This study presents the successful synthesis of a novel Z-scheme heterojunction composite film consisting of Ag/Bi_(2)MoO_(6)/BiOBr through electrochemical processes and ionexchange techniques,followed by the photodep...This study presents the successful synthesis of a novel Z-scheme heterojunction composite film consisting of Ag/Bi_(2)MoO_(6)/BiOBr through electrochemical processes and ionexchange techniques,followed by the photodeposition of noble metal silver(Ag)onto the composite structure.The catalytic efficiency of semiconductor photocatalysts is greatly improved by utilizing the localized surface plasmon resonance(LSPR)effect observed in Ag nanoparticles(NPs).Furthermore,the noble metal Ag serves as an intermediary bridge facilitating charge transfer between Bi_(2)MoO_(6)and BiOBr,while the formation of a Schottky barrier effectively inhibits the recombination of photo-generated electron-hole pairs.As a result,the Ag-deposited Bi_(2)MoO_(6)/BiOBr film exhibits superior photocatalytic performance in the reduction of CO_(2)compared to its unmodified counterpart.Our experimental results indicate a non-linear relationship between Ag deposition and the efficiency of photocatalytic CO_(2)reduction to CO,characterized by an initial increase in efficiency followed by a decline.The optimized 1.5%-Ag/Bi_(2)MoO_(6)/BiOBr film demonstrates exceptional photocatalytic activity,attaining a CO production rate of 13.65μmol/(g·h).This research explores the fundamental mechanisms that lead to improved photocatalytic CO_(2)reduction capabilities of the Ag/Bi_(2)MoO_(6)/BiOBr film.Our research offers important perspectives for the thoughtful design and production of highly efficient photocatalysts,which are essential for advancing sustainable energy solutions.展开更多
Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchan...Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.展开更多
The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution ...The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution in one dimension,resulting in limited regulation of electronic structure.Herein,we report a multidimensional coordination strategy to significantly break the symmetrical electron distribution of the metal single site to achieve highly efficient electrochemical CO_(2) reduction reaction(CO_(2) RR).Ni singleatom sites decorated with planar P and axial Cl atoms are successfully constructed on carbon support(Ni-NPCl-C).Ni-NPCl-C affords CO Faraday efficiency over 90%in a wide potential window range from-0.5 to-1.2 V and an ultrahigh turnover frequency of 1.17×10^(5)h^(-1),much superior to its counterparts with single-dimensional coordination.Ni-NPCl-C can be further applied as a bifunctional catalyst to construct a rechargeable Zn-CO_(2) battery.Spectroscopic characterizations and theoretical calculations demonstrate that the dual adjustments with axial Cl and planar P can synergistically disrupt the electron distribution in two dimensions to increase electrons around Ni sites with the upshift of the d-band center,thereby facilitating the formation of*COOH intermediates and improving the CO_(2) RR performance.展开更多
The in situ synthesis of TiO_(2)semiconductor photocatalysts using Ti_(3)C_(2)MXene materials offers a highly effective approach to mitigate environmental and energy challenges by selectively reducing CO_(2)to valuabl...The in situ synthesis of TiO_(2)semiconductor photocatalysts using Ti_(3)C_(2)MXene materials offers a highly effective approach to mitigate environmental and energy challenges by selectively reducing CO_(2)to valuable chemicals like CH_(4).However,the transformation of Ti_(3)C_(2)into TiO_(2)is usually accompanied by severe agglomeration of particles,which leads to a reduction in the number of intrinsic active sites,adversely affecting the adsorption and conversion of CO_(2).To address this problem,polymethyl methacrylate(PMMA)was employed as a hard template to fabricate a bowl-shaped TiO_(2)supported on carbon layer(TiO_(2)/C)hybrid photocatalyst by a calcination method.The results showed that the obtained sample had a sufficiently large specific surface area and numerous active sites for CO_(2)adsorption and activation.The excellent conductivity of the carbon layer facilitated the separation of photogenerated carriers produced by TiO_(2),enabling the obtained TiO_(2)/C complexes exhibit CO_(2)reduction rates to CO and CH_(4)of 1.84μmol‧g^(−1)‧h^(−1)and 5.32μmol‧g^(−1)‧h^(−1),respectively,with the CH_(4)selectivity of 74%.The precise utilization of templates to refine the morphology of MXene oxidation products was thus demostrated,offering a practical approach for the application of MXene in the photocatalysis.展开更多
Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespr...Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.展开更多
Modifying the chemical surrounding of N-doped carbon supported single-atom catalysts(SA/NCs)through heteroatom doping is a mainstream approach to optimize their performance for electrocatalytic CO_(2) reduction reacti...Modifying the chemical surrounding of N-doped carbon supported single-atom catalysts(SA/NCs)through heteroatom doping is a mainstream approach to optimize their performance for electrocatalytic CO_(2) reduction reaction.However,conventional SA/NCs mainly consists of in-plane metal sites feature with tightly symmetrical M–N_(4) coordination environments,limiting the regulatory strength of heteroatom doping.Herein,we proposed an edge-assisted heteroatom doping regulation strategy by constructing edge-type Ni sites supported on a hollow and leaf-shaped P-doped NC substrate(eNi/H-NPC).The two-dimensional leaf-shaped and hollow carbon can expose enriched edges.The edge structure can promote the accessibility of active sites,more importantly,intensifies electronic perturbation induced by heteroatom doping.Resultantly,the charge symmetry distribution of Ni–N_4 site is significantly disrupted,and energy barrier associated with the formation of*COOH intermediate is further diminished.eNi/HNPC achieves CO faradaic efficiency(FE_(CO))near 100%at-0.6 V versus reversible hydrogen electrode(vs.RHE)and maintains FE_(CO)over 90%from-0.6 to-1.1 V(vs.RHE)in H-type cells.Remarkably,in gas-diffusion flow cells,eNi/H-NPC exhibits FE_(CO)reaches 98.9%and 96.5%in neutral and acidic electrolytes with the CO current density reach 283.5,and 397.2 mA cm^(-2),respectively,which are much superior than that of the bulk material with dominant in-plane active sites.Moreover,eNi/H-NPC serves as an efficient cathode in Zn–CO_(2) batteries,realized a discharge power density of 4.1 mW cm^(-2),and exceptional cycling durability over 35 h.展开更多
Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior perf...Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior performance of amorphous CuNi alloys for CO_(2)electrochemical reduction.By integrating machine learning forcefields for efficient structure generation and density functional theory for subsequent structural refinement and property calculations,we reveal the potential of these disordered systems to outperform their crystalline counterparts.Machine learning forcefields can generate a bulk structure containing a mixture of Cu and Ni atoms,resulting in enhanced catalytic performance.Effective screening of the amorphous surfaces is used to identify undercoordinated Cu and Ni sites in the amorphous structure to synergistically promote selective CO production and favor ethanol formation over ethylene via the stabilization of the*COCHO intermediate,resulting in significantly lower Gibbs free energy changes compared to the crystalline counterpart.The varying atomic coordination environments on amorphous surfaces promote both C–C bond formation and subsequent proton-electron transfer,leading to ethanol formation.These findings demonstrate the superior catalytic performance of amorphous CuNi,highlighting its potential for efficient and selective electroreduction of CO_(2).展开更多
Efficient photocatalytic reduction of CO_(2)is crucial to decrease the atmospheric concentration of CO_(2).Pairing this process with H_(2)O_(2)production is of considerable importance for simultaneously producing valu...Efficient photocatalytic reduction of CO_(2)is crucial to decrease the atmospheric concentration of CO_(2).Pairing this process with H_(2)O_(2)production is of considerable importance for simultaneously producing value-added chemicals.However,the photocatalysts reported for such a process suffer from a high recombination rate of the surface/bulk charges,as well as inefficient enrichment and activation toward CO_(2)and O_(2),resulting in low conversion efficiency even in the presence of organic sacrificial agents and expensive metal co-catalysts.Herein,two 1,3,5-triphenylbenzene-based organic polymers with high ionic density and porosity are prepared through a facile Sonogashira polymerization.The ionic imidazolium sites embedded in the polymeric skeleton provide the two polymers(iCMP-1 and iCMP-2)with adsorptive selectivity for CO_(2)/N_(2) up to 98-102 at 273 K,facilitating the enrichment of CO_(2)and O_(2)molecules around the catalytic centers,thus boosting their catalytic conversion directly from air under solar light(100 mW cm^(-2)).Benefiting from the improved charge separation and broad light absorption,along with high CO_(2)and O_(2)uptake,iCMP-2 can deliver excellent CO and H_(2)O_(2)yields(611.8 and 810.6μmol h^(-1)g^(-1),respectively)under an atmosphere composed of water vapor and air without any co-catalysts.展开更多
Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm thr...Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.展开更多
The electrochemical reduction of CO_(2),as a renewable energy-driven electrochemical system,has emerged as an environmentally benign approach for producing valuable chemicals and fuels under mild reaction conditions.R...The electrochemical reduction of CO_(2),as a renewable energy-driven electrochemical system,has emerged as an environmentally benign approach for producing valuable chemicals and fuels under mild reaction conditions.Recent advances in the precise synthesis of metal nanoclusters,coupled with state-of-the-art characterization techniques,have enabled atomic-level investigation of structure-activity relationships in nanocatalysts.Due to their well-defined atomic architectures,the active metal sites within these nanocatalysts can be accurately identified,facilitating systematic studies on how compositions(structures)modulate catalytic performance.This review begins by summarizing recent advances in the controlled synthesis of atomically precise metal nanoclusters,followed by an overview of progress in the electrochemical reduction of CO_(2) to CO using nanoclusters as catalysts.Subsequently,we systematically investigate the effects of metal kernel characteristics and staple properties on catalytic activity,selectivity,and stability.Furthermore,current challenges are outlined,and prospective research directions are proposed in this rapidly evolving field.It is anticipated that this review will inspire further innovation in the synthesis of atomically precise nanocluster catalysts,promote a deeper mechanistic understanding of metal nanocluster-mediated electrochemical CO_(2) reduction,and push forward the related industrial applications.展开更多
Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for ca...Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.展开更多
A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer...A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.展开更多
Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by ...Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.展开更多
Integration of single-atom catalysts(SACs) onto metal-organic frameworks(MOFs) with porous channels has garnered significant interest in the field of CO_(2) reduction.However,MOFs are usually bulky can impede the diff...Integration of single-atom catalysts(SACs) onto metal-organic frameworks(MOFs) with porous channels has garnered significant interest in the field of CO_(2) reduction.However,MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge.In this study,we utilized firstly the post-synthetic single-atom chelation sites on zirconiumbased metal-organic cages(Zr-MOCs) to anchor cobalt(Co) atom to synthesize single-dispersible Zr T^(-1)-NH_(2)-IS-Co molecular cages for CO_(2) photoreduction.Experimental results demonstrate that Zr T^(-1)-NH_(2)-ISCo exhibits impressive catalytic performance,achieving syngas yields of up to 30.9 mmol g^(-1)h^(-1),ranking among the highest values of reported crystalline porous catalysts.Mechanistic insights reveal the newly introduced metal serving as the catalytic site and ^(*)COOH acts as a crucial intermediate in the CO_(2) reduction process.Furthermore,the successful synthesis of Zr T^(-1)-NH_(2)-IS-Ni and Zr T^(-1)-NH_(2)-IS-Mn show the universality of the modification strategies,with their CO_(2) catalytic activity surpassing that of Zr T^(-1)-NH_(2).展开更多
Presented herein are the delicate design and synthesis of S-scheme NiTiO_(3)/CdS heterostructures composed of CdS nanoparticles anchored on the surface of NiTiO_(3) nanorods for photocatalytic CO_(2) reduction.Systema...Presented herein are the delicate design and synthesis of S-scheme NiTiO_(3)/CdS heterostructures composed of CdS nanoparticles anchored on the surface of NiTiO_(3) nanorods for photocatalytic CO_(2) reduction.Systematic physicochemical studies demonstrate that NiTiO_(3)/CdS hybrid empowers superior light absorption and enhanced CO_(2) capture and activation.Electron spin resonance validates that the charge carriers in NiTiO_(3)/CdS follow a S-scheme transfer pathway,which powerfully impedes their recombination and promotes their separation.Importantly,the photogenerated holes on CdS are effectively consumed at the hero-interface by the electron from NiTiO_(3),preventing the photo-corrosion of the metal sulfide.As a result,with Co(bpy)_(3)^(2+)as a cocatalyst,NiTiO_(3)/CdS displays a considerable performance for CO_(2) reduction,affording a high CO yield rate of 20.8µmol h^(−1).Moreover,the photocatalyst also manifests substantial stability and good reusability for repeated CO_(2) reaction cycles in the created tandem photochemical system.In addition,the possible CO_(2) photoreduction mechanism is constructed on the basis of the intermediates monitored by in-situ diffuse reflectance infrared Fourier transform spectroscopy.展开更多
Electrochemical reduction reaction of pure CO_(2)(epCO_(2) RR)is highly promising since it could convert CO_(2) pollution into value-added chemicals(e.g.,CO,HCOOH,C_(2)H_(4),C_(2)H_(5) OH)under industrial-level curren...Electrochemical reduction reaction of pure CO_(2)(epCO_(2) RR)is highly promising since it could convert CO_(2) pollution into value-added chemicals(e.g.,CO,HCOOH,C_(2)H_(4),C_(2)H_(5) OH)under industrial-level current density with high selectivity above 90%.While the purification process of industrial flue gas into pure CO_(2) accounts for significant portion of CO_(2)-electrolysis cost.Direct flue-gas electroreduction offers a cost-effective alternative,while its practical implementation faces challenges such as low CO_(2) concentrations(<20 vol%)leading to small current density,competitive reactions such as oxygen reduction reaction,hydrogen evolution reaction,etc.,with more positive thermodynamic potentials than epCO_(2) RR.Therefore,this work reviews strategies to develop efficient and selective electrocatalysts that are resistant to non-CO_(2) active gasses such as O_(2),SO_(x),NO_(x),etc.,and treatment methods for such components in the flue gas.Significantly,the technoeconomic analysis of CO_(2) capture and purification integrated electrolysis process and direct flue gas reduction,is compared.Importantly,future research regarding direct electrochemical reduction of flue gas is proposed,including multifunctional catalyst design,complex reaction mechanism exploration,electrolysis system optimization,etc.展开更多
Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2)...Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.展开更多
The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Cova...The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Covalent organic frameworks(COFs)offer a promising approach for CO_(2)transformation but lack high efficiency and selectivity in the absence of metals.Here,we have incorporated a pyridine nitrogen component into the imine-COF conjugated structure(Tp Pym).This innovative system has set a record of producing a CO yield of 1565μmol g^(-1)within 6 h.The soft X-ray absorption fine structure measurement proves that Tp Pym has both better conjugation and electron cloud enrichment.The electronic structure distribution delays the charge-carrier recombination,as evidenced by femtosecond transient absorption spectroscopy.The energy band diagram and theoretical calculation show that the conduction-band potential of Tp Pym is lower and the reduction reaction of CO_(2)to CO is more likely to occur.展开更多
Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR pr...Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.展开更多
The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectr...The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective.Here,we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived Cd In_(2)S_(4)/In_(2)S_(3)heterojunction that exhibited stable and high selectivity.Multiple characterizations of the Cd In_(2)S_(4)/In_(2)S_(3)heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites,a high visible-light utilization rate(λ<600 nm),efficient charge separation,and a prolonged charge-carrier lifetime.Moreover,an S-scheme charge transfer mechanism,based on the interleaved band between the two components,improved the reduction capability of the electrons.Benefiting from the compositional and structural synergy,the yield CO by Cd In_(2)S_(4)/In_(2)S_(3)-250(CI-250)reached 135.62μmol·g^(-1)·h^(-1),which was 49.32 times and 32.88 times higher than that of In_(2)S_(3)and Cd In_(2)S_(4),respectively.The Cd In_(2)S_(4)/In_(2)S_(3)heterojunction exhibited a quantum efficiency of 4.23%with a CO selectivity of 71%.Four cycle tests confirmed the good stability and recyclability of the CI-250.This work provides a new approach for designing and preparing high-performance hollow MOFsbased photocatalysts for scalable and sustainable CO_(2)reduction.展开更多
基金Supported by the National Natural Science Foundation of China(21978196)Natural Science Foundation of Shanxi Province(201801D211008,202403021211018)+1 种基金Shanxi Provincial Education Department(S202413597023)Jincheng High Efficiency Conversion and Utilization Technology Innovation Center of CO2 Energy and Biomass Energy。
文摘This study presents the successful synthesis of a novel Z-scheme heterojunction composite film consisting of Ag/Bi_(2)MoO_(6)/BiOBr through electrochemical processes and ionexchange techniques,followed by the photodeposition of noble metal silver(Ag)onto the composite structure.The catalytic efficiency of semiconductor photocatalysts is greatly improved by utilizing the localized surface plasmon resonance(LSPR)effect observed in Ag nanoparticles(NPs).Furthermore,the noble metal Ag serves as an intermediary bridge facilitating charge transfer between Bi_(2)MoO_(6)and BiOBr,while the formation of a Schottky barrier effectively inhibits the recombination of photo-generated electron-hole pairs.As a result,the Ag-deposited Bi_(2)MoO_(6)/BiOBr film exhibits superior photocatalytic performance in the reduction of CO_(2)compared to its unmodified counterpart.Our experimental results indicate a non-linear relationship between Ag deposition and the efficiency of photocatalytic CO_(2)reduction to CO,characterized by an initial increase in efficiency followed by a decline.The optimized 1.5%-Ag/Bi_(2)MoO_(6)/BiOBr film demonstrates exceptional photocatalytic activity,attaining a CO production rate of 13.65μmol/(g·h).This research explores the fundamental mechanisms that lead to improved photocatalytic CO_(2)reduction capabilities of the Ag/Bi_(2)MoO_(6)/BiOBr film.Our research offers important perspectives for the thoughtful design and production of highly efficient photocatalysts,which are essential for advancing sustainable energy solutions.
基金financially supported the National Key R&D Program of China (No.2022YFA1502902)the National Natural Science Foundation of China (NSFC,Nos.22475152 and U21A20286)the 111 Project of China (No.D17003)。
文摘Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.
基金supported by the National Natural Science Foundation of China(Nos.22422806,22378136,and 22138003)the Guangdong Pearl River Talents Program(Nos.2021QN02C847and 2021ZT09Z109)+4 种基金the Natural Science Foundation of Guangdong Province(Nos.2024A1515011196 and 2023B1515040005)the Fundamental Research Funds for the Central Universities(Nos.2024ZYGXZR011,2025ZYGXZR025)the Science and Technology Program of Guangzhou(No.2025A04J5244)the State Key Laboratory of Pulp and Paper Engineering(No.2024ZD09)the TCL Young Talent Program。
文摘The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution in one dimension,resulting in limited regulation of electronic structure.Herein,we report a multidimensional coordination strategy to significantly break the symmetrical electron distribution of the metal single site to achieve highly efficient electrochemical CO_(2) reduction reaction(CO_(2) RR).Ni singleatom sites decorated with planar P and axial Cl atoms are successfully constructed on carbon support(Ni-NPCl-C).Ni-NPCl-C affords CO Faraday efficiency over 90%in a wide potential window range from-0.5 to-1.2 V and an ultrahigh turnover frequency of 1.17×10^(5)h^(-1),much superior to its counterparts with single-dimensional coordination.Ni-NPCl-C can be further applied as a bifunctional catalyst to construct a rechargeable Zn-CO_(2) battery.Spectroscopic characterizations and theoretical calculations demonstrate that the dual adjustments with axial Cl and planar P can synergistically disrupt the electron distribution in two dimensions to increase electrons around Ni sites with the upshift of the d-band center,thereby facilitating the formation of*COOH intermediates and improving the CO_(2) RR performance.
文摘The in situ synthesis of TiO_(2)semiconductor photocatalysts using Ti_(3)C_(2)MXene materials offers a highly effective approach to mitigate environmental and energy challenges by selectively reducing CO_(2)to valuable chemicals like CH_(4).However,the transformation of Ti_(3)C_(2)into TiO_(2)is usually accompanied by severe agglomeration of particles,which leads to a reduction in the number of intrinsic active sites,adversely affecting the adsorption and conversion of CO_(2).To address this problem,polymethyl methacrylate(PMMA)was employed as a hard template to fabricate a bowl-shaped TiO_(2)supported on carbon layer(TiO_(2)/C)hybrid photocatalyst by a calcination method.The results showed that the obtained sample had a sufficiently large specific surface area and numerous active sites for CO_(2)adsorption and activation.The excellent conductivity of the carbon layer facilitated the separation of photogenerated carriers produced by TiO_(2),enabling the obtained TiO_(2)/C complexes exhibit CO_(2)reduction rates to CO and CH_(4)of 1.84μmol‧g^(−1)‧h^(−1)and 5.32μmol‧g^(−1)‧h^(−1),respectively,with the CH_(4)selectivity of 74%.The precise utilization of templates to refine the morphology of MXene oxidation products was thus demostrated,offering a practical approach for the application of MXene in the photocatalysis.
基金supports from the National Natural Science Foundation of China(Grant Nos.12305372 and 22376217)the National Key Research&Development Program of China(Grant Nos.2022YFA1603802 and 2022YFB3504100)+1 种基金the projects of the key laboratory of advanced energy materials chemistry,ministry of education(Nankai University)key laboratory of Jiangxi Province for persistent pollutants prevention control and resource reuse(2023SSY02061)are gratefully acknowledged.
文摘Using photoelectrocatalytic CO_(2) reduction reaction(CO_(2)RR)to produce valuable fuels is a fascinating way to alleviate environmental issues and energy crises.Bismuth-based(Bi-based)catalysts have attracted widespread attention for CO_(2)RR due to their high catalytic activity,selectivity,excellent stability,and low cost.However,they still need to be further improved to meet the needs of industrial applications.This review article comprehensively summarizes the recent advances in regulation strategies of Bi-based catalysts and can be divided into six categories:(1)defect engineering,(2)atomic doping engineering,(3)organic framework engineering,(4)inorganic heterojunction engineering,(5)crystal face engineering,and(6)alloying and polarization engineering.Meanwhile,the corresponding catalytic mechanisms of each regulation strategy will also be discussed in detail,aiming to enable researchers to understand the structure-property relationship of the improved Bibased catalysts fundamentally.Finally,the challenges and future opportunities of the Bi-based catalysts in the photoelectrocatalytic CO_(2)RR application field will also be featured from the perspectives of the(1)combination or synergy of multiple regulatory strategies,(2)revealing formation mechanism and realizing controllable synthesis,and(3)in situ multiscale investigation of activation pathways and uncovering the catalytic mechanisms.On the one hand,through the comparative analysis and mechanism explanation of the six major regulatory strategies,a multidimensional knowledge framework of the structure-activity relationship of Bi-based catalysts can be constructed for researchers,which not only deepens the atomic-level understanding of catalytic active sites,charge transport paths,and the adsorption behavior of intermediate products,but also provides theoretical guiding principles for the controllable design of new catalysts;on the other hand,the promising collaborative regulation strategies,controllable synthetic paths,and the in situ multiscale characterization techniques presented in this work provides a paradigm reference for shortening the research and development cycle of high-performance catalysts,conducive to facilitating the transition of photoelectrocatalytic CO_(2)RR technology from the laboratory routes to industrial application.
基金supported by Basic and Applied Basic Research Foundation of Guangdong province(2024A1515110016 and2023A1515140020)National Natural Science Foundation of China(52070042,and 52300127)。
文摘Modifying the chemical surrounding of N-doped carbon supported single-atom catalysts(SA/NCs)through heteroatom doping is a mainstream approach to optimize their performance for electrocatalytic CO_(2) reduction reaction.However,conventional SA/NCs mainly consists of in-plane metal sites feature with tightly symmetrical M–N_(4) coordination environments,limiting the regulatory strength of heteroatom doping.Herein,we proposed an edge-assisted heteroatom doping regulation strategy by constructing edge-type Ni sites supported on a hollow and leaf-shaped P-doped NC substrate(eNi/H-NPC).The two-dimensional leaf-shaped and hollow carbon can expose enriched edges.The edge structure can promote the accessibility of active sites,more importantly,intensifies electronic perturbation induced by heteroatom doping.Resultantly,the charge symmetry distribution of Ni–N_4 site is significantly disrupted,and energy barrier associated with the formation of*COOH intermediate is further diminished.eNi/HNPC achieves CO faradaic efficiency(FE_(CO))near 100%at-0.6 V versus reversible hydrogen electrode(vs.RHE)and maintains FE_(CO)over 90%from-0.6 to-1.1 V(vs.RHE)in H-type cells.Remarkably,in gas-diffusion flow cells,eNi/H-NPC exhibits FE_(CO)reaches 98.9%and 96.5%in neutral and acidic electrolytes with the CO current density reach 283.5,and 397.2 mA cm^(-2),respectively,which are much superior than that of the bulk material with dominant in-plane active sites.Moreover,eNi/H-NPC serves as an efficient cathode in Zn–CO_(2) batteries,realized a discharge power density of 4.1 mW cm^(-2),and exceptional cycling durability over 35 h.
基金partially funded by EPSRC (EP/T022213/1, EP/W032260/1 and EP/P020194/1) via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202)part of the “Advancing Solid Interface and Lubricants by First Principles Material Design (SLIDE)” project that has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant agreement No. 865633)
文摘Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior performance of amorphous CuNi alloys for CO_(2)electrochemical reduction.By integrating machine learning forcefields for efficient structure generation and density functional theory for subsequent structural refinement and property calculations,we reveal the potential of these disordered systems to outperform their crystalline counterparts.Machine learning forcefields can generate a bulk structure containing a mixture of Cu and Ni atoms,resulting in enhanced catalytic performance.Effective screening of the amorphous surfaces is used to identify undercoordinated Cu and Ni sites in the amorphous structure to synergistically promote selective CO production and favor ethanol formation over ethylene via the stabilization of the*COCHO intermediate,resulting in significantly lower Gibbs free energy changes compared to the crystalline counterpart.The varying atomic coordination environments on amorphous surfaces promote both C–C bond formation and subsequent proton-electron transfer,leading to ethanol formation.These findings demonstrate the superior catalytic performance of amorphous CuNi,highlighting its potential for efficient and selective electroreduction of CO_(2).
基金supported by the Excellent Youth Foundation of Jiangxi Scientific Committee(no.20232ACB213012)National Science Foundation of Jiangxi Province of China(no.20242BAB25236)+2 种基金Jiangxi Talent Program(no.DHSQT32022005)Beijing Institute of Technology Research Fund Program for Young Scholars(XSQD-202215006)National Natural Science Foundation of China(no.22202008 and 22202039).
文摘Efficient photocatalytic reduction of CO_(2)is crucial to decrease the atmospheric concentration of CO_(2).Pairing this process with H_(2)O_(2)production is of considerable importance for simultaneously producing value-added chemicals.However,the photocatalysts reported for such a process suffer from a high recombination rate of the surface/bulk charges,as well as inefficient enrichment and activation toward CO_(2)and O_(2),resulting in low conversion efficiency even in the presence of organic sacrificial agents and expensive metal co-catalysts.Herein,two 1,3,5-triphenylbenzene-based organic polymers with high ionic density and porosity are prepared through a facile Sonogashira polymerization.The ionic imidazolium sites embedded in the polymeric skeleton provide the two polymers(iCMP-1 and iCMP-2)with adsorptive selectivity for CO_(2)/N_(2) up to 98-102 at 273 K,facilitating the enrichment of CO_(2)and O_(2)molecules around the catalytic centers,thus boosting their catalytic conversion directly from air under solar light(100 mW cm^(-2)).Benefiting from the improved charge separation and broad light absorption,along with high CO_(2)and O_(2)uptake,iCMP-2 can deliver excellent CO and H_(2)O_(2)yields(611.8 and 810.6μmol h^(-1)g^(-1),respectively)under an atmosphere composed of water vapor and air without any co-catalysts.
基金funded by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03017)China Postdoctoral Science Foundation(No.GZC20230373)+5 种基金Zhejiang Provincial Natural Science Foundation of China(No.LQ24B070010)CMA Key Open Laboratory of Transforming Climate Resources to Economy(No.2024004K)Natural Science Foundation of Huzhou City(No.2024YZ19)the National Natural Science Foundation of China(Nos.22202032,22406020 and 22406019)the Key Research and Development Projects of Xinjiang Uygur Autonomous Region,China(No.2022B02031)Joint Fund of the Zhejiang Provincial Natural Science Foundation of China(No.LBMHY25E060009)。
文摘Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.
基金supported financially by the following:Natural Science Foundation of China,Grant Numbers:21829501,21925303,22471275,21771186,22075291,21222301,21171170,21528303,U24A20480,92475105,22503108CASHIPS Director’s Fund(BJPY2019A02)+6 种基金the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(2020HSC-CIP005)the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(2022HSC-CIP018)Presidential Foundation of HFIPS of Chinese Academy of Sciences(no.YZJJ2023QN28)the HFIPS Director’s Fund(no.YZJJ-GGZX-2022-01)the CAS/SAFEA International Partner-ship Program for Creative Research Teamsthe Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(Grant Number:GZC20241744)Hefei Institute of Physical Science,Chinese Academy of Sciences(BR-E44BGGBR12B).
文摘The electrochemical reduction of CO_(2),as a renewable energy-driven electrochemical system,has emerged as an environmentally benign approach for producing valuable chemicals and fuels under mild reaction conditions.Recent advances in the precise synthesis of metal nanoclusters,coupled with state-of-the-art characterization techniques,have enabled atomic-level investigation of structure-activity relationships in nanocatalysts.Due to their well-defined atomic architectures,the active metal sites within these nanocatalysts can be accurately identified,facilitating systematic studies on how compositions(structures)modulate catalytic performance.This review begins by summarizing recent advances in the controlled synthesis of atomically precise metal nanoclusters,followed by an overview of progress in the electrochemical reduction of CO_(2) to CO using nanoclusters as catalysts.Subsequently,we systematically investigate the effects of metal kernel characteristics and staple properties on catalytic activity,selectivity,and stability.Furthermore,current challenges are outlined,and prospective research directions are proposed in this rapidly evolving field.It is anticipated that this review will inspire further innovation in the synthesis of atomically precise nanocluster catalysts,promote a deeper mechanistic understanding of metal nanocluster-mediated electrochemical CO_(2) reduction,and push forward the related industrial applications.
基金supported by the National Natural Science Foundation of China (22178149)Jiangsu Distinguished Professor Program+4 种基金Natural Science Foundation of Jiangsu Province for Outstanding Youth Scientists (BK20211599)Key R and D Project of Zhenjiang City (CQ2022001)Scientific Research Startup Foundation of Jiangsu University (Nos. 202096 and 22JDG020)Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment of Fuzhou University (SKLPEE-KF202310)the Opening Project of Structural Optimization and Application of Functional Molecules Key Laboratory of Sichuan Province (2023GNFZ-01)。
文摘Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.
基金Project(21471054)supported by the National Natural Science Foundation of China
文摘A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.
基金supported by the National Basic Research Program of China(973 Program2013CB632402)+7 种基金the National Natural Science Foundation of China(513201050015137219051402025and 21433007)the Natural Science Foundation of Hubei Province(2015CFA001)the Fundamental Research Funds for the Central Universities(WUT:2014-VII-010)the Self-Determined and Innovative Research Funds of State Key Laboratory of Advanced Technology for Material Synthesis and ProcessingWuhan University of Technology(2013-ZD-1)~~
文摘Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.
基金financially supported by the NSFC of China (Nos.22175033,22371033,22371032)Jilin Provincial Department of Science and Technology (No.20230508108RC)+1 种基金the Fundamental Research Funds for the Central Universities Excellent Youth Team Program (No.2412023YQ001)the Postdoctoral Fellowship Program of CPSF (No.GZC20230939)。
文摘Integration of single-atom catalysts(SACs) onto metal-organic frameworks(MOFs) with porous channels has garnered significant interest in the field of CO_(2) reduction.However,MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge.In this study,we utilized firstly the post-synthetic single-atom chelation sites on zirconiumbased metal-organic cages(Zr-MOCs) to anchor cobalt(Co) atom to synthesize single-dispersible Zr T^(-1)-NH_(2)-IS-Co molecular cages for CO_(2) photoreduction.Experimental results demonstrate that Zr T^(-1)-NH_(2)-ISCo exhibits impressive catalytic performance,achieving syngas yields of up to 30.9 mmol g^(-1)h^(-1),ranking among the highest values of reported crystalline porous catalysts.Mechanistic insights reveal the newly introduced metal serving as the catalytic site and ^(*)COOH acts as a crucial intermediate in the CO_(2) reduction process.Furthermore,the successful synthesis of Zr T^(-1)-NH_(2)-IS-Ni and Zr T^(-1)-NH_(2)-IS-Mn show the universality of the modification strategies,with their CO_(2) catalytic activity surpassing that of Zr T^(-1)-NH_(2).
基金financially supported by the National Natural Science Foundation of China(Nos.22372035,22302039,22311540011,and 21973014)the“111 Project”(No.D16008).
文摘Presented herein are the delicate design and synthesis of S-scheme NiTiO_(3)/CdS heterostructures composed of CdS nanoparticles anchored on the surface of NiTiO_(3) nanorods for photocatalytic CO_(2) reduction.Systematic physicochemical studies demonstrate that NiTiO_(3)/CdS hybrid empowers superior light absorption and enhanced CO_(2) capture and activation.Electron spin resonance validates that the charge carriers in NiTiO_(3)/CdS follow a S-scheme transfer pathway,which powerfully impedes their recombination and promotes their separation.Importantly,the photogenerated holes on CdS are effectively consumed at the hero-interface by the electron from NiTiO_(3),preventing the photo-corrosion of the metal sulfide.As a result,with Co(bpy)_(3)^(2+)as a cocatalyst,NiTiO_(3)/CdS displays a considerable performance for CO_(2) reduction,affording a high CO yield rate of 20.8µmol h^(−1).Moreover,the photocatalyst also manifests substantial stability and good reusability for repeated CO_(2) reaction cycles in the created tandem photochemical system.In addition,the possible CO_(2) photoreduction mechanism is constructed on the basis of the intermediates monitored by in-situ diffuse reflectance infrared Fourier transform spectroscopy.
基金financially supported by the National Natural Science Foundation of China(NSFC,52376193 and 52488201)the Fundamental Research Funds for the Central Universities(30925020107)。
文摘Electrochemical reduction reaction of pure CO_(2)(epCO_(2) RR)is highly promising since it could convert CO_(2) pollution into value-added chemicals(e.g.,CO,HCOOH,C_(2)H_(4),C_(2)H_(5) OH)under industrial-level current density with high selectivity above 90%.While the purification process of industrial flue gas into pure CO_(2) accounts for significant portion of CO_(2)-electrolysis cost.Direct flue-gas electroreduction offers a cost-effective alternative,while its practical implementation faces challenges such as low CO_(2) concentrations(<20 vol%)leading to small current density,competitive reactions such as oxygen reduction reaction,hydrogen evolution reaction,etc.,with more positive thermodynamic potentials than epCO_(2) RR.Therefore,this work reviews strategies to develop efficient and selective electrocatalysts that are resistant to non-CO_(2) active gasses such as O_(2),SO_(x),NO_(x),etc.,and treatment methods for such components in the flue gas.Significantly,the technoeconomic analysis of CO_(2) capture and purification integrated electrolysis process and direct flue gas reduction,is compared.Importantly,future research regarding direct electrochemical reduction of flue gas is proposed,including multifunctional catalyst design,complex reaction mechanism exploration,electrolysis system optimization,etc.
基金supported by the National Natural Science Foundation of China(Nos.22106105 and 22201180)the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-E00015)+2 种基金Shanghai Science and Technology Innovation Program(No.21DZ1206300)the Central Local Science and Technology Development Guidance Fund(No.YDZX20213100003002)Shanghai Science and Technology Commission Program(No.20060502200).
文摘Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.
基金supported by the National Natural Science Foundation of China(Nos.22375031,22202037,22472023)the Fundamental Research Funds for the Central Universities(Nos.2412023YQ001,2412023QD019,2412024QD014)+1 种基金supported by grants from the seventh batch of Jilin Province Youth Science and Technology Talent Lifting Project(No.QT202305)Science and Technology Development Plan Project of Jilin Province,China(No.20240101192JC)。
文摘The light-driven CO_(2)reduction reaction(CO_(2)RR)to CO is a very effective way to address global warming.To avoid competition with water photolysis,metal-free gas-solid CO_(2)RR catalysts should be investigated.Covalent organic frameworks(COFs)offer a promising approach for CO_(2)transformation but lack high efficiency and selectivity in the absence of metals.Here,we have incorporated a pyridine nitrogen component into the imine-COF conjugated structure(Tp Pym).This innovative system has set a record of producing a CO yield of 1565μmol g^(-1)within 6 h.The soft X-ray absorption fine structure measurement proves that Tp Pym has both better conjugation and electron cloud enrichment.The electronic structure distribution delays the charge-carrier recombination,as evidenced by femtosecond transient absorption spectroscopy.The energy band diagram and theoretical calculation show that the conduction-band potential of Tp Pym is lower and the reduction reaction of CO_(2)to CO is more likely to occur.
基金financial supports from the National Natural Science Foundation of China(52201237)the Talent Introduction Project of Chinese Academy of Sciences(E344011)+4 种基金the Shenzhen High Level Talent Team Project(KQTD2022110109364705)the Joint Research Project of China Merchants Group and SIAT(E2Z1521)the Cross Institute Joint Research Youth Team Project of SIAT(E25427)National Natural Science Foundation of China(52402136)the China Postdoctoral Science Foundation(E325281005)。
文摘Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(Nos.20240601047RC and YDZJ202201ZYTS629)Hainan Province Science and Technology Special Fund(No.ZDYF2022SHFZ090)+1 种基金the National Natural Science Foundation(Nos.22466017 and 22061014)the specific research fund of the Innovation Platform for Academicians of Hainan Province。
文摘The goal of photocatalytic CO_(2)reduction is to obtain a single energy-bearing product with high efficiency and stability.Consequently,constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective.Here,we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived Cd In_(2)S_(4)/In_(2)S_(3)heterojunction that exhibited stable and high selectivity.Multiple characterizations of the Cd In_(2)S_(4)/In_(2)S_(3)heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites,a high visible-light utilization rate(λ<600 nm),efficient charge separation,and a prolonged charge-carrier lifetime.Moreover,an S-scheme charge transfer mechanism,based on the interleaved band between the two components,improved the reduction capability of the electrons.Benefiting from the compositional and structural synergy,the yield CO by Cd In_(2)S_(4)/In_(2)S_(3)-250(CI-250)reached 135.62μmol·g^(-1)·h^(-1),which was 49.32 times and 32.88 times higher than that of In_(2)S_(3)and Cd In_(2)S_(4),respectively.The Cd In_(2)S_(4)/In_(2)S_(3)heterojunction exhibited a quantum efficiency of 4.23%with a CO selectivity of 71%.Four cycle tests confirmed the good stability and recyclability of the CI-250.This work provides a new approach for designing and preparing high-performance hollow MOFsbased photocatalysts for scalable and sustainable CO_(2)reduction.
