Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tai...Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.展开更多
Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon...Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.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
Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O cr...Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.展开更多
Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especi...Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.展开更多
The combination of solar energy and natural hydro-thermal systems will innovate the chemistry ofCO_(2)hydrogenation;however,the approach remains challenging due to the lack of robust and cost-effective catalytic syste...The combination of solar energy and natural hydro-thermal systems will innovate the chemistry ofCO_(2)hydrogenation;however,the approach remains challenging due to the lack of robust and cost-effective catalytic system.Here,Zn which can be recycled with solar energy-induced approach was chosen as the reductant and Co as catalyst to achieve robust hydrothermalCO_(2)methanation.Nanosheets of honeycomb ZnO were grown in situ on the Co surface,resulting in a new motif(Co@ZnO catalyst)that inhibits Co deacti-vation through ZnO-assistedCoOx reduction.The stabilized Co and interaction between Co and ZnO functioned collaboratively toward the full conversion ofCO_(2)–CH_(4).In situ hydrothermal infrared spectros-copy confirmed the formation of formic acid as an intermediate,thereby avoiding CO formation and unwanted side reaction pathways.This study presents a straightforward one-step process for both highly efficientCO_(2)conversion and catalyst synthesis,paving the way for solar-drivenCO_(2)methanation.展开更多
Integrating the CO_(2)capture process with the CO_(2)electrochemical reduction process into a single system can eliminate the need for storage and transportation following CO_(2)capture.This integrated process offers ...Integrating the CO_(2)capture process with the CO_(2)electrochemical reduction process into a single system can eliminate the need for storage and transportation following CO_(2)capture.This integrated process offers several advantages over multi-step cascade processes,including reduced costs and enhanced CO_(2)utilization.However,the integrated CO_(2)capture and electrochemical reduction(CCER)process encounters several challenges,including the low CO_(2)adsorption performance of the gas diffusion electrode(GDE)and catalyst,as well as the poor activity and selectivity of the catalyst for the electrochemical reduction of CO_(2).This review aims to systematically summarize the fundamentals of the CCER process.Based on an in-depth understanding of the CO_(2)mass transfer,adsorption,and electrochemical reduction processes,GDE design strategies based on the modulation of wettability and structure are discussed to enhance the CO_(2)capture capability at the GDE level.At the catalyst level,catalyst design strategies based on the introduction of CO_(2)capture sites and the construction of CO_(2)mass transfer channels were analyzed,and catalyst design strategies for enhanced CO_(2)capture were proposed.This review summarizes the most common catalysts for CO_(2)electrochemical reduction,such as Ni-based,Bi-based,and Cubased catalysts,and analyzes their design strategies based on reaction pathways for generating specific products.Finally,the problems and challenges of the CCER process are summarized and proposed,which provide ideas for the further application of this technology in the future.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low r...Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.展开更多
Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support...Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support interactions.In this study,we synthesized TiO_(2)supported Pt SACs(Pt1/TiO_(2)),with Pt single atoms dispersed on rutile(Pt1/R)and anatase(Pt1/A)phases of TiO_(2)for the reverse water-gas shift(RWGS)reaction.While both catalysts maintained 100%CO selectivity over time,Pt1/A achieved a CO_(2)conversion of 7.5%,significantly outperforming Pt1/R(3.6%).In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways:the COOH pathway was dominant on Pt1/A,whereas the–OH+HCO pathway was more competitive on Pt1/R.Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt1/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers.These findings provide valuable insights for the design of more efficient SAC systems in CO_(2)hydrogenation processes.展开更多
Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal s...Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal sites in 3D COFs predominantly exhibit symmetrical coordination,making them unsuitable for CO_(2)activation.Here,we design a 3D COF with 2,2'-pyridine linked around tetra-(4-anilyl)methane(TCM-Bpy-COF),where Co^(2+)is asymmetrically coordinated by bipyridine and acetates(TCMBpy-COF-CoAc).The TCM-Bpy-COF-CoAc exhibits outstanding photocatalytic CO_(2)reduction performance under weak visible light,achieving a CO evolution rate of 26,650μmol g^(-1)h^(-1)under 5 W of lightemitting-diode(LED)lamp and high apparent quantum efficiency.The performance far exceeds that of symmetrically coordinated bipyridine-Co-bipyridine TCM-Bpy-COF and surpasses most reported COF-based photocatalysts.In-situ spectral characterizations and theoretical calculations show that asymmetric N,O-coordination around the Co^(2+)center polarizes electron density and lowers reaction energy barriers of^(*)COOH intermediates,enhancing the conversion of CO_(2)to CO.This work inspires the design of 3D COF-based photocatalysts with highly catalytic efficiency.展开更多
Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited l...Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited light absorption,low photocarrier separation efficiency,Ni sintering,and carbon deposition hinder DRM stability.Herein,we regulated Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance the optical characteristics while addressing Ni sintering and carbon deposition issues.The(3Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst had insufficient Ni content,while the(9Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst showed excessive carbon deposition,leading to lower stability compared to the(6Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst,which achieved CH4 and CO_(2) rates to 231.0 μmol gcat^(-1)s^(-1) and 294.3 μmol gcat^(-1)s^(-1) ,respectively,at 973 K,with only 0.2 wt.%carbon deposition and no Ni sintering.This work adjusted Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance DRM performance,which has implications for improving other reactions.展开更多
The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development ...The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.展开更多
A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. ...A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction（SCR） performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.展开更多
The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O...The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.展开更多
基金supported by the National Natural Science Foundation of China(No.52300170).
文摘Catalytic CO_(2)-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis.Single-atom catalysts(SACs)with maximized atomic utilization,tailored electronic configurations and unique metal-support interactions,exhibit superior performance in CO_(2) activation and methanol synthesis.This review systematically compares reaction mechanisms and pathways across thermal,photocatalytic and electrocatalytic systems,emphasizing structure-activity relationships governed by active sites,coordination microenvironments and support functionalities.Through case studies of representative SACs,we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity.A critical analysis of reaction parameters(e.g.,temperature,pressure)reveals condition-dependent catalytic behaviors in thermal system,with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps.While thermal catalysis achieves industrially viable methanol yields,the scalability is constrained by energy-intensive operation and catalyst sintering.Conversely,photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations.To address the challenges,we propose strategic research priorities on precise design of active sites,synergy of multiple technological pathways,development of intelligent catalytic systems and diverse CO_(2) feedstock compatibility.These insights establish a framework for developing next-generation SACs,offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.
基金Supported by the National Key Research and Development Program of China(2023YFB4104500,2023YFB4104502)the National Natural Science Foundation of China(22138013)the Taishan Scholar Project(ts201712020).
文摘Against the backdrop of escalating global climate change and energy crises,the resource utilization of carbon dioxide(CO_(2)),a major greenhouse gas,has become a crucial pathway for achieving carbon peaking and carbon neutrality goals.The hydrogenation of CO_(2)to methanol not only enables carbon sequestration and recycling,but also provides a route to produce high value-added fuels and basic chemical feedstocks,holding significant environmental and economic potential.However,this conversion process is thermodynamically and kinetically limited,and traditional catalyst systems(e.g.,Cu/ZnO/Al_(2)O_(3))exhibit inadequate activity,selectivity,and stability under mild conditions.Therefore,the development of novel high-performance catalysts with precisely tunable structures and functionalities is imperative.Metal-organic frameworks(MOFs),as crystalline porous materials with high surface area,tunable pore structures,and diverse metal-ligand compositions,have the great potential in CO_(2)hydrogenation catalysis.Their structural design flexibility allows for the construction of well-dispersed active sites,tailored electronic environments,and enhanced metal-support interactions.This review systematically summarizes the recent advances in MOF-based and MOF-derived catalysts for CO_(2)hydrogenation to methanol,focusing on four design strategies:(1)spatial confinement and in situ construction,(2)defect engineering and ion-exchange,(3)bimetallic synergy and hybrid structure design,and(4)MOF-derived nanomaterial synthesis.These approaches significantly improve CO_(2)conversion and methanol selectivity by optimizing metal dispersion,interfacial structures,and reaction pathways.The reaction mechanism is further explored by focusing on the three main reaction pathways:the formate pathway(HCOO*),the RWGS(Reverse Water Gas Shift reaction)+CO*hydrogenation pathway,and the trans-COOH pathway.In situ spectroscopic studies and density functional theory(DFT)calculations elucidate the formation and transformation of key intermediates,as well as the roles of active sites,metal-support interfaces,oxygen vacancies,and promoters.Additionally,representative catalytic performance data for MOFbased systems are compiled and compared,demonstrating their advantages over traditional catalysts in terms of CO_(2)conversion,methanol selectivity,and space-time yield.Future perspectives for MOF-based CO_(2)hydrogenation catalysts will prioritize two main directions:structural design and mechanistic understanding.The precise construction of active sites through multi-metallic synergy,defect engineering,and interfacial electronic modulation should be made to enhance catalyst selectivity and stability.In addition,advanced in situ characterization techniques combined with theoretical modeling are essential to unravel the detailed reaction mechanisms and intermediate behaviors,thereby guiding rational catalyst design.Moreover,to enable industrial application,challenges related to thermal/hydrothermal stability,catalyst recyclability,and cost-effective large-scale synthesis must be addressed.The development of green,scalable preparation methods and the integration of MOF catalysts into practical reaction systems(e.g.,flow reactors)will be crucial for bridging the gap between laboratory research and commercial deployment.Ultimately,multi-scale structure-performance optimization and catalytic system integration will be vital for accelerating the industrialization of MOF-based CO_(2)-to-methanol technologies.
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the financial support from the National Natural Science Foundation of China (Nos.U23A20677,22022610 and 52400137)"Pioneer" and "Leading Goose" R&D Program of Zhejiang (Nos.2022C03146 and 2023C03017)+2 种基金China Postdoctoral Science Foundation (No.2024T170805)Zhejiang Provincial Natural Science Foundation of China (No.LDT23E06015B06)the support of the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University for assistance with the calculations。
文摘Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.
基金supported by the National Natural Science Foundation of China(No.51878292).
文摘Large-scale CO_(2)emissions have exacerbated the greenhouse effect,reinforcing the critical need for efficient CO_(2)mitigation methods.Plasma-catalytic technology enables CO_(2)conversion under mild conditions,especially for CO_(2)methanation(the Sabatier reaction),which has attracted significant attention due to its economic benefits and the potential for safe energy transportation via existing natural gas pipelines.The development of high-performance CO_(2)methanation catalysts remains an ongoing and long-term objective,and there is a lack of adequate in-situ characterization techniques to investigate the mechanisms.This study focuses on the Ni/La_(2)O_(3)(LN)catalyst and introduces two CO_(2)activation strategies through F and Na modifications:the Ni-Ov-Ni site activation with electron transfer from Ni0 under low-power conditions and basic site activation under high-power conditions.The LN-NaF catalysts enhance CO_(2)methanation activity across the entire power range compared to LN,achieving a CO_(2)conversion of 86.3%and CH4 selectivity of 99.4%.Additionally,LN-F(h)reaches a CH4 yield 4.15 times higher than that of LN at low power.Furthermore,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy with a self-made reactor are performed under plasma-catalytic conditions to reveal the CO_(2)adsorption and conversion mechanisms,indicating that different dopants(F,Na,and NaF)exhibit promoting effects on different intermediates,resulting in variations in CO_(2)methanation activity.This study provides valuable insights for improving catalyst performance and a thorough comprehension of mechanisms in CO_(2)methanation.
基金the National Natural Science Foundation of China(No.22108171)the Shanghai Key Laboratory of Hydrogen Science&Center of Hydrogen Science,Shanghai Jiao Tong University,China.
文摘The combination of solar energy and natural hydro-thermal systems will innovate the chemistry ofCO_(2)hydrogenation;however,the approach remains challenging due to the lack of robust and cost-effective catalytic system.Here,Zn which can be recycled with solar energy-induced approach was chosen as the reductant and Co as catalyst to achieve robust hydrothermalCO_(2)methanation.Nanosheets of honeycomb ZnO were grown in situ on the Co surface,resulting in a new motif(Co@ZnO catalyst)that inhibits Co deacti-vation through ZnO-assistedCoOx reduction.The stabilized Co and interaction between Co and ZnO functioned collaboratively toward the full conversion ofCO_(2)–CH_(4).In situ hydrothermal infrared spectros-copy confirmed the formation of formic acid as an intermediate,thereby avoiding CO formation and unwanted side reaction pathways.This study presents a straightforward one-step process for both highly efficientCO_(2)conversion and catalyst synthesis,paving the way for solar-drivenCO_(2)methanation.
基金supported by the National Natural Science Foundation of China(U23A20573,U23A20140)the Hebei Natural Science Foundation(B202420809,B2024208088)+2 种基金S&T Program of Hebei(242Q4301Z,22373709D)Project of Basic Research at Universities in Shijiazhuang(241790977A)Huang jin tai plan project of Hebei provincial department of education(HJZD202512)。
文摘Integrating the CO_(2)capture process with the CO_(2)electrochemical reduction process into a single system can eliminate the need for storage and transportation following CO_(2)capture.This integrated process offers several advantages over multi-step cascade processes,including reduced costs and enhanced CO_(2)utilization.However,the integrated CO_(2)capture and electrochemical reduction(CCER)process encounters several challenges,including the low CO_(2)adsorption performance of the gas diffusion electrode(GDE)and catalyst,as well as the poor activity and selectivity of the catalyst for the electrochemical reduction of CO_(2).This review aims to systematically summarize the fundamentals of the CCER process.Based on an in-depth understanding of the CO_(2)mass transfer,adsorption,and electrochemical reduction processes,GDE design strategies based on the modulation of wettability and structure are discussed to enhance the CO_(2)capture capability at the GDE level.At the catalyst level,catalyst design strategies based on the introduction of CO_(2)capture sites and the construction of CO_(2)mass transfer channels were analyzed,and catalyst design strategies for enhanced CO_(2)capture were proposed.This review summarizes the most common catalysts for CO_(2)electrochemical reduction,such as Ni-based,Bi-based,and Cubased catalysts,and analyzes their design strategies based on reaction pathways for generating specific products.Finally,the problems and challenges of the CCER process are summarized and proposed,which provide ideas for the further application of this technology in the future.
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)to form high-energy-density and high-value-added multicarbon products has attracted much attention.Selective reduction of CO_(2)to C^(2+)products face the problems of low reaction rate,complex mechanism and low selectivity.Currently,except for a few examples,copper-based catalysts are the only option capable of achieving efficient generation of C^(2+)products.However,the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO_(2)RR.In this review,we first discuss the mechanism of C^(2+)product generation.The structural factors promoting C^(2+)product generation are outlined,and the dynamic evolution of these structural factors is discussed.Furthermore,the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface.Finally,further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
文摘Single-atom catalysts(SACs)offer a promising approach for maximizing noble metals utilization in catalytic processes.However,their performance in CO_(2)hydrogenation is often constrained by the nature of metal-support interactions.In this study,we synthesized TiO_(2)supported Pt SACs(Pt1/TiO_(2)),with Pt single atoms dispersed on rutile(Pt1/R)and anatase(Pt1/A)phases of TiO_(2)for the reverse water-gas shift(RWGS)reaction.While both catalysts maintained 100%CO selectivity over time,Pt1/A achieved a CO_(2)conversion of 7.5%,significantly outperforming Pt1/R(3.6%).In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways:the COOH pathway was dominant on Pt1/A,whereas the–OH+HCO pathway was more competitive on Pt1/R.Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt1/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers.These findings provide valuable insights for the design of more efficient SAC systems in CO_(2)hydrogenation processes.
基金financial support from the National Natural Science Foundation of China(No.22072183)the Natural Science Foundation of Hunan Province,China(No.2022JJ30690)supported in part by the High Performance Computing Center of Central South University。
文摘Three-dimensional(3D)covalent organic frameworks(COFs)have attracted extensive attention as photocatalysts for CO_(2)reduction reactions.Introducing metal atoms is essential for enhancing activity,but previous metal sites in 3D COFs predominantly exhibit symmetrical coordination,making them unsuitable for CO_(2)activation.Here,we design a 3D COF with 2,2'-pyridine linked around tetra-(4-anilyl)methane(TCM-Bpy-COF),where Co^(2+)is asymmetrically coordinated by bipyridine and acetates(TCMBpy-COF-CoAc).The TCM-Bpy-COF-CoAc exhibits outstanding photocatalytic CO_(2)reduction performance under weak visible light,achieving a CO evolution rate of 26,650μmol g^(-1)h^(-1)under 5 W of lightemitting-diode(LED)lamp and high apparent quantum efficiency.The performance far exceeds that of symmetrically coordinated bipyridine-Co-bipyridine TCM-Bpy-COF and surpasses most reported COF-based photocatalysts.In-situ spectral characterizations and theoretical calculations show that asymmetric N,O-coordination around the Co^(2+)center polarizes electron density and lowers reaction energy barriers of^(*)COOH intermediates,enhancing the conversion of CO_(2)to CO.This work inspires the design of 3D COF-based photocatalysts with highly catalytic efficiency.
基金support from the National Natural Science Foundation of China(22078134)State Key Laboratory of Clean and Efficient Coal Utilization of Taiyuan University of Technology(SKL2022006)Natural Science Foundation of Chongqing(CSTB2023NSCQ-MSX0162)are greatly appreciated for the work.
文摘Dry reforming of methane(DRM)converts CH4 and CO_(2) to syngas.Photothermal DRM,which integrates temperature and light,is a sustainable method for storing solar energy in molecules.However,challenges such as limited light absorption,low photocarrier separation efficiency,Ni sintering,and carbon deposition hinder DRM stability.Herein,we regulated Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance the optical characteristics while addressing Ni sintering and carbon deposition issues.The(3Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst had insufficient Ni content,while the(9Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst showed excessive carbon deposition,leading to lower stability compared to the(6Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalyst,which achieved CH4 and CO_(2) rates to 231.0 μmol gcat^(-1)s^(-1) and 294.3 μmol gcat^(-1)s^(-1) ,respectively,at 973 K,with only 0.2 wt.%carbon deposition and no Ni sintering.This work adjusted Ni contents in(Ni/Ce_(0.8)Zr_(0.2)O_(2))@SiO_(2) catalysts to enhance DRM performance,which has implications for improving other reactions.
基金financially supported by the National Natural Science Foundation of China(22205205)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)under Grant No.21062337-Y。
文摘The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.
基金supported by the National Natural Science Foundation of China(21325731,21221004)the National High Technology Research and Development Program of China(863 Program)the State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex
文摘A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction（SCR） performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.
基金the National Key Project for Basic Research of China(973 Project)(No.2005CB221402)the China National Petroleum Corporation.
文摘The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.
