Alternating 3rd- to 2nd-Order Charge Reaction Kinetics on Bismuth Vanadate Photoanodes with Ultrathin Bismuth Metal-Organic-Frameworks.

The most challenging obstacle for photocatalysts to efficiently harvest solar energy is the sluggish surface redox reaction (e. g., oxygen evolution reaction, OER) kinetics, which is believed to originate from interface catalysis rather than the semiconductor photophysics. In this work, we developed a light-modulated transient photocurrent (LMTPC) method for investigating surface charge accumulation and reaction on the W-doped bismuth vanadate (W : BiVO4) photoanodes during photoelectrochemical water oxidation. Under illuminating conditions, the steady photocurrent corresponds to the charge transfer rate/kinetics, while the integration of photocurrent (I~t) spikes during the dark period is regarded as the charge density under illumination. Quantitative analysis of the surface hole densities and photocurrents at 0.6 V vs. reversible hydrogen electrode results in an interesting rate-law kinetics switch: a 3rd-order charge reaction behavior appeared on W : BiVO4, but a 2nd-order charge reaction occurred on W : BiVO4 surface modified with ultrathin Bi metal-organic-framework (Bi-MOF). Consequently, the photocurrent for water oxidation on W : BiVO4/Bi-MOF displayed a 50 % increment. The reaction kinetics alternation with new interface reconstruction is proposed for new mechanism understanding and/or high-performance photocatalytic applications.

Recent Advances and Challenges in Efficient Selective Photocatalytic CO2 Methanation.

Solar-driven carbon dioxide (CO2 ) methanation holds significant research value in the context of carbon emission reduction and energy crisis. However, this eight-electron catalytic reaction presents substantial challenges in catalytic activity and selectivity. In this regard, researchers have conducted extensive exploration and achieved significant developments. This review provides an overview of the recent advances and challenges in efficient selective photocatalytic CO2 methanation. It begins by discussing the fundamental principles and challenges in detail, analyzing strategies for improving the efficiency of photocatalytic CO2 conversion to CH4 comprehensively. Subsequently, it outlines the recent applications and advanced characterization methods for photocatalytic CO2 methanation. Finally, this review highlights the prospects and opportunities in this area, aiming to inspire CO2 conversion into high-value CH4 and shed light on the research of catalytic mechanisms.

Electronic Structure Modulation of Oxygen-Enriched Defective CdS for Efficient Photocatalytic H2 O2 Production.

Artificial photosynthesis for hydrogen peroxide (H2 O2 ) presents a sustainable and environmentally friendly approach to generate clean fuel and chemicals. However, the catalytic activity is hindered by challenges such as severe charge recombination, insufficient active sites, and poor selectivity. Here, a robust strategy is proposed to regulate the electronic structure of catalyst by the collaborative effect of defect engineering and dopant. The well designed oxygen-doped CdS nanorods with S2- defects and Cd2+ 4d10 electron configuration (CdS-O,Sv ) is successfully synthesized, and the Cd2+ active sites around S defects or oxygen atoms exhibit rapid charge separation, suppressed carrier recombination, and enhanced charge utilization. Consequently, a remarkable H2 O2 production rate of 1.62 mmol g-1  h-1 under air conditions is acquired, with an apparent quantum yield (AQY) of 9.96% at a single wavelength of 450 nm. This work provides valuable insights into the synergistic effect between defect and doping on catalytic activity.

Recent advances in ambient-stable black phosphorus materials for artificial catalytic nitrogen cycle in environment and energy.

Nitrogen cycle is crucial for the Earth's ecosystem and human-nature coexistence. However, excessive fertilizer use and industrial contamination disrupt this balance. Semiconductor-based artificial nitrogen cycle strategies are being actively researched to address this issue. Black phosphorus (BP) exhibits remarkable performance and significant potential in this area due to its unique physical and chemical properties. Nevertheless, its practical application is hindered by ambient instability. This review covers the synthesis methods of BP materials, analyzes their instability factors under environmental conditions, discusses stability improvement strategies, and provides an overview of the applications of ambient-stable BP materials in nitrogen cycle, including N2 fixation, NO3- reduction, NOx removal and nitrides sensing. The review concludes by summarizing the challenges and prospects of BP materials in the nitrogen cycle, offering valuable guidance to researchers.

Recent advances of pure/independent covalent organic framework membrane materials: preparation, properties and separation applications.

Covalent organic frameworks (COF) are porous crystalline polymers connected by covalent bonds. Due to their inherent high specific surface area, tunable pore size, and good stability, they have attracted extensive attention from researchers. In recent years, COF membrane materials developed rapidly, and a large amount of research work has been presented on the preparation methods, properties, and applications of COF membranes. This review focuses on the research on independent/pure continuous COF membranes. First, based on the membrane formation mechanism, COF membrane preparation methods are categorized into two main groups: bottom-up and top-down. Four methods are presented, namely, solvothermal, interfacial polymerization, steam-assisted conversion, and layer by layer. Then, the aperture, hydrophilicity/hydrophobicity and surface charge properties of COF membranes are summarized and outlined. According to the application directions of gas separation, water treatment, organic solvent nanofiltration, pervaporation and energy, the latest research results of COF membranes are presented. Finally, the challenges and future directions of COF membranes are summarized and an outlook provided. It is hoped that this work will inspire and motivate researchers in related fields.

Multifunctional Solar Evaporator with Adjustable Island Structure Improves Performance and Salt Discharge Capacity of Desalination.

Interfacial solar steam generation (ISSG) is the main method to get fresh water from seawater or wastewater. The balance between evaporation rate and salt resistance is still a major challenge for ISSG. Herein, a wood aerogel island solar evaporator (WAISE) with tunable surface structure and wettability by synthesizing poly(n-isopropylacrylamide)-modified multi-walled carbon nanotube photothermal layers. Compared to dense surface structure evaporators, interfacial moisture transport, thermal localization, and surface water vapor diffusion of WAISE are greatly promoted, and the evaporation rate of WAISE increased by 87.64%. WAISE allows for record performance of 200 h continuous operation in 20% NaCl solution without salt accumulation. In addition, the photo-thermal-electric device is developed based on WAISE with continuous water purification, power generation, and irrigation functions. This work provides a new direction for the development of multifunctional water purification systems.

Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes.

An oxidative strategy is reported to access α-oxo BMIDA gold carbenes directly from BMIDA-terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C-H bonds in the absence of the Thorpe-Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F-C alkylations. This chemistry provides rapid access to structurally diverse α-BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron-donating group that attenuates the high electrophilicity of the gold carbene center.

Biomimetic cellulose-nanocrystalline-based composite membrane with high flux for efficient purification of oil-in-water emulsions.

The massive discharge of oily wastewater and oil spills are causing serious pollution to water resources. It is urgent to require clean and efficient method of purifying oily emulsions. Although the separation membranes with selective wettability have been widely used in the efficient purification of oil/water emulsions. It is still very challenging to develop functional films that are environmentally friendly, fouling resistant, inexpensive, easy to prepare, easy to scale, and highly efficient. Cellulose nanocrystalline-based composite membranes (CCM) were prepared by surface-initiated atom transfer radical polymerization (SATRP) and vacuum self-assembly. The prepared CCM is superhydrophilic and superoleophobic underwater due to the hydrophilic nature of the modified cellulose-nanocrystalline and the micro-nano surface structure. The CCM shows high separation efficiency (> 99.9 %), high flux (16,692 L-1·m-2·h-1·bar-1) for surfactant-stabilized oil-in-water emulsions, good cycle stability and anti-fouling performance. This biomass-derived membrane is green, cheap, easy to manufacture, scalable, super-wettability, and durability, it promises to be an alternative to separation membranes in today's market.

Two-dimensional nanomaterials: synthesis and applications in photothermal catalysis.

Photothermal catalysis, as one of the emerging technologies with synergistic effects of photochemistry and thermochemistry, is highly attractive in the fields of environment and energy. Two-dimensional (2D) nanomaterials have received extensive attention toward photothermal catalysis because of their ultrathin layer structures, superior physical and optical properties, and high surface areas. These merits are beneficial for shortening the transfer distance of charge carriers, improving the efficiency of solar to thermal, and providing a great opportunity for the development of photothermal chemistry. In this review, we have summarized the state-of-art advances in various 2D nanomaterials with emphasis on the driving force and relevant mechanism of photothermal catalysis, including the involved three types, namely, localized surface plasmonic resonance (LSPR), nonradiative relaxation, and thermal vibrations of molecules. Moreover, the synthesis strategies of 2D materials and their photothermal applications in carbon dioxide (CO2) conversion, hydrogen (H2) production, volatile organic compounds (VOCs) degradation, and water (H2O) purification have been discussed in detail. Ultimately, the existing challenges and prospects of future development in the field are proposed. It is believed that this review will afford a great reference for the exploration of the high-efficiency 2D nanomaterials and their structure-activity relationship.

A 3D smart wood membrane with high flux and efficiency for separation of stabilized oil/water emulsions.

Oily sewage discharged from indiscriminate industrial and frequent oil spills have become a serious global problem. There is an urgent need to separate stable oil/water emulsions by efficient and environmentally friendly methods. Membrane separation technology has the advantages of low energy consumption and low cost, thus is an effective solution to the problems of oily wastewater. However, the manufacture of multifunctional membranes with high efficiency, high flux and self-cleaning using renewable materials remains a challenge. Herein, three-dimensional (3D) smart membranes with switchable superhydrophobic-hydrophilic surfaces were prepared by grafting photo-responsive poly-spiropyran (PSP) on wood-based substrates via surface atom transfer radical polymerization. This novel membrane can efficiently separate stabilized water-in-oil and oil-in-water emulsions due to reversible hydrophilic-hydrophobic transition by switching UV and visible light irradiation. Remarkably, after immobilization, the PSP grafted on the wood substrate exhibited a faster photo response effect than the free spiropyran (SP). More importantly, the prepared 3D smart membranes showed exceptional high flux (4392 L•m-2•h-1) and efficiency (above 99.99 %), good cycle stability (99.99 % after 12 times) and durability (available for at least 60 days) for the separation of surfactant-stabilized water-in-oil emulsions. This work opens a new avenue for the design of functional biomass-derived membranes for efficient and sustainable oily wastewater treatment with high flux, easy scale-up, and green regeneration.

A polydimethylsiloxane-based sponge for water purification and interfacial solar steam generation.

A better knowledge for the design and synthesis of low-cost, novel porous materials is highly desirable in various fields such as recyclable solar desalination and liquid recycling. Herein, a polydimethylsiloxane-based sponge with a web-like three-dimensional (3D) interconnected porous structure was developed for effective recovery of liquids and the continuous interfacial solar steam generation (ISSG). The sponge is capable of conducting directional transport of oil or organic solvents at temperatures above 32 °C while automatically controlling the desorption of the organic phase below 28 °C. The synergistic combination between high light absorption (above 95 %) and light-to-heat conversion efficiency (99.87 %) resulted in a considerably high seawater evaporation rate (1.66 Kg m-2h-1) under 1 sun. The self-regeneration of the evaporator is facilitated by the salt barrier function of the large channels of the smart sponge with high hydraulic conductivity. This sponge can maintain a maximum evaporation rate up to the 5 consecutive days operation with the co-benefit of real-time regeneration and the reversible switching of the wettability. The reusable smart sponge evaporators are highly efficient in generating clean water from seawater with satisfactory ion rejection rates (above 99.6 %). As such, the prepared sponge shows great potential in environmental restoration, metal recovery, and water regeneration.

Recent advances in high-crystalline conjugated organic polymeric materials for photocatalytic CO2 conversion.

The photocatalytic conversion of carbon dioxide (CO2) to high-value-added fuels is a meaningful strategy to achieve carbon neutrality and alleviate the energy crisis. However, the low efficiency, poor selectivity, and insufficient product variety greatly limit its practical applications. In this regard, conjugated organic polymeric materials including carbon nitride (g-C3N4), covalent organic frameworks (COFs), and covalent triazine frameworks (CTFs) exhibit enormous potential owing to their structural diversity and functional tunability. Nevertheless, their catalytic activities are largely suppressed by the traditional amorphous or weakly crystalline structures. Therefore, constructing relevant high-crystalline materials to ameliorate their inherent drawbacks is an efficient strategy to enhance the photocatalytic performance of conjugated organic polymeric materials. In this review, the advantages of high-crystalline organic polymeric materials including reducing the concentration of defects, enhancing the built-in electric field, reducing the interlayer hydrogen bonding, and crystal plane regulation are highlighted. Furthermore, the strategies for their synthesis such as molten-salt, solid salt template, and microwave-assisted methods are comprehensively summarized, while the modification strategies including defect engineering, element doping, surface loading, and heterojunction construction are elaborated for enhancing their photocatalytic activities. Ultimately, the challenges and opportunities of high-crystalline conjugated organic polymeric materials in photocatalytic CO2 conversion are prospected to give some inspiration and guidance for researchers.

Reaction Kinetics of Photoelectrochemical CO2 Reduction on a CuBi2O4-Based Photocathode.

The CO2 reduction reaction (CO2RR) is an essential step in natural photosynthesis and artificial photosynthesis to provide carbohydrate foods and hydrocarbon energy in the carbon-neutral cycle. However, the current solar conversion efficiencies and/or product selectivity of the CO2RR are very sluggish due to its complicated multiple-step charge transfer reactions. Here, we systematically investigate the charge transfer reaction rate during CO2 reduction on CuBi2O4 photocathodes, where the surface is modified with 3-aminopropyltriethoxysilane (APTES). We discover that the surface amine group increases the charge separation rate, significantly enhancing the surface charge transfer reaction rate. However, the surface acidity has less influence on the first-order reaction, indicating that a rate-determining step (RDS) exists in the early stage of the photoelectrochemical cell (PEC) processes. Moreover, the intensity-modulated photocurrent spectroscopy (IMPS) confirms that both surface charge transfer and the recombination rate on APTES-coated CuBi2O4 are larger than bare CuBi2O4 while possessing comparable charge transfer efficiencies. Overall, the surface charge transfer reactions under the PEC condition require designing more effective nanostructured photoelectrodes and powerful characterization methods to intrinsically increase the charge separation and transfer rate while reducing the recombination rate.

Construction of BiVO4/NiCo2O4 nanosheet Z-scheme heterojunction for highly boost solar water oxidation.

The sluggish water oxidation process is a severe obstacle for solar-driven water splitting. Therefore, it is imperative to develop a suitable photocatalyst with reduced energy barrier for strong oxidation. In this study, a Z-scheme BiVO4/NiCo2O4 (BVO/NCO) heterojunction system was designed by decorating ultrathin nickel-cobalt (NiCo2O4) spinel nanosheets on BiVO4 as an efficient photocatalyst for water oxidation. The unique structure of the system significantly reduced the energy barrier and improved the oxidation ability of BiVO4 to efficiently enhance the separation and transfer of the photogenerated carriers. Thus, the photocatalyst delivered an excellent O2 evolution performance of 1640.9 µmol∙g-1∙h-1 and showed 124% improved efficiency as compared to pristine BiVO4 and a quantum efficiency of 5.39% at 400 nm for O2 evolution. Additionally, the theoretical calculations revealed that the formation of *OOH was the rate-determining step for water oxidation. The decoration with NiCo2O4 significantly reduced the energy barrier between *O and *OOH, which eventually improved the photocatalytic performance of BVO/NCO. The results hold great promise for the potential application of spinel-based materials in efficient photocatalytic O2 evolution and offer fundamental insights into the design of efficient water oxidation heterojunctions.

Conductive metal and covalent organic frameworks for electrocatalysis: design principles, recent progress and perspective.

Metal and covalent organic frameworks (MOFs/COFs) are emerging promising candidates in the field of catalysts due to their porous nature, chemically well-defined active sites and structural diversity. However, they are typically provided with poor electrical conductivity, which is insufficient for them to work as satisfying electrocatalysts. Designing and fabricating MOFs/COFs with high conductivity presents a new avenue towards special electrochemical reactions. This minireview firstly highlighted the origin and design principles of conductive MOFs/COFs for electrocatalysis on the basis of typical charge transfer mechanisms, that is "through space", "extended conjugation" and "through bond". An overview of conductive MOFs/COFs used in the electrocatalytic carbon dioxide reduction reaction (CO2RR), water splitting and the oxygen reduction reaction (ORR) was then made to track the very recent progress. In the final remarks, the present challenges and perspectives for the use of conductive MOFs/COFs as electrocatalysts including their structural optimization, feasible applications and structure-activity correlation are proposed.

Highly Selective and Efficient Solar-Light-Driven CO2 Conversion with an Ambient-Stable 2D/2D Co2 P@BP/g-C3 N4 Heterojunction.

Renewable solar-driven carbon dioxide (CO2 ) conversion to highly valuable fuels is an economical and prospective strategy for both the energy crisis and ecological environment disorder. However, the selectivity and activity of current photocatalysts have great room for improvement due to the diversification and complexity of products. Here, an ambient-stable 2D/2D Co2 P@BP/g-C3 N4 heterojunction is designed for highly selective and efficient photocatalytic CO2 reduction reaction. The resulting Co2 P@BP/g-C3 N4 material has a remarkable conversion of CO2 to carbon monoxide (CO) with an ≈96% selectivity, coupled with a dramatically increased CO generation rate of 16.21 µmol g-1 h-1 , which is 5.4 times higher than pristine graphitic carbon nitride (g-C3 N4 ). In addition, this photocatalyst exhibits good ambient stability of black phosphorus (BP) without oxidation even over 180 days. The excellent photocatalytic selectivity and activity of Co2 P@BP/g-C3 N4 heterojunction are attributed to its lower energy barriers of *COOH, *CO, and *+CO in the process of CO2 reduction, coupled with rapid charge transfer at the heterointerfaces of BP/g-C3 N4 and Co2 P/BP. This is solidly verified by both density functional theory calculation and mechanism experiments. Therefore, this work holds great promise for an ambient-stable efficient and high selectivity photocatalyst in solar-driven CO2 conversion.

Observation of 4th-order water oxidation kinetics by time-resolved photovoltage spectroscopy.

Artificial photo-driven water oxidation has been proposed over half a century through a four-charge involved multiple-step oxygen evolution process. However, the knowledge of the intrinsic activity, such as the rate-law of the water oxidation reactions, has been inadequately studied. Up to date, the highest order reported is the third one under photoelectrochemical condition. In this work, we identified the fourth-order charge decay reactions on hematite by using a time-resolved surface photovoltage probe technique. A theoretical turnover frequency (TOF) > 100 nm-2·s-1 can be expected for O2 molecules when the hole density >0.1 nm-2. This work demonstrates a facile and robust method to investigate the high-order reaction kinetics. More excitingly, this research built the bridge between the rate-law, rate-determining step, and energy barrier of intermediates.

Photoenzymatic Catalytic Cascade System of a Pyromellitic Diimide/g-C3N4 Heterojunction to Efficiently Regenerate NADH for Highly Selective CO2 Reduction toward Formic Acid.

Photocatalytic reduction of carbon dioxide (CO2) holds great promise for both clean energy and environment protection. However, the low activity and poor selectivity of photocatalysts are the main bottlenecks. Herein, inspired by artificial photosynthesis and taking advantages of high efficiency and specificity of bioenzymes, we marry photo with enzyme to synergistically solve the above problems. A metal-free heterojunction of pyromellitic diimide/g-C3N4 (PDI/CN) with an excellent visible light response (λ < 660 nm) is fabricated for achieving a photoenzymatic catalytic cascade system, which efficiently regenerates nicotinamide adenine dinucleotide (NADH) and selectively reduces CO2 to formic acid (HCOOH). The highest NADH yield of the PDI/CN hybrid achieved is 75%, and the HCOOH generation rate achieved is 1.269 mmol g-1 h-1 with nearly 100% selectivity, which is much higher than those of the reported materials. The excellent photocatalytic performance is attributed to the unique photoenzymatic catalytic cascade system, heterointerface effect, good conductivity, and a wide sunlight response range of the PDI/CN heterojunction. This work provides an efficient strategy and a corresponding photocatalyst for the directional conversion of CO2 to HCOOH.

Ambient-Stable Black Phosphorus-Based 2D/2D S-Scheme Heterojunction for Efficient Photocatalytic CO2 Reduction to Syngas.

Black phosphorus (BP), an emerging remarkable photocatalytic semiconductor, is arousing strong interests in this field of solar-driven CO2 reduction, but its stability and activity are still facing huge challenges. Here, an ambient-stable and effective 2D/2D heterostructure of BP/bismuth tungstate (Bi2WO6) with oxygen vacancy is innovatively designed for syngas production via photocatalytic CO2 reduction. This work, not only resolves the stability problem of BP nanosheets by anchoring ultrasmall platinum (Pt) nanoparticles (∼2 nm) but also greatly improves the charge transfer efficiency by constructing S-scheme 2D/2D heterostructure with coupled oxygen defects. As a result, the generation rates of carbon monoxide (CO) and hydrogen (H2) remarkably reach 20.5 and 16.8 µmol g-1 h-1, respectively, which are much higher than that of reported BP-based materials, and the accomplished CO/H2 ratios (1:1-2:1) are exactly the most desirable syngas for industrial applications. Thus, this work constructs an efficient and ambient-stable BP-based photocatalyst for syngas production by CO2 reduction at mild conditions.

Fabrication of a TiO2/Fe2O3 Core/Shell Nanostructure by Pulse Laser Deposition toward Stable and Visible Light Photoelectrochemical Water Splitting.

Here, we report the fabrication of TiO2/Fe2O3 core/shell heterojunction nanorod arrays by a pulsed laser deposition (PLD) process and their further use as photoelectrodes toward high-performance visible light photoelectrochemical (PEC) water splitting. The morphology, phase, and carrier conduction mechanism of plain TiO2 and TiO2/Fe2O3 core/shell nanostructure were systematically investigated. PEC measurements show that the TiO2/Fe2O3 core/shell nanostructure enhances photocurrent density by nearly 2 times than the plain ones, increases visible light absorption from 400 to 550 nm, raises the on/off separation rate, and delivers high stability with only a 3% decrease of current density for tests of even more than 14 days. This work provides a method to design an efficient nanostructure by combination of a facile hydrothermal process and high-quality PLD process to fabricate a clean surface and excellent crystallinity for charge separation, transfer, and collection toward enhanced PEC properties.