Photoelectrochemical splitting of water with nanocrystalline Zn1−xMnxO thin films: First-principle DFT computations supporting the systematic experimental endeavor

Photoelectrochemical splitting of water with nanocrystalline Zn_1−xMn_xO thin films was investigated. ZnO thin films with 1, 3, 5 and 7% at. Mn incorporation were synthesized by sol–gel method and characterized by X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray Photoelectron spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM) and UV–Vis spectroscopy. Mn incorporation coupled with variation in sintering temperature led to significant microstructural changes, which tentatively influenced the magnitude of optical absorption and charge carrier mobility, thereby impacting the performance of such systems towards photoelectrochemical splitting of water. Electronic structure computations based on first principle density functional theory (DFT) revealed electronic states of Mn being responsible for the marginally recorded red shift in bandgap energy. Photoelectrochemical measurements using thin films of 1% at. Mn:ZnO sintered at 600 °C yielded 3 times enhanced photocurrent at zero bias due to improved optical absorption. Plausible explanations for the effect have also been offered.     

Enhanced photoelectrochemical water splitting in hierarchical porous ZnO/Reduced graphene oxide nanocomposite synthesized by sol-gel method

Today the utilization of solar energy to split water and its conversion to hydrogen and oxygen has been considered as a powerful way to solve the environmental crisis. Hierarchical porous nanostructured ZnO and ZnO/reduced graphene oxide (rGO) composite photoanodes are synthesized by innovated sol-gel method using triethylenetetramine (TETA) as a stabilizer. The hierarchical porous ZnO structure containing large agglomerates each consisting of tiny nanoparticles are formed. The X-ray diffraction analysis and Raman spectroscopy confirm the in-situ reduction of graphene oxide sheets during synthesis and formation of ZnO/rGO nanocomposite. Although the band gap and transmittance of the porous nanocomposites do not dramatically change by rGO addition, the main photoluminescence peak quenches entirely showing prolonging exciton lifetime. The ZnO/rGO porous structure achieved remarkably improved current density (1.02 mA cm^?2 at 1.5 V vs. Ag/AgCl) in 1 wt% rGO, up to 12 times higher compared to the bare ZnO (0.09 mA cm^?2 at 1.5 V vs. Ag/AgCl), which attributes to positive role of ZnO hierarchical porous structure and rGO electron separation/transportation. These findings provide new insights into the broad applicability of this methodology for promising future semiconductor/graphene composite in the field of photoelectrochemical water splitting.     

Enhanced photocatalytic hydrogen evolution based on efficient electron transfer in triphenylamine-based dye functionalized Au@Pt bimetallic core/shell nanocomposite

An efficient photocatalytic hydrogen evolution system based on triphenylamine-based dye functionalized bimetallic Au@Pt core/shell nanocomposite (Au@Pt-TPAD) was reported. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and UV–vis absorption spectra suggested that Au@Pt-TPAD nanocomposite consisted of a bimetallic nanoparticle with Au core and Pt shell nanostructure. The photoelectrochemical result suggested that photoinduced electrons could efficiently transfer from the triphenylamine derivative molecules to the bimetallic nanoparticles. Photocatalytic results showed that the Au@Pt₂-TPAD bimetallic nanocomposite could be used as a stable photoinduced H₂ evolution photocatalyst. Compared with the monometallic counterpart (Au-TPAD or Pt-TPAD), the bimetallic nanocomposite showed much higher catalytic activity for the photocatalytic hydrogen evolution. The amount of hydrogen evolution on the optimal catalyst under 12 h UV–vis light irradiation was about 37.5 μmol. The enhancement of the photocatalytic activity might be attributed to the synergistic effect between the two metals in bimetallic nanoparticles with core/shell structure. This investigation might open up new opportunities for the development of dye functionalized heterometallic nanocomposite with enhanced photocatalytic performance.     

Structural properties and enhanced photoelectrochemical performance of ZnO films decorated with Cu2O nanocubes

Combination of ZnO and Cu₂O semiconductors is remarkable for efficient photovoltaic cells and enhanced photoelectrochemical (PEC) performance due to the high electronic energy band alignment of these materials and their controllable electronic structure at the interface. This study reports on a systematic analysis of the effects of Cu₂O nanocube doping on the structural properties and PEC performance of ZnO films. ZnO samples doped with Cu₂O were prepared by a practical electrochemical method. Characterization of the materials was performed by XRD, Raman, FTIR spectroscopy and electrochemical techniques. The XRD, Raman, FTIR spectroscopy analyses indicated a single phase of ZnO for the lower Cu₂O deposition time, while a secondary phase of Cu₂O evolved for the 5 min deposition time. This study showed that ZnO doped with Cu₂O grown for 3 min had the best PEC performance. ZnO/Cu₂O photoelectrodes are recommended as an attractive, competitive and alternative candidate for advanced PEC sensing and this may be for the extended field of water splitting into oxygen and hydrogen under sunlight.     

Synthesis of uniform ZnO/ZnS/CdS nanorod films with ion-exchange approach and photoelectrochemical performances

The uniform ZnO/ZnS/CdS core–shell nanorod film was synthesized by a two-step ion-exchange method. The crystal structure, morphology, composition and optical property of as-prepared films were characterized by X-ray diffraction (XRD), Raman, Scanning electron microscope (SEM), Transmission electron microscope (TEM), Energy dispersive X-ray Detector (EDX) and UV–vis techniques. The results showed that the ZnO nanorod arrays can be used as sacrificial templates to synthesize uniform ZnS layer and further transform into CdS by simple ion-exchange approach. The CdS content in the films can be adjusted easily by changing the reaction temperature. The intimate contact between core and shell can be observed by high-resolution TEM image, which decrease the crystal boundary potential barrier and then facilitate the photogenerated charges transfer between the different phases. In this experiment, the ZnO/ZnS/CdS nanorod films were used in the photoelectrochemical (PEC) hydrogen production. And it is found that the film prepared at 70 °C (first step) and 100 °C (second step) gives a maximum photocurrent density and photo conversion efficiency.     

ZnO/Cu2O-decorated rGO: Heterojunction photoelectrode with improved solar water splitting performance

In present work, we report a facile fabrication process to improve the photoelectrochemical (PEC) performance of ZnO-based photoelectrodes. In order to achieve that, the Cu₂O nanocubes are cathodic-deposited on the as-prepared ZnO nanorods. Then rGO nanosheets are electrodeposited on the ZnO/Cu₂O heterostructures. The fabricated photoelectrodes are systematically studied in detail by different characterization techniques such as powder X-ray diffraction, micro-Raman, X-ray photoelectron spectroscopy, ultraviolet diffused reflectance spectroscopy and photoluminescence spectroscopy analysis. Morphologies of the fabricated photoelectrodes are investigated through electron microscopy in scanning and transmission mode. To evaluate the PEC performance of the fabricated photoelectrodes, the line scan voltammetry (LSV) measurement is performed using a three-electrode system in 0.5-M Na₂SO₄ electrolyte solution under stimulated light illumination at 100 mW/cm² from a 300-W Xenon Arc lamp coupled with an AM 1.5G filter using a three-electrode system. The photocurrent measurement demonstrates that the photoelectrodes based on ZnO/Cu₂O/rGO possess enhanced PEC performance compared to the pristine ZnO and ZnO/Cu₂O photoelectrodes. The photocurrent density of ZnO/Cu₂O/rGO-15 photoelectrode (10.11 mA/cm²) is ∼9 and ∼3 times higher than the photoelectrodes based on pristine ZnO (1.06 mA/cm²) and ZnO/Cu₂O (3.22 mA/cm²). The enhanced PEC performance of ZnO/Cu₂O/rGO photoelectrode is attributed to the excellent light absorption properties of Cu₂O and excellent catalytic and charge transport properties of rGO. Experimental results reveal that the proposed functional nanomaterials have a great potential in water splitting applications.     

Photocatalytic activity of Ag–TiO2-graphene ternary nanocomposites and application in hydrogen evolution by water splitting

TiO₂-graphene (P25-GR, PG) nanocomposite was fabricated with P25 and graphite oxide through a hydrothermal method, and then Ag nanoparticles (Ag NPs) was assembled in P25-GR (Ag-P25-GR, APG) under microwave-assisted chemical reduction. The prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscopy (TEM), photoluminescence spectrum (PL), UV–vis absorption spectrum (UV–vis) and Raman spectrum, respectively. The results showed that Ag NPs were well dispersed on the surface of PG with metallic state. The ternary Ag-P25-GR (APG) nanocomposites possessed the extended light absorption range and more efficient charge separation properties compared to binary P25-GR (PG). Methylene blue photodegradation experiment proved that surface plasmon resonance (SPR) phenomenon had an effect on photoreaction efficiency. The corresponding hydrogen evolution rate of APG prepared with 0.002 M AgNO₃ solution was 7.6 times than pure P25 and 2.7 times than PG in the test condition. The improved photocatalytic performance can be attributed to the presence of GR and SPR effect, leading to the longer lifetime of photo-generated electron–hole pairs and faster interfacial charge transfer rate. This work indicates that the photoactivity of ternary GR-based nanocomposites is superior to the binary one. We expected our work could give a new train of thought on exploration of GR-based nanocomposites.     

Electronic structure and water splitting under visible-light irradiation of Zn and Ag co-doped In(OH)ySz photocatalysts

Zinc and silver co-doped In(OH)_yS_z with nanocubic blocks morphology were prepared by a one-step hydrothermal method and their photocatalytic activities were investigated. The as-synthesized products were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) and UV–visible spectroscopy. The electron microscope observations revealed that the particle sizes of Zn-doped In(OH)_yS_z crystals were smaller than that of the non-doped In(OH)_yS_z, which accords with BET results. While Zn–Ag co-doped In(OH)_yS_z showed the nanocubic blocks with different particle sizes. The UV–vis spectra indicate that the single Zn ions doping leads to the absorbance band shifts toward lower wavelength upon increasing the Zn doping. Consequently, the band gap of In(OH)_yS_z also increases gradually with increasing the Zn doping. In contrast, an obvious red-shift is observed for Zn–Ag co-doped In(OH)_yS_z solid solution, which mainly attributed to the transition from Ag 4d + S 3p orbitals to Zn 4s + In 5s orbitals. The sample doped with 4 mol% Ag and Zn was found to have the highest activity, which is 20 times that of the In(OH)_yS_z.     

Visible light driven nanocrystal anatase TiO2 doped by Ce from sol–gel method and its photoelectrochemical water splitting properties

Visible light driven nanocrystal anatase TiO₂ was prepared by doping rare earth element Ce through sol–gel method. UV–Vis diffusion reflectance spectrum indicated its absorption edge extended to about 550 nm, red shifting about 170 nm compared with that without doping. Ce doping TiO₂ showed obvious anodic photocurrent effect for water splitting under visible light irradiation (λ > 420 nm) in photoelectrochemical measurement with three electrodes configuration. Ce doping TiO₂ showed higher photocurrent density than that of without doping TiO₂ under full arc irradiation. Furthermore, the electronic structures for CeO₂ and TiO₂ were analyzed theoretically based on the first principle calculation. As a result, the electronic structure for Ce doping TiO₂ is proposed as the overlap and some degree of hybridization among splitting occupied Ce 4f and unoccupied Ce 4f with O 2p and Ti 3d respectively. The visible light responsive property is mainly due to the transition from O 2p hybridizing with occupied Ce 4f to unoccupied Ce 4f overlapping with Ti 3d.     

Nanostructured Ti-doped hematite (α-Fe2O3) photoanodes for efficient photoelectrochemical water oxidation

We present a form of hematite (α-Fe₂O₃) nanostructured architecture suitable for photoelectrochemical water oxidation that is easily synthesized by a pulsed laser deposition (PLD) method. The architecture is a column-like porous nanostructure consisting of nanoparticles 30–50 nm in size with open channels of pores between the columns. This nanostructured film is generated by controlling the kinetic energy of the ablated species during the pulsed laser deposition process. In a comparison with the nanostructured film, hematite thin film was also synthesized by PLD. All of the developed films were successfully doped with 1.0 at% of titanium. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and UV–visible spectroscopy were used to characterize the films. To fabricate the photoelectrochemical (PEC) cell, Ti-doped hematite films were used as the working electrode, Ag/AgCl as the reference electrode, platinum wire as the counter electrode and an aqueous solution of 1 M NaOH as the electrolyte. The photovoltaic characteristics of all cells were investigated under AM 1.5G sunlight illumination of 100 mW/cm². The photocurrent density was enhanced by approximately 220% using nanostructured film at 0.7 V versus Ag/AgCl compared to hematite thin film, and the highest photocurrent density of 2.1 mA/cm² at 0.7 V/Ag/AgCl was obtained from the 1.0 at% Ti-doped hematite nanostructured film. The enhanced photocurrent density is attributed to its effective charge collection due to its unique column-like architecture with a large surface area.     

Estimation of electrochemical charge storage capability of ZnO/CuO/reduced graphene oxide nanocomposites

Nanocomposites of ZnO/CuO with rGO were synthesized using sonochemical and thermal treatment methods. The formation of ZnO and CuO phases on the rGO sheets and both ZnO/CuO in the ternary component nanocomposites were confirmed from IR spectroscopy and X-ray photoelectron spectroscopy. The microstructure of the nanocomposites as revealed by TEM and FE-SEM suggested that CuO was decorated as nano-rods, whereas ZnO particles retained the spherical shape. In case of ternary nanocomposite, both nano-rods and spherical particles were agglomerated on the rGO sheets. The pseudocapacitive behavior of ZnO-rGO nanocomposite corresponded to relatively higher specific capacitance (344.6 F/g) compared with other nanocomposites. The galvanostatic cyclic charge/discharge (GCD) tests also confirmed that ZnO-rGO nanocomposite could provide the highest specific energy (21.7 Wh/kg) and power density (129.8 kW/kg) at 0.4 A/g compared with CuO-rGO and ZnO/CuO-rGO.     

Cu–MoS2/rGO hybrid material for enhanced hydrogen evolution reaction performance

Cu doped MoS₂ (Cu–MoS₂)/reduced graphene oxide (rGO) (Cu–MoS₂/rGO) hybrid material is fabricated by a facile one-step solvothermal method. The X-ray diffraction (XRD) results suggest that the doping of Cu does not alter the crystal structure of MoS₂. X-ray photoelectron spectroscopy (XPS) analysis reveal that the doping of Cu atoms influences the electronic structure of MoS₂, which is favorable to increase active sites of edges. Electrochemical impedance spectroscopy (EIS) results indicate that Cu–MoS₂/rGO performed a faster charge-transfer in comparison to MoS₂/rGO hybrid. In addition, the resultant Cu–MoS₂/rGO catalyst with Cu/Mo mole ratio of 9% exhibits a lower overpotential of 199 mV at 10 mA cm⁻², small Tafel slop of 44 mV dec⁻¹ and cycling stability, indicative of enhanced electrocatalytic activity towards HER. The improved performance is attributed to the increased active sites and a synergistic effect between copper and molybdenum, leading to electronic structure change and charge redistribution of MoS₂.     

Solvothermal synthesis of SnNb2O6 nanoplates and enhanced photocatalytic H2 evolution under visible light

Well-defined SnNb₂O₆ nanoplates are synthesized here by a facile template-free solvothermal route in a mixed solvent of water and ethanol without an organic surfactant. The synthesized nanoplates have widths ranging from 200 to 400 nm and thicknesses in a range of 20–30 nm. The nanoplates were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), UV–Vis spectroscopy, Raman spectrometry, and by the Brunauer–Emmett–Teller method. The variation of the lattice parameters and the optical properties of the nanoplates were discussed in detail based on the crystal and electronic structure. The SnNb₂O₆ nanoplates exhibited greatly enhanced photocatalytic activity in terms of the reduction of water for H₂ generation under visible light irradiation as compared to the same compound prepared by a solid–state reaction method. This was mainly attributed to its higher surface area and extremely high two-dimensional anisotropy, which provided a short migration distance along the thickness direction.     

Photoelectrocatalytic degradation of amoxicillin over quaternary ZnO/ZnSe/CdSe/MoS2 hierarchical nanorods

Quaternary semiconductor film consists of ZnO, ZnSe, CdSe and MoS₂ was designed to establish a core-shell structure to achieve the photoelectrochemical oxidation of amoxicillin. The hybrid photoelectrode was fabricated on a FTO substrate from bath deposition methods. The hierarchical ZnSe/CdSe/MoS₂ shell was covered uniformly on ZnO nanorod core which provided a direct pathway for electron transfer, large surface area to enhance light absorption and increase active sites. The quaternary photoelectrode exhibited a photocurrent density of 26.86 mA/cm² at 0 V vs. Ag/AgCl under UV–visible light illumination, which was 31.9 times, 16.7 times and 1.6 times of that of the bare ZnO nanorods, binary ZnO/ZnSe and ternary ZnO/ZnSe/CdSe photoelectrodes, respectively. 10 ppm of amoxicillin was completely degraded in 30 min by the quaternary working electrode with an applied bias of 0.5 V vs. Ag/AgCl. The reusability and stability of quaternary electrode was demonstrated by 3-run recycling experiments. The enhanced photoelectrochemical performance of quaternary photoelectrode can be attributed to the enhancement of light absorption and increased active sites from the coverage of visible-active layers, the accelerated charge separation from the formation of p-n junction and reduced photocorrosion of CdSe from the protection of MoS₂ on the surface.     

Z-scheme heterojunction ZnSnO3/rGO/MoS2 nanocomposite for excellent photocatalytic activity towards mixed dye degradation

In this work, a novel (ZnSnO₃/rGO/MoS₂) nanocomposite was prepared and its photocatalytic performances were investigated. The synthesised ZnSnO₃ spheres were well dispersed over the surface of rGO sheet and MoS₂ layers (ZSGM). The structural, morphological and elemental properties of the composites were examined by XRD, SEM, HRTEM and EDS. The surface chemical composition and functional groups of the elements interlinked in the composites were identified from XPS and FTIR analysis. BET and Raman analysis indicate the effective formation between MoS₂/rGO/ZnSnO₃ ternary heterostructure nanocomposite. The suppressed photogenic charge carrier's recombination rate was investigated by PL analysis. From UV analysis, the bandgap of ZSGM nanocomposite was successfully tuned from 3.13 eV to 2.70 eV, leading to high photocatalytic performance by mixed dye pollutant under UV-visible light illumination. The ZSGM photocatalyst achieved highest removal rate of 0.0131 min^?1 for Rh B degradation, and 0.0153 min^?1 for MB dye degradation and efficiency was 78% (Rh B) and 86% (MB), respectively in 100 min, which shows dramatically enhanced activity than other samples. In the presence of rGO/MoS₂ in ZS, ZSGM photocatalysts exhibit higher catalytic activity due to a lower bandgap, more absorption in the visible region, and suppressed recombination rate of photogenerated e^?/h⁺ pairs.     

Photoelectric properties of BiVO4 thin films deposited on fluorine doped tin oxide substrates by a modified chemical solution deposition process

BiVO₄ films deposited on Fluorine doped tin oxide glass substrates were successfully prepared by a modified chemical solution deposition process. Structure and optical spectrum analysis show that the resultant BiVO₄ films consist entirely of monoclinic scheelite structure and have a narrow band gap of ～2.66 eV. The films were investigated by photoelectrochemical and photovoltaic measurements with regard to hydrogen production and solar energy conversion under visible light. The BiVO₄ photoanodes show significantly higher visible light induced photoelectrochemical performance (～1.1 mA/cm² at 1.0 V vs. Ag/AgCl) than those reported ones, which is very promising for splitting water to H₂ and O₂. A Schottky BiVO₄ solar cell was also investigated for comparison with photoelectrochemical measurements. The correlation between the photoelectrochemical and photovoltaic behavior for BiVO₄ was explained. Our research should provide important support for the applications of BiVO₄ films or its modified forms such as doping and nanocomposite in heterojunction photoelectrochemical cells and solar cells with suitable energy level alignment at the interface.     

Photoelectrochemical and structural characterization of carbon-doped WO3 films prepared via spray pyrolysis

Carbon-doped tungsten trioxide (WO₃) films were produced using a spray-pyrolysis methodology, with glucose used as the carbon dopant source. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV–vis, scanning electron microscopy, and solid-state nuclear magnetic resonance. The photoelectrochemical activity was evaluated under near UV–visible light and visible light only irradiation conditions. The presence of carbonate-type species in the C-doped sample was confirmed by XPS and SSNMR. The C-doped WO₃ electrodes exhibited photocurrent densities up to 1.6 mA/cm² in 1 M HCl electrolyte and as high as 2.6 mA/cm² with the addition of methanol as a sacrificial agent. A high contribution (∼50%) of the photocurrent density was observed from visible light. C-doped WO₃ produced approximately 50% enhanced photocurrent densities compared with the undoped WO₃ electrode synthesized using the same procedures. The photoelectrochemical performance was optimized with respect to several synthetic parameters, including dopant concentration, calcination temperature and film thickness. These results indicate the potential for further development of WO₃ photocatalysts by simple wet chemical methods, and provide useful information towards understanding the structure and enhanced photoelectrochemical properties of these materials.     

Factors affecting the production of H2 by water splitting over a novel visible-light-driven photocatalyst GaFeO3

A d¹⁰ photocatalyst, GaFeO₃ having a band gap of ∼2.7 eV, exhibits significant activity for the overall splitting of water under visible light (>395 nm) irradiation, in the absence of sacrificial reagent or a noble metal co-catalyst. The doping of an anion led to considerable enhancement in activity, the S-doped catalysts displaying better activity compared to the samples containing nitrogen. Even though the H₂/O₂ yields were affected by preparation-dependent grain morphology, no direct relationship was observed between the photoactivity of a sample and its specific surface area. The techniques of HRTEM, SEM, XPS, Laser Raman, UV–visible and photoluminescence spectroscopy have enabled to demonstrate that, besides the grain morphology, certain lattice imperfections and microstructure may also play a crucial role in water splitting activity of a photocatalyst. The factors responsible for catalyst deactivation are examined.     

Vertically-heterostructured TiO2-Ag-rGO ternary nanocomposite constructed with {001} facetted TiO2 nanosheets for enhanced Pt-free hydrogen production

TiO₂ nanosheets with high ratio of {001} facets were coupled with reduced graphene oxide (rGO) nanosheets through the link of silver (Ag) nanoparticles, forming a novel ternary nanocomposite photocatalyst with a vertical heterostructure, TiO₂-Ag-rGO. The vertical anchoring of TiO₂-Ag nanosheets between rGO sheets was confirmed by transmission electron microscopy (TEM), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Due to excellent separation of electron-hole pairs in the TiO₂ nanosheets, enhanced electron transfer to rGO via Ag nanoparticles, the TiO₂-Ag-rGO nanocomposite exhibited an outstanding performance in photocatalytic hydrogen production, with a hydrogen production rate of 593.56 μmol g^?1 h^?1. This study provides new insights to the development of Pt-free photocatalysts for hydrogen production.     

Cd1−xZnxS supported on SBA-16 as photocatalysts for water splitting under visible light: Influence of Zn concentration

Cd_1−xZn_xS solid solutions (x = 0.05–0.3) supported on mesoporous silica SBA-16 substrate with 3D cubic structure were investigated for hydrogen production from water splitting under visible light. The influence of Zn concentration (x) in the Cd_1−xZn_xS solid solution and support morphology were investigated. The bare SBA-16 substrate was synthetized by the hydrothermal method whereas the Cd_1−xZn_xS photocatalysts were prepared by coprecipitation of metal sulfides from aqueous solutions of Cd²⁺ and Zn²⁺ using Na₂S as precipitating agent. An attempt has been made to determine the photocatalyst structures using several techniques including elemental analysis, N₂ adsorption–desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS) and Raman spectroscopy. Surface characterization of the samples by XPS indicates that Cd_1−xZn_xS nanoparticles are unevenly distributed on both external surface and within the pore network. An increase of the band gap energy with increasing Zn loading up to x = 0.2 in the Cd_1−xZn_xS solid solution was observed. As a consequence, H₂ evolution increases gradually with an increase of the Zn loading in the photocatalysts from 0.05 to 0.2 wt% being the Cd_0.8Zn_0.2S/SBA-16 system the most active among the catalysts studied. The highest activity of this photocatalyst was explained in terms not only of its large band gap energy but also by the enhancement of the interaction between the particles of solid solution and the SBA-16 substrate.