Ultrathin layer TAFC on BiVO4 with ligand-to-metal charge transfer enhances built-in electric field for boosting photoelectrochemical water oxidation.

To reveal the mechanism of charge transfer between interfaces of BiVO4-based heterogeneous materials in photoelectrochemical water splitting system, the cocatalyst was grown in situ using tannic acid (TA) as a ligand and Fe and Co ions as metal centers (TAFC), and then uniformly and ultra-thinly coated on BiVO4 to form photoanodes. The results show that the BiVO4/TAFC achieves a superior photocurrent density (4.97 mA cm-2 at 1.23 VRHE). The charge separation and charge injection efficiencies were also significantly higher, 82.0 % and 78.9 %, respectively. From XPS, UPS, KPFM, and density functional theory calculations, Ligand-to-metal charge transfer (LMCT) acts as an electron transport highway in TAFC ultrathin layer to promote the concentration of electrons towards metal center, leading to an increase in the work function, which enhances the built-in electric field and further improves the charge transport. This study demonstrated that the LMCT pathway on TA-metal complexes enhances the built-in electric field in BiVO4/TAFC to promote charge transport and thus enhance water oxidation, providing a new understanding of the performance improvement mechanism for the surface-modified composite photoanodes.

A Self-Assembled MOF-Escherichia Coli Hybrid System for Light-Driven Fuels and Valuable Chemicals Synthesis.

The development of semi-artificial photosynthetic systems, which integrate metal-organic frameworks (MOFs) with industrial microbial cell factories for light-driven synthesis of fuels and valuable chemicals, represents a highly promising avenue for both research advancements and practical applications. In this study, an MOF (PCN-222) utilizing racemic-(4-carboxyphenyl) porphyrin and zirconium chloride (ZrCl4) as primary constituents is synthesized. Employing a self-assembly process, a hybrid system is constructed, integrating engineered Escherichia coli (E. coli) to investigate light-driven hydrogen and lysine production. These results demonstrate that the light-irradiated biohybrid system efficiently produce H2 with a quantum efficiency of 0.75% under full spectrum illumination, the elevated intracellular reducing power NADPH is also observed. By optimizing the conditions, the biohybrid system achieves a maximum lysine production of 18.25 mg L-1, surpassing that of pure bacteria by 332%. Further investigations into interfacial electron transfer mechanisms reveals that PCN-222 efficiently captures light and facilitates the transfer of photo-generated electrons into E. coli cells. It is proposed that the interfacial energy transfer process is mediated by riboflavin, with facilitation by secreted small organic acids acting as hole scavengers for PCN-222. This study establishes a crucial foundation for future research into the light-driven biomanufacturing using E. coli-based hybrid systems.

Diversity and potential host-interactions of viruses inhabiting deep-sea seamount sediments.

Seamounts are globally distributed across the oceans and form one of the major oceanic biomes. Here, we utilized combined analyses of bulk metagenome and virome to study viral communities in seamount sediments in the western Pacific Ocean. Phylogenetic analyses and the protein-sharing network demonstrate extensive diversity and previously unknown viral clades. Inference of virus-host linkages uncovers extensive interactions between viruses and dominant prokaryote lineages, and suggests that viruses play significant roles in carbon, sulfur, and nitrogen cycling by compensating or augmenting host metabolisms. Moreover, temperate viruses are predicted to be prevalent in seamount sediments, which tend to carry auxiliary metabolic genes for host survivability. Intriguingly, the geographical features of seamounts likely compromise the connectivity of viral communities and thus contribute to the high divergence of viral genetic spaces and populations across seamounts. Altogether, these findings provides knowledge essential for understanding the biogeography and ecological roles of viruses in globally widespread seamounts.

Anthraquinone-based polymer modified BiVO4 photoanode with strong electron-withdrawing functional groups for boasting photoelectrochemical water oxidation.

The photoelectrochemical (PEC) performance ofBiVO4 is limited by sluggish water oxidation kinetics and severe carrier recombination. Herein, a novel high-performance BiVO4/NiFe-NOAQ photoanode is prepared by a simple one-step hydrothermal method, using BiVO4 and 1-Nitroanthraquinone (NOAQ) as raw materials. The BiVO4/NiFe-NOAQ photoanode has an excellent photocurrent density of 5.675 mA cm-2 at 1.23 VRHE, which is 3.35 times higher than that of the pure BiVO4 (1.693 mA cm-2) photoanode. The BiVO4/NiFe-NOAQ shows a significant improvement in charge separation efficiency (86.12 %) and charge injection efficiency (87.86 %). The improvement is ascribable to the NiFe-NOAQ form a type II heterojunction with BiVO4 to inhibit carrier recombination. More importantly, the kinetic isotope experiment suggests that the proton-coupled electron transfer (PCET) process can enhance the charge transfer of BiVO4/NiFe-NOAQ. The contact angle measurements show that modifying functional groups enhanced the hydrophilicity of BiVO4/NiFe-NOAQ, which can further accelerate the PCET process. The XPS and PL results as well as the tauc plot indicate that the strong electron-withdrawing ability of -NO2 which can promote the extension of π conjugation, results in more π electron delocalization and produces more efficient active sites, thus achieving efficient photoelectrochemical water oxidation.

Inducing spin polarization via Co doping in the BiVO4 cell to enhance the built-in electric field for promotion of photocatalytic CO2 reduction.

The efficiency of CO2 photocatalytic reduction is severely limited by inefficient separation and sluggish transfer. In this study, spin polarization was induced and built-in electric field was strengthened via Co doping in the BiVO4 cell to boost photocatalytic CO2 reduction. Results showed that owing to the generation of spin-polarized electrons upon Co doping, carrier separation and photocurrent production of the Co-doped BiVO4 were enhanced. CO production during CO2 photocatalytic reduction from the Co-BiVO4 was 61.6 times of the BiVO4. Notably, application of an external magnetic field (100 mT) further boosted photocatalytic CO2 reduction from the Co-BiVO4, with 68.25 folds improvement of CO production compared to pristine BiVO4. The existence of a built-in electric field (IEF) was demonstrated through density functional theory (DFT) simulations and kelvin probe force microscopy (KPFM). Mechanism insights could be elucidated as follows: doping of magnetic Co into the BiVO4 resulted in increased the number of spin-polarized photo-excited carriers, and application of a magnetic field led to an augmentation of intrinsic electric field due to a dipole shift, thereby extending carrier lifetime and suppressing charges recombination. Additionally, HCOO- was a crucial intermediate in the process of CO2RR, and possible pathways for CO2 reduction were proposed. This study highlights the significance of built-in electric fields and the important role of spin polarization for promotion of photocatalytic CO2 reduction.

Strain Engineering of Cd0.5 Zn0.5 S Nanocrystal for Efficient Photocatalytic Hydrogen Evolution from Wasted Plastic.

The challenge of synthesizing nanocrystal photocatalysts with adjustable lattice strain for effective waste-to-energy conversion is addressed in this study. Cd0.5 Zn0.5 S (CZS) nanocrystals are synthesized by a simple solvothermal method, regulation of the ratio between N, N-dimethylformamide, and water solvent are shown to provoke expansion and contraction, inducing an adjustable lattice strain ranging from -1.2% to 5.6%. With the hydrolyzed wasted plastic as a sacrificial agent, the 5.6% lattice-strain CZS exhibited a robust hydrogen evolution activity of 1.09 mmol m-2  h-1 (13.83 mmol g-1  h-1 ), 4.5 times that of pristine CZS. Characterizations and density functional theory calculation demonstrated that lattice expansion increases the spatial distance between the valence band maximum and conduction band minimum, thus reducing carrier recombination and promoting charge transfer. Additionally, lattice expansion induces surface S vacancies and adsorbed OH groups, further enhancing redox reactions. This study focuses on the synchronous regulation of crystal structure, charge separation/transport, and surface reactions through lattice strain engineering, which providing a reference for the rational design of new photocatalysts for effective waste-to-energy conversion.

Biomass-Derived Carbon Quantum Dots Chemical Bonding with Sn-Doped Bi2 O2 CO3 Endowed Fast Carriers' Dynamics and Stabilized Oxygen Vacancies for Efficient Decontamination of Combined Pollutants.

Surface defects on photocatalysts could promote carrier separation and generate unsaturated sites for chemisorption and reactant activation. Nevertheless, the inactivation of oxygen vacancies (OVs) would deteriorate catalytic activity and limit the durability of defective materials. Herein, bagasse-derived carbon quantum dots (CQDs) are loaded on the Sn-doped Bi2 O2 CO3 (BOC) via hydrothermal procedure to create Bi─O─C chemical bonding at the interface, which not only provides efficient atomic-level interfacial electron channels for accelerating carriers transfer, but also enhances durability. The optimized Sn-BOC/CQDs-2 achieves the highest photocatalytic removal efficiencies for levofloxacin (LEV) (88.7%) and Cr (VI) (99.3%). The elimination efficiency for LEV and Cr (VI) from the Sn-BOC/CQDs-2 is maintained at 55.1% and 77.0% while the Sn-BOC is completely deactivated after four cycle tests. Furthermore, the key role of CQDs in stabilization of OVs is to replace OVs as the active center of H2 O and O2 adsorption and activation, thereby preventing reactant molecules from occupying OVs. Based on theoretical calculations of the Fukui index and intermediates identification, three possible degradation pathways of LEV are inferred. This work provides new insight into improving the stability of defective photocatalysts.

A Novel Non-Fullerene D-A Interface with Two Asymmetrical Electron Acceptors Facilitates Charge and Energy Transfer for Effective Carbon Dioxide Reduction.

Converting carbon dioxide (CO2 ) into high-value chemicals using solar energy remains a formidable challenge. In this study, the CSC@PM6:IDT6CN-M:IDT8CN-M non-fullerene small-molecule organic semiconductor is designed with highly efficient electron donor-acceptor (D-A) interface for photocatalytic reduction of CO2 . Atomic Force Microscope and Transmission Electron Microscope images confirmed the formation of an interpenetrating fibrillar network after combination of donor and acceptor. The CO yield from the CSC@PM6:IDT6CN-M:IDT8CN-M reached 1346 µmol g-1  h-1 , surpassing those of numerous reported inorganic photocatalysts. The D-A structure effectively facilitated charge separation to enable electrons transfer from the PM6 to IDT6CN-M:IDT8CN-M. Meanwhile, attributing to the dipole moments of the strong intermolecular interactions between IDT6CN-M and IDT8CN-M, the intermolecular forces are enhanced, and laminar stacking and π-π stacking are strengthened, thereby reinforcing energy transfer between acceptor molecules and significantly enhanced charge separation. Moreover, the strong internal electric field in the D-A interface enhanced the excited state lifetime of PM6:IDT6CN-M:IDT8CN-M. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that carboxylate (COOH*) is the predominant intermediate during CO2 reduction, and possible pathways of CO2 reduction to CO are deduced. This study presents a novel approach for designing materials with D-A interface to achieve high photocatalytic activity.

Small Molecule Cocktails Promote Fibroblast-to-Leydig-like Cell Conversion for Hypogonadism Therapy.

Male hypogonadism arises from the inadequate production of testosterone (T) by the testes, primarily due to Leydig cell (LC) dysfunction. Small molecules possess several advantages, including high cell permeability, ease of synthesis, standardization, and low effective concentration. Recent investigations have illuminated the potential of small molecule combinations to facilitate direct lineage reprogramming, removing the need for transgenes by modulating cellular signaling pathways and epigenetic modifications. In this study, we have identified a specific cocktail of small molecules, comprising forskolin, DAPT, purmorphamine, 8-Br-cAMP, 20α-hydroxycholesterol, and SAG, capable of promoting the conversion of fibroblasts into Leydig-like cells (LLCs). These LLCs expressed key genes involved in testosterone synthesis, such as Star, Cyp11a1, and Hsd3b1, and exhibited the ability to secrete testosterone in vitro. Furthermore, they successfully restored serum testosterone levels in testosterone-castrated mice in vivo. The small molecule cocktails also induced alterations in the epigenetic marks, specifically H3K4me3, and enhanced chromosomal accessibility on core steroidogenesis genes. This study presents a reliable methodology for generating Leydig-like seed cells that holds promise as a novel therapeutic approach for hypogonadism.

Sn and dual-oxygen-vacancy in the Z-scheme Bi2Sn2O7/Sn/NiAl-layered double hydroxide heterojunction synergistically enhanced photocatalytic activity toward carbon dioxide reduction.

Photocatalytic conversion of carbon dioxide (CO2) into high value-added chemicals is an attractive yet challenging process, primarily due to the readily recombination of hole-electron pairs in photocatalysts. Herein, dual-oxygen-vacancy mediated Z-scheme Bi2Sn2O7/Sn/NiAl-layered double hydroxide (VO,O-20BSL) heterojunctions were hydrothermally synthesized and subsequently modified with Sn monomers to enhance photocatalytic activity toward CO2 reduction. The abundance of oxygen vacancies endowed the VO,O-20BSL with extended optical adsorption, enhanced charges separation, and superior CO2 adsorption and activation. The interfacial charges transfer of the VO,O-20BSL was demonstrated to follow a Z-scheme mechanism via photochemical deposition of metal/metal oxide. Under visible light irradiation, the VO,O-20BSL exhibited the highest yields of carbon monoxide (CO) and methane (CH4), with values of 72.03 and 0.85 umol·g-1·h-1, respectively, which were 2.66 and 1.57 times higher than that of the VO-NiAl-layered double hydroxide (VO-1LDH). In situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) revealed that carboxylic acid groups (COOH*) and aldehyde groups (CHO*) were the predominant intermediates during CO2 reduction, and accordingly, possible CO2 reduction pathways and mechanism were proposed. This study presents a feasible approach to incorporate dual vacancies into Z-scheme heterojunctions for CO2 reduction.

Electrochemical surface reconstruction of Prussian blue-modified nickel sulfide to form iron-nickel bilayer hydroxyl oxides for efficient and stable oxygen evolution reaction processes.

The oxygen evolution reaction (OER) is an important semi-reaction in the electrocatalytic water splitting for hydrogen energy production, and the development of efficient and low-cost electrocatalysts to solve the problem of slow 4-electron transport kinetics in the OER process is key. In this work, a pre-electrocatalyst with the heterogeneous interfacial structure, Prussian blue-modified nickel sulfide with sulfur vacancies (PB/NS-Sv), was designed and then converted to iron-nickel bilayer hydroxyl oxides in oxygen-rich vacancies (FeOOH/NiOOH-Ov@NS) through electrochemical oxidative reconstruction to obtain a truly stable and efficient active material. The study utilized in situ Raman to observe the transition from PB/NS-Sv to FeOOH/NiOOH-Ov@NS during the reaction. The electronic density of states in FeOOH/NiOOH-Ov@NS is regulated by the bilayer hydroxyl metal oxide synergistic effect and the abundant oxygen defect of Mental-OOH-Ov, which significantly improves OER catalytic performance. FeOOH/NiOOH-Ov@NS requires a low overpotential of only 257 mV in 1 mol/L KOH at 100 mA cm-2 current density, has a small Tafel slope of 35.2 mV dec-1 and has excellent stability for 150 h at 100 mA cm-2 current density, making it a promising candidate for industrial applications.

Redox-active ligands enhance oxygen evolution reaction activity: Regulating the spin state of ferric ions and accelerating electron transfer.

Metal-organic frameworks (MOFs) are considered as one of the most promising catalysts for oxygen evolution reaction (OER). However, only a few have introduced redox-active ligands into MOFs and explored their role in the OER process. In this work, we synthesized FeNi DHBQ/NF using the redox-active ligand 2,5-dihydroxy-1,4-benzoquinone (DHBQ), which exhibited excellent redox activity and required only 207 and 242 mV overpotentials to achieve current densities of 10 and 100 mA cm-2. Our research confirms that (i) the doping of Fe leads to the formation of Ni â†’ O â†’ Fe electron transfer channels in the MOFs and stronger electron transfer, attributed to the stronger d-π conjugation between the metal center and the ligand and reduced the d-orbital crystal field splitting energy of Fe3+; (ii) the rate determination step (RDS) in the OER process of the catalyst is the formation of O*, while Fe and redox-active ligands effectively regulate the adsorption energy of oxygen-containing intermediates, reducing the energy barrier of the RDS; (iii) the redox-active ligands can act as "electron reservoirs" in the electrochemical process, making Ni more readily oxidized to Ni3+ or even Ni4+ at low potentials, which is beneficial to the subsequent OER process.

Adjusting the valence band center of Co-Ni-bimetallic sulfides through lattice expansion and stacking faults triggered by strain engineering to boost oxygen evolution reaction.

Stress engineering can improve catalytic performance by straining the catalyst lattice. An electrocatalyst, Co3S4/Ni3S2-10%Mo@NC, was prepared with abundant lattice distortion to boost oxygen evolution reaction (OER). With the assistance of the intramolecular steric hindrance effect of metal-organic frameworks, slow dissolution by MoO42- of the Ni substrate and recrystallization of Ni2+ was observed in the process of Co(OH)F crystal growth with mild temperature and short time reaction. The lattice expansion and stacking faults created defects inside the Co3S4 crystal, improved the material conductivity, optimized the valence band electron distribution of the material, and promoted the rapid conversion of the reaction intermediates. The presence of reactive intermediates of the OER under catalytic conditions was investigated using operando Raman spectroscopy. The electrocatalysts exhibited super high performance, a current density of 10 mA cm-2 at an overpotential of 164 mV and 100 mA cm-2 at 223 mV, which were comparable to those of integrated RuO2. Our work for the first time demonstrates that the dissolution-recrystallization triggered by strain engineering is a good modulation approach to adjust the structure and surface activity of catalyst, suggesting promising industrial application.

Amorphous dominated metal hydroxide-organic framework with compositional and structural heterogeneity for enhancing anodic electro-oxidation reactions.

Inorganic-organic hybrids are promising anode catalysts to realize high activity and stability. Herein, an amorphous-dominated transition metal hydroxide-organic framework (MHOF) with isostructural mixed-linker was successfully synthesized on nickel foam (NF) substrate. The designed IML24-MHOF/NF exhibited remarkable electrocatalytic activity with an ultralow overpotential of 271 mV for oxygen evolution reaction (OER) and a potential of 1.29 V vs. reversible hydrogen electrode for urea oxidation reaction (UOR) at 10 mA·cm-2. Furthermore, the IML24-MHOF/NF||Pt-C cell required only 1.31 V for urea electrolysis at 10 mA·cm-2, which was much smaller than traditional water splitting (1.50 V). When coupled with UOR, the hydrogen yield rate was faster (1.04 mmol·h-1) than with OER (0.32 mmol·h-1) at 1.6 V. The structure characterizations, together with operando monitoring, including operando Raman, Fourier transform infrared, electrochemical impedance spectroscopy, and alcohol molecules probe, revealed that: (1) amorphous IML24-MHOF/NF prefers self-adaptive reconstruction into active intermediate species against the external stimulus; (2) pyridine-3,5-dicarboxylate-incorporation into parent framework reconfigures electronic structure of system, thus mediating the absorption of oxygen-containing reactants during anodic oxidation reactions, such as O* and COO*. This work provides a new approach for boosting the catalytic activity of anodic electro-oxidation reactions by trimming the structure of MHOF-based catalysts.

Unraveling the π-interaction of NiFe-based metal-organic frameworks with enhanced oxygen evolution: Optimizing electronic structure and facilitating electron transfer modulation.

Metal-organic frameworks (MOFs) with conjugation carboxylate ligands as electrocatalysts can significantly improve oxygen evolution reaction (OER), but the role of π-interaction on the reactive sites of OER is often neglected. We intend to unravel the mechanism of how π-interaction enhances OER performance. The results of Rietveld refinement, density functional theory (DFT) calculations, and in-situ Raman spectra show that π-interaction can efficiently modulate the local spin configuration of metal centers, facilitate γ-Ni1-xFexOOH active species with high-valence Ni sites modified by high-spin Fe, accelerate electron transfer, optimize the d-band center together with the beneficial rate-determining step of OER. NiFe-BPDC MOFs/NF with 0.8559 eV π-interaction energy generated γ-Ni1-xFexOOH in only 60 s at 1.4 V, demonstrating that π-interaction promotes the rapid generation of highly active reactive sites. Furthermore, the results of in-situ Raman and electron paramagnetic resonance (EPR) spectra reveal that the deprotonation and deoxygenation steps of OER are accompanied by changes in the oxidation state of metal ions and the generation of oxygen vacancies on the surface of catalysts. In addition, NiFe-BPDC MOFs/NF rapidly completes the deprotonation and deoxygenation steps, and it requires only 288 mV overpotential to reach 100 mA/cm2 with 100 h of stability, suggesting promising industrial application.

Dual modification based on electrostatic repulsion of bentonite and SPR effect of Bi facilitate charge transfer of Bi2WO6 for antibiotics degradation.

Development of efficient photocatalysts is vital for light-driven removal of refractory antibiotics. Herein, Bi2WO6 microspheres were successfully anchored on the surface of bentonite, and metallic Bi was reduced in-situ by a one-step solvothermal method. Notably, the Bi/Bi2WO6/BT with a mass ratio of 0.15:1:0.1 exhibited the best photocatalytic activity toward degradation of tetracycline (TC) and ciprofloxacin (CIP) after 120 min of visible light irradiation, and their reaction rate constants were 8.0 and 5.5 folds higher than that of pristine Bi2WO6, respectively. The boosted photocatalytic activity over Bi/Bi2WO6/BT was ascribed to the establishment of electrostatic repulsion and SPR effect, which synergistically promoted charges transfer, thus achieving more h+ and ·O2- radical generation. Moreover, possible TC and CIP degradation pathways over Bi/Bi2WO6/BT were proposed based on the identified intermediates, and most of the intermediates were less toxic than TC and CIP. The study provides options to develop high-efficiency photocatalytic composites for contaminants elimination using semiconductors and readily available bentonite.

Flower-like microspheres Z-scheme Bi2Sn2O7/NiAl-LDH heterojunction for boosting photocatalytic CO2 reduction under visible light.

Fabrication of efficient photocatalysts with great visible light utilization ability, rapid carriers' separation, and suitable redox potential is essential for improving photocatalytic CO2 reduction. Herein, flower-like microspheres Bi2Sn2O7/NiAl-layered double hydroxide (BSO/LDH) heterojunctions were prepared by hydrothermal process for CO2 reduction. The Bi2Sn2O7 nanoparticles were dispersed on NiAl-LDH nanosheets, with tight contact interface, which facilitated charges transfer and exposing more catalytic active sites. Results of photochemical deposition of metal/metal oxide demonstrated that interfacial charges transfer of the BSO/LDH followed Z-scheme mechanism, endowing more desired redox potential and more efficient carriers separation. The 30%-BSO/LDH showed the highest CO and CH4 yields of 37.91 and 1.18 µmol g-1 h-1 under visible light irradiation, 3.4 and 2.0 times higher than those from the NiAl-LDH, respectively. The main intermediates during CO2 reduction were carboxylate (COOH*) and aldehyde group (CHO*), and CO2 reduction pathways and mechanism were proposed accordingly. This study provided referential strategy for designing efficient heterojunction photocatalysts for CO2 conversion.

Z-scheme CoAl-layereddoublehydroxide/indium vanadate heterojunction for enhanced and highly selective photocatalytic reduction of carbon dioxide to carbon monoxide.

Development of efficient photocatalysts is essential for carbon dioxide (CO2) photocatalytic reduction. In this study, Z-scheme CoAl-layered double hydroxide (LDH)/indium vanadate (InVO4) heterojunction photocatalysts were synthesized using hydrothermal method, and their performance toward CO2 reduction and mechanism were determined. Results of characterizations showed that the CoAl-LDH/InVO4-30 exhibited desired morphology, the most efficient photogenerated carriers separation and charge transfer, and the highest photocurrent response. X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) manifested that charge transfer of the CoAl-LDH/InVO4 conformed to Z-scheme mechanism. The CoAl-LDH/InVO4-30 exhibited the highest carbon monoxide (CO) yield of 174.4 µmol g-1 within 2 h of reaction, which was 2.46 and 9.79 times of pure CoAl-LDH and InVO4, respectively. The CO selectivity was up to nearly 100%. Moreover, in-situ fourier transform infrared spectroscopy (ISFT-IR) demonstrated that bicarbonate (HCO3*) and carboxylate (COOH*) were the main intermediates during the CO2 reduction process, and possible CO2 reduction pathways were proposed. This work provides a reference for construction of Z-scheme LDH-based heterojunctions for efficient CO2 photoreduction.

Visible light driven antibiotics degradation using S-scheme Bi2WO6/CoIn2S4 heterojunction: Mechanism, degradation pathways and toxicity assessment.

S-scheme heterojunction photocatalysts with strong redox ability and excellent photocatalytic activity are highly desired for photocatalytic degradation of pollutants. Herein, S-scheme Bi2WO6/CoIn2S4 heterojunctions were synthesized using hydrothermal method. The photo-induced carriers transfer mechanism of the S-scheme Bi2WO6/CoIn2S4 heterojunction was clarified by band structure analysis, ultraviolet photoelectron spectrometer (UPS), electron spin resonance (ESR) and radical trapping experiments. Significant enhance of light absortion, and more efficient carriers separation were observed from the Bi2WO6/CoIn2S4 with CoIn2S4 nanoclusters growing on the surface of petal-like Bi2WO6 nanosheets. TC degradation efficiency of 90% was achieved by Bi2WO6/CoIn2S4 (15:1) within 3 h of irradiation, and ·O2-and ·OH radicals were dominated contributors. Possible decomposition pathways of TC were proposed, and ECOSAR analysis showed that most of the intermediates exhibited lower ecotoxicity than TC. This work provides reference on the constructing ternary-metal-sulfides-based S-scheme heterojunctions for improving photocatalytic performance.

Microelectronic structure changes electron utilization: Core-shell structure catalysts with electron library and quantum dots for photocatalytic hydrogen production.

Photocatalysis is facing huge challenges especially the separation and efficient utilization of photocarriers. Herein, we report that a ternary hollow core-shell photocatalyst is synthesized by template and self-assembled method. The experimental results show that the electron separation efficiency and utilization efficiency are significantly improved, not only because the ternary hollow core-shell structure spatially separates the oxidation area MnOx from the reduction area Co-MOF, but also because lots of emergent electrons are stored in Co-MOF as an electronic library, contributing to the formation of surface polarization to support the requirement call from the CoP quantum dots (QDs) as active-sites. It's the first report that the effectively separated electron-rich and electron-poor microelectronic states of the tunable Co-MOF promotes electron utilization by affecting the storage capacity of the electron library promoting photocatalytic hydrogen production. The tests show that Mn@Cd-CoP QDs/MCN (35.31 mmol/h/g), Mn@Cd-CoP QDs/BCN (23.69 mmol/h/g) and Mn@Cd-CoP QDs (11.08 mmol/h/g) have the better hydrogen production performances, which is about 38 times, 26 times and 12 times higher than CdS (0.9244 mmol/h/g), respectively. The pioneering exploration about the ternary hollow core-shell structure bonded with MOFs materials with abundant CoP QDs will open up a new perspective to design high-performance for solar-chemical energy conversion.