Ultrathin Visible‐Light‐Driven Mo Incorporating In2O3–ZnIn2Se4 Z‐Scheme Nanosheet Photocatalysts

Inspired by natural photosynthesis, the design of new Z‐scheme photocatalytic systems is very promising for boosting the photocatalytic performance of H₂ production and CO₂ reduction; however, until now, the direct synthesis of efficient Z‐scheme photocatalysts remains a grand challenge. Herein, it is demonstrated that an interesting Z‐scheme photocatalyst can be constructed by coupling In₂O₃ and ZnIn₂Se₄ semiconductors based on theoretical calculations. Experimentally, a class of ultrathin In₂O₃–ZnIn₂Se₄ (denoted as In₂O₃–ZISe) spontaneous Z‐scheme nanosheet photocatalysts for greatly enhancing photocatalytic H₂ production is made. Furthermore, Mo atoms are incorporated in the Z‐scheme In₂O₃–ZISe nanosheet photocatalyst by forming the Mo? Se bond, confirmed by X‐ray photoelectron spectroscopy, in which the formed MoSe₂ works as cocatalyst of the Z‐scheme photocatalyst. As a consequence, such a unique structure of In₂O₃–ZISe–Mo makes it exhibit 21.7 and 232.6 times higher photocatalytic H₂ evolution activity than those of In₂O₃–ZnIn₂Se₄ and In₂O₃ nanosheets, respectively. Moreover, In₂O₃–ZISe–Mo is also very stable for photocatalytic H₂ production by showing almost no activity decay for 16 h test. Ultraviolet–visible diffuse reflectance spectra, photoluminescence spectroscopy, transient photocurrent spectra, and electrochemical impedance spectroscopy reveal that the enhanced photocatalytic performance of In₂O₃–ZISe–Mo is mainly attributed to its widened photoresponse range and effective carrier separation because of its special structure.     

Role of annealing temperature on microstructural and electro-optical properties of ITO films produced by sputtering

This study probes the effect of annealing temperature on electrical, optical and microstructural properties of indium tin oxide (ITO) films deposited onto soda lime glass substrates by conventional direct current (DC) magnetron reactive sputtering technique at 100 watt using an ITO ceramic target (In₂O₃:SnO₂, 90:10 wt%) in argon atmosphere at room temperature. The films obtained are exposed to the calcination process at different temperature up to 700 °C. X–ray diffractometer (XRD), ultra violet-visible spectrometer (UV–vis) and atomic force microscopy (AFM) measurements are performed to characterize the samples. Moreover, phase purity, surface morphology, optical and photocatalytic properties of the films are compared with each other. The results obtained show that all the properties depend strongly on the annealing temperature. XRD results indicate that all the samples produced contain the In₂O₃ phase only and exhibit the polycrystalline and cubic bixbite structure with more intensity of diffraction lines with increasing the annealing temperature until 400 °C; in fact the strongest intensity of (222) peak is obtained for the sample annealed at 400 °C, meaning that the sample has the greatest ratio I ₂₂₂/I ₄₀₀ and the maximum grain size (54 nm). As for the AFM results, the sample prepared at 400 °C has the best microstructure with the lower surface roughness. Additionally, the transmittance measurements illustrate that the amplitude of interference oscillation is in the range from 78 (for the film annealed at 400 °C) to 93 % (for the film annealed at 100 °C). The refractive index, packing density, porosity and optical band gap of the ITO thin films are also evaluated from the transmittance spectra. According to the results, the film annealed at 400 °C obtains the better optical properties due to the high refractive index while the film produced at 100 °C exhibits much better photoactivity than the other films as a result of the large optical energy band gap.     

Synthesis and photocatalytic performance of the electrospun Bi2Fe4O9 nanofibers

Bi₂Fe₄O₉ nanofibers were successfully synthesized by an electrospinning method combined with a sol–gel process. The as-spun nanofibers were annealed at different temperatures ranging from 500 to 700 °C and a pure orthorhombic phase was obtained at 700 °C. The thermo-decomposition behavior, structure, morphology, optical property, and the specific surface area of the nanofibers were characterized by thermogravimetry and differential scanning calorimetry, X-ray diffraction, field emission scanning electron microscopy, UV-vis diffuse reflectance spectroscopy and photoluminescene spectroscopy, and specific surface analyzer, respectively. The results indicated that the diameter and morphology of the fiber changed with different calcination temperatures. Moreover, the results of UV-vis diffuse reflectance spectroscopy revealed that the Bi₂Fe₄O₉ nanofiber could be a photocatalyst under a visible light irradiation and the bandgap value was determined to be 2.1 eV based on the Kubelka–Munk theory. The photocatalytic activity of the obtained nanofibers was evaluated by the degradation of methyl orange. A favorable degradation rate of 45 % was obtained for the sample annealed at 600 °C under the illumination of visible light for 3 h and an enhanced efficiency up to 70 % with recycling stability could be obtained with the aid of H₂O₂ for the pure-phase sample annealed at 700 °C. These results demonstrated that the electrospun Bi₂Fe₄O₉ nanofibers could be a promising visible light photocatalyst.     

In-situ synthesis and characterizations of Bi2(O,S)3/Zn(O,S) composites for visible light hexavalent chromium reduction

Heterojunction construction with low band gap materials is an effective way of utilizing UV light active materials under visible light irradiation. Here, we report the synthesis of Bi₂(O,S)₃/Zn(O,S) heterostructure using simple solvothermal method without surfactant. The catalysts were investigated with different characterization techniques. All the composite catalysts showed high light absorption capacity in the whole visible light spectrum. The catalytic activity of the catalysts was evaluated by Cr(VI) reduction. While pure Zn(O,S) catalyst showed no significant Cr(VI) reduction, higher photocatalytic activity than individual components were exhibited after heterojunction construction with Bi₂(O,S)₃. 20-BiZnOS catalyst with Bi/Zn molar percentage of 20% showed the best photocatalytic activity among the composites with 99.5% Cr(VI) reduction within 12 min under visible light irradiation. Heterojunction formation between Bi₂(O,S)₃ and Zn(O,S) nanoparticle, and selective adsorption of Cr(VI) and desorption of Cr(III) on the surface of 20-BiZnOS composite catalyst were ascribed to the enhanced photocatalytic activity of the composite catalyst.     

Controllable synthesis of SnO2 photocatalyst with superior photocatalytic activity for the degradation of methylene blue dye solution

SnO₂ photocatalyst was successfully synthesised by novel chemical route in hydrothermal environment and annealed at two different temperatures viz 550 and 600 °C, respectively. The crystal structure, optical properties, surface and bulk morphology have been characterised using various tools like X-ray diffraction (XRD), UV visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscope (TEM) and scanning electron microscope (SEM). Cubic, spheres and porous like morphology of SnO₂ photocatalyst was successfully confirmed using SEM micrographs and TEM. In addition to this the photocatalytic activity was evaluated towards the degradation of methylene blue dye solution. SnO₂ photocatalyst annealed at 600 °C exhibits excellent photocatalytic efficiency which may be attributed to the unique morphology, high crystalline nature and charge separation. The photocatalyst efficiency was further tested towards the concentration of dye, catalyst dosage and pH of the dye. The involvement of ?OH in the photocatalytic reaction was evidenced using trapping experiment by employing different scavengers. The photocatalyst was moderately active, stable upto its fifth usage and stability of the photocatalyst before and after the photocatalytic reaction was also been studied using XRD and SEM.     

Assembly of WO<Subscript>3</Subscript> nanosheets/Bi<Subscript>24</Subscript>O<Subscript>31</Subscript>Br<Subscript>10</Subscript> nanosheets composites with superior photocatalytic activity for degradation of tetracycline hydrochloride

In this work, a high-performance composite photocatalyst composed of WO₃ nanosheets and Bi₂₄O₃₁Br₁₀ nanosheets was successfully synthesized. The photocatalytic activity of the obtained samples was studied by the degradation of tetracycline hydrochloride under visible light irradiation. The results showed that Bi₂₄O₃₁Br₁₀ modified with the appropriate amount of WO₃ nanosheet exhibits higher catalytic activity and stability during the photocatalytic processes, and the holes (h⁺) is involved in the photolysis reaction as the main active species. The crystallization, morphology, optical and electrochemical properties of the as-prepared composite photocatalyst were characterized, and the mechanism of high photocatalytic activity was also explored. The optimal sample (10%-WO₃/Bi₂₄O₃₁Br₁₀) exhibited the best performance for tetracycline hydrochloride (TC) degradation, and more than 80% of the TC was degraded after 60 min under light irradiation. The degradation rate constant k was about 3.34-fold and 1.54-fold higher than pure WO₃ and Bi₂₄O₃₁Br₁₀, respectively. Its high photocatalytic performance can be attributed to the following reasons: the appropriate conduction band and valence band positions between WO₃ and Bi₂₄O₃₁Br₁₀, the close contact between the two visible light-driven photocatalysts, and the effective separation of the spatial charge. Our work may help to further expand the potential application of oxygen-rich bismuth oxyhalides photocatalyst in wastewater treatment, and provide a new strategy for the modification of nanostructured photocatalysts.     

Oxygen-rich TiO2 decorated with C-Dots: Highly efficient visible-light-responsive photocatalysts in degradations of different contaminants

Providing novel photocatalysts with high photocatalytic efficiency is of great significance. In the present work, hydrogen peroxide and carbon dots (C-Dots) were utilized to enhance the photocatalytic performance of TiO₂ under visible light. The fabricated TiO₂-peroxo/C-Dots photocatalysts were analyzed by XRD, HRTEM, SEM, EDX, BET, FT-IR, XPS, PL, UV–Vis DRS, EIS, and photocurrent density. Photocatalytic abilities of the nanocomposites were evaluated by photocatalytic removal of RhB, MO, MB, fuchsine, and Cr (VI) upon visible-light illumination. The results demonstrated that the binary nanocomposites exhibited remarkably enhanced photocatalytic activity compared with the TiO₂ and TiO₂-peroxo photocatalysts. The best photocatalytic performance was obtained using 0.75?mL of C-Dots, which was approximately 79.2, 17.1, 71.4, and 40.5 times higher than the pure TiO₂ for degradations of RhB, MO, MB, and fuchsine, respectively. Furthermore, the TiO₂-peroxo/C-Dots nanocomposites exhibited high stability in consecutive photocatalytic processes. Based on the results, the TiO₂-peroxo/C-Dots photocatalyst is expected to become a promising photocatalyst for practical applications in water purification.     

Investigation on deep level defects in rapid thermal annealed undoped n-type InP

Deep levels in rapid thermal annealed Pd/n-InP Schottky contacts have been studied using deep level transient spectroscopy. It is observed that the as-deposited Pd/n-InP Schottky sample exhibit two deep levels with activation energies of 0.53 and 0.70 eV. In samples annealed at 400 °C, three deep levels having activation energies 0.18, 0.30 and 0.86 eV below the conduction band are observed and for samples annealed at 500 °C, four deep levels with activation energies 0.33, 0.44, 0.70 and 0.82 eV are observed. Fourier transform infrared spectroscopy measurements have been carried out on undoped as-deposited and annealed InP wafers at 300, 400 and 500 °C. The measurements revealed high concentration of hydrogen complexes in the form of V_InH₄ existing in InP wafer. The results show that V_InH₄ complex annihilates with increase of annealing temperature and results in the formation of P _In ²⁺ and V _P ⁺ defects at 0.70 and 0.44 eV, respectively.     

Synthesis,characterization, photocatalytic evaluation,and toxicity studies of TiO2–Fe3+ nanocatalyst

Based on our previous work on the green preparation of Ag–TiO₂ photocatalyst with bactericidal activity under visible light, we extended our studies to the synthesis of TiO₂–Fe³⁺ materials with enhanced photocatalytic activity for the degradation of recalcitrant organic pollutants in water. TiO₂–Fe³⁺ nanopowders were synthesized using a robust, environmentally friendly procedure. Established amounts of Fe(NO₃)₃·9H₂O and titanium tetraisopropoxide (TTIP) were mixed using glacial acetic acid as solvent. Hydrolysis of TTIP–Fe³⁺ was accomplished using a 30 % (W/V) Arabic gum aqueous solution. TiO₂–Fe³⁺ nanopowders were obtained by thermal treatment at 400 °C. In order to elucidate the structure of these photocatalysts, microscopic and spectroscopic characterization techniques were applied. The high resolution transmission electron microscopy (HRTEM) analysis indicated the presence of uniformly distributed particles with average particle size of about 9 nm. According to the HRTEM lattice fringes, ring pattern, and selected area electron diffraction pattern, the crystalline part of the samples consists of anatase (PDF 01-086-1157 with the lattice constant of 3.7852, 9.5139 Å and 90°) as dominant phase. X-ray photoelectron spectroscopy (XPS) was applied to determine the oxidation state of iron. The XPS provides evidence for Fe³⁺ surface species in the TiO₂–Fe³⁺ composite. Complete degradation of aqueous solutions (20 ppm) of methylene blue and/or methyl orange was accomplished after 4 h of treatment using 150 mg of TiO₂–Fe³⁺/150 mL of dye solution. The in vitro toxicity of the materials was tested. The materials showed no toxicity against human red blood cells.     

Effect of holmium doping on the structure and photocatalytic behavior of TiO2-based nanosheets

A series of holmium-doped TiO₂-based nanosheet (Ho-TNS) photocatalysts with different Ho/Ti molar ratios were prepared via a simple hydrothermal method. The photocatalysts were characterized by field-emission scanning electron microscope, high-resolution transmission electron microscope, X-ray diffraction (XRD), Raman Spectroscopy, X-ray photoemission spectroscopy, nitrogen adsorption–desorption isotherm measurement, ultraviolet–visible light diffuse reflectance spectra (DRS), and fluorescence spectra (FL). The TEM images of Ho-TNS exhibit clearly sheet-like structures and existence of the (201) plane of H₂Ti₃O₇. The increased (101) peak intensity in XRD spectrum and the enhanced E _g mode (141 cm^?1) in Raman spectrum indicate that Ho doping has obvious influence on the formation and structure of Ho-TNS, which can be explained by the formation of Ho–O–Ti bonds. With the doping ratio (Ho/Ti molar ratio) increasing from 0 to 2.0 %, the absorption edge shifts to a longer wavelength, and the band-gap of photocatalysts reduces from 3.18 to 3.07 eV. The decline of FL intensity implies that the photocatalysts with higher Ho content have higher electron–hole separation efficiency. However, after Ho doping, the surface structure of specimens is significantly altered, which will lead to the specific surface areas and adsorption capacity decrease. Under the combined effect of the variables, the photocatalyst with a doping ratio of 1.0 % reaches the best photoactivity, which is 1.90-fold and 12.38-fold higher compared with undoped TNS and P25 under visible light, respectively. The high photoactivity of the prepared Ho-TNS indicates that it may be useful for dealing with wastewater.     

Enhanced photocatalytic activity of Mg0.05Zn0.95O thin films prepared by sol–gel method through a cycle

Mg_0.05Zn_0.95O thin films were prepared on silicon substrates by a sol–gel dip-coating technique. Microstructure, surface topography and optical properties of the thin films were characterized by X-ray diffraction, atom force microscopy, Fourier transform infrared spectrophotometer and fluorescence spectrometer. The results show that the thin film annealed at 700 °C has the largest average grain size and exhibits the best c-axis preferred orientation. As annealing temperature increases to 800 °C, the grain along c-axis has been suppressed. Roughness factor and average particle size increase with the increase of annealing temperature. The IR absorption peak appearing at about 416 cm^?1 is assigned to hexagonal wurtzite ZnO. The thin film annealed at 700 °C has the maximum oxygen vacancy, which can be inferred from the green emission intensity. Photocatalytic results show that the thin film annealed at 700 °C exhibits remarkable photocatalytic activity, which may be attributed to the larger grain size, roughness factor and concentration of oxygen vacancy. Enhanced photocatalytic activity of Mg_0.05Zn_0.95O thin films after a cycle may be attributed to the increase of surface oxygen vacancy and photocorrosion of amorphous MgO on the surface of thin film under UV irradiation.     

Reduced graphene oxide and CdTe nanoparticles co-decorated TiO2 nanotube array as a visible light photocatalyst

TiO₂ nanotube array (TiO₂ NT) was co-decorated by reduced graphene oxide (RGO) and CdTe nanoparticles (NPs) through a simple one-step electrodeposition process. RGO film was formed on the top surface of TiO₂ NT and CdTe NPs homogeneously dispersed within the RGO sheets and on the inner/outer walls of TiO₂ NT. Resulting from the synergetic effect of RGO and CdTe, the photocatalytic activity of the ternary RGO/CdTe–TiO₂ NT photocatalyst far exceeded those of bare TiO₂ NT, RGO-TiO₂ NT, and CdTe–TiO₂ NT photocatalysts in the degradation of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) under simulated solar light or visible light irradiation. After 180-min UV–Vis (or visible light) irradiation, almost 100 % (or 96 %) 2,4-D removal efficiency was achieved on RGO/CdTe–TiO₂ NT, much higher than 42 % (or 2 %) on bare TiO₂ NT, 58 % (or 10 %) on RGO–TiO₂ NT, and 52 % (or 41 %) on CdTe–TiO₂ NT. This study will inspire better design of advanced photocatalysts with high visible-light photocatalytic activity.     

Crystal structure and photocatalytic properties of titanate nanotubes prepared by chemical processing and subsequent annealing

Anatase TiO₂ nanoparticles were synthesized from sol–gel processing, and they were used as a precursor for titanate nanotubes (TNT) formation. TNT were synthesized under reflux heating of anatase TiO₂ in concentrated NaOH solution followed by repeated washing with distilled water and 0.1 M HCl. The nanotubular structure was preserved till 450 °C, above which nanorod formation started. The as-synthesized nanotubes were found to have mixed crystal structure of anatase and Na _x H_2?x Ti₃O₇·nH₂O (where 0 < x <  2), contrary to what has been reported before. The XRD peaks of titanate were slightly shifted to higher angles upon calcination along with prominent anatase peaks. Complete transformation to nanorods occurred at 600 °C and crystal structure was transformed to Na₂Ti₆O₁₃ and anatase. Sodium presence in TNT was confirmed by EDX, and Na–O and H–O–H along with Ti–OH vibrations were found by FTIR. Ti–OH/H–O–H vibrations were less prominent for samples calcined at 500 °C and above, which confirms structural water loss is associated with morphological change. The as-synthesized TNTs had a specific surface area of 157 m² g^?1, and it decreased by increasing calcination temperature. TNTs were applied to methylene blue aqueous solution to observe their decolorization capability under UV irradiation. The as-synthesized TNTs showed enhanced photocatalytic decolorization as compared to anatase titania nanoparticles due to presence of Ti–OH groups and higher specific surface area. The photocatalytic activity reduced when TNTs were annealed at high temperatures. The changes in the photocatalytic activity are related to the existence of hydroxyl groups in the structure, decrease in specific surface area of annealed nanotubes, change in morphology from nanotubes to nanorods, and bandgap shift to visible light when TNTs were calcined at higher temperatures.     

New photocatalysts based on MIL-53 metal-organic frameworks for the decolorization of methylene blue dye

The photocatalytic decolorization of methylene blue dye in aqueous solution using a novel photocatalyst MIL-53(Fe) metal-organic frameworks was investigated under UV-vis light and visible light irradiation. The effect of electron acceptor H(2)O(2), KBrO(3) and (NH(4))(2)S(2)O(8) addition on the photocatalytic performance of MIL-53(Fe) was also evaluated. The results show that MIL-53(Fe) photocatalyst exhibited photocatalytic activity for MB decolorization both under UV-vis light and visible light irradiation, and the MB decolorization over MIL-53(Fe) photocatalyst followed the first-order kinetics. The addition of different electron acceptors all enhances the photocatalytic performance of MIL-53(Fe) photocatalyst, and the enhanced rate follows the order of H(2)O(2)>(NH(4))(2)S(2)O(8)>KBrO(3) under UV-vis light irradiation, while in the order of (NH(4))(2)S(2)O(8)>H(2)O(2)>KBrO(3) under visible light irradiation. Moreover, MIL-53(Fe) did not exhibit any obvious loss of the activity for MB decolorization during five repeated usages. The photocatalytic activities over MIL-53(M) (M=Al, Fe), the isostructure to MIL-53(Fe), indicate that the metal centers show nil effect on the photocatalytic activity of MIL-53(M) photocatalysts.     

Synthesis of novel Cu doped anatase TiO<Subscript>2</Subscript> catalysts and assessment of the influence of Nb concentration on the photocatalytic and electrochemical properties

In the present study, Cu doped (Ti_0.8Cu_xO_2?x/2) and (Cu, Nb) co-doped (Ti_0.8Cu_x?y Nb_yO_2?(x?y/2+y)) TiO₂ photocatalysts were fabricated by sol–gel method. The catalysts were polycrystalline in nature with preferential orientation along (101) plane answering to anatase phase of TiO₂. Higher Nb concentration results in the formation of secondary phase (Nb₂O₅). A decrease in average crystallite size was noticed with the addition of Nb concentration in Cu doped TiO₂ photocatalyst. The formation of anatase phase was also fixed by Raman spectra. The TEM photograph confirmed the co-doped TiO₂ photocatalyst in nanometer range of about 15 nm and the particles were in hexagonal shape. The doping of Nb⁵⁺ ions inspired a shift in the absorption threshold towards the visible spectral range (red shift) compared to Cu doped TiO₂ catalyst. The photocatalysts have direct bandgaps of 3.253 to 2.974 eV. Semiconducting properties were investigated through electrochemical impedance spectroscopy. The results indicate that the presence of Nb⁵⁺ ions into Cu doped TiO₂ has enhanced the efficiency of electrochemical conductivity. Photocatalytic performance was assessed from the sample degradation by illuminating methylene blue dye under visible light exposure. It is found that TCN3 photocatalyst bleaches MB much faster than all others. Also it exhibits great improvement of photocatalytic activity (96.86%) within 120 min. The photocatalytic degradation process is explained using the pseudo first order kinetics and it fits well with higher correlation coefficient. All these analyses elucidate that the incorporation of Nb⁵⁺ ions might tune the structural, optical, electrochemical and phocatalytic properties of Cu doped TiO₂ photocatalysts.     

Photocatalytic degradation of phenol in aqueous solution by rare earth-doped SnO2 nanoparticles

The influence of heterogeneous semiconductors on the photodegradation of phenol in water was investigated using doped tin dioxide (SnO₂) nanoparticles. Photocatalysts of SnO₂ were synthesized with lanthanum (La), cerium (Ce), and neodymium (Nd) dopants. These photocatalysts were synthesized from tin tetrachloride by sol–gel method with different dopant concentrations, and its photocatalytic degradation was investigated up to 0.8 % under UV-A light in aqueous suspensions. The photocatalytic oxidation reactions were studied by varying photocatalyst composition, light intensity, reaction time, pH of the reaction medium, and phenol concentration. It was found that the photocatalytic activity of rare earth-doped SnO₂ for phenol decomposition under UV light irradiation was considerably higher than that of pure SnO₂ nanoparticles. The experimental results also indicate that more than 95 % phenol was effectively oxidized in the presence of an aqueous suspension of La: SnO₂ nanoparticles within 120 min of UV light irradiation.     

Effect of annealing temperature on structural,optical and humidity sensing properties of indium tin oxide (ITO) thin films

Tin doped indium oxide (ITO) thin films were prepared by sol–gel spin coating method with In (NO₃)·3H₂O and SnCl₄·5H₂O as indium and tin sources, respectively. The as deposited samples were annealed at various temperature such as, 300, 400, 500 and 600?°C for 2 h in ambient atmosphere. The grown ITO thin films are polycrystalline in nature with cubic structure of In₂O₃ with the space group La3 and the results are in good agreement with the standard JCPDS data (card no#06-0416). In addition crystalline size increases with increasing annealing temperature from 25 to 55 nm. Polycrystalline with uniform smooth surface was observed by SEM micrographs. The optical band gap energy was found to be decreased from 3.85 to 3.23 eV as the annealing temperature is increased from 300 to 600?°C. The humidity sensing performance (high sensitivity and fast response time) was significantly improved for 600?°C thin films samples, which is probably due to smaller energy band gap and physisorption between the water molecules and the surface of the thin films. The films were further characterized by PL and EDS analysis. The effect of temperature on humidity sensing mechanism of ITO thin films is also discussed.     

Reductive Transformation of Layered‐Double‐Hydroxide Nanosheets to Fe‐Based Heterostructures for Efficient Visible‐Light Photocatalytic Hydrogenation of CO

Conversion of syngas (CO, H₂) to hydrocarbons, commonly known as the Fischer–Tropsch (FT) synthesis, represents a fundamental pillar in today's chemical industry and is typically carried out under technically demanding conditions (1–3 MPa, 300–400 °C). Photocatalysis using sunlight offers an alternative and potentially more sustainable approach for the transformation of small molecules (H₂O, CO, CO₂, N₂, etc.) to high‐valuable products, including hydrocarbons. Herein, a novel series of Fe‐based heterostructured photocatalysts (Fe‐x) is successfully fabricated via H₂ reduction of ZnFeAl‐layered double hydroxide (LDH) nanosheets at temperatures (x) in the range 300–650 °C. At a reduction temperature of 500 °C, the heterostructured photocatalyst formed (Fe‐500) consists of Fe⁰ and FeO_x nanoparticles supported by ZnO and amorphous Al₂O₃. Fe‐500 demonstrates remarkable CO hydrogenation performance with very high initial selectivities toward hydrocarbons (89%) and especially light olefins (42%), and a very low selectivity towards CO₂ (11%). The intimate and abundant interfacial contacts between metallic Fe⁰ and FeO_x in the Fe‐500 photocatalyst underpins its outstanding photocatalytic performance. The photocatalytic production of high‐value light olefins with suppressed CO₂ selectivity from CO hydrogenation is demonstrated here.     

Biomimetic Photocatalytic System Designed by Spatially Separated Cocatalysts on Z-scheme Heterojunction with Identified Charge-transfer Processes for Boosting Removal of U(VI)

Designing highly efficient photocatalysts with rapid migration of photogenerated charges and surface reaction kinetics for the photocatalytic removal of uranium (U(VI)) from uranium mine wastewater remains a significant challenge. Inspired by natural photosynthesis, a biomimetic photocatalytic system is assembled by designing a novel hollow nanosphere MnO_x@TiO₂@CdS@Au (MTCA) with loading MnO_x and Au nano particles (Au NPs) cocatalysts on the inner and outer surfaces of the TiO₂@CdS. The spatially separated cocatalysts efficiently drive the photogenerated charges to migrate in opposite directions, while the Z-scheme heterogeneous shell further separates the interfacial charges. Theoretical calculation identifies multiple consecutive forward charge transfers without charge recombination within MTCA. Thus, MTCA could efficiently remove 99.61% of U(VI) after 15 min of simulated sunlight irradiation within 3 mmol L⁻¹ NaHCO₃ with 0.231 min⁻¹ of the reduction rate constant, outperforming most previously reported photocatalysts. MTCA further significantly removes 91.83% of U(VI) from the natural uranium mining wastewater under sunlight irradiation. This study provides a novel approach to designing an ideal biomimetic photocatalyst for remediating environmental pollution.     

Two-dimensional photocatalyst design: A critical review of recent experimental and computational advances

In recent years, two-dimensional (2D) semiconductor photocatalysts have been widely applied in water splitting, CO₂ reduction, N₂ fixation, as well as many other important photoreactions. Photocatalysts in the form of 2D nanosheet possess many inherent advantages over traditional 3D nanopowder photocatalysts, including improved light absorption characteristics, shorter electron and hole migration paths to the photocatalysts’ surface (thus minimizing undesirable electron-hole pair recombination), and abundant surface defects which allow band gap modulation and facilitate charge transfer from the semiconductor to adsorbates. When synergistically exploited and optimized, these advantages can impart 2D photocatalysts with remarkable activities relative to their 3D counterparts. Accordingly, a wide range of experimental approaches is now being explored for the synthesis of 2D photocatalysts, with computational methods increasingly being used for identification of promising new 2D photocatalytic materials. Herein, we critically review recent literatures related to 2D photocatalyst development and design. Particular emphasis is placed on 2D photocatalyst synthesis and the importance of computational studies for the fundamental understanding of 2D photocatalyst electronic structure, band gap structure, charge carrier mobility and reaction pathways. We also explore the practical challenges of using 2D photocatalysts, such as their difficulty to synthesize in large quantity and also their characterization. The overarching aim of this review is to provide a snapshot of recent work targeting high-performance 2D photocatalysts for efficient solar energy conversion, thus laying a firm base for future advancements in this rapidly expanding area of photocatalysis research.