Conduction Band Potential Research Articles

G-C3N4/PP-CDs Heterostructure with Lewis acidity and alkalinity promoted photocatalytic CO2 reduction to CH3OH

It is expected that photocatalytic reduction of carbon dioxide to produce valuable chemicals play an important role in achieving carbon neutrality goals. Photogenerated electron-hole separation efficiency is one of the factors determining photocatalytic activity. Herein, carbon dots with oxygen-containing protoporphyrin (PP-CDs) were loaded on g-C3N4 nanosheets form a heterostructure by a facile mechanical stirring method. The g-C3N4/PP-CDs-3 has a conduction band potential of −1.31 eV and a bandgap of 2.51 eV, in the absence of any added photosensitizer and sacrificial agent under illumination, the methanol yield achieved 357.5 μmol·g−1·h−1, which is 2.2 times than that of g-C3N4 (162.1 μmol·g−1·h−1), after four cycles, the photocatalytic activity remained unchanged. Based on the experimental and characterizations results, it is indicated that the photocatalytic reduction performance of CO2 to methanol was improved mainly attributed to the visible light absorption and the high Lewis acidity and alkalinity. Furthermore, the steric hindrance was provided for photogenerated electron-hole recombination due to the recombination of carbon points his work offers a promising strategy for constructing efficient photocatalysts to achieve CO2 to CH3OH transformation.

Enhanced piezocatalytic RhB degradation with ZnSnO3 Nanocube-modified Bi4Ti3O12 composite catalyst by harnessing ultrasonic energy

With the increasing demand for effective methods to address environmental pollution, piezocatalysis has emerged as a promising approach for pollutant degradation under mechanical energy. However, the development of highly efficient piezocatalytic materials remains a challenge. This study aimed to increase the piezocatalytic activity of bismuth titanate (Bi4Ti3O12) by modifying it with zinc stannate (ZnSnO3) nanocubes. The composite catalysts were synthesized using a straightforward deposition and calcination process. The calcination process ensured the tight adhesion of ZnSnO3 nanocubes to the Bi4Ti3O12 surface, while facilitating strong interactions between ZnSnO3 and Bi4Ti3O12, which enhanced electron transfer and heterojunction structure formation. Band structure analysis indicated that Bi4Ti3O12 has higher conduction band and valence band potentials than ZnSnO3, forming a type-II heterojunction. Bi4Ti3O12 possesses a higher Fermi level than ZnSnO3, resulting in interfacial electron drift and formation of a built-in electric field, which further promotes the directional transfer and separation efficiency of charge carriers within the composite catalyst. This hypothesis was confirmed by surface photovoltage spectroscopy, piezoelectric current response, and electrochemical analysis. Consequently, the ZnSnO3/Bi4Ti3O12 composite exhibited significantly improved piezocatalytic performance in RhB degradation, achieving a degradation efficiency of 80 % within 90 min under ultrasonic vibration. The degradation rate of the optimal sample was 8.2 times that of Bi4Ti3O12 and 6.3 times that of ZnSnO3. Additionally, experiments to detect reactive species were conducted to elucidate the mechanism behind the piezocatalytic RhB degradation. Holes and hydroxyl radicals were the main reactive species. This study may offer new insights into the design of efficient piezocatalytic materials.

Novel CoFe2O4 / LaAlO3 nanocomposites: An impressive photocatalyst with p-n hetero-junction for improved H2 generation under visible exposure

The present work is devoted to the synthesis of perovskite LaAlO3 by Sol-Gel approach and its application for the photo-evolution of H2 in conjunction with cobalt ferrite CoFe2O4 prepared by nitrate route. The thermal analysis (TG/DSC) showed that the formation is completed at 600 °C. The X-ray diffraction (XRD) pattern is characteristic of a single phase, crystallizing in a rhombohedral symmetry with a crystallite size of 36 nm. The SEM micrographs revealed a homogeneous structure with an agglomeration of shaped grains (40–80 nm). The forbidden band (3.39 eV), calculated from diffuse reflectance data, is assigned to the ligand charge transfer O2−: 2p → Al3+: 3s orbital. As prepared, LaAlO3 is an n-type semiconductor as demonstrated from the capacitance - potential (C−2 - E) graph with an electron density of 9.4 × 1014 cm−3 due to oxygen under-stoichiometry. Attention was directed to photo-electrochemistry in connection with water reduction into hydrogen. With a negative conduction band potential (−0.11 VSCE), H2 generation can be synergized over the hetero-system by visible light. The photocatalytic capability of CoFe2O4 25%/LaAlO3 revealed a high H2 generation of 963 μmol g−1 in the alkaline electrolyte (NaOH, 0.1 M) with a catalyst dose of 1 mg mL−1, which is 1.3 times more than CoFe2O4 under similar conditions. Photoactivity is significantly improved by 60%, up to 2400 μmol g−1 in the presence of oxalate C2O42− as a hole scavenger in the hetero-junction, two hydrogen release tests were successfully recorded. The higher H2 production in the hetero-junction system is attributed to the lower recombination rate of electron/hole (e−/h+) in the material, due to the large band bending at the solid interfacial.

1O2‐Mediated Selective Oxidation of 5‐hydroxymethylfurfural to 2,5‐diformylfuran by Ag/Ag3PO4 under Visible Light Irradiation

AbstractThe synthesis of 2,5‐diformylfuran (DFF) through photocatalytic oxidation of 5‐hydroxymethylfurfural (HMF) is an attractive approach. In this manuscript, a photocatalytic selective oxidation strategy for HMF was developed, using Ag/Ag3PO4 as the photocatalyst and O2 as the oxidizing agent. The prepared catalyst was characterized systematically by SEM, XRD, XPS, UV‐Vis, PL spectra, and so on. In contrast to previous photocatalytic oxidation strategies for HMF conversion, this catalytic system could efficiently generate 1O2 without other reactive oxygen species (ROS) under visible light irradiation. DFF would be obtained with about 90 % selectivity. Moreover, the exclusive formation of 1O2 was linked to the more positive conduction band potential (+0.90 eV) of Ag/Ag3PO4, confirmed by an array of characterization techniques. Additionally, the stability of the catalyst was assessed through cyclic testing and analyses including XRD, and XPS. Nonetheless, this catalytic system could potentially serve as a robust platform for various selective oxidation reactions in the future, due to its exclusive presence of 1O2 without the involvement of other ROS.

Facilitating charge transport by phenyl-substitution and sulfate-intercalation on carbon nitride tubes for highly efficient photocatalytic hydrogen evolution

Despite challenges still remain, simultaneous regulation of light absorption, carrier separation and efficient exposed active sites of carbon nitride for the photocatalytic production of hydrogen (H2) are essential to help alleviate the energy crisis and achieve carbon neutrality. Using in-plane phenyl groups doping and interlayer sulfate groups modification, we demonstrated an eco-friendly and facile method for excogitating porous tubular graphitic carbon nitride (PhSO-TCN2.5). The PhSO-TCN2.5 has hollow tubular morphology with ultrathin pore walls, which offers more exposed active sites, shortened charge diffusion path and readily available diffusion channels. More importantly, the in-plane phenyl groups doping and interlayer sulfate groups modification enabled significant intense the visible light absorption, accelerated carrier transfer due to the electron transport channel between the interlayers. Meanwhile, PhSO-TCN2.5 possesses exceptionally adjusted band gap structure and more negative conduction band potential. Accordingly, the above synergistic effects contribute to the efficient photocatalytic efficiency in H2 evolution to 8709.29 μmol g−1 h−1. In addition to the apparent quantum yield of 12.0% at 420 nm, that far exceeds the reported tubular and functional group-modified carbon nitride photocatalysts. This document offers guidance on designing and producing photocatalysts with high efficiency.

Graphitic carbon nitride loaded with FeOOH quantum dots for synergistic photocatalysis-Fenton inactivation of pathogenic marine bacteria: Mechanisms and coupling coefficients

Sustainable and environmental benign technologies for inactivation of pathogenic marine bacteria in ballast water remains a challenge. Herein, graphitic carbon nitride (g-C3N4) loaded with FeOOH quantum dots (QDs) were fabricated and a synergistic photocatalysis-Fenton system was established, which inactivated Vibrio alginolyticus (7 log) in ballast water within 30 min under visible light irradiation. The bacterial inactivation rate constant in the coupling system was 26.5 and 6.6 times higher than traditional photocatalysis and Fenton system, respectively, exhibiting 88.8 % of synergistic coupling coefficient. The bactericidal efficiency remained consistent across varying pH levels, allowing direct application of this method in alkaline marine conditions. Free radicals including OH and O2− were proved to be the predominant contributors in the coupling system. The loading of FeOOH QDs could upshift conduction band potential of g-C3N4, thus photogenerated electrons were more easily trapped by O2 to enhance the separation of charge carriers. The photogenerated electrons also accelerated the faster circulation of Fe(III)/Fe(II), which further inhibited electron-hole recombination. Furthermore, bacterial inactivation mechanisms were elucidated by examining total protein changes, intracellular ROSs level and enzyme activities. This work offers innovative approaches for marine bacterial inactivation and ballast water disinfection, which can also find applications in other environmental-related fields.

Enhanced terahertz ISBT in GaAsBi/AlGaAs quantum well: impact of doping modulation

One of the pivotal characteristics of quantum wells (QW) designed for applications in filters or modulators is its absorption coefficient. This study investigates the combined influence of doping and active layer thickness on the absorption coefficient in GaAsBi/AlGaAs quantum wells. The self-consistent coupling between Schrödinger and Poisson equations was employed for this purpose. A comprehensive analysis of conduction band structure, energy levels, potentials, and densities is presented. This analysis discerns the effects of doping on intersubband transitions (ISBTs) in the terahertz (THz) frequency domain. An introduction of a donor impurity into the system greatly influenced the intersubband absorption coefficient, increasing its intensity and causing the optical response to shift toward the lowest frequency. The obtained resonant peak energies, situated within the terahertz spectrum, hint at promising applications for GaAsBi-based devices within this frequency band.

Full prediction of band potentials in semiconductor materials

A machine learning (ML) framework to predict the physical band potentials for a range of semiconductor materials, from metal sulfide, oxide, and nitride, to oxysulfide and oxynitride, is hereby described. A valence band maximum (VBM) model was established via the transfer learning of a large dataset of 2D materials (1382 samples, but with incorrect VBM potentials) onto a much smaller dataset of physically measured VBM for bulk 3D materials (87 samples) on a crystal graph convolutional neural network. This resulted in predictions with experimental accuracy (RMSE = 0.27 eV), which is a 3-fold improvement compared with ML trained on the physical dataset without transfer learning (RMSE = 0.75 eV). When combined with the bandgap prediction model (RMSE = 0.29 eV), a full prediction of conduction and valence band potentials can be made, which to the best of our knowledge, is the first for any ML framework. The variation of band potentials across low-index surfaces was predicted correctly and verified with reported physical potentials. In fact, the framework is able to capture variation in band potentials associated with minor atomic position alterations. Based on this, a general trend between surface atomic displacement and VBM shift was observed across various semiconductor materials. The model is not yet able to cope with major rearrangement of atomic sequence on surface layers, i.e., surface reconstructions, since it was not trained with such data but can be easily done so with specifically designed dataset. As an example application, the ML framework was used for the screening of potential photocatalytic materials for visible light water splitting. A total of 824 materials was successfully identified, including those experimentally-verified in the literature.

Comparative study of physical properties of As2Se3 and (As2Se3)90Ge10 glassy alloys doped with metallic impurities

To examine the compositional and chemical effects on the glassy system, one must first understand its network structure. Alloying glassy systems cause significant conformal and configurational changes. The optical and physical parameters of As2Se3 and (As2Se3)90Ge10 glassy alloys doped with metallic impurities (X = Bi, Cd, Pb, Sb) have been evaluated. A comparison of the physical properties of glassy alloys has been made as the doping elements increase, i.e., from binary to ternary to quaternary system, and an effort has been made to correlate the optical and physical parameters. The optical density (Dop) and penetration depth (δ) have been calculated from the reported absorption coefficient (α) data. The mean coordination number (<r>) and the number of floppy modes (Mf) calculations show that the floppy regions are decreasing, and hence, the rigidity is increasing when As–Se is doped with Ge and As–Se-Ge is doped with X. The density (ρ) and packing density (PD) have also been evaluated, which are interrelated to the parameters like refractive index (n) and δ. Cohesive energy (CE), mean bond energy (<E>), and glass transition temperature (Tg) values give an insight into the stability and average crosslinking of the system with alloying. The conduction and valence band potentials have supported the optical bandgap (Egopt) values variation.

Halogen-functionalized covalent organic frameworks for photocatalytic Cr(VI) reduction under visible light

Covalent organic frameworks (COFs) are a type of novel organic catalysts which show great potential in the treatment of environmental contaminations. Herein, we synthesized three isoreticular halogen-functionalized (F, Cl and Br) porphyrin COFs for visible-light (420 nm ≤ λ ≤ 780 nm) photocatalytic reduction of Cr(VI) to Cr(III). Halogen substituents with tunable electronegativity can regulate the band structure and modulate the charge carrier kinetics of COFs. In the absence of any sacrificial reagent, the isoreticular COFs exhibited good photocatalytic reduction activity of Cr(VI). Particularly, the TAPP-2F showed nearly 100 % conversion efficiency and the highest reaction rate constants (k) on account of the strong electronegativity of F substituent. Experimental results and theoretical calculations showed that the conduction band (CB) potentials of COFs became more negative and charge carrier separation increased with the enhancement of electronegativity (Br < Cl < F), which could provide sufficient driving force for the photoreduction of Cr(VI) to Cr(III). The halogen substituents strategy for regulating the electronic structure of COFs can provide opportunities for designing efficient photocatalysts for environmental remediation. Meanwhile, the mechanistic insights reported in this study help to understand the photocatalytic degradation pathways of heavy metals.

Enhancing photoelectrocatalytic efficiency by tuning graphitic carbon nitride characteristics for production of heterojunctions with W-BiVO4

The escalating interest in utilizing solar energy for photocatalytic applications to address energy crises has spurred extensive research in developing efficient systems. Monoclinic BiVO4 is known for its superior photocatalytic capabilities; however, challenges like a high recombination rate and an unsuitable conduction band potential for the hydrogen evolution reaction limit its application. To overcome these challenges, doping BiVO4 with W (WB) and forming heterojunctions with graphitic carbon nitride (g-C3N4) are promising strategies to reduce charge recombination and increase visible light sensibility. This study shows that the hydrothermal treatment of g-C3N4 modifies its morphology and interaction with BiVO4 and W-BiVO4. Notably, our findings reveal a significant difference in the photoresponse between the combination of W-BiVO4 with g-C3N4, produced upon hydrothermal treatment (MHWB), and the combination with g-C3N4 produced without hydrothermal treatment (MDWB). The MHWB combination enhances the photoresponse by twice. Also, MHWB shows a higher activity for photocatalytic degradation of tetracycline.

Cu2O photocathodes prepared by thermal reduction of CuO: Influence of O2 concentration on photocurrent stability

Copper oxide (CuO and Cu2O) p-type semiconducting photocathodes have gained attention for hydrogen production (proton reduction), due to their appropriate conduction band potentials and light sensitivity in the visible. However, photocorrosion is the main handicap for both compounds. In this work, the transformation of CuO layers deposited via spray pyrolysis on conductive FTO (fluorine doped tin oxide on glass) into Cu2O via thermal reduction was studied. Optimal conditions for obtaining Cu2O were found by in situ temperature-controlled XRD. Synthesis of Cu2O films was finally carried out under moderate temperature and vacuum conditions (380 °C, 1·10−2 mbar). The influence of 3 different oxygen concentration in the electrolyte on the stability of the Cu2O electrodes under light and electrical bias was studied, and it was found that the O2 content had a high impact on the photoelectrochemical performance of Cu2O electrodes. The stability of the electrodes against self-reduction was demonstrated.

Bimetallic NH2-MIL-101(Fe, Co) as highly efficient photocatalyst for nitrogen fixation

Developing effective catalysts for N2 photofixation at ambient conditions is highly desirable but still challenging. Herein, we reported a novel Co-doped NH2-MIL-101(Fe) (NM-Fe) bimetallic organic framework (BMOF) for visible-light-driven catalytic N2 fixation. It was found that the doping of Co ions could effectively enhance light-harvesting, reduce the conduction band potential, suppress the recombination of photogenerated carriers, and promote the activation of N2. Consequently, the photocatalytic N2 reduction efficiency of bimetallic NH2-MIL-101(Fe, Co) (NM-Fe-Co) was obviously boosted. The sample with the optical Co/Fe molar ratio of 0.15, namely NM-Fe-0.15Co, enabled an ammonia evolution rate up to 335.7 µmol g−1 h−1 without the aid of any sacrificial agents, a 4.4-fold increase over the monometallic NM-Fe baseline. Additionally, the bimetallic NM-Fe-Co displayed excellent stability. The possible reaction mechanism of nitrogen fixation over NM-Fe-Co was proposed based on in-situ infrared analysis. Our study demonstrates a promising strategy for designing potent MOF-based catalysts for N2 photofixation.

Photocatalytic Optical Hollow Fiber with Enhanced Visible-light-driven CO2 Reduction.

A visible-light-driven CO2 reduction optical fiber is fabricated using graphene-like nitrogen-doped composites and hollow quartz optical fibers to achieve enhanced activity, selectivity, and light utilization for CO2 photoreduction. The composites are synthesized from a lead-based metal-organic framework (TMOF-10-NH2) and g-C3N4 nanosheet (CNNS) via electrostatic self-assembly. The TMOF-10-NH2/g-C3N4 (TMOF/CNNS) photocatalyst with an S-type heterojunction is coated on optical fiber. The TMOF/CNNS coating, which has a bandgap energy of 2.15eV, has good photoinduced capability at the coating interfaces, high photogenerated electron-hole pair yield, and high charge transfer rate. The conduction band potential of the TMOF/CNNS coating is more negative than that for CO2 reduction. Moreover, TMOF facilitates the CO desorption on its surface, thereby improving the selectivity for CO production. High CO2 photoreduction and selectivity for CO production is demonstrated by the TMOF/CNNS-coated optical fiber with the cladding/core diameter of 2000/1000µm, 10 wt% TMOF in CNNS, coating thickness of 25µm, initial CO2 concentration of 90 vol%, and relative humidity of 88% RH under the excitation wavelength of 380-780nm. Overall, the photocatalytic hollow optical fiber developed herein provides an effective and efficient approach for the enhancement of light utilization efficiency of photocatalysts and selective CO2 reduction.

Ligand-controlled photocatalysis of sulfur dots/MoS2 nanocomposite for degradation of dye and antibiotic

Manipulating surface organic ligands has emerged as a useful strategy to enhance the efficiency of catalysis. Here, a novel photocatalyst of S dots/MoS2 nanocomposite with the ligand of polyethylene glycol 400 (PEG) or poly (sodium-p-styrenesulfonate) (PSS) was synthesized. Compared to pure S dots and MoS2, S dots/MoS2 nanocomposite modified with PEG inhibited the photocatalytic activity, while the S dots/MoS2 nanocomposite modified with PSS exhibited improved photocatalysis efficiency. And degradation efficiency of S dots/MoS2-PSS was achieved to be 88% (120 min) and 83% (90 min) for degradation of Rhodamine B (RhB) and Doxycycline hydrochloride (DOX), respectively. It was found that the ligand mainly affect the energy gap and the conduction band potential of the photocatalyst, leading to different photocatalysis activity. When S dots-PSS and MoS2 were combined, the photoelectric conversion performance was enhanced and the recombine of the photogenerated carriers were depressed. And the low conduction band potential of photogenerated electron facilitate to produce of •OH and •O2- radical. This study provides a new photocatalysts and also give a reference on the ligands option of designing efficient photocatalysts.

Mechanism analysis of photocatalytic activity on Semiconductor-Type-Modulated heterojunctions

The construction of heterojunction is one of the most popular strategies to improve the performance of photocatalysts, but the influence of heterojunction types on their photocatalytic behaviors is rarely investigated. Here, the p-n and n-n type heterojunctions were constructed through combining p-type BiOBr (p-BOB) or n-type BiOBr (n-BOB) with n-type g-C3N4 (CN), and their photocatalytic performances were evaluated through RhB degradation and production of H2 in comparison with that of pure n-/p- BiOBr semiconductor. The n-n type heterojunction n-BOB/CN exhibits more excellent photocatalytic performance than that of p-n type heterojunction p-BOB/CN though the latter presents more efficient separation of photogenerated carriers with the strongest photocurrent response and the smallest impedance under the driven of strong built-in electric field. The step-scheme (S-scheme) charge transfer mechanism in n-BOB/CN heterojunction was proposed based on the calculation of work functions and the corresponding valance or conduction band potential, which is responsible for the more excellent photocatalytic performance of n-BOB/CN than that of p-BOB/CN.

Fe vacancies in FeOCl enhanced reactive oxygen species generation for photocatalytic elimination of emerging pollutants

Reactive oxygen species (ROS) play an important role when using semiconductor photocatalysts in water remediation. Nonetheless, the insufficient conduction band potentials, as well as the limited mobility and quick recombination of charge carriers, often inhibit the ROS generation by many pristine photocatalysts. Here, we prepared FeOCl with tunable Fe-vacancy concentrations by using a NaCl-assisted thermal decomposition method. The defective FeOCl exhibited significantly higher rates of degradation and mineralization for organic pollutants compared to the non-defective FeOCl. This superior performance is attributed to the much faster superoxide (O2•−) and singlet oxygen (1O2) generation. Based on the experimental data and DFT simulations, Fe vacancies serve as electron trapping sites, leading to enhanced carrier lifetime and mobility, and can also reduce the conduction band potential of FeOCl, hence facilitating the formation of ROS. This study provides useful insights for developing cation-defected inorganic semiconductors and for improving the efficiency of O2 activation in photocatalysis.

Highly Efficient Photocatalytic H2O2 Production over a Zn0.3Cd0.7S/MXene Photocatalyst for Degradation of Emerging Pollutants under Visible-Light Irradiation.

Hydrogen peroxide (H2O2) is an ideal green product with a broad range of applications, and visible-light-driven photocatalytic H2O2 production is deemed a sustainable and eco-friendly strategy. Herein, various ZnxCd1-xS/MXene photocatalysts with a Schottky junction were prepared for photocatalytic H2O2 production. The obtained Zn0.3Cd0.7S/MXene (ZCM-0.3) hybrid presented the highest photocatalytic H2O2 production rate in pure neutral water of 1160 μmol h-1 g-1, which was further improved to 2178.58 μmol h-1 g-1 in the presence of isopropanol as the sacrificial reagent. The experimental results demonstrated that the sufficient visible-light-harvesting ability and appropriate conduction band potential of the Zn0.3Cd0.7S solid solution, the excellent conductivity and two-electron selectivity of MXene, and the construction of Schottky junctions at the Zn0.3Cd0.7S/MXene interface resulted in the fast transfer and separation of the photogenerated charge carriers and the targeted reduction of oxygen to H2O2. The photocatalytic mechanism for H2O2 production was studied and proposed. Moreover, a simple photo-Fenton system consisting of ZnxCd1-xS/MXene and ferrous ions (Fe2+) was constructed and applied for the degradation of various emerging pollutants, which also performed effectively and exhibited universality across different pollutants. Overall, this study presents a novel and useful strategy to convert solar energy into chemical energy through efficient H2O2 production and provides an effective alternative for the degradation of emerging pollutants.

Effect of adding silver on photocatalytic properties of ZnAl2O4 nanopowder synthesized using microemulsion and polyacrylamide gel methods for recycled water

In recent decades, water purification and removal of organic pollutants such as organic dyes have been among the most important issues. Photocatalyst is one of the most effective methods for recycled water to eliminate organic pollutants and break them down into safe compounds. One of the most significant factors for determining the efficiency of photocatalyst nanoparticles is the utilization of new synthesis methods. Microemulsion and polyacrylamide gel methods are the two methods that were used for the synthesis of zinc aluminate nanoparticles for this study. The powders obtained from these two synthesis methods were characterized using the X-ray diffraction (XRD) technique, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and ultraviolet–visible spectroscopy (UV–Vis) which were utilized as photocatalysts in the photocatalytic degradation reaction of methylene blue (MB). The results demonstrated that the nanoparticles synthesized in both methods were of single-phase zinc aluminate with a spinel structure. The crystallite size obtained for zinc aluminate synthesized using the microemulsion method was 21.7 nm, whereas, in the polyacrylamide gel method, it was 26.3 nm. Microscopic images represented smaller and more uniform particle sizes in the nanoparticles obtained by the microemulsion method. The band gap energy of zinc aluminate nanoparticles obtained using microemulsion and polyacrylamide gel methods was 4.15 and 3.82 eV, respectively. Similarly, the results of MB removal showed that zinc aluminate nanoparticles synthesized using the microemulsion method and polyacrylamide gel, respectively, were 100% and 71% after 120 min. In the second phase of this study, silver nanoparticles were added to zinc aluminate nanoparticles during the synthesis process. X-ray diffraction showed that silver nanoparticles are formed metallically next to zinc aluminate. Moreover, the addition of silver decreased the crystallite size and slightly increased the band gap energy of zinc aluminate. The results of MB dye degradation tests in the presence of ZnAl2O4–Ag nanocomposites showed that the kinetics of dye degradation increased when the silver increased up to 5 wt%. Finally, the mechanism studied on dye degradation using scavenger agents showed that the main agents of dye degradation are the superoxide radical and the holes created in the valence band. It was consistently confirmed by examining the valence and conduction band potentials and also by comparing these potentials with those responsible for producing superoxide and hydroxyl radicals.

Hollow cubic CuSe@CdS with tunable size for plasmon-induced Vis-NIR driven photocatalytic properties.

The rational design of the dimension and geometry of a plasmonic semiconductor cocatalyst is vitally important for efficient utilization of near-infrared (NIR) light and superior photocatalytic hydrogen generation. Herein, hollow cubic CuSe@CdS composites with different sizes and strong localized surface plasmon resonance (LSPR) were prepared by selenizing size-tunable Cu2O templates and loading CdS nanoparticles. The size of hollow cubic CuSe can affect the surface area and the conduction band potential through the size effect, regulating the carrier behavior of the CuSe@CdS heterojunction. The CuSe@CdS composites show enhanced and wide absorption in the full spectrum due to the LSPR effect of CuSe. Meanwhile, the composites show excellent photocatalytic hydrogen capacity in the full spectrum in a 0.35 M Na2S/0.25 M Na2SO3 sacrificial reagent solution. The best hydrogen production rate of CSCE2 is 1.518 mmol g-1 h-1 (5.54 times higher than that of CdS) under Vis light (780 > λ > 420 nm) irradiation and 0.28 mmol g-1 h-1 under NIR light (λ > 780 nm) illumination. Interestingly, the photocatalytic activity for H2 under Vis-NIR light (λ > 420 nm) is about 3 times (up to 4.45 mmol g-1 h-1) higher than that without NIR light assistance, due to the photothermal effect. Various analyses and DFT calculations demonstrate that the p-n heterojunction formed in the composites consists of p-type CuSe and n-type CdS, which achieves efficient carrier transfer and separation under the synergistic effect of the size effect and the photothermal effect. In addition, the expansion of the photocatalytic performance to the NIR range is mainly due to the "hot-electron" injection mechanism induced by the LSPR effect of CuSe. The reasonable design coupled with the plasmonic materials offers a new path to achieving the highly efficient conversion of solar energy to hydrogen energy.