Visible light-driven photocatalytic activity of Cu2O/ZnO/Kaolinite-based composite catalyst for the degradation of organic pollutant.

Herein, we design to synthesize a novel Cu2O/ZnO/kaolinite composite catalyst by co-precipitation method. The synthesized composite catalysts were labeled as 5CZK, 10CZK, 15CZK, and 20CZK which represent 5, 10, 15, and 20% of Cu2O, respectively, on ZnO/kaolinite. The photocatalyst samples were characterized with different instruments. Moreover, the methylene blue (MB) dye was used as a target organic pollutant and the degradation was evaluated under visible light irradiation. The highest performance for the degradation of MB was achieved by 10CZK catalyst and degrades 93% within 105 min. However, ZnO (Z), Cu2O/ZnO (CZ), 5CZK, 15CZK, and 20CZK composite catalysts, degrades 28, 66, 76, 71, and 68% of MB dye, respectively. The enhanced degradation efficiency of 10CZK composites catalyst could be due to the higher adsorption properties from metakaolinite and the light-responsive properties of the Cu2O/ZnO samples under visible light. Hence, the resulting composite catalyst could be applicable for environmental remediation.

Boosted visible-light-induced photo-Fenton degradation of organic pollutants over a novel direct Z-scheme NH2-MIL-125(Ti)@FeOCl heterojunction catalyst.

Improving the charge separation, charge transfer, and effective utilization is crucial in a photocatalysis system. Herein, we prepared a novel direct Z-scheme NH2-MIL-125(Ti)@FeOCl (Ti-MOF@FeOCl) composite photocatalyst through a simple method. The prepared composite catalyst was utilized in the photo-Fenton degradation of Rhodamine B (RhB) and ciprofloxacin (CIP). The Ti-MOF@FeOCl (10FeTi-MOF) catalyst exhibited the highest catalytic performance and degraded 99.1 and 66% of RhB and CIP, respectively. However, the pure NH2-MIL-125(Ti) (Ti-MOF) and FeOCl catalysts achieved only 50 and 92% of RhB and 50 and 37% of CIP, respectively. The higher catalytic activities of the Ti-MOF@FeOCl composite catalyst could be due to the electronic structure improvements, photoinduced charge separations, and charge transfer abilities in the catalyst system. The composite catalysts have also enhanced adsorption and visible light-responsive properties, allowing for efficient degradation. Furthermore, the electron paramagnetic resonance (EPR) signals, the reactive species trapping experiments, and Mott-Schottky (M - S) measurements revealed that the photogenerated superoxide radical (•O2-), hydroxyl radical (•OH), and holes (h+) played a vital role in the degradation process. The results also demonstrated that the Ti-MOF@FeOCl heterojunction composite catalysts could be a promising photo-Fenton catalyst system for the environmental remediation. Environmental implications The discharging of toxic contaminants such as organic dyes, antibiotics, and other emerging pollutants to the environment deteriorates the ecosystem. Specifically, the residues of organic pollutants recognized as a threat to ecosystem and a cause for carcinogenic effects. Among them, ciprofloxacin is one of antibiotics which has biological resistance, and metabolize partially in the human or animal bodies. It is also difficult to degrade ciprofloxacin completely with traditional treatment methods. Similarly, organic dyes are also toxic and a cause for carcinogenic effects. Therefore, effective degradation of organic pollutants such as RhB and ciprofloxacin with appropriate method is crucial.

Photocatalytic activity of the biogenic mediated green synthesized CuO nanoparticles confined into MgAl LDH matrix.

The global concern over water pollution caused by organic pollutants such as methylene blue (MB) and other dyes has reached a critical level. Herein, the Allium cepa L. peel extract was utilized to fabricate copper oxide (CuO) nanoparticles. The CuO was combined with MgAl-layered double hydroxides (MgAl-LDHs) via a co-precipitation method with varying weight ratios of the CuO/LDHs. The composite catalysts were characterized and tested for the degradation of MB dye. The CuO/MgAl-LDH (1:2) showed the highest photocatalytic performance and achieved 99.20% MB degradation. However, only 90.03, 85.30, 71.87, and 35.53% MB dye was degraded with CuO/MgAl-LDHs (1:1), CuO/MgAl-LDHs (2:1), CuO, and MgAl-LDHs catalysts, respectively. Furthermore, a pseudo-first-order rate constant of the CuO/MgAl-LDHs (1:2) was 0.03141 min-1 while the rate constants for CuO and MgAl-LDHs were 0.0156 and 0.0052 min-1, respectively. The results demonstrated that the composite catalysts exhibited an improved catalytic performance than the pristine CuO and MgAl-LDHs. The higher photocatalytic performances of composite catalysts may be due to the uniform distribution of CuO nanoparticles into the LDH matrix, the higher surface area, and the lower electron and hole recombination rates. Therefore, the CuO/MgAl-LDHs composite catalyst can be one of the candidates used in environmental remediation.

Room-temperature synthesis of a Zr-UiO-66 metal-organic framework via mechanochemical pretreatment for the rapid removal of EDTA-chelated copper from water.

Treatment of heavy metal pollution in complexed states within water bodies presents significant challenges in the current water treatment field. Adsorption as a means for the removal of heavy metals is characterized by its simplicity of operation, stable effluent, and minimal equipment requirements. Metal-organic frameworks (MOFs) as adsorbents hold significant interest for applications in water treatment. In this study, we investigated a green synthesis approach for the ball-milling pretreated synthesis of UiO-66(Zr) at room temperature, abbreviated as UiO-66(Zr)-rm. Besides having the same thermal stability and crystal structure as the product from microwave-assisted synthesis (UiO-66(Zr)-mw), the resulting UiO-66(Zr)-rm features smaller particle size and superior mesoporous structure. The adsorption efficiency and mechanism for removing EDTA-chelated copper (EDTA-CuII), a complexed heavy metal in water, were extensively analyzed. UiO-66(Zr)-rm presented a maximum adsorption capacity over EDTA-CuII of 43 mg g-1 and a much higher adsorption rate (0.16 g (mg h)-1) than UiO-66(Zr)-mw (0.06 g (mg h)-1). Hierarchically mesostructured defects allow the sorbate to have more effective diffusion in a shorter time to achieve faster adsorption kinetics. Benefiting from the mild synthesis conditions and nontoxic solvents, UiO-66(Zr) has the potential to be produced at a scaled-up level, thereby exhibiting excellent adsorption performance for the removal of complexed heavy metals in the future.

Biological Renewable Cellulose-Templated Zn1-XCuXO/Ag2O Nanocomposite Photocatalysts for the Degradation of Methylene Blue.

Herein, Cellulose-templated Zn1-XCuXO/Ag2O nanocomposites were prepared using biological renewable cellulose extracted from water hyacinth (Eichhornia crassipes). Cellulose-templated Cu-doped ZnO catalysts with different amounts of Cu as the dopants (1, 2, 3, and 4%) were prepared and denoted CZ-1, CZ-2, CZ-3, and CZ-4, respectively, for simplicity. The prepared catalysts were tested for the degradation of methylene blue (MB), and 2% Cu-doped ZnO (CZ-2) showed the best catalytic performance (82%), while the pure ZnO, CZ-1, CZ-3, and CZ-4 catalysts exhibited MB dye degradation efficiencies of 54, 63, 65, and 60%, respectively. The best catalyst (CZ-2) was chosen to further improve the degradation efficiency. Different amounts of AgNO3 (10, 15, 30, and 45 mg) were used for the deposition of Ag2O on the surface of CZ-2 and denoted CZA-10, CZA-15, CZA-30, and CZA-45, respectively. Among the composite catalysts, CZA-15 showed remarkable degradation efficiency and degraded 94% of MB, while the CZA-10, CZA-30, and CZA-45 catalysts showed 90, 81, and 79% degradation efficiencies, respectively, under visible light within 100 min of irradiation. The enhanced catalytic performance could be due to the smaller particle size, the higher electron and hole separation and charge transfer efficiencies, and the lower agglomeration in the composite catalyst system. The results also demonstrated that the Cu-doped ZnO prepared with cellulose as a template, followed by the optimum amount of Ag2O deposition, could have promising applications in the degradation of organic pollutants.

Recent progress on plant extract-mediated biosynthesis of ZnO-based nanocatalysts for environmental remediation: Challenges and future outlooks.

The plant extract mediated green synthesis of nanomaterials has attracts enormous interest due to its cost-effectiveness, greener, and environmentally friendly. It is also considered as an alternative and facile method in which the phytochemicals can be used as a natural capping and reducing agents and helped to produce nanomaterials with high surface area, different sizes, and shapes. One of the materials fabricated using green methods is zinc oxide (ZnO) semiconductor due to its enormous applications in different field areas. In this review, an overview of recent progress on green synthesized ZnO-based catalysts and various modification methods for the purpose of enhancing the catalytic activity of ZnO and the corresponding structural-activity and interactions towards the removal of pollutants are highlighted. Particularly, the plant extract mediated ZnO-based photocatalysts application for the removal of pollutants via photocatalytic degradation, reduction reaction, and adsorption mechanism are demonstrated. Besides, the opportunities, challenges, and future outlooks of ZnO-based materials for environmental remediation with green and sustainable methods are also included. We believe that this review is a timely and comprehensive review on the recent progress related to plant extract mediated ZnO-based nanocatalysts synthesis and applications for environmental remediation.

Sulfur Substitution and Defect Engineering in an Unfavored MnMoO4 Catalyst for Efficient Hydrogen Evolution under Visible Light.

A novel and nonstoichiometric Mn1-xMo(S,O)4-y oxysulfide catalyst with oxygen vacancies and a partial Mo6+-to-Mo4+ transition after the substitution of sulfur was synthesized for an efficient photocatalytic hydrogen evolution reaction (PHER). With appropriate sulfur substitution, a MnMoO4 semiconductor with a wide band gap was converted to Mn1-xMo(S,O)4-y with a narrow gap and a suitable band position for PHER. MnMo oxysulfide of 50 mg achieved a high PHER rate of 415.8 µmol/h under visible light, an apparent quantum efficiency (AQE) of 4.31% at 420 nm, and a solar-to-hydrogen (STH) conversion efficiency of 1.28%. Oxygen vacancies (VO) surrounded by low coordination metal atoms act as active reaction sites, which strengthen water adsorption and activation. Here, we demonstrate that sulfur substitution of MnMoO4 for lowering its wide band gap can not only disturb the strict periodicity of the lattice but also the valence states of Mn and Mo for enhancing PHER via material design.

g-C3N4-Co3O4 Z-Scheme Junction with Green-Synthesized ZnO Photocatalyst for Efficient Degradation of Methylene Blue in Aqueous Solution.

A simple wet chemical ultrasonic-assisted synthesis method was employed to prepare visible light-driven g-C3N4-ZnO-Co3O4 (GZC) heterojunction photocatalysts. X-ray diffraction (XRD), scanning electromicroscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), ultraviolet (UV), and electrochemical impedance spectroscopy (EIS) are used to characterize the prepared catalysts. XRD confirms the homogenous phase formation of g-C3N4, ZnO, and Co3O4, and the heterogeneous phase for the composites. The synthesized ZnO and Co3O4 by using cellulose as a template show a rod-like morphology. The specific surface area of the catalytic samples increases due to the cellulose template. The measurements of the energy band gap of a g-C3N4-ZnO-Co3O4 composite showed red-shifted optical absorption to the visible range. The photoluminescence (PL) intensity decreases due to the formation of heterojunction. The PL quenching and EIS result shows that the reduction of the recombination rate and interfacial resistance result in charge carrier kinetic improvement in the catalyst. The photocatalytic performance in the degradation of MB dye of the GZC-3 composite was about 8.2-, 3.3-, and 2.5-fold more than that of the g-C3N4, g-C3N4-ZnO, and g-C3N4-Co3O4 samples. The Mott-Schottky plots of the flat band edge position of g-C3N4, ZnO, Co3O4, and Z-scheme g-C3N4-ZnO-Co3O4 photocatalysts may be created. Based on the stability experiment, GZC-3 shows greater photocatalytic activity after four recycling cycles. As a result, the GZC composite is environmentally friendly and efficient photocatalyst and has the potential to consider in the treatment of dye-contaminated wastewater.

Green Synthesis of a CuO-ZnO Nanocomposite for Efficient Photodegradation of Methylene Blue and Reduction of 4-Nitrophenol.

CuO-ZnO nanocomposites (NCs) were synthesized using an aqueous extract of Verbascum sinaiticum Benth. (GH) plant. X-ray diffraction (XRD), spectroscopic, and microscopic methods were used to explore the crystallinity, optical properties, morphology, and other features of the CuO-ZnO samples. Furthermore, catalytic performances were investigated for methylene blue (MB) degradation and 4-nitrophenol (4-NP) reduction. According to the results, CuO-ZnO NCs with 20 wt % CuO showed enhanced photocatalytic activity against MB dye with a 0.017 min-1 rate constant compared to 0.0027 min-1 for ZnO nanoparticles (NPs). Similarly, a ratio constant of 5.925 min-1 g-1 4-NP reductions was achieved with CuO-ZnO NCs. The results signified enhanced performance of CuO-ZnO NCs relative to ZnO NPs. The enhancement could be due to the synergy between ZnO and CuO, resulting in improved absorption of visible light and reduced electron-hole (e-/h+) recombination rate. In addition, variations in the CuO content affected the performance of the CuO-ZnO NCs. Thus, the CuO-ZnO NCs prepared using V. sinaiticum Benth. extract could make the material a desirable catalyst for the elimination of organic pollutants.

Biogenic Synthesis of Cu-Doped ZnO Photocatalyst for the Removal of Organic Dye.

The Cu-doped ZnO photocatalysts were prepared with a green and coprecipitation approach by using water hyacinth (Eichhornia crassipes) aquatic plant extract. In the preparation process, different amount of copper precursors such as 1, 2, 3, 4, and 5% of molar ratio were added to zinc nitrate precursors and abbreviated as Cu-ZnO (1%), Cu-ZnO (2%), Cu-ZnO (3%), Cu-ZnO (4%), and Cu-ZnO (5%), respectively. The characterization of the obtained samples was carried out, and the removal of the methylene blue (MB) dye was examined. Out of all catalysts, Cu-ZnO (3%) had the best photocatalytic performance and 89% of the MB dye was degraded. However, the degradation performances of blank (without catalysts), ZnO, Cu-ZnO (1%), Cu-ZnO (2%), Cu-ZnO (4%), and Cu-ZnO (5%) catalysts were 6, 54, 69, 83, 80, and 73%, respectively. Therefore, the use of water hyacinth plant extract with the optimum amount of Cu added to ZnO during the preparation of the catalyst could have a promising application in the degradation of organic pollutants.

Water hyacinth plant extract mediated green synthesis of Cr2O3/ZnO composite photocatalyst for the degradation of organic dye.

The Cr2O3/ZnO composite catalysts with varying the amount of chromium precursors abbreviated as 0.02CrZn, 0.04CrZn, 0.06CrZn, 0.08CrZn, 0.1CrZn, and fixed the amount of Zn precursor (0.1 M) were prepared by using water hyacinth (Eichhornia crassipes) extract as a template/capping agent. The prepared catalysts were characterized and the catalytic performances of the catalysts were also checked for the degradation of methylene blue (MB) dye. The photocatalytic MB dye degradation by 0.08CrZn catalyst was achieved and 85% of MB dye was degraded within 90 min irradiation time. However, 0.1CrZ, 0.06CrZ, 0.04CrZ, 0.02CrZ, ZnO, and Cr2O3 catalysts degrade only 80, 74, 79, 76, 52, and 74% of MB dye, respectively. The catalytic performances indicated that the addition of optimum amount of chromium precursor in the preparation of Cr2O3/ZnO composite catalysts with the aid of Eichhornia crassipes plant extract enhances the catalytic activities. This performance enhancement could be as a result of reducing the electron/hole pair separation and the porosity resulted from the plant extract in the catalyst system.

Synthesis and photocatalytic activities of a CuO/TiO2 composite catalyst using aquatic plants with accumulated copper as a template.

A CuO/TiO2 composite photocatalyst was synthesized by using a hydrolysis method. In the synthesis of the CuO/TiO2 composite catalyst, the aquatic plant Eichhornia crassipes containing accumulated copper was used and combined with titanium chloride precursor. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-Vis diffuse spectroscopy (DRS), and N2 adsorption-desorption isotherms were used for CuO/TiO2 characterization. The results showed that the CuO/TiO2 synthesized with Eichhornia crassipes as a template had smaller crystallite size (12.6 nm), higher specific surface area (109 m2 g-1), and higher pore volume (0.135 cm3 g-1). The catalytic activity of the CuO/TiO2 composite catalyst was also investigated by the degradation of phenol under ultraviolet (UV) and visible light irradiation, showing excellent catalytic activity. Complete removal of phenol was achieved at 80 and 120 min under UV and visible light sources, respectively. The catalytic performances may be due to the higher porosity and surface area of the composite catalyst. The Eichhornia crassipes aquatic plant also controls the crystal growth and prevents aggregation, which could enhance the catalytic activity. Moreover, the formation of the p-n CuO/TiO2 heterojunction also facilitates the separation of electrons and holes, and improves the photocatalytic activity of the material.

A noble bimetal oxysulfide CuVOS catalyst for highly efficient catalytic reduction of 4-nitrophenol and organic dyes.

A novel copper-vanadium bimetallic oxysulfide (CuVOS) nanoparticle catalyst was successfully synthesized by a facile method. The samples were characterized by X-ray photoelectron spectrometry (XPS), X-ray diffractometry (XRD), field-emission scanning electron microscopy (FE-SEM), UV-Vis diffuse spectroscopy (DRS), Fourier transform infrared spectroscopy (FTIR), and N2 adsorption-desorption isotherms. In order to check the catalytic efficiencies toward reduction reaction, 4-nitrophenol (4-NP) and other organic dyes such as rhodamine-B (RhB), methylene blue (MB), and methyl orange (MO) were used. The results showed that the CuVOS prepared in the presence of a suitable amount of N2H4 during the synthesis of the nanoparticles exhibited the fastest reduction capabilities by using NaBH4 as a reducing agent. It was demonstrated that a 100 mL 4-NP (20 ppm) solution was completely reduced by 5 mg CuVOS-3 within 2 min. Moreover, the complete reduction of 100 mL of MO, RhB, and MB solutions of 100 ppm was also achieved by 5 mg CuVOS-3 within 2 min, 6 min, and 5 min, respectively. Hence, the CuVOS is an efficient catalyst for reducing 4-NP and organic dyes and can have great potential for industrial application.