Adsorptive and Photocatalytic Degradation of Imidacloprid Pesticide from Wastewater via the ZrP/NiSe 2 nanocomposite

Adsorptive and Photocatalytic Degradation of Imidacloprid Pesticide from Wastewater via the ZrP/NiSe 2 nanocomposite | 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 Adsorptive and Photocatalytic Degradation of Imidacloprid Pesticide from Wastewater via the ZrP/NiSe 2 nanocomposite Mina Izadi, Kiumars Bahrami, Homa Targhan This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4933424/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 In this study, ZrP/NiSe 2 nanocomposite was constructed for the first time. Characterizations were carried out by FT-IR, XRD, EDX mapping and FESEM, confirming the nanocomposite formation. The resulting sustainable ZrP/NiSe 2 nanocomposite exhibit improved photocatalytic activity in the visible area to remove imidacloprid from water compared to pure ZrP and NiSe 2 nanoparticles. Improving the performance of this nanocomposite can be the result of the integration of ZrP and NiSe 2 at the nanoscale and the synergistic enhancement of their activity. Furthermore, ZrP/NiSe 2 and ZrP can remove significant percentages of imidacloprid from aqueous solutions through adsorption. This result can be explained by the high adsorption affinity of ZrP toward organic pollutants with protonable groups. Physical sciences/Chemistry Physical sciences/Nanoscience and technology Photocatalytic degradation Imidacloprid Zirconium phosphate Nickel selenide nanocomposite Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Pesticides are used to control the harmful pests and thus improve agricultural production. Therefore, pesticides are an important component of the agricultural industry. However, the use of pesticides brings various adverse environmental impacts. Imidacloprid (Fig. 1 ), a potent neonicotinoid insecticide, is one of the most widely used pesticides, which is commonly used in seed treatment to control the insects. This insecticide is highly toxic having good solubility and stability in water and its widespread application has caused significant environmental concerns.( 1 , 2 ) In recent decades, the scientific community has devoted a significant deal of effort to developing innovative and functional materials that can be applied in water and wastewater treatment, which has further accelerated the development of photocatalytic technology.( 3 , 4 ) Due to their outstanding physical and chemical properties, α-zirconium phosphate (α-ZrP) and its derivatives have been widely investigated in adsorption processes for the removal and degradation of pollutants from wastewater,( 5 , 6 ) medical field, namely in the drug delivery,( 7 , 8 ) ion-exchange processes ( 9 , 10 ), photocatalysis processes ( 11 , 12 ), anti-corrosion technology ( 13 , 14 ) and composite material preparation to allow their application in various fields ( 15 , 16 ). α-ZrP has been extensively investigated as catalysts and catalyst supports for a wide variety of applications due to its superior properties.( 17 – 24 ) However, α-ZrP do not show satisfactory visible-light photocatalytic activity, due to a broad band gap.( 11 ) Combination of α-ZrP with semiconductor has been proposed as an impactful solution to improve photocatalytic performance of the α-ZrP for the degradation of organic pollutants.( 12 ) Nickel selenide (NiSe 2 ) is an inorganic compound exhibiting wide range of applications including fields of electrocatalysis, high-temperature superconductors, energy storage gadgets, photocatalyst and electrocatalysts.( 25 , 26 ) NiSe 2 also offers several advantages including excellent electronic properties, chemical stability, having the appropriate band gap energy to absorb visible light (1.98 eV), low cost, low toxicity, and bio-compatibility.( 27 – 29 ) As mentioned earlier, NiSe 2 has an adequate band gap to absorb visible light, however, due to the electron-hole pair recombination, its photocatalytic performance is not as efficient as expected. Literature on photocatalysis applications of NiSe 2 highlights the employment of a pronged strategy for enhancing the photocatalytic performance of activity of NiSe 2 , namely; forming composites.( 29 ) The photocatalytic activity of NiSe 2 -based composites on photodegradation of various organic pollutants in aqueous medium has been studied recently. Zhong et al.( 25 ) reported that 9 mol% NiSe 2 composited BiVO 4 exhibited high photocatalytic performance for photodegradation Rhodamine B (RhB) under visible light compared to pure BiVO 4 . Coupling NiSe 2 with TiO 2 exhibited improved photocatalytic efficiency in the photodegradation of RhB compared to pure ones.( 26 ) Recently, Waseem Luo et al.( 29 ) have been studied the photocatalytic activity of NiSe 2 /Ag 3 PO 4 nanocomposite for the photodegradation of RhB and Bisphenol A (BPA) pollutants. The 20% NiSe 2 /Ag 3 PO 4 nanocomposite as a promising photocatalyst effectively degraded 10 ppm RhB in 20 min and 20 ppm BPA in 30 min under visible light. Reduced graphene oxide (rGO) incorporated NiSe 2 nanocomposite has been synthesized and its photocatalytic performance was investigated via the degradation of RhB. The as-prepared nanocomposite showed 98.8% degradation of RhB after 120 min under visible light irradiation.( 30 ) Herein, we prepared a nanocomposite by combining NiSe 2 with ZrP and successfully used it for the removal of Imidacloprid pesticide in aqueous solution. In view of the photocatalytic and adsorption potential of NiSe 2 and ZrP nanoparticles, we speculate that ZrP/NiSe 2 nanocomposite should be effective to eliminate water organic pollutants. Experimental Materials and apparatus All chemicals and solvents were purchased from Merck (Germany) or Fluka (Switzerland). The Fourier-transform infrared (FT-IR) spectra of the samples were recorded with the KBr pellet method on a PerkinElmer PE-1600-FTIR spectrometer. The field emission scanning electron microscope (FESEM) images were recorded using a TESCAN VEGA 3, Czech microscope. X-ray diffraction (XRD) spectra were recorded using an X-ray diffractometer (PANalytical X'Pert PRO, Netherlands) with Cu Kα radiation (λ = 1.54 Å). Synthesis of NiSe 2 nanoparticles Initially, 6.6 mmol selenium powder was added into 2 mL of hydrazine hydrate. After a few minutes of sonication, 3.3 mmol Ni(NO 3 ) 2 •6H 2 O was added with ultra-sonication to form a homogeneous solution. The mixture was then transferred to a 50 mL Teflon-lined autoclave which was maintained at 180°C for 24 h. The autoclave was then cooled to room temperature and the NiSe 2 particles were collected by filtration. Subsequently, the obtained particles were washed with deionized water until pH = 7 and were dried for 24 h in a vacuum oven at 60°C.( 31 ) Synthesis of ZrP nanoparticles To synthesize ZrP, 3.22 g Zirconium oxychloride (ZrOCl 2 •8H 2 O) was dissolved in deionized water and slowly dropped into the 40 mL diluted phosphoric acid solution (11 mol.L − 1 ) under continuous stirring. After refluxing in an oil bath100°C for 24, the product was filtered and rinsed with deionized water several times to remove unreacted phosphoric acid and other impurities until the pH of the filtrate was neutral. Eventually, the sample was dried overnight in a vacuum oven at 60°C to obtain the ZrP powder.( 32 ) Synthesis of ZrP/NiSe 2 nanocomposite We have used a straightforward surface soaking method to prepare ZrP/NiSe 2 nanocomposite. First, ZrP powder (0.1 g) was dispersed in deionized water (10 mL) by centrifuging for 30 min. After adding NiSe 2 nanoparticles (0.05 g), the suspension was sonicated for 30 min and stirred at room temperature for 24 hours. Eventually, the ZrP/NiSe 2 powder was collected by centrifugation, washed three times with distilled water, and dried overnight at 50°C. Photocatalytic degradation of imidacloprid Photocatalytic degradation experiments of imidacloprid (10 mL of 20 ppm) were conducted under visible light irradiation (LED lamp). The lamp was placed at a distance of 30 cm from the surface of the test solution. The temperature of the system was simply controlled by using a water bath. The irradiated solution was sampled every 15 min. The concentration of imidacloprid was quantified by UV–Vis spectrophotometry (Shimadzu, CPS-240A). Results and discussion Characterization of the photocatalysts A set of characterization techniques, such as FT-IR and, XRD, EDX mapping and FESEM, was used to get better insight into the structural properties of the prepared ZrP, NiSe 2 and ZrP/NiSe 2 samples. XRD patterns of the synthesized ZrP, NiSe 2 and ZrP/NiSe 2 samples are illustrated in Fig. 2 . Figure 2 represents the XRD pattern of cubic NiSe 2 , which exhibits the characteristic peaks at 2θ values of 30.01, 33.64, 36.96, 42.94, 50.82, 53.26, 55.59, 57.89, 62.30, 72.66, and 74.65° in lattice planes (200), (210), (211), (220), (311), (222), (023), (321), (400), (421), and (332), respectively.( 33 ) Figure 2 also shows the XRD pattern of ZrP sample. The XRD pattern shows diffraction peaks at 2θ values of 11.84, 20.04, 25.14 and 34.13° respectively assigned to the (002), (110), (112), (020) planes, respectively, indicating the crystalline nature of the as-prepared ZrP.( 34 , 35 ) The typical reflection observed at 2θ values of 11.8°, due to the (002) crystallographic planes, indicates the interlayer distance of ZrP crystals. The interlayer distance of ZrP calculated by Bragg Eq. (2d sin θ = n λ) was 7.47 Å.( 11 ) The XRD pattern of Zrp/NiSe 2 nanocomposite (Fig. 2 ) demonstrates the presence of ZrP as well as NiSe 2 peaks. The NiSe 2 characteristic peaks were obtained at 2θ values of 30.02, 33.67, 37.00, 42.98, 50.82, 53.13, 55.66, 57.91, 72.75, and 74.76° and ZrP characteristic peaks were obtained at 2θ values of 11.73, 19.98, 24.79, and 34.50°. The interlayer distance of the ZrP in ZrP/NiSe 2 composite calculated according to Bragg equation was 7.53 Å. Figure 3 presents the FTIR spectra of ZrP and NiSe 2 and ZrP/NiSe 2 nanocomposite. For the pure NiSe 2 nanoparticles, a broad band observed around 3300 − 3600 cm − 1 and a peak at 1622 cm − 1 could be attributed to the stretching and bending vibrations of the water’s hydroxyl groups adsorbed at the surface of NiSe 2 , respectively. The stretching vibrations of Ni–Se bonds were characterized by a broad peak in the region of 500 to 800 cm − 1 .( 28 , 36 ) For the pure α-ZrP nanoparticles, the sharp band located at 1041 cm − 1 can be assigned to the symmetrical stretching vibration peak of PO 4 3− groups. The characteristic peak at 594 cm − 1 can be ascribed to Zr − O bonds.( 12 ) FT-IR spectra recorded for ZrP/NiSe 2 nanocomposite exhibits all of the characteristic peaks of ZrP and of NiSe 2 , indicating the presence of both nanoparticles in the nanocomposite composition. These results are in agreement with XRD results shown in Fig. 2 . As expected, the EDX spectrum of the ZrP/NiSe 2 nanocomposite (Fig. 3 ) clearly shows the presence of zirconium, phosphorus, nickel and selenium atoms in the composite combination. Furthermore, as can be seen in the EDX mapping (Fig. 4 ), the zirconium, phosphorus, nickel and selenium elements are homogeneously dispersed on the surface of the ZrP/NiSe 2 nanocomposite. The surface morphologies of the synthesized NiSe 2 , ZrP and ZrP/NiSe 2 samples was investigated using FESEM (Fig. 5 ). The NiSe 2 sample well exhibit a cubic-like morphology, as shown in Figs. 5 A and 5 B. The morphology of the ZrP was vividly shown in Figs. 5 C and 5 D at various magnifications (500 nm and 200 nm). The as-prepared ZrP particles formed disk shapes, as seen in Fig. 5 C and 5 D. It is clear that the ZrP disks have good uniformity. When the ZrP/NiSe 2 nanocomposite is formed using a straightforward surface soaking method, SEM images are obtained and shown in Fig. 5 E and 5 F. It can be seen that the particles of NiSe 2 were attached to the ZrP in the ZrP/NiSe 2 nanocomposite. Consequently the results of the FT-IR, XRD, EDX mapping and FESEM characterization techniques confirm the successful preparation of ZrP, NiSe 2 and ZrP/NiSe 2 samples. Photocatalytic degradation studies The catalytic activity evaluation of the as-synthesized ZrP, NiSe 2 and ZrP/NiSe 2 samples was done on the removal of imidacloprid from the aqueous solution. The results of the study of imidacloprid removal are summarized in Fig. 6 and Table 1 . Preliminary tests on the catalytic activity of ZrP and NiSe 2 samples as well as ZrP/NiSe 2 for removal of imidacloprid displayed that ZrP and NiSe 2 samples were less active and the ZrP/NiSe 2 nanocomposite showed the highest photocatalytic activity in removal of imidacloprid than that of the pure ZrP and NiSe 2 photocatalysts (Fig. 6 A). It seems that the combination and synergistic effect of NiSe 2 and ZrP play an important role for improvement of the photocatalytic activity of ZrP/NiSe 2 nanocomposite. In contrast, only small percentage of the pesticide (8.25%) was degraded in the absence of a photocatalyst, after 90 min of irradiation. Furthermore, ZrP/NiSe 2 and ZrP can remove significant percentages of imidacloprid from aqueous solutions through adsorption (43.26% and 43.69%, respectively) under dark conditions (Fig. 6 B). These results were predicted because the high adsorption affinity of ZrP toward organic pollutants with protonable groups has already been described.( 6 ) The effect of irradiation time on removal of imidacloprid in the presence of ZrP/NiSe 2 was also monitored. As expected, the imidacloprid concentration decreases by increasing the irradiation time (Fig. 6 C). Nevertheless, when the irradiation time increases from 90 min to 105 min, there was no significant change in the concentration of imidacloprid (Fig. 6 C). The dosage of photocatalyst is a key factor that influence the percent removal of the pollutant. Therefore, the impact of ZrP/NiSe 2 dose on removal of the pesticide was also investigated. The increase in ZrP/NiSe 2 dose from 0.03 g to 0.05 g resulted in corresponding increase in percentage of imidacloprid removal (Table 1 , Entry 7). However, further increasing ZrP/NiSe 2 dose to 0.07 g would only lead to a slight increase in the percentage of imidacloprid removal (Table 1 , Entry 8). The percent removal of the pesticide is affected by the initial concentration. As a result, the percentage removal of imidacloprid decreased with an increase in initial concentration from 10 to 20 ppm (Table 1 , Entry 9). In order to indicate the main active specie in the photodegradation of imidacloprid pesticide, the effects were evaluated when using isopropyl alcohol (IPA) as a hydroxyl radical scavenger, and p-benzoquinone (BQ) as a superoxide radical scavenger and EDTA as a hole scavenger. As shown in Fig. 6 D, after the addition of IPA, an efficiency decrease in catalytic performance of ZrP/NiSe 2 was observed, indicating that the hydroxyl radicals play a vital role in the degradation of imidacloprid. Although, the addition of p-benzoquinone and EDTA did not affect imidacloprid removal significantly (Fig. 6 D). Table 1 Summary of the removal of imidacloprid in photocatalytic and photochemical systems within 90 min. Entry Photocatalyst Catalyst dose (g) Light source Initial imidacloprid conc. (ppm) Imidacloprid Removal [%] 1 ZrP/NiSe 2 0.05 Vis. 20 70.67 2 ZrP 0.05 Vis. 20 51.52 3 NiSe 2 0.05 Vis. 20 47.50 4 - - Vis. 20 8.25 5 ZrP/NiSe 2 0.05 - 20 43.26 6 ZrP 0.05 - 20 43.69 7 ZrP/NiSe 2 0.03 Vis. 20 49.28 8 ZrP/NiSe 2 0.07 Vis. 20 77.51 9 ZrP/NiSe 2 0.05 Vis. 10 79.63 The ZrP/NiSe 2 nanocomposite was recyclable without much loss of activity. After each, the ZrP/NiSe 2 nanocomposite separated from the reaction medium by centrifugation. The used catalyst was washed several times with water, dried at 50°C and further reused consecutively for 3 times. The ZrP/NiSe 2 nanocomposite showed 61.19% imidacloprid removal at 3th cycle (Fig. 7 ). Conclusion The ZrP/NiSe 2 nanocomposite was prepared with the purpose of creating recyclable catalytic system for removal of Imidacloprid pesticide from water. Detailed characterization results indicate the successful preparation of ZrP/NiSe 2 nanocomposite. Our results suggested the improved photocatalytic performance of ZrP/NiSe 2 nanocomposite. Furthermore, the ZrP/NiSe 2 nanocomposite can keep the good performance after three times of recycle. Declarations Author Contribution K.B. conceived the original idea and supervised the project. M.I. carried out the experiment. H.T helped supervise the project. M.I. and H.T. wrote the main manuscript text. All authors reviewed the manuscript. Data Availability Statements All data generated or analyzed during this study are included in this published article. References Targhan, H. et al. Adsorptive and photocatalytic degradation of imidacloprid pesticide from wastewater via the fabrication of ZIF-CdS/Tpy quantum dots. Chem. Eng. J. 482 , 148983 (2024). Targhan, H. et al. Photocatalytic removal of imidacloprid pesticide from wastewater using CdS QDs passivated by CQDs containing thiol groups. Sci. Rep. 14 (1), 530 (2024). Muscetta, M. & Russo, D. Photocatalytic applications in wastewater and air treatment: A patent review (2010–2020). Catalysts . 11 (7), 834 (2021). Ahuja, T., Brighu, U. & Saxena, K. Recent advances in photocatalytic materials and their applications for treatment of wastewater: A review. J. Water Process. Eng. 53 , 103759 (2023). Mu, W. et al. Controlled fabrication of flower-like α-zirconium phosphate for the efficient removal of radioactive strontium from acidic nuclear wastewater. J. Mater. Chem. A . 5 (46), 24388–24395 (2017). Pica, M. Treatment of wastewaters with zirconium phosphate based materials: A review on efficient systems for the removal of heavy metal and dye water pollutants. Molecules . 26 (8), 2392 (2021). Dıaz, A. et al. Zirconium phosphate nano-platelets: a novel platform for drug delivery in cancer therapyw. Chem. Commun. 48 , 1754–1756 (2012). Saxena, V., Diaz, A., Clearfield, A., Batteas, J. D. & Hussain, M. D. Zirconium phosphate nanoplatelets: a biocompatible nanomaterial for drug delivery to cancer. Nanoscale . 5 (6), 2328–2336 (2013). Wiikinkoski, E. W., Harjula, R. O., Lehto, J. K., Kemell, M. L. & Koivula, R. T. Effects of synthesis conditions on ion exchange properties of α-zirconium phosphate for Eu and Am. Radiochim. Acta . 105 (12), 1033–1042 (2017). Pathania, D., Thakur, M. & Mishra, A. Alginate-Zr (IV) phosphate nanocomposite ion exchanger: Binary separation of heavy metals, photocatalysis and antimicrobial activity. J. Alloys Compd. 701 , 153–162 (2017). Ye, Z. et al. α-Zirconium phosphate nanocrystals with various morphology for photocatalysis. Chem. Phys. Lett. 709 , 96–102 (2018). Qing, S. et al. Photocatalytic activity investigation of α-zirconium phosphate nanoparticles compositing with C3N4 under ultraviolet light. ACS omega . 5 (43), 27873–27879 (2020). Lv, Z. et al. Design Polyaniline/α-Zirconium Phosphate Composites for Achieving Self-Healing Anti-Corrosion of Carbon Steel. Nanomaterials . 14 (1), 76 (2023). Sheng, X. et al. Waterborne epoxy resin/polydopamine modified zirconium phosphate nanocomposite for anticorrosive coating. Ind. Eng. Chem. Res. 58 (36), 16571–16580 (2019). Xie, H., Lai, X., Li, H. & Zeng, X. Fabrication of ZrP nanosheet decorated macromolecular charring agent and its efficient synergism with ammonium polyphosphate in flame-retarding polypropylene. Compos. Part A: Appl. Sci. Manufac. 105 , 223–234 (2018). Jiang, F., Sun, H., Chen, L., Lei, F. & Sun, D. Dispersion-tribological property relationship in mineral oils containing 2D layered α-zirconium phosphate nanoplatelets. Friction . 8 (4), 695–707 (2020). Thakur, M. et al. Efficient photocatalytic degradation of toxic dyes from aqueous environment using gelatin-Zr (IV) phosphate nanocomposite and its antimicrobial activity. Colloids Surf., B . 157 , 456–463 (2017). Pica, M. et al. Nanosized zirconium phosphate/AgCl composite materials: A new synergy for efficient photocatalytic degradation of organic dye pollutants. J. Mater. Chem. A . 3 (10), 5525–5534 (2015). Hajipour, A. R. & Karimi, H. Hexagonal zirconium phosphate nanoparticles as an efficient and recyclable catalyst for selective solvent-free alkylation of phenol with cyclohexanol. Appl. Catal. A . 482 , 99–107 (2014). Chen, R., Wang, J., Wang, H., Yao, W. & Zhong, J. Photocatalytic degradation of methyl orange in aqueous solution over titania-pillared α-zirconium phosphate. Solid State Sci. 13 (3), 630–635 (2011). Wen, M., Mori, K., Kuwahara, Y. & Yamashita, H. Visible-light‐responsive carbon dioxide reduction system: rhenium complex intercalated into a zirconium phosphate layered matrix. ChemCatChem . 7 (21), 3519–3525 (2015). Liu, J., Wang, F., Gu, Z. & Xu, X. Styrene epoxidation over Ag-γ-ZrP catalyst prepared by ion-exchange. Catal Commun. 10 (6), 868–871 (2009). Lai, G-H. et al. Preparation of highly-stable and recyclable novel Au/ZrP composite catalyst for 4-nitrophenol reduction. J. Taiwan Inst. Chem. Eng. 95 , 525–531 (2019). Tuteja, J., Choudhary, H., Nishimura, S. & Ebitani, K. Direct synthesis of 1, 6-hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source. ChemSusChem . 7 (1), 96–100 (2014). Shen, S. et al. Construction of NiSe2/BiVO4 Schottky junction derived from work function discrepancy for boosting photocatalytic activity. J. Alloys Compd. 875 , 160071 (2021). Maryam, R. et al. Enhanced photocatalytic and antibacterial activity of NiSe2–TiO2 nanocomposites under visible light. Opt. Mater. 143 , 114183 (2023). Shen, S. et al. NiSe 2/CdS composite nanoflakes photocatalyst with enhanced activity under visible light. RSC Adv. 10 (69), 42008–42013 (2020). Khaladkar, S. R. et al. In situ growth of NiSe 2 nanoparticles on gC 3 N 4 nanosheets for an efficient hydrogen evolution reaction. Mater. Adv. 5 (10), 4345–4353 (2024). Rani, M. et al. NiSe2/Ag3PO4 nanocomposites for enhanced Visible light photocatalysts for environmental remediation applications. Catalysts . 13 (6), 929 (2023). Mahalakshmi, K., Jenila, R. M., Potheher, I. V., Lakshmi, V. & Thangaraj, V. Bifunctional rGO incorporated NiSe2 nanocomposite as a photocatalyst and an electrode in supercapacitor. J. Alloys Compd. 972 , 172699 (2024). Hayat, M. et al. Exploring the electrochemical properties of CuSe-decorated NiSe2 nanocubes for battery-supercapacitor hybrid devices. Chemosphere . 340 , 139720 (2023). Han, L. et al. Synthesis and Performance of Functionalized α-Zirconium Phosphate Modified with Octadecyl Isocyanate. J. Nanomaterials . 2018 (1), 5873871 (2018). Jansi Rani, B. et al. CoNiSe2 nanostructures for clean energy production. ACS omega . 5 (24), 14702–14710 (2020). Pica, M. et al. De-ethylation and cleavage of rhodamine B by a zirconium phosphate/silver bromide composite photocatalyst. Catalysts . 9 (1), 3 (2018). Khanal, S., Lu, Y., Dang, L., Ali, M. & Xu, S. Effects of α-zirconium phosphate and zirconium organophosphonate on the thermal, mechanical and flame retardant properties of intumescent flame retardant high density polyethylene composites. RSC Adv. 10 (51), 30990–31002 (2020). Khan, B. A. et al. NiSe2 nanocrystals intercalated rGO sheets as a high-performance asymmetric supercapacitor electrode. Ceram. Int. 48 (4), 5509–5517 (2022). Additional Declarations No competing interests reported. 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-4933424","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":359349797,"identity":"6cbef892-c296-4183-b374-c9df5a8da90b","order_by":0,"name":"Mina Izadi","email":"","orcid":"","institution":"Razi University","correspondingAuthor":false,"prefix":"","firstName":"Mina","middleName":"","lastName":"Izadi","suffix":""},{"id":359349798,"identity":"56bbdfce-b590-4ceb-9bca-d1a4ddf4338e","order_by":1,"name":"Kiumars Bahrami","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA4ElEQVRIiWNgGAWjYBACCQYeBmYQg429AUgagJiMDURq4TlAqhYGiQQiHSbZwHvwc+Eeu2g+ybcPP/4oYJDnb2Bu+4BPizQDX7L0jGfJuW3S6cYSEgYMhjMOMDbPwKdFjoHHQJrnADNQSxqDhIEBA+MGBsZmvA4DajH+zXOgPrdN8hjzjwQDBnuCWqQZeMyAthzObZNgY5M4YMCQSFCLZDNfmjXPgeO5bTxpbJYNBhLJMw4T0CJxvPfwbZ4D1bnz248x3/zxx8a2v739MV4t0EhBGIEhMgpGwSgYBaOADAAAnZg7KTNdNEoAAAAASUVORK5CYII=","orcid":"","institution":"Razi University","correspondingAuthor":true,"prefix":"","firstName":"Kiumars","middleName":"","lastName":"Bahrami","suffix":""},{"id":359349799,"identity":"0f59af25-9655-4571-ad7e-d8c95977544d","order_by":2,"name":"Homa Targhan","email":"","orcid":"","institution":"Razi University","correspondingAuthor":false,"prefix":"","firstName":"Homa","middleName":"","lastName":"Targhan","suffix":""}],"badges":[],"createdAt":"2024-08-18 13:03:32","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4933424/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4933424/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":65574596,"identity":"8d97762a-8603-4fac-ba58-e46a00c97512","added_by":"auto","created_at":"2024-09-30 07:20:29","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":4063,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular structure of imidacloprid.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/627e32b43c0f0588cdac96e1.png"},{"id":65575518,"identity":"77034022-84d3-4aa3-90be-4ccbb0f34cd3","added_by":"auto","created_at":"2024-09-30 07:28:29","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":58724,"visible":true,"origin":"","legend":"\u003cp\u003eXRD pattern of pristine ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/89bf811f99fb43a7932a80b9.png"},{"id":65575517,"identity":"25b6b7f4-705f-47d6-af54-28d238324ac1","added_by":"auto","created_at":"2024-09-30 07:28:29","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":55333,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of pristine ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/eb5ba128a58ecf6f1902eb4f.png"},{"id":65575520,"identity":"78786ab6-4682-44b1-ac81-a8e16745e396","added_by":"auto","created_at":"2024-09-30 07:28:29","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":424402,"visible":true,"origin":"","legend":"\u003cp\u003eThe EDX mapping of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/9a3f3d461c71b3da550dfcc3.png"},{"id":65574600,"identity":"1681ae4d-5ddf-4d0d-b7f9-ac863aed442e","added_by":"auto","created_at":"2024-09-30 07:20:29","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":286332,"visible":true,"origin":"","legend":"\u003cp\u003eFESEM images of NiSe\u003csub\u003e2 \u003c/sub\u003e(A and B), ZrP (C and D) and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite (E and F) at 500 nm and 200 nm\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/37f6e79c2939bafcaea2acb5.png"},{"id":65574598,"identity":"7ef35bb6-0ec9-49dd-bbc1-f7b370b1412d","added_by":"auto","created_at":"2024-09-30 07:20:29","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":94595,"visible":true,"origin":"","legend":"\u003cp\u003e(A) Removal of imidacloprid using ZrP, NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e photocatalysts; (B) Removal of imidacloprid using ZrP and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e under dark conditions; (C) Effect of the time on the removal of imidacloprid in the presence of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e; (D) Percent removal of imidacloprid using ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e in the presence of scavengers. Conditions: [imidacloprid] = 20 ppm, catalyst dose = 0.05 g, pH = 7, and 25 °C.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/69631b296b6f247ccd3513ba.png"},{"id":65574602,"identity":"77dcc9ba-ec07-4043-88c1-0a6975a2e71d","added_by":"auto","created_at":"2024-09-30 07:20:29","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":40212,"visible":true,"origin":"","legend":"\u003cp\u003eReusability of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e for imidacloprid removal from water.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/daee8df225a8fede21a2aa54.png"},{"id":72753150,"identity":"48b711c5-f1fe-403f-a419-d8154071224f","added_by":"auto","created_at":"2025-01-01 16:01:27","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1478591,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4933424/v1/5fad36a3-ea06-481d-b92f-142fbe261d85.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Adsorptive and Photocatalytic Degradation of Imidacloprid Pesticide from Wastewater via the ZrP/NiSe 2 nanocomposite","fulltext":[{"header":"Introduction","content":"\u003cp\u003ePesticides are used to control the harmful pests and thus improve agricultural production. Therefore, pesticides are an important component of the agricultural industry. However, the use of pesticides brings various adverse environmental impacts. Imidacloprid (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), a potent neonicotinoid insecticide, is one of the most widely used pesticides, which is commonly used in seed treatment to control the insects. This insecticide is highly toxic having good solubility and stability in water and its widespread application has caused significant environmental concerns.(\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e)\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn recent decades, the scientific community has devoted a significant deal of effort to developing innovative and functional materials that can be applied in water and wastewater treatment, which has further accelerated the development of photocatalytic technology.(\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eDue to their outstanding physical and chemical properties, α-zirconium phosphate (α-ZrP) and its derivatives have been widely investigated in adsorption processes for the removal and degradation of pollutants from wastewater,(\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e) medical field, namely in the drug delivery,(\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e) ion-exchange processes (\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e), photocatalysis processes (\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e), anti-corrosion technology (\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e) and composite material preparation to allow their application in various fields (\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eα-ZrP has been extensively investigated as catalysts and catalyst supports for a wide variety of applications due to its superior properties.(\u003cspan additionalcitationids=\"CR18 CR19 CR20 CR21 CR22 CR23\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e) However, α-ZrP do not show satisfactory visible-light photocatalytic activity, due to a broad band gap.(\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e) Combination of α-ZrP with semiconductor has been proposed as an impactful solution to improve photocatalytic performance of the α-ZrP for the degradation of organic pollutants.(\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eNickel selenide (NiSe\u003csub\u003e2\u003c/sub\u003e) is an inorganic compound exhibiting wide range of applications including fields of electrocatalysis, high-temperature superconductors, energy storage gadgets, photocatalyst and electrocatalysts.(\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e) NiSe\u003csub\u003e2\u003c/sub\u003e also offers several advantages including excellent electronic properties, chemical stability, having the appropriate band gap energy to absorb visible light (1.98 eV), low cost, low toxicity, and bio-compatibility.(\u003cspan additionalcitationids=\"CR28\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e) As mentioned earlier, NiSe\u003csub\u003e2\u003c/sub\u003e has an adequate band gap to absorb visible light, however, due to the electron-hole pair recombination, its photocatalytic performance is not as efficient as expected. Literature on photocatalysis applications of NiSe\u003csub\u003e2\u003c/sub\u003e highlights the employment of a pronged strategy for enhancing the photocatalytic performance of activity of NiSe\u003csub\u003e2\u003c/sub\u003e, namely; forming composites.(\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eThe photocatalytic activity of NiSe\u003csub\u003e2\u003c/sub\u003e-based composites on photodegradation of various organic pollutants in aqueous medium has been studied recently. Zhong et al.(\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e) reported that 9 mol% NiSe\u003csub\u003e2\u003c/sub\u003e composited BiVO\u003csub\u003e4\u003c/sub\u003e exhibited high photocatalytic performance for photodegradation Rhodamine B (RhB) under visible light compared to pure BiVO\u003csub\u003e4\u003c/sub\u003e. Coupling NiSe\u003csub\u003e2\u003c/sub\u003e with TiO\u003csub\u003e2\u003c/sub\u003e exhibited improved photocatalytic efficiency in the photodegradation of RhB compared to pure ones.(\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e) Recently, Waseem Luo et al.(\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e) have been studied the photocatalytic activity of NiSe\u003csub\u003e2\u003c/sub\u003e/Ag\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e nanocomposite for the photodegradation of RhB and Bisphenol A (BPA) pollutants. The 20% NiSe\u003csub\u003e2\u003c/sub\u003e/Ag\u003csub\u003e3\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e nanocomposite as a promising photocatalyst effectively degraded 10 ppm RhB in 20 min and 20 ppm BPA in 30 min under visible light. Reduced graphene oxide (rGO) incorporated NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite has been synthesized and its photocatalytic performance was investigated via the degradation of RhB. The as-prepared nanocomposite showed 98.8% degradation of RhB after 120 min under visible light irradiation.(\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eHerein, we prepared a nanocomposite by combining NiSe\u003csub\u003e2\u003c/sub\u003e with ZrP and successfully used it for the removal of Imidacloprid pesticide in aqueous solution. In view of the photocatalytic and adsorption potential of NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP nanoparticles, we speculate that ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite should be effective to eliminate water organic pollutants.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials and apparatus\u003c/h2\u003e \u003cp\u003eAll chemicals and solvents were purchased from Merck (Germany) or Fluka (Switzerland). The Fourier-transform infrared (FT-IR) spectra of the samples were recorded with the KBr pellet method on a PerkinElmer PE-1600-FTIR spectrometer. The field emission scanning electron microscope (FESEM) images were recorded using a TESCAN VEGA 3, Czech microscope. X-ray diffraction (XRD) spectra were recorded using an X-ray diffractometer (PANalytical X'Pert PRO, Netherlands) with Cu Kα radiation (λ\u0026thinsp;=\u0026thinsp;1.54 \u0026Aring;).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis of NiSe\u003csub\u003e2\u003c/sub\u003e nanoparticles\u003c/h2\u003e \u003cp\u003eInitially, 6.6 mmol selenium powder was added into 2 mL of hydrazine hydrate. After a few minutes of sonication, 3.3 mmol Ni(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026bull;6H\u003csub\u003e2\u003c/sub\u003eO was added with ultra-sonication to form a homogeneous solution. The mixture was then transferred to a 50 mL Teflon-lined autoclave which was maintained at 180\u0026deg;C for 24 h. The autoclave was then cooled to room temperature and the NiSe\u003csub\u003e2\u003c/sub\u003e particles were collected by filtration. Subsequently, the obtained particles were washed with deionized water until pH\u0026thinsp;=\u0026thinsp;7 and were dried for 24 h in a vacuum oven at 60\u0026deg;C.(\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e)\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis of ZrP nanoparticles\u003c/h2\u003e \u003cp\u003eTo synthesize ZrP, 3.22 g Zirconium oxychloride (ZrOCl\u003csub\u003e2\u003c/sub\u003e\u0026bull;8H\u003csub\u003e2\u003c/sub\u003eO) was dissolved in deionized water and slowly dropped into the 40 mL diluted phosphoric acid solution (11 mol.L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) under continuous stirring. After refluxing in an oil bath100\u0026deg;C for 24, the product was filtered and rinsed with deionized water several times to remove unreacted phosphoric acid and other impurities until the pH of the filtrate was neutral. Eventually, the sample was dried overnight in a vacuum oven at 60\u0026deg;C to obtain the ZrP powder.(\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e)\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite\u003c/h2\u003e \u003cp\u003eWe have used a straightforward surface soaking method to prepare ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite. First, ZrP powder (0.1 g) was dispersed in deionized water (10 mL) by centrifuging for 30 min. After adding NiSe\u003csub\u003e2\u003c/sub\u003e nanoparticles (0.05 g), the suspension was sonicated for 30 min and stirred at room temperature for 24 hours. Eventually, the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e powder was collected by centrifugation, washed three times with distilled water, and dried overnight at 50\u0026deg;C.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003ePhotocatalytic degradation of imidacloprid\u003c/h2\u003e \u003cp\u003ePhotocatalytic degradation experiments of imidacloprid (10 mL of 20 ppm) were conducted under visible light irradiation (LED lamp). The lamp was placed at a distance of 30 cm from the surface of the test solution. The temperature of the system was simply controlled by using a water bath. The irradiated solution was sampled every 15 min. The concentration of imidacloprid was quantified by UV\u0026ndash;Vis spectrophotometry (Shimadzu, CPS-240A).\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003eCharacterization of the photocatalysts\u003c/h2\u003e \u003cp\u003eA set of characterization techniques, such as FT-IR and, XRD, EDX mapping and FESEM, was used to get better insight into the structural properties of the prepared ZrP, NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e samples.\u003c/p\u003e \u003cp\u003eXRD patterns of the synthesized ZrP, NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e samples are illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e represents the XRD pattern of cubic NiSe\u003csub\u003e2\u003c/sub\u003e, which exhibits the characteristic peaks at 2θ values of 30.01, 33.64, 36.96, 42.94, 50.82, 53.26, 55.59, 57.89, 62.30, 72.66, and 74.65\u0026deg; in lattice planes (200), (210), (211), (220), (311), (222), (023), (321), (400), (421), and (332), respectively.(\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e also shows the XRD pattern of ZrP sample. The XRD pattern shows diffraction peaks at 2θ values of 11.84, 20.04, 25.14 and 34.13\u0026deg; respectively assigned to the (002), (110), (112), (020) planes, respectively, indicating the crystalline nature of the as-prepared ZrP.(\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e) The typical reflection observed at 2θ values of 11.8\u0026deg;, due to the (002) crystallographic planes, indicates the interlayer distance of ZrP crystals. The interlayer distance of ZrP calculated by Bragg Eq.\u0026nbsp;(2d sin θ\u0026thinsp;=\u0026thinsp;n λ) was 7.47 \u0026Aring;.(\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eThe XRD pattern of Zrp/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) demonstrates the presence of ZrP as well as NiSe\u003csub\u003e2\u003c/sub\u003e peaks. The NiSe\u003csub\u003e2\u003c/sub\u003e characteristic peaks were obtained at 2θ values of 30.02, 33.67, 37.00, 42.98, 50.82, 53.13, 55.66, 57.91, 72.75, and 74.76\u0026deg; and ZrP characteristic peaks were obtained at 2θ values of 11.73, 19.98, 24.79, and 34.50\u0026deg;. The interlayer distance of the ZrP in ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e composite calculated according to Bragg equation was 7.53 \u0026Aring;.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e presents the FTIR spectra of ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite. For the pure NiSe\u003csub\u003e2\u003c/sub\u003e nanoparticles, a broad band observed around 3300\u0026thinsp;\u0026minus;\u0026thinsp;3600 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and a peak at 1622 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e could be attributed to the stretching and bending vibrations of the water\u0026rsquo;s hydroxyl groups adsorbed at the surface of NiSe\u003csub\u003e2\u003c/sub\u003e, respectively. The stretching vibrations of Ni\u0026ndash;Se bonds were characterized by a broad peak in the region of 500 to 800 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.(\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eFor the pure α-ZrP nanoparticles, the sharp band located at 1041 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e can be assigned to the symmetrical stretching vibration peak of PO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e3\u0026minus;\u003c/sup\u003e groups. The characteristic peak at 594 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e can be ascribed to Zr\u0026thinsp;\u0026minus;\u0026thinsp;O bonds.(\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eFT-IR spectra recorded for ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite exhibits all of the characteristic peaks of ZrP and of NiSe\u003csub\u003e2\u003c/sub\u003e, indicating the presence of both nanoparticles in the nanocomposite composition. These results are in agreement with XRD results shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs expected, the EDX spectrum of the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e) clearly shows the presence of zirconium, phosphorus, nickel and selenium atoms in the composite combination. Furthermore, as can be seen in the EDX mapping (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e), the zirconium, phosphorus, nickel and selenium elements are homogeneously dispersed on the surface of the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe surface morphologies of the synthesized NiSe\u003csub\u003e2\u003c/sub\u003e, ZrP and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e samples was investigated using FESEM (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). The NiSe\u003csub\u003e2\u003c/sub\u003e sample well exhibit a cubic-like morphology, as shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eA and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eB. The morphology of the ZrP was vividly shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eC and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eD at various magnifications (500 nm and 200 nm). The as-prepared ZrP particles formed disk shapes, as seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eC and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eD. It is clear that the ZrP disks have good uniformity. When the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite is formed using a straightforward surface soaking method, SEM images are obtained and shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eE and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eF. It can be seen that the particles of NiSe\u003csub\u003e2\u003c/sub\u003e were attached to the ZrP in the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eConsequently the results of the FT-IR, XRD, EDX mapping and FESEM characterization techniques confirm the successful preparation of ZrP, NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e samples.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003ePhotocatalytic degradation studies\u003c/h2\u003e \u003cp\u003eThe catalytic activity evaluation of the as-synthesized ZrP, NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e samples was done on the removal of imidacloprid from the aqueous solution. The results of the study of imidacloprid removal are summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003ePreliminary tests on the catalytic activity of ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e samples as well as ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e for removal of imidacloprid displayed that ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e samples were less active and the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite showed the highest photocatalytic activity in removal of imidacloprid than that of the pure ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e photocatalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eA). It seems that the combination and synergistic effect of NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP play an important role for improvement of the photocatalytic activity of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite. In contrast, only small percentage of the pesticide (8.25%) was degraded in the absence of a photocatalyst, after 90 min of irradiation.\u003c/p\u003e \u003cp\u003eFurthermore, ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP can remove significant percentages of imidacloprid from aqueous solutions through adsorption (43.26% and 43.69%, respectively) under dark conditions (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eB). These results were predicted because the high adsorption affinity of ZrP toward organic pollutants with protonable groups has already been described.(\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e)\u003c/p\u003e \u003cp\u003eThe effect of irradiation time on removal of imidacloprid in the presence of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e was also monitored. As expected, the imidacloprid concentration decreases by increasing the irradiation time (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eC). Nevertheless, when the irradiation time increases from 90 min to 105 min, there was no significant change in the concentration of imidacloprid (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eC).\u003c/p\u003e \u003cp\u003eThe dosage of photocatalyst is a key factor that influence the percent removal of the pollutant. Therefore, the impact of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e dose on removal of the pesticide was also investigated. The increase in ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e dose from 0.03 g to 0.05 g resulted in corresponding increase in percentage of imidacloprid removal (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Entry 7). However, further increasing ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e dose to 0.07 g would only lead to a slight increase in the percentage of imidacloprid removal (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Entry 8).\u003c/p\u003e \u003cp\u003eThe percent removal of the pesticide is affected by the initial concentration. As a result, the percentage removal of imidacloprid decreased with an increase in initial concentration from 10 to 20 ppm (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Entry 9).\u003c/p\u003e \u003cp\u003eIn order to indicate the main active specie in the photodegradation of imidacloprid pesticide, the effects were evaluated when using isopropyl alcohol (IPA) as a hydroxyl radical scavenger, and p-benzoquinone (BQ) as a superoxide radical scavenger and EDTA as a hole scavenger. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eD, after the addition of IPA, an efficiency decrease in catalytic performance of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e was observed, indicating that the hydroxyl radicals play a vital role in the degradation of imidacloprid. Although, the addition of p-benzoquinone and EDTA did not affect imidacloprid removal significantly (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eD).\u003c/p\u003e \u003cp\u003e \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\u003eSummary of the removal of imidacloprid in photocatalytic and photochemical systems within 90 min.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eEntry\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePhotocatalyst\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCatalyst dose (g)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eLight source\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eInitial imidacloprid conc. (ppm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eImidacloprid Removal [%]\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP/NiSe\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e70.67\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e51.52\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eNiSe\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e47.50\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e8.25\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP/NiSe\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e43.26\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e43.69\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP/NiSe\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e49.28\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP/NiSe\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e77.51\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZrP/NiSe\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eVis.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e79.63\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\u003eThe ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite was recyclable without much loss of activity. After each, the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite separated from the reaction medium by centrifugation. The used catalyst was washed several times with water, dried at 50\u0026deg;C and further reused consecutively for 3 times. The ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite showed 61.19% imidacloprid removal at 3th cycle (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite was prepared with the purpose of creating recyclable catalytic system for removal of Imidacloprid pesticide from water. Detailed characterization results indicate the successful preparation of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite. Our results suggested the improved photocatalytic performance of ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite. Furthermore, the ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite can keep the good performance after three times of recycle.\u003c/p\u003e "},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eK.B. conceived the original idea and supervised the project. M.I. carried out the experiment. H.T helped supervise the project. M.I. and H.T. wrote the main manuscript text. All authors reviewed the manuscript.\u003c/p\u003e\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eData Availability Statements\u003c/h2\u003e \u003cp\u003eAll data generated or analyzed during this study are included in this published article.\u003c/p\u003e \u003c/div\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eTarghan, H. et al. Adsorptive and photocatalytic degradation of imidacloprid pesticide from wastewater via the fabrication of ZIF-CdS/Tpy quantum dots. \u003cem\u003eChem. Eng. J.\u003c/em\u003e \u003cb\u003e482\u003c/b\u003e, 148983 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTarghan, H. et al. Photocatalytic removal of imidacloprid pesticide from wastewater using CdS QDs passivated by CQDs containing thiol groups. \u003cem\u003eSci. Rep.\u003c/em\u003e \u003cb\u003e14\u003c/b\u003e (1), 530 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMuscetta, M. \u0026amp; Russo, D. Photocatalytic applications in wastewater and air treatment: A patent review (2010\u0026ndash;2020). \u003cem\u003eCatalysts\u003c/em\u003e. \u003cb\u003e11\u003c/b\u003e (7), 834 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAhuja, T., Brighu, U. \u0026amp; Saxena, K. Recent advances in photocatalytic materials and their applications for treatment of wastewater: A review. \u003cem\u003eJ. Water Process. Eng.\u003c/em\u003e \u003cb\u003e53\u003c/b\u003e, 103759 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMu, W. et al. Controlled fabrication of flower-like α-zirconium phosphate for the efficient removal of radioactive strontium from acidic nuclear wastewater. \u003cem\u003eJ. Mater. Chem. A\u003c/em\u003e. \u003cb\u003e5\u003c/b\u003e (46), 24388\u0026ndash;24395 (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePica, M. Treatment of wastewaters with zirconium phosphate based materials: A review on efficient systems for the removal of heavy metal and dye water pollutants. \u003cem\u003eMolecules\u003c/em\u003e. \u003cb\u003e26\u003c/b\u003e (8), 2392 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDıaz, A. et al. Zirconium phosphate nano-platelets: a novel platform for drug delivery in cancer therapyw. \u003cem\u003eChem. Commun.\u003c/em\u003e \u003cb\u003e48\u003c/b\u003e, 1754\u0026ndash;1756 (2012).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSaxena, V., Diaz, A., Clearfield, A., Batteas, J. D. \u0026amp; Hussain, M. D. Zirconium phosphate nanoplatelets: a biocompatible nanomaterial for drug delivery to cancer. \u003cem\u003eNanoscale\u003c/em\u003e. \u003cb\u003e5\u003c/b\u003e (6), 2328\u0026ndash;2336 (2013).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWiikinkoski, E. W., Harjula, R. O., Lehto, J. K., Kemell, M. L. \u0026amp; Koivula, R. T. Effects of synthesis conditions on ion exchange properties of α-zirconium phosphate for Eu and Am. \u003cem\u003eRadiochim. Acta\u003c/em\u003e. \u003cb\u003e105\u003c/b\u003e (12), 1033\u0026ndash;1042 (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePathania, D., Thakur, M. \u0026amp; Mishra, A. Alginate-Zr (IV) phosphate nanocomposite ion exchanger: Binary separation of heavy metals, photocatalysis and antimicrobial activity. \u003cem\u003eJ. Alloys Compd.\u003c/em\u003e \u003cb\u003e701\u003c/b\u003e, 153\u0026ndash;162 (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYe, Z. et al. α-Zirconium phosphate nanocrystals with various morphology for photocatalysis. \u003cem\u003eChem. Phys. Lett.\u003c/em\u003e \u003cb\u003e709\u003c/b\u003e, 96\u0026ndash;102 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQing, S. et al. Photocatalytic activity investigation of α-zirconium phosphate nanoparticles compositing with C3N4 under ultraviolet light. \u003cem\u003eACS omega\u003c/em\u003e. \u003cb\u003e5\u003c/b\u003e (43), 27873\u0026ndash;27879 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLv, Z. et al. Design Polyaniline/α-Zirconium Phosphate Composites for Achieving Self-Healing Anti-Corrosion of Carbon Steel. \u003cem\u003eNanomaterials\u003c/em\u003e. \u003cb\u003e14\u003c/b\u003e (1), 76 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSheng, X. et al. Waterborne epoxy resin/polydopamine modified zirconium phosphate nanocomposite for anticorrosive coating. \u003cem\u003eInd. Eng. Chem. Res.\u003c/em\u003e \u003cb\u003e58\u003c/b\u003e (36), 16571\u0026ndash;16580 (2019).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXie, H., Lai, X., Li, H. \u0026amp; Zeng, X. Fabrication of ZrP nanosheet decorated macromolecular charring agent and its efficient synergism with ammonium polyphosphate in flame-retarding polypropylene. \u003cem\u003eCompos. Part A: Appl. Sci. Manufac.\u003c/em\u003e \u003cb\u003e105\u003c/b\u003e, 223\u0026ndash;234 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJiang, F., Sun, H., Chen, L., Lei, F. \u0026amp; Sun, D. Dispersion-tribological property relationship in mineral oils containing 2D layered α-zirconium phosphate nanoplatelets. \u003cem\u003eFriction\u003c/em\u003e. \u003cb\u003e8\u003c/b\u003e (4), 695\u0026ndash;707 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eThakur, M. et al. Efficient photocatalytic degradation of toxic dyes from aqueous environment using gelatin-Zr (IV) phosphate nanocomposite and its antimicrobial activity. \u003cem\u003eColloids Surf., B\u003c/em\u003e. \u003cb\u003e157\u003c/b\u003e, 456\u0026ndash;463 (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePica, M. et al. Nanosized zirconium phosphate/AgCl composite materials: A new synergy for efficient photocatalytic degradation of organic dye pollutants. \u003cem\u003eJ. Mater. Chem. A\u003c/em\u003e. \u003cb\u003e3\u003c/b\u003e (10), 5525\u0026ndash;5534 (2015).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHajipour, A. R. \u0026amp; Karimi, H. Hexagonal zirconium phosphate nanoparticles as an efficient and recyclable catalyst for selective solvent-free alkylation of phenol with cyclohexanol. \u003cem\u003eAppl. Catal. A\u003c/em\u003e. \u003cb\u003e482\u003c/b\u003e, 99\u0026ndash;107 (2014).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChen, R., Wang, J., Wang, H., Yao, W. \u0026amp; Zhong, J. Photocatalytic degradation of methyl orange in aqueous solution over titania-pillared α-zirconium phosphate. \u003cem\u003eSolid State Sci.\u003c/em\u003e \u003cb\u003e13\u003c/b\u003e (3), 630\u0026ndash;635 (2011).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWen, M., Mori, K., Kuwahara, Y. \u0026amp; Yamashita, H. Visible-light‐responsive carbon dioxide reduction system: rhenium complex intercalated into a zirconium phosphate layered matrix. \u003cem\u003eChemCatChem\u003c/em\u003e. \u003cb\u003e7\u003c/b\u003e (21), 3519\u0026ndash;3525 (2015).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu, J., Wang, F., Gu, Z. \u0026amp; Xu, X. Styrene epoxidation over Ag-γ-ZrP catalyst prepared by ion-exchange. \u003cem\u003eCatal Commun.\u003c/em\u003e \u003cb\u003e10\u003c/b\u003e (6), 868\u0026ndash;871 (2009).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLai, G-H. et al. Preparation of highly-stable and recyclable novel Au/ZrP composite catalyst for 4-nitrophenol reduction. \u003cem\u003eJ. Taiwan Inst. Chem. Eng.\u003c/em\u003e \u003cb\u003e95\u003c/b\u003e, 525\u0026ndash;531 (2019).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTuteja, J., Choudhary, H., Nishimura, S. \u0026amp; Ebitani, K. Direct synthesis of 1, 6-hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source. \u003cem\u003eChemSusChem\u003c/em\u003e. \u003cb\u003e7\u003c/b\u003e (1), 96\u0026ndash;100 (2014).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eShen, S. et al. Construction of NiSe2/BiVO4 Schottky junction derived from work function discrepancy for boosting photocatalytic activity. \u003cem\u003eJ. Alloys Compd.\u003c/em\u003e \u003cb\u003e875\u003c/b\u003e, 160071 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMaryam, R. et al. Enhanced photocatalytic and antibacterial activity of NiSe2\u0026ndash;TiO2 nanocomposites under visible light. \u003cem\u003eOpt. Mater.\u003c/em\u003e \u003cb\u003e143\u003c/b\u003e, 114183 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eShen, S. et al. NiSe 2/CdS composite nanoflakes photocatalyst with enhanced activity under visible light. \u003cem\u003eRSC Adv.\u003c/em\u003e \u003cb\u003e10\u003c/b\u003e (69), 42008\u0026ndash;42013 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKhaladkar, S. R. et al. In situ growth of NiSe 2 nanoparticles on gC 3 N 4 nanosheets for an efficient hydrogen evolution reaction. \u003cem\u003eMater. Adv.\u003c/em\u003e \u003cb\u003e5\u003c/b\u003e (10), 4345\u0026ndash;4353 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRani, M. et al. NiSe2/Ag3PO4 nanocomposites for enhanced Visible light photocatalysts for environmental remediation applications. \u003cem\u003eCatalysts\u003c/em\u003e. \u003cb\u003e13\u003c/b\u003e (6), 929 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMahalakshmi, K., Jenila, R. M., Potheher, I. V., Lakshmi, V. \u0026amp; Thangaraj, V. Bifunctional rGO incorporated NiSe2 nanocomposite as a photocatalyst and an electrode in supercapacitor. \u003cem\u003eJ. Alloys Compd.\u003c/em\u003e \u003cb\u003e972\u003c/b\u003e, 172699 (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHayat, M. et al. Exploring the electrochemical properties of CuSe-decorated NiSe2 nanocubes for battery-supercapacitor hybrid devices. \u003cem\u003eChemosphere\u003c/em\u003e. \u003cb\u003e340\u003c/b\u003e, 139720 (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHan, L. et al. Synthesis and Performance of Functionalized α-Zirconium Phosphate Modified with Octadecyl Isocyanate. \u003cem\u003eJ. Nanomaterials\u003c/em\u003e. \u003cb\u003e2018\u003c/b\u003e (1), 5873871 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJansi Rani, B. et al. CoNiSe2 nanostructures for clean energy production. \u003cem\u003eACS omega\u003c/em\u003e. \u003cb\u003e5\u003c/b\u003e (24), 14702\u0026ndash;14710 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePica, M. et al. De-ethylation and cleavage of rhodamine B by a zirconium phosphate/silver bromide composite photocatalyst. \u003cem\u003eCatalysts\u003c/em\u003e. \u003cb\u003e9\u003c/b\u003e (1), 3 (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKhanal, S., Lu, Y., Dang, L., Ali, M. \u0026amp; Xu, S. Effects of α-zirconium phosphate and zirconium organophosphonate on the thermal, mechanical and flame retardant properties of intumescent flame retardant high density polyethylene composites. \u003cem\u003eRSC Adv.\u003c/em\u003e \u003cb\u003e10\u003c/b\u003e (51), 30990\u0026ndash;31002 (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKhan, B. A. et al. NiSe2 nanocrystals intercalated rGO sheets as a high-performance asymmetric supercapacitor electrode. \u003cem\u003eCeram. Int.\u003c/em\u003e \u003cb\u003e48\u003c/b\u003e (4), 5509\u0026ndash;5517 (2022).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"Photocatalytic degradation, Imidacloprid, Zirconium phosphate, Nickel selenide, nanocomposite","lastPublishedDoi":"10.21203/rs.3.rs-4933424/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4933424/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIn this study, ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite was constructed for the first time. Characterizations were carried out by FT-IR, XRD, EDX mapping and FESEM, confirming the nanocomposite formation. The resulting sustainable ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e nanocomposite exhibit improved photocatalytic activity in the visible area to remove imidacloprid from water compared to pure ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e nanoparticles. Improving the performance of this nanocomposite can be the result of the integration of ZrP and NiSe\u003csub\u003e2\u003c/sub\u003e at the nanoscale and the synergistic enhancement of their activity. Furthermore, ZrP/NiSe\u003csub\u003e2\u003c/sub\u003e and ZrP can remove significant percentages of imidacloprid from aqueous solutions through adsorption. This result can be explained by the high adsorption affinity of ZrP toward organic pollutants with protonable groups.\u003c/p\u003e","manuscriptTitle":"Adsorptive and Photocatalytic Degradation of Imidacloprid Pesticide from Wastewater via the ZrP/NiSe 2 nanocomposite","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-09-30 07:20:24","doi":"10.21203/rs.3.rs-4933424/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":"6d7154cf-24cb-4634-b788-868c07ec0e8a","owner":[],"postedDate":"September 30th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":38237808,"name":"Physical sciences/Chemistry"},{"id":38237809,"name":"Physical sciences/Nanoscience and technology"}],"tags":[],"updatedAt":"2025-01-01T15:53:18+00:00","versionOfRecord":[],"versionCreatedAt":"2024-09-30 07:20:24","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4933424","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4933424","identity":"rs-4933424","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}