Efficient Photocatalytic Water Research Articles

Photocatalytic hydrogen production and sulfamerazine degradation via a novel dual S-scheme photocatalyst: Nanocomposite synthesis, characterization and mechanism insights

Creating highly effective photocatalysts is crucial for harnessing solar energy to degrade pollutants and produce hydrogen (H₂). In this study, we successfully synthesized a novel dual S-scheme iron oxide (Fe₂O₃)/bismuth oxide (Bi₂O₃)/titanium dioxide (TiO₂) ternary photocatalyst using a straightforward method. This photocatalyst was employed for efficient photocatalytic water splitting and the degradation of the antibiotic sulfamerazine (SMZ) under visible light. Various characterization and photoelectrochemical techniques, including scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area analysis (BET), photocurrent measurements, Mott-Schottky analysis, photoluminescence (PL), electrochemical impedance spectroscopy (EIS), and electron spin resonance (ESR), were utilized to analyze the synthesized materials. Among the synthesized nanocomposites, the 15 wt% Fe₂O₃/Bi₂O₃/TiO₂ (15FeBi/TiO₂) composite demonstrated exceptional photocatalytic efficiency, achieving 98 % SMZ degradation and a hydrogen production rate of 590.36 μmol/g·h. Experimental results, including scavenging tests and ESR findings, highlighted the crucial role of hydroxyl radicals (•OH) and superoxide radicals (•O₂−) in the photocatalytic process. Moreover, liquid chromatography-mass spectrometry (LC-MS) results proposed three degradation pathways, and quantitative structure-activity relationship (QSAR) analysis showed that the toxicity of intermediates was effectively reduced. The 15FeBi/TiO₂ photocatalyst also exhibited excellent reusability, retaining about 85 % of its initial activity after five cycles, and proved effective against various pollutants and in real water matrices. This research contributes to the design and development of high-activity heterojunction photocatalysts for superior clean energy generation and pollutant degradation under visible light.

Efficient Photocatalytic Hydrogen Evolution via Cocatalyst Loaded Al-doped SrTiO3

The growing reliance on fossil fuels is causing significant environmental issues, prompting the search for renewable energy sources. Hydrogen energy, which produces only water vapor, is a promising solution. This study focuses on developing an aluminum-doped SrTiO3 photocatalyst with dual cocatalysts (Rh/Cr2O3 and CoOOH) for efficient photocatalytic water splitting. Using a simple chemical deposition method, high-purity and crystalline SrTiO3 was synthesized and thoroughly characterized. The results show that the modified SrTiO3 achieved significantly higher photocatalytic activity, with Rh/Cr2O3/SrTiO3@Al/CoOOH producing 11.04 mmol g–1 h–1 of H2 and 4.69 mmol g–1 h–1 of O2. This work demonstrates the effectiveness of dual cocatalyst deposition and aluminum doping in enhancing photocatalytic performance by improving charge separation and reducing recombination.

Data-Efficient Active Learning for Thermodynamic Integration: Acidity Constants of BiVO4 in Water.

The protonation state of molecules and surfaces is pivotal in various disciplines, including (electro-)catalysis, geochemistry, biochemistry, and pharmaceutics. Accurately and efficiently determining acidity constants is critical yet challenging, particularly when explicitly considering the electronic structure, thermal fluctuations, anharmonic vibrations, and solvation effects. In this research, we employ thermodynamic integration accelerated by com- mittee Neural Network potentials, training a single machine learning model that accurately describes the relevant protonated, deprotonated, and intermediate states. We investigate two deprotonation reactions at the BiVO4 (010)-water interface, a promising candidate for efficient photocatalytic water splitting. Our results illustrate the convergence of the required ensemble averages over simulation time and of the final acidity constant as a function of the Kirkwood coupling parameter. We demonstrate that simulation times on the order of nanoseconds are required for statistical convergence. This time scale is currently unachievable with explicit ab-initio molecular dynamics simulations at the hybrid DFT level of theory. In contrast, our machine learning workflow only requires a few hundred DFT single point calculations for training and testing. Exploiting the extended time scales accessible, we furthermore asses the effect of commonly applied bias potentials. Thus, our study significantly advances calculating free energy differences with ab-initio accuracy.

Newfound 2D In2S3 allotropy monolayers for efficient photocatalytic overall water splitting to produce hydrogen

Allotropy structures may induce different electronic and optical properties, which implies that one can acquire novel performance by screening its allotropy structures. Here, we demonstrate that two In2S3 allotropy monolayers with excellent photocatalytic performance for water splitting to produce hydrogen are screened from 1038 In2S3 allotropy monolayers. The phonon dispersions are calculated for 39 allotropes with the lowest formation energies, which confirms that 16 allotropes have dynamic stability, including the only one reported in the literature. The results of overpotentials of band edges demonstrate that 8 allotropes match the potential requirements of overall water splitting. The thermodynamic stability of these allotropes is further confirmed for the obtained allotropes. Then, two allotropes with maximum solar-to-hydrogen efficiency of 17.78% and 29.32% are screened. The Gibbs free energy with the solvent effect indicates that one allotrope can proceed photocatalytic hydrogen/oxygen evolution reactions spontaneously. Therefore, the newfound In2S3 allotropy monolayers have potential applications in photocatalytic overall water splitting for hydrogen generation.

Rational Design of ZnO/Sc2CF2 Heterostructure with Tunable Electronic Structure for Water Splitting: A First-Principles Study

Heterostructures are highly promising photocatalyst candidates for water splitting due to their advanced properties than those of pristine components. The ZnO/Sc2CF2 heterostructure was designed in this work, and its electronic structure was investigated to explore its potential for water splitting. The assessments of binding energy, phonon spectrum, ab initio molecular dynamics, and elastic constants provide strong evidence for its stability. The ZnO/Sc2CF2 heterostructure has an indirect band gap of 1.93 eV with a type-Ⅰ band alignment. The electronic structure can be modified with strain, leading to a transition in band alignment from type-Ⅰ to type-Ⅱ. The heterostructure is suitable for water splitting since its VBM and CBM stride over the redox potential. The energy barrier and built-in electric field, resulting from the charge transfer, facilitate the spatial separation of photogenerated carriers, enhancing their utilization efficiency for redox processes. The photogenerated carriers in the heterostructures with lattice compression greater than 6% follow the direct-Z transfer mechanism. The ZnO/Sc2CF2 heterostructure is confirmed with high photocatalytic activity by a Gibbs free energy change of HER, which is 0.89 eV and decreases to −0.52 eV under an 8% compressive strain. The heterostructure exhibits a remarkable enhancement in both absorption range and intensity, which can be further improved with strains. All these findings suggest that the ZnO/Sc2CF2 heterostructure is an appreciated catalyst for efficient photocatalytic water splitting.

Single-Particle Imaging Photoinduced Charge Transfer of Ferroelectric Polarized Heterostructures for Photocatalysis.

Piezoelectric-assisted photocatalysis has a huge potential in solving the energy shortage and environmental pollution problems, and imaging their detailed charge-transfer process can provide in-depth understanding for the development of high-active piezo-photocatalysts; however, it is still challenging. Herein, topotactic heterostructures of TiO2@BaTiO3 (TO@BTO-S) were constructed by the epitaxial growth of ferroelectric BaTiO3 mesocrystals on TiO2-{001} facets, resulting in a ferroelectric photocatalyst with a polarization orientation on the surface. Notably, the photoinduced charge transfer in ferroelectric TiO2@BaTiO3 was accurately monitored and directly visualized at the single-particle level by the advanced photoluminescence (PL) imaging microscopy systems. The longer PL lifetime of TO@BTO-S demonstrated the efficient charge separation caused by a built-in electric field, which is constructed by the polarization orientation of BaTiO3 mesocrystals. Therefore, the TO@BTO-S heterostructure exhibits efficient piezoelectric-assisted photocatalytic pure water splitting, which is 290 times higher than photocatalysis. This work revealed time/spatial-resolved photoinduced charge transfer in piezoelectric assistance photocatalysts at the single-particle level and demonstrated the great role of polarization orientation in promoting charge transfer for photocatalysis.

Two-dimensional ferroelastic semiconductors InXY (X = S, Se; Y = Cl, Br, I): Promising candidates for photocatalytic water splitting with tunable electronic anisotropy

We have identified a class of two-dimensional ferroelastic monolayers, denoted as InXY (where X = S, Se; Y = Cl, Br, I), through first-principles calculations. The dynamic, thermal, and mechanical stabilities of these InXY monolayers are validated by phonon dispersion spectra, AIMD calculations, and elastic constants, respectively. These monolayers exhibit semiconducting behavior with bandgaps ranging from 1.94 to 2.85 eV and possess excellent ferroelasticity with strong ferroelastic signals and moderate ferroelastic switching barriers. Notably, the band edge positions of InSBr and InSI monolayers are observed to stride the water redox potentials at pH = 0, indicating their potential as photocatalysts for water splitting in acidic environments. We also explored the effects of biaxial strain on the band edge alignments and photocatalytic performance of these monolayers. Moreover, the InXY monolayers exhibit excellent anisotropic optical absorption across the visible to ultraviolet regions, along with high anisotropic carrier transport. The coupling of ferroelastic and anisotropic properties in these monolayers offers promising opportunities for designing controllable electronic devices, thereby expanding their potential applications in multifunctional materials. Our findings reveal that the InXY monolayers are promising candidates for efficient photocatalytic water splitting and controllable optoelectronic applications.

Aqueous glass-coated CsPbI3 quantum dots implanted in g-C3N4 nanosheets for efficient photocatalytic water splitting and H2O2 generation

Increasing visible light harvesting and improving charge carrier separation and transfer efficiency are crucial for photocatalytic H2O2 generation using graphitic carbon nitrides (g-C3N4) based catalysts. In this paper, a high temperature solid synthesis was developed to create water stable SiO2 glass coated CsPbI3 (CsPbI3@SiO2) quantum dots (QDs) with high brightness and extraordinary stability. These CsPbI3@SiO2 QDs were implanted in superior thin g-C3N4 nanosheets via a solvothermal synthesis. The red-emission of CsPbI3 QDs and the blue emission of g-C3N4 nanosheets were quenched after incorporation to confirm that photogenerated electron transition occurred. The further polymerization of g-C3N4 during solvothermal treatment resulted in CsPbI3@SiO2/g-C3N4 with well-developed interface to improve the charge transfer efficiency. A type II heterostructure formed after CsPbI3@SiO2 QDs incorporated with g-C3N4 nanosheets. The heterostructure revealed enhanced photocatalytic H2 and H2O2 generation, in which the evolution rate of H2O2 was 2454.4 μmol·g−1·h−1 while the photocatalytic H2 generation rate was 2463.1 μmol·g−1·h−1. The mechanism test indicated that the photocatalytic production of H2O2 was carried through a two-step single-electron redox process. Superoxide radicals were important intermediates for the generation of H2O2. This study provides a new scheme for the preparation of g-C3N4 based heterojunction photocatalyst for efficient photocatalytic production of H2O2 and H2.

Efficient photocatalytic water decontamination over a wide pH range by C and O co-doped carbon nitride with tunable band structure

The metal-free, non-toxic, and highly tunable structure of carbon nitride confers unique advantages in photocatalytic advanced oxidation processes. Regulating the generation of radical and non-radical species during photocatalysis to maintain high degradation efficiency across different water matrices is of great practical significance for the application of carbon nitride. In this study, a C and O co-doped modified carbon nitride (UCN) with a high specific surface area was developed for efficient photodegradation of p-chlorophenol (p-Cl) without exogenous oxidants. Characterizations demonstrated that UCN in higher specific surface area exposed more active sites. Additionally, with rising doping levels, UCN exhibited enhanced light absorption capability and a narrower bandgap, which favored the separation of photogenerated electron-hole pairs. The primary active species were identified as holes, accompanied by the generation of superoxide radicals (·O2–) and singlet oxygen (1O2) depending on the pH value. Under acidic conditions, 1O2 was predominantly generated, whereas ·O2– dominated under alkaline conditions. As a result, the removal efficiency of p-Cl was enhanced under both strongly acidic and alkaline conditions. The pseudo-first-order rate constants for p-Cl removal at pH 3, 7, and 11 were 0.0558, 0.0354, and 0.0443 min−1, respectively. Moreover, combining DFT calculations and LC-MS data, analysis on the intermediate products of p-Cl degradation revealed unique characteristics at different pH values, further proving the flexible tunability and providing insights into the practical application of modified carbon nitride.

Janus NbOBrI monolayer for efficient photocatalytic overall water splitting

Due to the presence of a built-in electric field, two-dimensional Janus materials can effectively reduce photogenerated carrier recombination while promoting carrier separation. In this work, the viability of Janus NbOBrI monolayer as a high-efficiency photocatalyst for water splitting was examined using first-principles calculations. The results demonstrate that the Janus NbOBrI monolayer exhibits appropriate band-edge potentials, significant visible light absorptions, high carrier separation efficiency and high enough carrier mobility along the Peierls distortion direction. Moreover, we have determined the variations in the Gibbs free energy for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) at various pHs, and found that the OER can occur spontaneously in the light environment. Applying -1.5 % uniaxial strain in the a(b) direction of the NbOBrI monolayer helps to increase the reduction potential and provide sufficient power for the HER, resulting in a solar-to-hydrogen (STH) efficiency of 8.9 % (9.3 %).

Strain-Induced Photocatalytic H2 Production over BiVO4 in Pure Water without Any Cocatalyst.

In this study, BiVO4 nanosheets (BiVO4-NS) were prepared by a facile hydrothermal method. It is found that sonication-induced strain can effectively promote the H2 production over BiVO4-NS in the presence of pure water without any cocatalysts. With the assistance of the sonication, the H2 production over BiVO4-NS is 1.344 mmol·g-1 after 3 h simulated sunlight irradiation, which is 24.8 times higher than that of BiVO4-NS without sonication (0.054 mmol·g-1). In addition, the products of water oxidation are determined to be hydroxyl radicals and hydrogen peroxide. Moreover, BiVO4-NS also shows obviously enhanced photoactivity than that of the commercially available BiVO4 nanoparticles (BiVO4-C). The improved photoactivity of BiVO4-NS is attributed to the effective charge separation and low charge transfer resistance. The underlying mechanism of sonication-promoted water splitting is investigated by a variety of controlled experiments. The results show that ultrasonic waves can produce obvious strain inside the sample, which results in lattice distortion of BiVO4. Therefore, the conduction band of BiVO4 is obviously negative shifted, which is beneficial for H2 production. In addition, the strain in BiVO4 also produces local polarization of the sample, which effectively promotes the charge transfer and separation process. It is hoped that our study could provide a new strategy for achieving efficient photocatalytic water splitting.

Silicate minerals enable the efficient photocatalytic RWGS reaction

Silicate minerals are the most abundant minerals on Earth’s crust and can originate from rock-forming minerals with the low risk to the environment. Herein, the chain pyroxene mineral NaFeSi2O6 nanosheets loaded with highly dispersed Cu nanoparticles have been used as an archetype platform for the efficient photocatalytic reverse water gas shift (RWGS) reaction. The resultant Cu/NaFeSi2O6 catalyst demonstrated high performance metrics in the gas-phase photocatalytic hydrogenation of CO2 to CO, with a yield as high as 13144 μmol gcat–1 h–1. It is shown that the coordinately unsaturated Fe atom in NaFeSi2O6 can serve as a robust Lewis acid site for adsorbing and activating CO2 molecules, while the metal/support interface facilitates the formation of intermediate species and the subsequent production of CO products through hydrogen spillover. The surface plasmon resonance (SPR) effect of Cu further promotes the injection of hot electrons into NaFeSi2O6 and the carrier separation and migration at the Schottky heterojunction. This low-cost and earth-abundant mineral-based catalyst exhibits 100 h of long-term photocatalytic stability, indicating its potential as a promising and feasible candidate for the future development of renewable synthetic fuels.

Efficient Holes Abstraction by Precisely Decorating Ruthenium Single Atoms and RuOx Clusters on ZnIn2S4 for Photocatalytic Pure Water Splitting.

Developing efficient photocatalysts for two-electron water splitting with simultaneous H2O2 and H2 generation shows great promise for practical application. Currently, the efficiency of two-electron water splitting is still restricted by the low utilization of photogenerated charges, especially holes, of which the transfer rate is much slower than that of electrons. Herein, Ru single atoms and RuOx clusters are co-decorated on ZnIn2S4 (RuOx/Ru-ZIS) to employ as multifunctional sites for efficient photocatalytic pure water splitting. Doping of Ru single atoms in the ZIS basal plane enhances holes abstraction from bulk ZIS by regulating the electronic structure, and RuOx clusters offer a strong interfacial electric field to remarkably promote the out-of-plane migration of holes from ZIS. Moreover, Ru single atoms and RuOx clusters also serve as active sites for boosting surface water oxidation. As a result, an excellent H2 and H2O2 evolution rates of 581.9 µmolg-1h-1 and 464.4 µmolg-1h-1 is achieved over RuOx/Ru-ZIS under visible light irradiation, respectively, with an apparent quantum efficiency (AQE) of 4.36% at 400nm. This work paves a new way to increase charge utilization by manipulating photocatalyst using single atom and clusters.

Lattice Distortion Induced Ta‐doped BaTiO3 for Efficient Photocatalytic Water Splitting for Hydrogen Production

AbstractBaTiO3, as a perovskite type material with excellent chemical stability and suitable conduction, has been widely studied in the field of photocatalysis. However, it can only absorb ultraviolet light because of its wide band gap. Herein, the lifetime of photogenerated electrons of BaTiO3 doped with Ta5+ can be enhanced. To study the band structure and photocatalytic performance of Ta‐doped BaTiO3, sol‐gel assisted solid‐phase method was employed to prepare BaTiO3 doped with varying Ta5+ doping amounts, and the structure characteristic and formation mechanism of the Ta‐doped BaTiO3 were analyzed. The results showed that the heat treatment temperature reached 1052.7 °C, sufficient thermodynamic conditions were obtained for Ta5+ to dope into the BaTiO3 lattice, and lattice distortion occurred in BaTiO3. Meanwhile, the particle size after doping decreased with the increase of Ta5+ doping amount. The 1.25 mol %Ta5+‐doped BaTiO3 had the lowest band gap (3.077 eV), and the photocatalytic water splitting had the best hydrogen evolution activity, which was 2.4 times that of BaTiO3. Furthermore, the conductance potential of 1.25 mol %Ta5+‐doped BaTiO3 was more negative than that of BaTiO3, which improved the thermodynamic advantage of the photocatalytic water splitting, and it had higher and more stable photoresponse and photogenerated carrier migration rate.

Interfacial B-O bonding modulated S-scheme B-doped N-deficient C3N4/O-doped-C3N5 for efficient photocatalytic overall water splitting

Photocatalytic overall pure water splitting is a promising method for generating green hydrogen energy under mild conditions. However, this process is often hindered by sluggish electron-hole separation and transport. To address this, a step-scheme (S-scheme) B-doped N-deficient C3N4/O-doped C3N5 (BN-C3N4/O-C3N5) heterojunction with interfacial B-O bonds has been constructed. Utilizing Pt and Co(OH)2 as co-catalysts, BN-C3N4/O-C3N5 S-scheme heterojunction demonstrates significantly enhanced photocatalytic activity for overall pure water splitting under visible light, achieving H2 and O2 evolution rates of 40.12 and 19.62 µmol/h, respectively. Systematic characterizations and experiments revealed the performance-enhancing effects of the enhanced built-in electric field and the interfacial B-O bonding. Firstly, the strengthened built-in electric field provides sufficient force for rapid interfacial electron transport. Secondly, by reducing the transport energy barrier and transfer distance, the interfacial B-O bonds facilitate rapid recombination of electrons and holes with relatively low redox potential via the S-scheme charge-transfer route, leaving the high-potential electrons and holes available for H+ reduction and OH− oxidation reactions. Overall, the photocatalytic efficiency of BN-C3N4/O-C3N5 S-scheme heterojunction was significantly improved, making it a promising approach for green hydrogen production through overall pure water splitting.

Economical, one-pot, and green synthesis of plant-based carbon quantum dots for efficient visible-light photocatalytic dye degradation and water purification

BackgroundGreen, in-situ, one-pot, facile, and economical synthesis of efficient photocatalysts to destroy emerging aqueous contaminants is essential. MethodBiocompatible carbon quantum dots (CQDs) photocatalysts were successfully synthesized from a plant source called garden thyme as a low-cost precursor by one-step calcination method. CQDs were synthesized in both pure form and co-doped with fluorine and boron indicating size of <10 nm and favorable quantum yield of 40%. Four key factors including synthesis temperature, synthesis time, fluorine and boron weight ratios, and CQDs size were investigated on removal rates of organic pollutant Rhodamine B (RhB). Significant findings10%F-10%B co-doped CQDs with synthesized at 400 ºC for 5 h with a size of <10 nm, showed the highest photocatalytic RhB degradation performances of 86.1% and 89% within 40 and 60 min, respectively. This improved performance was originated from synergetic influences of quantum size, co-doping, promising quantum yield, and great visible light harvesting, that satisfactorily separated and transported light-created electron-hole pair. Trapping experimental data approved that hydroxyl radicals were dominant reactive species that oxidized RhB on F,B co-doped CQDs catalysts upon visible light radiation. Overall, CQDs could be easily synthesized as a green and super-cheap photocatalyst and would be effective for wastewater treatments.

Pivotal role of water vapor–mediated defect engineering on SrTiO3 nanofiber toward efficient photocatalytic water splitting

The oxygen vacancies (OVs) have played key roles as either charge carrier traps for inhibiting recombination or directly as active sites for photocatalytic redox reactions. In this study, the population and types of oxygen vacancies within the electrospun SrTiO3 nanofibers were modulated through water vapor and air atmosphere annealing respectively. Combining the distinctive 1D nanofibrous structure with optimized OVs, the water vapor–mediated OVs-rich SrTiO3 nanofibers achieved a significant enhancement in specific surface area and porosity, effectively suppressing the recombination of photogenerated carriers. The OVs can effectively promote the conversion of photon excitons into charge carriers, accelerate the carrier separation, and facilitate surface redox reaction. The optimized water vapor–mediated STO-W-700 exhibited abundant active sites and rapid surface charge separation/migration across the nanofibers, leading to an exceptional hydrogen production performance of 296.82 μmolg/h. During the photocatalytic process, the OVs act synergistically with nearby metal sites to optimize the adsorption energy of reactants. This work not only provides an effective pathway for manipulating oxygen vacancies through water vapor–mediated defect engineering strategy, but also reveals a new water splitting mechanism, laying the foundation for further research and development of efficient solar energy conversion technologies.

Phase junction CdS decorated by plasmonic Cu1.8S: Realizing directed carriers transfer path and broad solar light-response for efficient photocatalytic water splitting

Phase engineering is an emerging strategy for tuning the electronic structure by manipulating atomic configuration and accumulating the carrier transfer, making it important in the field of photocatalysis. In this paper, Cu1.8S@phase junction CdS is successfully synthesized. Phase junction CdS (HCC) exhibits band bending to optimize the separation and transfer of photogenerated carriers. The introduction of plasmonic Cu1.8S not only endows CdS with a broad photoresponse ability to the near-infrared (NIR) light region and a photothermal effect but also forms the p-n junction to further accelerate the carrier separation rate. The synergistic effect of phase junction and p-n junction realizes an excellent photocatalytic hydrogen activity in the full spectrum. Cu1.8S@HCC exhibits an H2 production rate of 3.7 mmol·g−1·h−1 and 374 μmol·g−1·h−1 under Visible (Vis)-light (780 ≥ λ ≥ 420 nm) and NIR light (λ ≥ 780 nm) illumination, which is 31 times and 9 times higher than the Vis-light driven photocatalytic H2 rate of cubic CdS and HCC. Importantly, through detailed characterization and density functional theory (DFT) calculations, the migration pathway of charge carriers and the reactive active site in multiple interfaces are determined. This work presents an exploitation of advanced photocatalysts in multiple phases for excellent solar energy conversion.

High-Throughput Computational Screening of Novel Two-Dimensional Covalent Organic Frameworks for Efficient Photocatalytic Overall Water Splitting.

The pursuit of efficient photocatalysts toward photocatalytic water splitting has attracted wide attention. However, the low efficiency of photocatalytic reactions due to the rapid electron-hole recombination and the time-consuming searching process hinder the development of high-performance photocatalysts. Here, we proposed a data-driven screening procedure for covalent organic frameworks (COFs) as overall solar water-splitting photocatalysts. Based on a COF database through assembling different Cores and Linkers, three COFs are predicted to be efficient photocatalysts for overall solar water splitting after high-throughput computational screening. We found that the photogenerated electrons and holes are well separated on single COF photocatalysts without material engineering, and both hydrogen and oxygen evolution reactions can occur spontaneously on the three screened COFs under visible light radiation. This kind of novel COF screened by a data-driven screening procedure offers new perspectives for advancing efficient photocatalysts.

Enhanced charge separation via ZnIn2S4@S-doped-C3N4 S-scheme heterojunction for efficient photocatalytic water splitting under visible light

Heterojunction photocatalysts possess high efficiency in photogenerated electron-hole separation, which give significant advantages in the field of solar hydrogen production. Herein, a novel ZnIn2S4@S doped g-C3N4 (ZIS@SCN) heterojunction with mesoporous structure was prepared for photocatalytic water splitting under visible light. Characterization showed that the element of S was successfully introduced into g-C3N4 (CN) by replacing N to form C–S–C bonds and significantly enhanced the visible light absorption ability. The constructed heterojunction exhibited excellent photocatalytic hydrogen evolution under visible light. The best performance belonged to the sample of ZIS@100SCN. The corresponding H2 production rate reached 9.3 mmol h−1 g−1, which was 1.87-fold higher than that of the undoped one. More importantly, the heterojunction realized overall water splitting of H2 and O2 evolution simultaneously with good stability. The mechanism analysis indicted that introducing the element of S could regulate the band structure of CN and induce the charge transfer switching of a ZnIn2S4@g-C3N4 (ZIS@CN) photocatalyst from Ⅰ-type to S-scheme, which promoted the efficient spatial charge separation and maintained the high redox ability of the ZIS and SCN. This work provides an insight in construction high performance S-scheme heterojunction for water splitting with a doping method.