Solubility-Boosted Molecular Sieving-Based Separation for Purification of Acetylene in Core–Shell IL@MOF Composites

Considering the small amount of CO₂ as a contaminant in industrial gas mixtures, developing CO₂-selective adsorbents exhibit advantages in directly obtaining pure C₂H₂ in one-step to reduce the energy consumption. However, it is still a great challenge due to the essential molecular feature of C₂H₂, including the triple bond and high polarizability. Herein, a simple but effective CO₂-facilitated transport strategy is presented to realize the overwhelming adsorption of CO₂ over C₂H₂ by constructing core–shell composite structures using ionic liquid (IL) and metal-organic framework (MOF). With the aid of excellent solubility of CO₂ in IL and almost total exclusion of C₂H₂, the obtained materials boost molecular sieving-based separation of CO₂/C₂H₂. Density functional theory calculations combining molecular dynamic simulations revealed the solution-diffusion mechanism for CO₂, which is rarely reported in solid adsorbents. Ideal adsorbed solution theory selectivity for CO₂/C₂H₂ with 1/1 and 1/3 volume ratios can reach over 10⁴ and 4000 at 100 kPa with a high CO₂ uptake of 40.3 cm³ g⁻¹, superior to those of the reported materials so far. More importantly, this solution-based separation strategy can avoid the difficulty for precise control of the regulation of adsorbent structure, which may be beneficial to practical production.     

Facile “Spot‐Heating” Synthesis of Carbon Dots/Carbon Nitride for Solar Hydrogen Evolution Synchronously with Contaminant Decomposition

The use of solar energy to produce the clean hydrogen (H₂) energy from water splitting is a promising means of renewable energy conversion. High activation barriers for O₂ generation associated with the rate‐limiting steps require utilization of noble metal‐based cocatalysts, which complicates the fabrication procedure and compromises the stability of the catalyst. Here, a homogenous “spot heating” approach is designed via the ultrasonic cavitation effect for evenly embedding highly crystalline carbon quantum dots (CQDs) on 2D C₃N₄ nanosheets. Based on density functional calculations and electrochemical experiments, the optimal introduction of CQDs into C₃N₄ not only extends light absorption spectrum, but also reduces effective mass of electrons (e^?), facilitating photocarrier transport from excited sites. And, more importantly, the well‐organized CQDs with superior peroxidase mimetic activity can increase catalytic H₂ production through the process of (i) 2H₂O → H₂O₂ + H₂; (ii) H₂O₂→2 ? OH; (iii) ?OH + bisphenol A→ Final Products, with H₂ production rate (152 µmol g^?1 h^?1) several times higher than that for pure C₃N₄. This work demonstrates an ideal platform for efficient H₂ production with synergetic organic contaminant degradation, thereby opening possibilities for coupling energy conversion with environmental remediation.     

Cu/Cu2O Interconnected Porous Aerogel Catalyst for Highly Productive Electrosynthesis of Ethanol from CO2

Use of Cu and Cu⁺ is one of the most promising approaches for the production of C₂ products by the electrocatalytic CO₂ reduction reaction (CO₂RR) because it can facilitate CO₂ activation and C C dimerization. However, the selective electrosynthesis of C₂₊ products on Cu⁰ Cu⁺ interfaces is critically limited due to the low electrocatalytic production of ethanol relative to ethylene. In this study, a novel porous Cu/Cu₂O aerogel network is introduced to afford high ethanol productivity by the electrocatalytic CO₂RR. The aerogel is synthesized by a simple chemical redox reaction of a precursor and a reducing agent. CO₂RR results reveal that the Cu/Cu₂O aerogel produces ethanol as the major product, exhibiting a Faradaic efficiency (FE_EtOH) of 41.2% and a partial current density (J_EtOH) of 32.55 mA cm⁻² in an H-cell reactor. This is the best electrosynthesis performance for ethanol production reported thus far. Electron microscopy and electrochemical analysis results reveal that this dramatic increase in the electrosynthesis performance for ethanol can be attributed to a large number of Cu⁰ Cu⁺ interfaces and an increase of the local pH in the confined porous aerogel network structure with a high-surface-area.     

Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

Proton Turnover Dominated Cascade Route for CO2 Photoreduction

Photoreduction carbon dioxide (CO₂) and water (H₂O) into valuable chemicals is a huge potential to mitigate immoderate CO₂ emissions and energy crisis. To date, tremendous attention is concentrated on the improvement of independent CO₂ reduction or H₂O oxidation behaviors. However, the simultaneous control of efficient electron and hole utilization is still a huge challenge due to the complex cascade redox reactions. Here, a proton turnover exists in the whole CO₂ photoreduction process is discovered, which is defined as the pivot to concatenate the hole and electron behaviors. As a demonstration of the concept, the efficient activated hydrogen (*H) production centers of copper (Cu) and rapid hydrogenation centers of nickel (Ni) are coupled by an alloying strategy, and the proton turnover behaviors could be directly determined by adjustment of the molar ratios of Cu_xNi_y. Moreover, Cu₃Ni₁–TiO₂ exhibits the highest electron selectivity of 93.7% for methane (CH₄) production with a rate of 175.9 µmol g⁻¹ h⁻¹, while Cu₁Ni₅–TiO₂ reaches up to the highest carbon monoxide (CO) electron selectivity and generation rate at 84.4% and 164.6 µmol g⁻¹ h⁻¹, respectively. Consequently, the experimental and theoretical analysis all clarify the predominate proton turnover effect during the overall CO₂ photoreduction process, which directly determines the categories and generated efficiency of C-based products by regulating variable reaction pathways. Therefore, the revelation of the proton turnover pivot could broaden the new sights by bidirectional optimization of dynamics during the overall CO₂ photoreduction system, which favors the efficient, selective, and stable photocatalytic CO₂ reduction with H₂O.     

Engineering the Pore Structure and Functionality of Ionic Porous Polymers for Separating Acetylene over Carbon Dioxide

Precise engineering of organic porous polymers to realize the selective separation of structurally similar gases presents a great challenge. In this study, a new class of ionic porous polymers P(Ph3Im-Br-nDVB) with a high ionic density and microporous surface area are constructed through a facile copolymerization strategy, providing an efficient path to rational control over pore structure and functionality. The first example of ionic porous organic polymers is reported to address the challenge of discriminating the subtle difference of C₂H₂ and CO₂, which have almost identical molecular sizes and similar physicochemical properties, which achieve the highest C₂H₂/CO₂ selectivity (17.9) among porous organic polymers. These ionic porous polymers exhibit high stability and excellent dynamic breakthrough performance for binary C₂H₂/CO₂ mixtures, indicating their practical feasibility. Modeling studies reveal that anions are the specific binding sites for preferential C₂H₂ capture because of Br⁻···HCCH interactions. This study not only demonstrates an efficient strategy to build novel ionic porous polymers integrating abundant micropores and ionic sites but also sheds some light on the development of functionalized materials for the separation of structurally similar gas molecules.     

1D SnO2 with Wire‐in‐Tube Architectures for Highly Selective Electrochemical Reduction of CO2 to C1 Products

Electrochemical reduction of CO₂ (ERC) into useful products, such as formic acid and carbon monoxide, is a fascinating approach for CO₂ fixation as well as energy storage. Sn‐based materials are attractive catalysts for highly selective ERC into C₁ products (including HCOOH and CO), but still suffer from high overpotential, low current density, and poor stability. Here, One‐dimensional (1D) SnO₂ with wire‐in‐tube (WIT) structure is synthesized and shows superior selectivity for C₁ products. Using the WIT SnO₂ as the ERC catalyst, very high Faradaic efficiency of C₁ products (>90%) can be achieved at a wide potential range from ?0.89 to ?1.29 V versus RHE, thus substantially suppressing the hydrogen evolution reaction. The electrocatalyst also exhibits excellent long‐term stability. The improved catalytic activity of the WIT SnO₂ over the commercial SnO₂ nanoparticle indicates that higher surface area and large number of grain boundaries can effectively enhance the ERC activity. Synthesized via a facile and low‐cost electrospinning technology, the reduced WIT SnO₂ can serve as a promising electrocatalyst for efficient CO₂ to C₁ products conversion.     

Pyrolysis of tertiarybutylphosphine

The reaction mechanism for the pyrolysis of tertiarybutylphosphine (TBP) has been studied in an atmospheric pressure flow tube reactor using a time-of-flight mass spectrometer to analyze the gaseous products. D₂ was used as the carrier gas in order to label the reaction products. The temperature and time dependence of TBP pyrolysis were investigated above a silica surface, which was found to have no effect on TBP decomposition. However, the pyrolysis rate and products are strongly dependent on the input TBP concentration, suggesting the TBP pyrolysis involves second order reactions. A simple free radical mechanism model is proposed which includes 4 major reactions: C₄H₉PH₂ = C₄H₉ + PH₂ C₄H₉ + C₄H₉PH₂ = C₄H₁₀ + C₄H₁₀ + C₄H₉PH C₄H₉PH = C₄H₉ + PH C₄H₉ = C₄H₈ + H. Arrhenius parameters for these reactions are reported.     

Nanoscale Management of CO Transport in CO2 Electroreduction: Boosting Faradaic Efficiency to Multicarbon Products via Nanostructured Tandem Electrocatalysts

Tandem catalysis presents a promising strategy to improve the selectivity toward multicarbon products in the electrocatalytic carbon dioxide reduction reaction (CO₂RR). For CO₂RR, CO is a critical intermediate for producing multicarbon products. However, the management of CO localization and CO diffusion remains underexplored despite its critical role. Herein, a 3D tandem catalyst electrode with silver nanoparticles (Ag NPs) is designed to generate CO as an intermediate product within a copper (Cu) nanoneedle array. Via this nanostructured design, CO₂ forms C²⁺ products with a high Faradaic efficiency (FEC²⁺) of 64% in an H-cell and 70% in a flow cell with a current density of 350 mA cm⁻². These figures-of-merit are currently among the top literature reports. More importantly, in situ Raman spectroscopy and finite-element method calculations are employed to elucidate the origins of enhanced selectivity. These approaches reveal the crucial role of prolonging the CO diffusion path length for improving CO utilization during CO₂ conversion with tandem catalyst systems. The favorable CO2RR FEC²⁺ in two distinct environments (H-cell and flow cell) further corroborates that this effect is not limited to a particular reactor environment. Overall, this study provides new insights for designing tandem catalysts for improved CO₂RR selectivity to C²⁺ products.     

Electrophoretic Nuclei Assembly for Crystallization of High‐Performance Membranes on Unmodified Supports

Metal–organic framework (MOF) films have recently emerged as highly permselective membranes yielding orders of magnitude higher gas permeance than that from the conventional membranes. However, synthesis of highly intergrown, ultrathin MOF films on porous supports without complex support‐modification has proven to be a challenge. Moreover, there is an urgent need of a generic crystallization route capable of synthesizing a wide range of MOF structures in an intergrown, thin‐film morphology. Herein, a novel electrophoretic nuclei assembly for crystallization of highly intergrown thin‐films (ENACT) approach, that allows synthesis of ultrathin, defect‐free ZIF‐8 on a wide range of unmodified supports (porous polyacrylonitrile, anodized aluminum oxide, metal foil, porous carbon and graphene), is reported. As a result, a remarkably high H₂ permeance of 8.3 × 10^?6 mol m^?2 s^?1 Pa^?1 and ideal gas selectivities of 7.3, 15.5, 16.2, and 2655 for H₂/CO₂, H₂/N₂, H₂/CH₄, and H₂/C₃H₈, respectively, are achieved from an ultrathin (500 nm thick) ZIF‐8 membrane. A high C₃H₆ permeance of 9.9 × 10^?8 mol m^?2 s^?1 Pa^?1 and an attractive C₃H₆/C₃H₈ selectivity of 31.6 are obtained. The ENACT approach is straightforward, reproducible and can be extended to a wide range of nanoporous crystals, and its application in the fabrication of intergrown ZIF‐7 films is demonstrated.     

Pyrolysis of tertiarybutylphosphine at low pressure

The pyrolysis of tertiarybutylphosphine (TBP) has been studied in the low pressure conditions used for chemical beam epitaxy (CBE). The pyrolysis studies were carried out in low pressure reactors of two different configurations, one of which is a cracker cell designed for use in a CBE system. The reaction products were studied using a quadrupole mass spectrometer. The products observed are accounted for by a reaction mechanism involving homolysis of the parent TBP molecule to produce PH₂ and C₄H₉ radicals. These undergo subsequent reactions to form the stable products C₄H₈, PH₃ and H₂, with smaller amounts of P and P₂ being produced. The production of the sub-hydride PH₂ using this cracker cell design indicates that the use of partially cracked TBP may be a promising technique for reducing the amount of carbon incorporated into the growing epitaxial layer.     

Regulating the Metallic Cu–Ga Bond by S Vacancy for Improved Photocatalytic CO2 Reduction to C2H4

Artificial photosynthesis, which converts carbon dioxide into hydrocarbon fuels, is a promising strategy to overcome both global warming and energy crisis. Herein, the geometric position of Cu and Ga on ultra-thin CuGaS₂/Ga₂S₃ is oriented via a sulfur defect engineering, and the unprecedented C₂H₄ yield selectivity is ≈93.87% and yield is ≈335.67 µmol g⁻¹ h⁻¹. A highly delocalized electron distribution intensity induced by S vacancy indicates that Cu and Ga adjacent to S vacancy form Cu–Ga metallic bond, which accelerates the photocatalytic reduction of CO₂ to C₂H₄. The stability of the crucial intermediates (*CHOHCO) is attributed to the upshift of the d-band center of ultra-thin CGS/GS. The C–C coupling barrier is intrinsically reduced by the dominant exposed Cu atoms on the 2D ultra-thin CuGaS₂/Ga₂S₃ in the process of photocatalytic CO₂ reduction, which captures *CO molecules effectively. This study proposes a new strategy to design photocatalyst through defect engineering to adjust the selectivity of photocatalytic CO₂ reduction.     

Unique PCoN Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)?N?C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)?Co(δ⁺)?N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

Unique P?Co?N Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)? N? C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)? Co(δ⁺)? N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

An In Situ Simultaneous Reduction‐Hydrolysis Technique for Fabrication of TiO2‐Graphene 2D Sandwich‐Like Hybrid Nanosheets: Graphene‐Promoted Selectivity of Photocatalytic‐Driven Hydrogenation and Coupling of CO2 into Methane and Ethane

A novel, in situ simultaneous reduction‐hydrolysis technique (SRH) is developed for fabrication of TiO₂‐‐graphene hybrid nanosheets in a binary ethylenediamine (En)/H₂O solvent. The SRH technique is based on the mechanism of the simultaneous reduction of graphene oxide (GO) into graphene by En and the formation of TiO₂ nanoparticles through hydrolysis of titanium (IV) (ammonium lactato) dihydroxybis, subsequently in situ loading onto graphene through chemical bonds (Ti–O–C bond) to form 2D sandwich‐like nanostructure. The dispersion of TiO₂ hinders the collapse and restacking of exfoliated sheets of graphene during reduction process. In contrast with prevenient G‐TiO₂ nanocomposites, abundant Ti³⁺ is detected on the surface of TiO₂ of the present hybrid, caused by reducing agent En. The Ti³⁺ sites on the surface can serve as sites for trapping photogenerated electrons to prevent recombination of electron–hole pairs. The high photocatalytic activity of G‐TiO₂ hybrid is confirmed by photocatalytic conversion of CO₂ to valuable hydrocarbons (CH₄ and C₂H₆) in the presence of water vapor. The synergistic effect of the surface‐Ti³⁺ sites and graphene favors the generation of C₂H₆, and the yield of the C₂H₆ increases with the content of incorporated graphene. The work may open a new doorway for new significant application of graphene for selectively catalytic C–C coupling reaction     

Ice‐Assisted Synthesis of Black Phosphorus Nanosheets as a Metal‐Free Photocatalyst: 2D/2D Heterostructure for Broadband H2 Evolution

A 2D/2D heterojunction of black phosphorous (BP)/graphitic carbon nitride (g‐C₃N₄) is designed and synthesized for photocatalytic H₂ evolution. The ice‐assisted exfoliation method developed herein for preparing BP nanosheets from bulk BP, leads to high yield of few‐layer BP nanosheets (≈6 layers on average) with large lateral size at reduced duration and power for liquid exfoliation. The combination of BP with g‐C₃N₄ protects BP from oxidation and contributes to enhanced activity both under λ > 420 nm and λ > 475 nm light irradiation and to long‐term stability. The H₂ production rate of BP/g‐C₃N₄ (384.17 µmol g^?1 h^?1) is comparable to, and even surpasses that of the previously reported, precious metal‐loaded photocatalyst under λ > 420 nm light. The efficient charge transfer between BP and g‐C₃N₄ (likely due to formed N? P bonds) and broadened photon absorption (supported both experimentally and theoretically) contribute to the excellent photocatalytic performance. The possible mechanisms of H₂ evolution under various forms of light irradiation is unveiled. This work presents a novel, facile method to prepare 2D nanomaterials and provides a successful paradigm for the design of metal‐free photocatalysts with improved charge‐carrier dynamics for renewable energy conversion.     

Simultaneously Tuning Band Structure and Oxygen Reduction Pathway toward High-Efficient Photocatalytic Hydrogen Peroxide Production Using Cyano-Rich Graphitic Carbon Nitride

The demands for green production of hydrogen peroxide have triggered extensive studies in the photocatalytic synthesis, but most photocatalysts suffer from rapid charge recombination and poor 2e⁻ oxygen reduction reaction (ORR) selectivity. Here, a novel composite photocatalyst of cyano-rich graphitic carbon nitride g-C₃N₄ is fabricated in a facile manner by sodium chloride-assisted calcination on dicyandiamide. The obtained photocatalysts exhibit superior activity (7.01 mm  h⁻¹ under λ  ≥  420 nm, 16.05 mm  h⁻¹ under simulated sun conditions) for H₂O₂ production and 93% selectivity for 2e⁻ ORR, much higher than that of the state-of-the-art photocatalyst. The porous g-C₃N₄ with Na dopants and cyano groups simultaneously optimize two limiting steps of the photocatalytic 2e⁻ ORR: photoactivity, and selectivity. The cyano groups can adjust the band structure of g-C₃N₄ to achieve high activity. They also serve as oxygen adsorption sites, in which local charge polarization facilitates O₂ adsorption and protonation. With the aid of Na⁺, the O₂ is reduced to produce more superoxide radicals as the intermediate products for H₂O₂ synthesis. This work provides a facile approach to simultaneously tune photocatalytic activity and 2e⁻ ORR selectivity for boosting H₂O₂ production, and then paves the way for the practical application of g-C₃N₄ in environmental remediation and energy supply.     

High Quantum Efficiency Zn2+ Doped Lead Manganese Halide @PET Film Used for Wide Color Gamut Backlit Display

Organic–inorganic manganese halide with environmentally friendly properties has become a new candidate material for backlight display applications. In this article, tetraethylammonium bromide (C₈H₂₀N)₂MnBr₄ is synthesized by a simple room temperature evaporation method. The tetrahedral coordinated Mn²⁺ demonstrates a green emission peak at 523 nm and a commendable photoluminescence quantum yield (PLQY) of 81.7%. To improve its stability, different proportions of Zn²⁺ are incorporated, leading to the discovery of (C₈H₂₀N)₂Mn_0.95Zn_0.05Br₄ as the most stable variant with a high PLQY of 84.3%. Additionally, by utilizing a sandwich method and double-layer polyethylene terephthalate (PET) film encapsulation, the powder-to-binder ratio and thickness gradient are optimized, resulting in the ideal (C₈H₂₀N)₂Mn_0.95Zn_0.05Br₄@PET film with a powder-to-binder ratio of 1:2 and a thickness of 0.5 mm. Remarkably, the film exhibits superior stability against water, heat, and photo degradation. Finally, the light conversion film prepared from (C₈H₂₀N)₂Mn_0.95Zn_0.05Br₄@K₂SiF₆: Mn⁴⁺@PET composite material is applied to backlight display, and the color gamut covers 112% of NTSC 1953 and 83% of Rec. 2020. This study provides a feasible route for developing environmentally friendly, low-cost, and high-performance liquid crystal displays.     

Single-Atom Metal Sites Anchored Hydrogen-Bonded Organic Frameworks for Superior “Two-In-One” Photocatalytic Reaction

Photoredox catalysis is a green solution for organics transformation and CO₂ conversion into valuable fuels, meeting the challenges of sustainable energy and environmental concerns. However, the regulation of single-atomic active sites in organic framework not only influences the photoredox performance, but also limits the understanding of the relationship for photocatalytic selective organic conversion with CO₂ valorization into one reaction system. As a prototype, different single-atomic metal (M) sites (M²⁺ = Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) in hydrogen-bonded organic frameworks (M-HOF) backbone with bridging structure of metal-nitrogen are constructed by a typical “two-in-one” strategy for superior photocatalytic C N coupling reactions integrated with CO₂ valorization. Remarkably, Zn-HOF achieves 100% conversion of benzylamine oxidative coupling reactions, 91% selectivity of N-benzylidenebenzylamine and CO₂ conversion in one photoredox cycle. From X-ray absorption fine structure analysis and density functional theory calculations, the superior photocatalytic performance is attributed to synergic effect of atomically dispersed metal sites and HOF host, decreasing the reaction energy barriers, enhancing CO₂ adsorption and forming benzylcarbamic acid intermediate to promote the redox recycle. This work not only affords the rational design strategy of single-atom active sites in functional HOF, but also facilitates the fundamental insights upon the mechanism of versatile photoredox coupling reaction systems.     

In Situ Topochemical Transformation of ZnIn2S4 for Efficient Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran

Photocatalytic selective oxidation of 5-hydroxymethylfurfural (HMF) coupled H₂ production offers a promising approach to producing valuable chemicals. Herein, an efficient in situ topological transformation tactic is developed for producing porous O-doped ZnIn₂S₄ nanosheets for HMF oxidation cooperative with H₂ evolution. Aberration-corrected high-angle annular dark-field scanning TEM images show that the hierarchical porous O-ZIS-120 possesses abundant atomic scale edge steps and lattice defects, which is beneficial for electron accumulation and molecule adsorption. The optimal catalyst (O-ZIS-120) exhibits remarkable performance with 2,5-diformylfuran (DFF) yields of 1624 µmol h⁻¹ g⁻¹ and the selectivity of >97%, simultaneously with the H₂ evolution rate of 1522 µmol h⁻¹ g⁻¹. Mechanistic investigations through theoretical calculations show that O in the O-ZIS-120 lattice can reduce the oxidation energy barrier of hydroxyl groups of HMF. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) results reveal that DFF^* (C₄H₂(CHO)₂O^*) intermediate has a weak interaction with O-ZIS-120 and desorb as the final product. This study elucidates the topotactic structural transitions of 2D materials simultaneously with electronic structure modulation for efficient photocatalytic DFF production.