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
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
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
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
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
Photothermal catalysis is a promising technology to convert CO_(2)into high value-added products.Here,we show that loading Ru NPs on TiO_(2)achieved a remarkable photothermal synergistic effect and the Ru-TiO_(2)demon...Photothermal catalysis is a promising technology to convert CO_(2)into high value-added products.Here,we show that loading Ru NPs on TiO_(2)achieved a remarkable photothermal synergistic effect and the Ru-TiO_(2)demonstrated a high efficiency for the photothermal conversion of low CO_(2)concentration to CH_(4)at the gas-solid interface.The photothermal activity of the Ru-TiO_(2)(217.9μmol/(g·h))was nearly 6 times higher than pure thermal activity(38.08μmol/(g·h)),and nearly 20 times than the photocatalytic activity(10.9μmol/(g·h)).We revealed that the light excitation could drive the generated electrons from TiO_(2)to Ru particles,beneficial to CO_(2)reduction,while external heating showed no influence on the charge separation of the Ru-TiO_(2).Hence,the photothermal synergy is not a heat-assisted photocatalytic process,but a photo-assisted thermal catalytic process.We finally demonstrated that the CO_(2)was firstly converted to CO,and the CO was further hydrogenated to CH_(4).The introduction of light could promote the activation of intermediate CO species at the Ru-Ti interface sites,thus greatly accelerating CO hydrogenation to CH_(4).This work contributes to further understanding of the mechanism of photothermal catalytic CO_(2)reduction.展开更多
Halide perovskite-based heterojunctions have emerged as promising candidates for solar energy conversion and storage due to their unique photophysical properties.However,the current bottleneck lies in the insufficient...Halide perovskite-based heterojunctions have emerged as promising candidates for solar energy conversion and storage due to their unique photophysical properties.However,the current bottleneck lies in the insufficient separation of photogenerated carriers at the interface,primarily due to challenges in the controllable growth of perovskite on the substrate.Herein,we present a growth strategy for depositing lead-free Cs_(3)Sb_(2)Br_(9)perovskite nanocrystals onto the surface of Co_(3)O_(4)with the assistance of polyacrylic acid(PAA),generating a step-scheme(S-scheme)heterojunction denoted as Co_(3)O_(4)-Cs_(3)Sb_(2)Br_(9).The utilization of PAA as a template can effectively regulate the nucleation and growth of Cs_(3)Sb_(2)Br_(9),thereby significantly enhancing the charge separation efficiency of the Co_(3)O_(4)-Cs_(3)Sb_(2)Br_(9)heterojunction compared to its counterpart formed without PAA assistance.Under simulated solar light irradiation(100 mW·cm^(-2)),the cerium-doped Co_(3)O_(4)-Cs_(3)Sb_(2)Br_(9)heterojunction exhibits excellent photocatalytic CO_(2)reduction activity without the need for any sacrificial agent.Specifically,the CO yield reaches up to 700.7μmol·g^(-1)·h^(-1),marking a 2.8-fold increase over the sample synthesized without PAA mediation.This polymer-assisted in-situ growth strategy should open up a new avenue for designing and developing more efficient photocatalytic materials based on halide perovskites.展开更多
The electrochemical reduction of carbon dioxide(CO_(2))into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy con...The electrochemical reduction of carbon dioxide(CO_(2))into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy conversion.Substantial efforts have been made to improve the understanding of CO_(2)reduction reaction(CO_(2)RR)mechanisms by computational and spectroscopic studies.An in-depth understanding of CO_(2)RR mechanism can provide the guidance and criteria for designing high-efficiency catalysts,and hence,steering CO_(2)RR to desired products.This review systematically discusses the formation mechanisms and reaction pathways of various CO_(2)RR products,including C_(1)products(CO,HCOOH,and CH_(4)),C_(2)products(C_(2)H_(4),C_(2)H_(5)OH,and CH_(3)COOH),and C_(3+)products(C_(3)H_(6),C_(3)H_(7)OH,and others).The reaction pathways are elucidated by analyzing the adsorption behavior,energy barriers,and intermediate coupling steps involved in the generation of each product.Particular emphasis is placed on the key intermediates,such as^(*)OCHO,^(*)COOH,^(*)CO,^(*)OCCOH,and^(*)CCO,which play crucial roles in determining the product selectivity.The effects of catalyst composition,morphology,and electronic structure on the adsorption and activation of these intermediates are also discussed.Moreover,advanced characterization techniques,including in-situ spectroscopy and isotopic labeling experiments,are highlighted for their contributions to unraveling the reaction mechanisms.The review aims to provide critical insights to reveal the activity-determining para meters and underlying CO_(2)RR mechanisms,which will guide the rational design of next-generation electrocatalysts for selective CO^(2)RR towards high-value products.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
Using natural minerals to eliminate harmful Cr(Ⅵ)under sustainable sunshine has significant potential.Herein,Palygorskite nanorods were utilized as carriers for the in-situ synthesis of CaIn_(2)S_(4) photocatalysts t...Using natural minerals to eliminate harmful Cr(Ⅵ)under sustainable sunshine has significant potential.Herein,Palygorskite nanorods were utilized as carriers for the in-situ synthesis of CaIn_(2)S_(4) photocatalysts through a simple one-pot thermal process,enabling the efficient reduction of Cr(Ⅵ).With a Palygorskite to CaIn_(2)S_(4) mass ratio of 5%,the conversion rate of Cr(Ⅵ)reached 98%after 60min of visible-light exposure,with a remarkable reaction rate of 0.0633 min^(-1).The effective integration of CaIn_(2)S_(4) with Palygorskite led to a more uniform dispersion of CaIn_(2)S_(4),exposing more reactive sites.Moreover,the establishment of a heterojunction between CaIn_(2)S_(4) and Palygorskite facilitated the transport of photogenerated electrons from CaIn_(2)S_(4),enhancing the efficiency of charge separation.These factors contribute to the improved photocatalytic performance.Additionally,the developed composite photocatalysts demonstrated excellent stability under light exposure and could be reused efficiently.Trapping tests on active substances revealed that e-played key roles in the Cr(Ⅵ)reduction.This research suggests the potential of using natural minerals to fabricate composite photocatalysts capable of effectively removing pollutants from the environment using solar energy.展开更多
Membrane electrode assembly(MEA)is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO_(2) reduction reaction(CO_(2)RR).In MEAs,a square-shaped cross-sec...Membrane electrode assembly(MEA)is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO_(2) reduction reaction(CO_(2)RR).In MEAs,a square-shaped cross-section in the flow channel is normally adopted,the configuration optimization of which could potentially enhance the performance of the electrolyzer.This paper describes the numerical simulation study on the impact of the flow-channel cross-section shapes in the MEA electrolyzer for CO_(2)RR.The results show that wide flow channels with low heights are beneficial to the CO_(2)RR by providing a uniform flow field of CO_(2),especially at high current densities.Moreover,the larger the electrolyzer,the more significant the effect is.This study provides a theoretical basis for the design of high-performance MEA electrolyzers for CO_(2)RR.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 Ti-Al alloy was synthesized using the aluminothermic reduction of TiO_(2),with CaO and MgF_(2)serving as flux components.Investigations were conducted to ascertain the effects of MgF_(2)content on the alloy-slag s...The Ti-Al alloy was synthesized using the aluminothermic reduction of TiO_(2),with CaO and MgF_(2)serving as flux components.Investigations were conducted to ascertain the effects of MgF_(2)content on the alloy-slag separation,alloy microstructure,composition,phase constitution,overall alloy yield,and aluminothermic reduction of TiO_(2).Results indicate that MgF_(2)enhances the separation of the alloy from slag and promotes the formation of the TiAl phase within the alloy matrix.Nevertheless,an overabundance of MgF_(2)reduces the interfacial tension between the Al reductant and the slag,leading to significant loss of Al.This adversely affects alloy-slag separation,escalates the incorporation of oxide inclusions in the alloy,and severely reduces the recovery rate of alloy.Concurrently,the alloy has a phase transition from TiAl to Ti_(3)Al.The optimum condition for alloy-slag separation and alloy integrity is realized at the MgF_(2)content of 10wt%.Kinetic analysis at this flux ratio determines the activating energy for the Al-TiO_(2)-CaO-MgF_(2)system,which is 409.729 kJ/mol,and the order of kinetics is n=0.38.展开更多
In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low...In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low photogenerated charge separation efficiency and the lack of effective active sites seriously constrain the reaction efficiencies of semiconductor photocatalysts for N_(2) reduction of ammonia synthesis.Therefore,the rational design of catalytic materials is the key to enhance the photocatalytic N_(2) reduction reaction of ammonia synthesis.Transition metal Ru as the active center not only accelerates the adsorption and activation of N_(2) molecules,but also has good selectivity for N_(2) reduction.Moreover,the interaction between the metal and the support can effectively regulate the electronic structure of the active site,accelerate the photogenerated electron transfer,and significantly enhance the photocatalytic activity.Based on this,this review systematically investigates the Ru co-semiconductors to realize efficient photocatalytic N_(2) reduction for ammonia synthesis,and introduces its basic principles.Specifically,the Ru co-semiconductor photocatalytic material systems are introduced,such as TiO2-based,g-C3N4-based,and metal oxide materials,including the design of catalysts,crystal structures,and other characteristics.In addition,the modification strategies of photocatalytic N_(2) reduction ammonia synthesis materials are also presented,including loading/doping,defect engineering,construction of heterojunctions,and crystal surface modulation.Furthermore,the progress and shortcomings of the application of Ru co-semiconductors in these processes are summarized and comprehensively discussed,and the future outlook of Ru co-semiconductors in photocatalytic N_(2) reduction ammonia synthesis applications is proposed.展开更多
Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field are highly promising piezo-photocatalytic candidate materials.In addition,developing structural design and revealing polarization ...Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field are highly promising piezo-photocatalytic candidate materials.In addition,developing structural design and revealing polarization enhancement in-depth mechanism are top priorities.Herein,we introduce the intergrowth ferroelectrics Bi_(7)Ti_(4)NbO_(21)thin-layer nanosheets for piezo-photocatalytic CO_(2)reduction.Density functional theory(DFT)calculations indicate that interlayer lattice mismatch leads to increased tilting and rotation angle of Ti/NbO_(6)octahedra on perovskite-like layers,serving as the main reason for increased polarization.Furthermore,the tilting and rotation angle of the interlayer octahedron further increase under stress,suggesting a stronger driving force generated to facilitate charge carrier separation efficiency.Meanwhile,Bi_(7)Ti_(4)NbO_(21)nanosheets provide abundant active sites to effectively adsorb CO_(2)and acquire sensitive stress response,thereby presenting synergistically advanced piezo-photocatalytic CO_(2)reduction activity with a high CO generation rate of 426.97μmol g^(-1)h^(-1).Our work offers new perspectives and directions for initiating and investigating the mechanisms of high-performance intergrowth piezo-photocatalysts.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
A Co_(3)O_(4)/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selec-tive photocatalytic CO_(2)reduction.The optimized Co_(3)O_(4)/BiOBr-0.8 catalyst exhibited CO and CH_(4)evo...A Co_(3)O_(4)/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selec-tive photocatalytic CO_(2)reduction.The optimized Co_(3)O_(4)/BiOBr-0.8 catalyst exhibited CO and CH_(4)evolution rates of 112.2 and 5.5µmol·g^(-1)·h^(-1),respectively,representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr.The heterojunction demonstrated broadened light absorption,enhanced photoelectrochemical activity,reduced charge-transfer resistance,and improved separation efficiency of photogenerated carriers(e^(-)/h^(+)).These synergistic effects were attributed to the formation of a Z-scheme heterostructure,which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.展开更多
To explain the influence mechanism of MgO on the consolidation and reduction characteristics of roasted iron pellets,the properties and structure of pellets were investigated from multi-dimensions.It indicated that th...To explain the influence mechanism of MgO on the consolidation and reduction characteristics of roasted iron pellets,the properties and structure of pellets were investigated from multi-dimensions.It indicated that the MgO addition decreased the reduction swelling index(RSI)and reduction degree of pellets in both CO and H_(2)atmospheres.During the stepwise reduction process of Fe2O3→Fe3O4→FeO,the reduction behaviour of pellets in CO and H_(2)was similar,while the reduction rate of pellets in H_(2)atmosphere was almost twice as high as that in CO atmosphere.During the stepwise reduction process of FeO→Fe,the RSI of pellets showed a logarithmic increase in CO atmosphere and a linear decrease in H_(2)atmosphere.As investigated by first-principles calculations,C and Fe mainly formed chemical bonds,and the CO reduction process released energy,promoting the formation of iron whiskers.However,H and Fe produced weak physical adsorption,and the H_(2)reduction process was endothermic,inhibiting the generation of iron whiskers.With Mg2+doping in FexO,the nucleation region of iron whiskers expanded in CO reduction process,and the morphology of iron whiskers transformed from“slender”to“stocky,”reducing RSI of the pellets.展开更多
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 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 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.
基金supported by the National Natural Science Foundation of China(Nos.22276204 and 22025604).
文摘Photothermal catalysis is a promising technology to convert CO_(2)into high value-added products.Here,we show that loading Ru NPs on TiO_(2)achieved a remarkable photothermal synergistic effect and the Ru-TiO_(2)demonstrated a high efficiency for the photothermal conversion of low CO_(2)concentration to CH_(4)at the gas-solid interface.The photothermal activity of the Ru-TiO_(2)(217.9μmol/(g·h))was nearly 6 times higher than pure thermal activity(38.08μmol/(g·h)),and nearly 20 times than the photocatalytic activity(10.9μmol/(g·h)).We revealed that the light excitation could drive the generated electrons from TiO_(2)to Ru particles,beneficial to CO_(2)reduction,while external heating showed no influence on the charge separation of the Ru-TiO_(2).Hence,the photothermal synergy is not a heat-assisted photocatalytic process,but a photo-assisted thermal catalytic process.We finally demonstrated that the CO_(2)was firstly converted to CO,and the CO was further hydrogenated to CH_(4).The introduction of light could promote the activation of intermediate CO species at the Ru-Ti interface sites,thus greatly accelerating CO hydrogenation to CH_(4).This work contributes to further understanding of the mechanism of photothermal catalytic CO_(2)reduction.
基金supported by the National Key R&D Program of China(No.2022YFA1502902)the National Natural Science Foundation of China(Nos.U21A20286 and 22475152)+2 种基金the Natural Science Foundation of Tianjin City(No.17JCJQJC43800)the Programme of Introducing Talents of Discipline to Universities(111 Project)Tianjin Research Innovation Project for Postgraduate Students(No.2022BKY156).
文摘Halide perovskite-based heterojunctions have emerged as promising candidates for solar energy conversion and storage due to their unique photophysical properties.However,the current bottleneck lies in the insufficient separation of photogenerated carriers at the interface,primarily due to challenges in the controllable growth of perovskite on the substrate.Herein,we present a growth strategy for depositing lead-free Cs_(3)Sb_(2)Br_(9)perovskite nanocrystals onto the surface of Co_(3)O_(4)with the assistance of polyacrylic acid(PAA),generating a step-scheme(S-scheme)heterojunction denoted as Co_(3)O_(4)-Cs_(3)Sb_(2)Br_(9).The utilization of PAA as a template can effectively regulate the nucleation and growth of Cs_(3)Sb_(2)Br_(9),thereby significantly enhancing the charge separation efficiency of the Co_(3)O_(4)-Cs_(3)Sb_(2)Br_(9)heterojunction compared to its counterpart formed without PAA assistance.Under simulated solar light irradiation(100 mW·cm^(-2)),the cerium-doped Co_(3)O_(4)-Cs_(3)Sb_(2)Br_(9)heterojunction exhibits excellent photocatalytic CO_(2)reduction activity without the need for any sacrificial agent.Specifically,the CO yield reaches up to 700.7μmol·g^(-1)·h^(-1),marking a 2.8-fold increase over the sample synthesized without PAA mediation.This polymer-assisted in-situ growth strategy should open up a new avenue for designing and developing more efficient photocatalytic materials based on halide perovskites.
基金financially supported by the National Natural Science Foundation of China(Grants 22225901,21975237 and 51702312)the Fundamental Research Funds for the Central Universities(Grant WK2340000101)+5 种基金the USTC Research Funds of the Double First-Class Initiative(Grant YD2340002007 and YD9990002017)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(Grant RERU2022007)the China Postdoctoral Science Foundation(Grants 2023M733371,2024M750006 and 2023T160617)Postdoctoral Fellowship Program(Grade C)of China Postdoctoral Science Foundation(GZC20230008)the Natural Science Foundation Youth Project of Anhui Province(2408085QB065)the Postdoctoral Research Funding Project of Anhui Province(2023B727)。
文摘The electrochemical reduction of carbon dioxide(CO_(2))into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy conversion.Substantial efforts have been made to improve the understanding of CO_(2)reduction reaction(CO_(2)RR)mechanisms by computational and spectroscopic studies.An in-depth understanding of CO_(2)RR mechanism can provide the guidance and criteria for designing high-efficiency catalysts,and hence,steering CO_(2)RR to desired products.This review systematically discusses the formation mechanisms and reaction pathways of various CO_(2)RR products,including C_(1)products(CO,HCOOH,and CH_(4)),C_(2)products(C_(2)H_(4),C_(2)H_(5)OH,and CH_(3)COOH),and C_(3+)products(C_(3)H_(6),C_(3)H_(7)OH,and others).The reaction pathways are elucidated by analyzing the adsorption behavior,energy barriers,and intermediate coupling steps involved in the generation of each product.Particular emphasis is placed on the key intermediates,such as^(*)OCHO,^(*)COOH,^(*)CO,^(*)OCCOH,and^(*)CCO,which play crucial roles in determining the product selectivity.The effects of catalyst composition,morphology,and electronic structure on the adsorption and activation of these intermediates are also discussed.Moreover,advanced characterization techniques,including in-situ spectroscopy and isotopic labeling experiments,are highlighted for their contributions to unraveling the reaction mechanisms.The review aims to provide critical insights to reveal the activity-determining para meters and underlying CO_(2)RR mechanisms,which will guide the rational design of next-generation electrocatalysts for selective CO^(2)RR towards high-value products.
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supported by the National Natural Science Foundation of China(Nos.22206065 and 22109059)the Jinling Institute of Technology's Doctor Start-up Fund(No.jitb-202024)the Natural Science Foundation of Jiangsu Province(No.BK20221167).
文摘Using natural minerals to eliminate harmful Cr(Ⅵ)under sustainable sunshine has significant potential.Herein,Palygorskite nanorods were utilized as carriers for the in-situ synthesis of CaIn_(2)S_(4) photocatalysts through a simple one-pot thermal process,enabling the efficient reduction of Cr(Ⅵ).With a Palygorskite to CaIn_(2)S_(4) mass ratio of 5%,the conversion rate of Cr(Ⅵ)reached 98%after 60min of visible-light exposure,with a remarkable reaction rate of 0.0633 min^(-1).The effective integration of CaIn_(2)S_(4) with Palygorskite led to a more uniform dispersion of CaIn_(2)S_(4),exposing more reactive sites.Moreover,the establishment of a heterojunction between CaIn_(2)S_(4) and Palygorskite facilitated the transport of photogenerated electrons from CaIn_(2)S_(4),enhancing the efficiency of charge separation.These factors contribute to the improved photocatalytic performance.Additionally,the developed composite photocatalysts demonstrated excellent stability under light exposure and could be reused efficiently.Trapping tests on active substances revealed that e-played key roles in the Cr(Ⅵ)reduction.This research suggests the potential of using natural minerals to fabricate composite photocatalysts capable of effectively removing pollutants from the environment using solar energy.
基金the National Key R&D Program of China(No.2021YFA1501503)the National Natural Science Foundation of China(Nos.22250008,22121004,22108197)+3 种基金the Haihe Laboratory of Sustainable Chemical Transformations(No.CYZC202107)the Natural Science Foundation of Tianjin City(No.21JCZXJC00060)the Program of Introducing Talents of Discipline to Universities(No.BP0618007)the Xplorer Prize for financial support。
文摘Membrane electrode assembly(MEA)is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO_(2) reduction reaction(CO_(2)RR).In MEAs,a square-shaped cross-section in the flow channel is normally adopted,the configuration optimization of which could potentially enhance the performance of the electrolyzer.This paper describes the numerical simulation study on the impact of the flow-channel cross-section shapes in the MEA electrolyzer for CO_(2)RR.The results show that wide flow channels with low heights are beneficial to the CO_(2)RR by providing a uniform flow field of CO_(2),especially at high current densities.Moreover,the larger the electrolyzer,the more significant the effect is.This study provides a theoretical basis for the design of high-performance MEA electrolyzers for CO_(2)RR.
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National Natural Science Foundation of China(52074052)。
文摘The Ti-Al alloy was synthesized using the aluminothermic reduction of TiO_(2),with CaO and MgF_(2)serving as flux components.Investigations were conducted to ascertain the effects of MgF_(2)content on the alloy-slag separation,alloy microstructure,composition,phase constitution,overall alloy yield,and aluminothermic reduction of TiO_(2).Results indicate that MgF_(2)enhances the separation of the alloy from slag and promotes the formation of the TiAl phase within the alloy matrix.Nevertheless,an overabundance of MgF_(2)reduces the interfacial tension between the Al reductant and the slag,leading to significant loss of Al.This adversely affects alloy-slag separation,escalates the incorporation of oxide inclusions in the alloy,and severely reduces the recovery rate of alloy.Concurrently,the alloy has a phase transition from TiAl to Ti_(3)Al.The optimum condition for alloy-slag separation and alloy integrity is realized at the MgF_(2)content of 10wt%.Kinetic analysis at this flux ratio determines the activating energy for the Al-TiO_(2)-CaO-MgF_(2)system,which is 409.729 kJ/mol,and the order of kinetics is n=0.38.
基金supported by Taishan Scholars Foundation of Shandong province(tsqn 201909058)。
文摘In recent years,photocatalytic N_(2) reduction for ammonia synthesis at room temperature and atmospheric pressure has gradually become a research hotspot,exhibiting extremely high development potential.However,the low photogenerated charge separation efficiency and the lack of effective active sites seriously constrain the reaction efficiencies of semiconductor photocatalysts for N_(2) reduction of ammonia synthesis.Therefore,the rational design of catalytic materials is the key to enhance the photocatalytic N_(2) reduction reaction of ammonia synthesis.Transition metal Ru as the active center not only accelerates the adsorption and activation of N_(2) molecules,but also has good selectivity for N_(2) reduction.Moreover,the interaction between the metal and the support can effectively regulate the electronic structure of the active site,accelerate the photogenerated electron transfer,and significantly enhance the photocatalytic activity.Based on this,this review systematically investigates the Ru co-semiconductors to realize efficient photocatalytic N_(2) reduction for ammonia synthesis,and introduces its basic principles.Specifically,the Ru co-semiconductor photocatalytic material systems are introduced,such as TiO2-based,g-C3N4-based,and metal oxide materials,including the design of catalysts,crystal structures,and other characteristics.In addition,the modification strategies of photocatalytic N_(2) reduction ammonia synthesis materials are also presented,including loading/doping,defect engineering,construction of heterojunctions,and crystal surface modulation.Furthermore,the progress and shortcomings of the application of Ru co-semiconductors in these processes are summarized and comprehensively discussed,and the future outlook of Ru co-semiconductors in photocatalytic N_(2) reduction ammonia synthesis applications is proposed.
基金support from the Natural Science Foundation of Jiangsu Province(BK20220596)Innovative science and technology platform project of cooperation between Yangzhou City and Yangzhou University,China(No.YZ202026305)+1 种基金Natural Science Foundation of China(21922202,21673202 and 22272147)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Intergrowth ferroelectric semiconductors with excellent spontaneous polarization field are highly promising piezo-photocatalytic candidate materials.In addition,developing structural design and revealing polarization enhancement in-depth mechanism are top priorities.Herein,we introduce the intergrowth ferroelectrics Bi_(7)Ti_(4)NbO_(21)thin-layer nanosheets for piezo-photocatalytic CO_(2)reduction.Density functional theory(DFT)calculations indicate that interlayer lattice mismatch leads to increased tilting and rotation angle of Ti/NbO_(6)octahedra on perovskite-like layers,serving as the main reason for increased polarization.Furthermore,the tilting and rotation angle of the interlayer octahedron further increase under stress,suggesting a stronger driving force generated to facilitate charge carrier separation efficiency.Meanwhile,Bi_(7)Ti_(4)NbO_(21)nanosheets provide abundant active sites to effectively adsorb CO_(2)and acquire sensitive stress response,thereby presenting synergistically advanced piezo-photocatalytic CO_(2)reduction activity with a high CO generation rate of 426.97μmol g^(-1)h^(-1).Our work offers new perspectives and directions for initiating and investigating the mechanisms of high-performance intergrowth piezo-photocatalysts.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
文摘A Co_(3)O_(4)/BiOBr heterojunction was synthesized via a facile one-step solvothermal method for highly selec-tive photocatalytic CO_(2)reduction.The optimized Co_(3)O_(4)/BiOBr-0.8 catalyst exhibited CO and CH_(4)evolution rates of 112.2 and 5.5µmol·g^(-1)·h^(-1),respectively,representing 6.3-fold and 3.9-fold enhancements over pristine BiOBr.The heterojunction demonstrated broadened light absorption,enhanced photoelectrochemical activity,reduced charge-transfer resistance,and improved separation efficiency of photogenerated carriers(e^(-)/h^(+)).These synergistic effects were attributed to the formation of a Z-scheme heterostructure,which facilitated solar energy utilization and electron reduction capacity while suppressing carrier recombination.
基金support from the National Natural Science Foundation of China(52174290).
文摘To explain the influence mechanism of MgO on the consolidation and reduction characteristics of roasted iron pellets,the properties and structure of pellets were investigated from multi-dimensions.It indicated that the MgO addition decreased the reduction swelling index(RSI)and reduction degree of pellets in both CO and H_(2)atmospheres.During the stepwise reduction process of Fe2O3→Fe3O4→FeO,the reduction behaviour of pellets in CO and H_(2)was similar,while the reduction rate of pellets in H_(2)atmosphere was almost twice as high as that in CO atmosphere.During the stepwise reduction process of FeO→Fe,the RSI of pellets showed a logarithmic increase in CO atmosphere and a linear decrease in H_(2)atmosphere.As investigated by first-principles calculations,C and Fe mainly formed chemical bonds,and the CO reduction process released energy,promoting the formation of iron whiskers.However,H and Fe produced weak physical adsorption,and the H_(2)reduction process was endothermic,inhibiting the generation of iron whiskers.With Mg2+doping in FexO,the nucleation region of iron whiskers expanded in CO reduction process,and the morphology of iron whiskers transformed from“slender”to“stocky,”reducing RSI of the pellets.
