can be spilled during OER. Based on these dates, further confirmed the efficient modification of phosphate promoted the transfer of electrons in NiSi-P.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, a phosphate-modified nickel silica nanosheet with significant oxygen evolution activity toward water spliting was successfully prepared by hydrothermal synthesis and vapor deposition. Through the cross-linked silicate nanosheets, the heteroatom effect of VMT, and the synergistic effect of P species, NiSi-P exhibited lower overpotentials (334 mV) at 10 mA\u0026middot;cm\u003csup\u003e-2\u003c/sup\u003e, smaller Tafel slopes (66.5 mV dec\u003csup\u003e-1\u003c/sup\u003e) and relatively stable durability to OER. And the high oxidation nickel species promoted the surface reconstitution of the NCS-P, The NiSi-P prepared in this study served as a low-cost and sustainable electrochemical water-splitting electrocatalyst, providing a new approach to the design of silicates in electrocatalysis.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003e1. Preparation of silica from the VMT\u0026nbsp;\u003c/strong\u003e2 g of VMT (150 molybdenum) was dispersed in 80 mL of HCl aqueous solution (2 M), and the suspension was magnetically stirred at 50\u0026nbsp;°C\u0026nbsp;water bath for 8 h, The suspension was then separated by suction filtration and washed with deionized water and ethanol several times until the pH of the filtrate reached 6.8. Subsequently, the obtained solid was dried in a vacuum drying oven at 60\u0026nbsp;°C\u0026nbsp;for 12 h. The final product after grinding was labeled as V-SiO\u003csub\u003e2\u003c/sub\u003e nanosheets.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e2. Preparation of NiSi-P\u0026nbsp;\u003c/strong\u003eNiSi-P was synthesized by using VMT derived SiO\u003csub\u003e2\u003c/sub\u003e as a silicon source. Typically, 0.4239 g\u0026nbsp;of NiCl\u003csub\u003e2\u003c/sub\u003e·6H\u003csub\u003e2\u003c/sub\u003eO was add to 4 mL of water and stirred for 20 min. Then, 0.14 g\u0026nbsp;of SiO\u003csub\u003e2\u003c/sub\u003e (the molar ratio of metal to silicon was 4:5) and 4 mL of NH\u003csub\u003e3\u003c/sub\u003e·H\u003csub\u003e2\u003c/sub\u003eO (25wt%) were sequentially added to the above mixture. After 30 min, the mixture solution was transferred into a 40 mL Teflon-lined stainless steel autoclave and heated at 180\u0026nbsp;°C\u0026nbsp;for 24 h. When the solution has cooled down to room temperature naturally, the green powder was centrifuged and washed three times with anhydrous ethanol and then dried in a vacuum drying oven at 60 °C\u0026nbsp;for 24 h. For further phosphating, 0.01 g green powder and 0.30 g\u0026nbsp;of NaH\u003csub\u003e2\u003c/sub\u003ePO\u003csub\u003e2\u003c/sub\u003e·H\u003csub\u003e2\u003c/sub\u003eO were paced in the downstream and upstream of the tube furnace, respectively. Subsequently, it was heated at different calcination temperatures for 2 h at a heating rate of 5 °C\u0026nbsp;min\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003ein N\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eatmosphere. The final products are labelled as NiSi-P-X (x indicates the phosphating temperature). The NiSi-P-325 showed the best OER performance, so, the NiSi-P notation refers to NiSi-P-325.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis study was financially supported by the Thousand Talents Plan of Jiangxi Province (jxsq2023201068) and the National Natural Science Foundation of China (22065016, 22265013, 22061020) and National Key R\u0026amp;D Program of China (2022YFA1203200).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflicts of Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThere are no conflicts to declare.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eBeniya A (2019) Higashi Towards dense single-atom catalysts for future automotive applications. Nat Catal 2:590\u0026ndash;602\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYang Q, Jiang Y, Zhuo H, Mitchell EM (2023) Yu. Recent progress of metal single-atom catalysts for energy applications. Nano Energy 111:108404\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi D, Shao X, Umair MM, Hou F, Li S, Tang Y, Cao L et al (2024) Superhydrophilic cobalt-doped NiFe LDH graphite felt with enriched oxygen vacancy as an efficient oxygen evolution electrocatalyst in alkaline media. J Hydrog Energy 80:11\u0026ndash;21\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLin X, Liu J, Qiu X, Liu B, Wang X, Chen L et al (2023) Ru-FeNi Alloy Heterojunctions on Lignin-derived Carbon as Bifunctional Electrocatalysts for Efficient Overall Water Splitting. Angewandte Chemie-International Ed Angew Chem Int Ed 135:e202306333\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang X, Yang Q, Singh S, Borrmann H, Hasse V, Yi C et al (2024) Topological semimetals with intrinsic chirality as spin-controlling electrocatalysts for the oxygen evolution reaction. Nat. Energy 1\u0026ndash;9\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang D et al (2024) Optimal Electrocatalyst Design Strategies for Acidic Oxygen Evolution. Adv Sci 2401975\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJiang F, Li Y (2024) Pan Design Principles of Single-Atom Catalysts for Oxygen Evolution Reaction: From Targeted Structures to Active Sites. Adv Mater 36:2306309\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRetuerto M, Pascual L, Torrero J, Salam MA, Tolosana-Moranchel \u0026Aacute;, Gianolio D et al (2022) Highly active and stable OER electrocatalysts derived from Sr\u003csub\u003e2\u003c/sub\u003eMIrO\u003csub\u003e6\u003c/sub\u003e for proton exchange membrane water electrolyzers. Nat Commun 13:7935\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang H, Xu H, Wang L, Ouyang C, Liang H, Zhong S (2023) A Metal\u0026ndash;Organic Frameworks Derived 1T-MoS\u003csub\u003e2\u003c/sub\u003e with Expanded Layer Spacing for Enhanced Electrocatalytic Hydrogen Evolution. Small 19:2205736\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHe T, Bruening M, Espinosa M, Agapie T (2024) Novel Silicate Platform as Weakly-Coordinating Anions for Diverse Organometallic and Electrochemical Applications. Angew Chem Int Ed e202417136\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChen X, Zhou S, Zhang X, Chen S, Wang L, Zhang C et al (2024) Research progress on the preparation of transition metal-modified zeolite catalysts and their catalytic performance for the purification of engine exhausts. J Mater Chem 12:16293\u0026ndash;16328\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang Y, Wang C, Chen X, Dong X, Meng C, Huang C (2021) Bamboo leaves as sustainable sources for the preparation of amorphous carbon/iron silicate anode and nickel\u0026ndash;cobalt silicate cathode materials for hybrid Supercapacitors. ACS Appl Energy Mater 4:9328\u0026ndash;9340\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMu Y, Zhang Y, Pei X, Dong X, Kou Z, Cui M (2022) Dispersed FeO nanoparticles decorated with Co\u003csub\u003e2\u003c/sub\u003eSiO\u003csub\u003e4\u003c/sub\u003e hollow spheres for enhanced oxygen evolution reaction. J Adv Colloid Interface Sci 611:235\u0026ndash;245\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAnantharaj S, Aravindan V (2020) Developments and perspectives in 3D transition-metal‐based electrocatalysts for neutral and near‐neutral water electrolysis. Adv Energy Mater 10:1902666\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQiu C, Jiang J (2015) Ai When Layered Nickel\u0026ndash;Cobalt Silicate Hydroxide Nanosheets Meet Carbon Nanotubes: A Synergetic Coaxial Nanocable Structure for Enhanced Electrocatalytic Water Oxidation. ACS Appl Mater Interfaces 8:945\u0026ndash;951\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQiu C, Ai L (2018) Jiang Layered Phosphate-Incorporated Nickel\u0026ndash;Cobalt Hydrosilicates for Highly Efficient Oxygen Evolution Electrocatalysis. ACS Sustain Chem Eng 6:4492\u0026ndash;4498\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhu J, Xia L, Yang W, Yu R, Zhang W, Luo W et al (2022) Activating inert sites in cobalt silicate hydroxides for oxygen evolution through atomically doping. Energy Environ Mater 5:655\u0026ndash;661\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang J, Li Z, Bai G, Wang Q, Zhang J, Wang W et al (2023) Nickel-iron layered silicate nanomembrane as efficient electrocatalyst for oxygen evolution reaction in alkaline media. Fuel 332\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePlach\u0026aacute; P, Kov\u0026aacute;ř J, Vaněk M, Mikeska K, Škrlov\u0026aacute; O, Dutko et al (2020) Adsorption of nerve agent simulants onto vermiculite structure: Experiments and modelling. J Hazard Mater 382:121001\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMa L, Huang H, Feng W, Chen L, Xia L, Yu Y et al (2022) 2D Catalytic, Chemodynamic, and Ferroptotic Vermiculite Nanomedicine. Adv Funct Mater 32:2208220\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJi X, Ge L, Liu C, Tang Z, Xiao Y, Chen W et al (2021) Capturing functional two-dimensional nanosheets from sandwich-structure vermiculite for cancer theranostics. Nat Commun 12:1124\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMeng Z (2021) Wang The effect of different promoters (La\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, CeO\u003csub\u003e2\u003c/sub\u003e, and ZrO\u003csub\u003e2\u003c/sub\u003e) on the catalytic activity of the modified vermiculite-based bimetallic NiCu/EXVTM-SiO\u003csub\u003e2\u003c/sub\u003e catalyst in methane dry reforming. ACS omega 6:29651\u0026ndash;29658\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang L, Wang X, Yin\u0026amp; J (2016) Wang Insights into the physicochemical characteristics from vermiculite to silica nanosheets. Appl Clay Sci 132\u0026ndash;133:17\u0026ndash;23\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKozhevnikov IV, Chibiryaev AM (2021) Martyanov One-pot synthesis of TMOS from SiO\u003csub\u003e2\u003c/sub\u003e-enriched minerals and supercritical MeOH in a flow reactor. Chem Eng J 426:131871\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYang H, Guo J, Chu L, Huang Z, Liu Z, Wang L et al (2023) Self-assembly of Fe-MOF on vermiculite nanosheets with enhanced catalytic activity. Appl Clay Sci 245:107138\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang Q, Zhang Y, Jiang H (2018) Hu\u0026amp; C. Meng. In situ generated Ni\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e on mesoporous heteroatom-enriched carbon derived from natural bamboo leaves for high-performance supercapacitors. ACS Appl Energy 1:3396\u0026ndash;3409\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYu Y, Movick WJ, Obata K, Yoshida S (2024) Takanabe Mn-Na\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e4\u003c/sub\u003e/SiO\u003csub\u003e2\u003c/sub\u003e-tridymite with improved stability and selectivity for high-pressure oxidative coupling of methane. Chem Eng J 500:156938\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRong Q, Long L-L, Zhang X, Huang Y-X (2015) Yu Layered cobalt nickel silicate hollow spheres as a highly-stable supercapacitor material. Appl Energy 153:63\u0026ndash;69\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAnanias D, Rainho JP, Ferreira A, Lopes M, Morais CM, Rocha J et al (2002) Synthesis and characterization of Er (III) and Y (III) sodium silicates: Na\u003csub\u003e3\u003c/sub\u003eErSi\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e, a new infrared emitter. Chem Mater 14:1767\u0026ndash;1772\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKim P, Jones SC, Hotchkiss PJ, Haddock JN, Kippelen B, Marder SR et al (2007) Phosphonic acid-modified barium titanate polymer nanocomposites with high permittivity and dielectric strength. Adv Mater 19:1001\u0026ndash;1005\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang Y, Wang C, Dong X, Jiang H, Hu T, Meng C et al (2021) Alkali etching metal silicates derived from bamboo leaves with enhanced electrochemical properties for solid-state hybrid supercapacitors. Chem Eng J 417:127964\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAusteria M, Dao HT, Mai M (2023) Kim Dual-phase cobalt phosphide/phosphate hybrid interactions via iridium nanocluster interfacial engineering toward efficient overall seawater splitting. Appl Catal 327:122467\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDu M, Shang J, Mao (2017) Song Hierarchical MoP/Ni\u003csub\u003e2\u003c/sub\u003eP heterostructures on nickel foam for efficient water splitting. J Mater Chem 5:15940\u0026ndash;15949\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKong D, Zhang M, Xiao Y, Hu J, Zhao W, Han L et al (2019) Insights into the structural evolution and Li/O loss in high-Ni layered oxide cathodes. Nano Energy 59:327\u0026ndash;335\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJohnson AM (2023) Johnson Thermally Robust yet Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)‐Like Materials Based on Si\u0026thinsp;\u0026ndash;\u0026thinsp;O Bonds. Angew Chem Int Ed 135:e202315085\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHu R, Xiao J, Wang T, Chen G, Chen L, Tian X (2020) Engineering of phosphate-functionalized biochars with highly developed surface area and porosity for efficient and selective extraction of uranium. Chem Eng J 379:122388\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFan J, Wang L, Xiang X, Liu Y, Shi N, Lin Y et al (2024) Porous Flower-Like Nanoarchitectures Derived from Nickel Phosphide Nanocrystals Anchored on Amorphous Vanadium Phosphate Nanosheet Nanohybrids for Superior Overall Water Splitting. Small Methods 8:2301279\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Vermiculite, Nickel silicate, Phosphorus modification, Oxygen evolution reaction","lastPublishedDoi":"10.21203/rs.3.rs-5991362/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5991362/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe pursuit of clean and sustainable energy sources has intensified the research focus on water electrolysis, particularly the oxygen evolution reaction (OER), which serves as a pivotal step in hydrogen generation. However, the development of efficient and cost-effective OER catalysts remains a major bottleneck hindering the widespread adoption of water electrolysis technology. In this work, utilizing vermiculite (VMT), an abundant and environmentally friendly clay mineral, was employed as the precursor to obtain SiO\u003csub\u003e2\u003c/sub\u003e(V-SiO\u003csub\u003e2\u003c/sub\u003e). We have successfully synthesized a novel phosphate-modified layered nickel silicate Ni\u003csub\u003e3\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e(OH)\u003csub\u003e4\u003c/sub\u003e (NiSi-P) derived from the VMT through a combination of hydrothermal and vapor deposition method. Electrochemical evaluations in 1.0 M KOH revealed that NiSi-P exhibited remarkable OER performance, achieving a low overpotential of 334 mV at 10 mA·cm\u003csup\u003e-2\u003c/sup\u003e, significantly outperforming unmodified nickel silicate (NiSi, 564 mV). This improvement is attributed to the unique structural features and surface chemistry of NiSi-P, which facilitate efficient charge transfer and protonation/deprotonation during the catalytic process. This study provided an idea for the application of low-cost silicate materials in electrocatalytic water splitting in OER.\u003c/p\u003e","manuscriptTitle":"Phosphorus-modified Basic Nickel Silicate Derivated from Vermiculite for Efficient Oxygen Evolution Reaction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-03-25 09:58:12","doi":"10.21203/rs.3.rs-5991362/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"ed0c61cb-af15-421b-abee-738162be1ed2","owner":[],"postedDate":"March 25th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":44307396,"name":"Earth and environmental sciences/Environmental sciences/Environmental impact"},{"id":44307397,"name":"Earth and environmental sciences/Environmental social sciences/Environmental impact"}],"tags":[],"updatedAt":"2025-03-25T09:58:14+00:00","versionOfRecord":[],"versionCreatedAt":"2025-03-25 09:58:12","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5991362","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5991362","identity":"rs-5991362","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}