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
Some active metal oxides(Al_(2)O_(3),TiO_(2),and Cr_(2)O_(3))were selected as dopants to the Al_(2)O_(3)-based ceramic shells for investment casting of K417G superalloy.The effects of dopant types and contents(0,2,5,a...Some active metal oxides(Al_(2)O_(3),TiO_(2),and Cr_(2)O_(3))were selected as dopants to the Al_(2)O_(3)-based ceramic shells for investment casting of K417G superalloy.The effects of dopant types and contents(0,2,5,and 8 wt.%)on the wettability and interfacial reaction between the alloy and shell were investigated by a sessile-drop experiment.The results show that increasing the Al_(2)O_(3) doping contents(0−8 wt.%)reduces the porosity(21.74%−10.08%)and roughness(3.22−1.34μm)of the shell surface.The increase in Cr_(2)O_(3) dopant content(2−8 wt.%)further exacerbates the interfacial reaction,leading to an increase in the thickness of the reaction layer(2.6−3.1μm)and a decrease in the wetting angle(93.9°−91.0°).The addition of Al_(2)O_(3) and TiO_(2) dopants leads to the formation of Al_(2)TiO_(5) composite oxides in the reaction products,which effectively inhibits the interfacial reaction.The increase in TiO_(2) dopant contents(0−8 wt.%)further promotes the formation of Al_(2)TiO_(5),which decreases the thickness of the interfacial reaction layer(3.9−1.2μm)and increases the wetting angle(95.0°−103.8°).The introduced dopants enhance the packing density of the shell surface,while simultaneously suppress the diffusion of active metal elements from the alloy matrix to the interface.展开更多
With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.展开更多
Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent material...Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent materials were successfully synthesized by loading TEPA onto the pore MgO/ZrO_(2)carriers in the paper.The pore structure and surface characteristic of the samples were analyzed by using XRD,BET,FT-IR and SEM.The adsorbent materials exhibited microcrystalline state,and the crystallinity of all samples gradually decreased as the increase of TEPA content.The pore structure analysis indicated that the modification of MgO-ZrO_(2)adsorbents with TEPA led to the decrease of the specific surface areas,but the narrow micro-mesopore size distributions ranging from 1.8-12 nm in the adsorbents still were maintained.FT-IR spectrum results further verified the successful loading of TEPA.The adsorption capacity of the adsorbents for CO_(2)were tested by using an adsorption apparatus equipped with gas chromatography.The results indicated that when the TEPA loading reached 50%,the sample exhibited the maximum adsorption value for CO_(2),reaching 4.07 mmol/g under the operation condition of 75℃and atmospheric pressure.This result could be assigned to not only the base active sites but also the coexistence of both micropore and mesopore in the adsorbent.After three cycles tests for CO_(2)capture,the adsorption value of the sample for CO_(2)can also reached 95%of its original adsorption capacity,which verified the excellent cyclic operation stability.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
The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) ...The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.展开更多
High-entropy alloy(HEA)offer tunable composition and surface structures,enabling the creation of novel active sites that enhance catalytic performance in renewable energy application.However,the inherent surface compl...High-entropy alloy(HEA)offer tunable composition and surface structures,enabling the creation of novel active sites that enhance catalytic performance in renewable energy application.However,the inherent surface complexity and tendency for elemental segregation,which results in discrepancies between bulk and surface compositions,pose challenges for direct investigation via density functional theory.To address this,Monte Carlo simulations combined with molecular dynamics were employed to model surface segregation across a broad range of elements,including Cu,Ag,Au,Pt,Pd,and Al.The analysis revealed a trend in surface segregation propensity following the order Ag>Au>Al>Cu>Pd>Pt.To capture the correlation between surface site characteristics and the free energy of multi-dentate CO_(2)reduction intermediates,a graph neural network was designed,where adsorbates were transformed into pseudo-atoms at their centers of mass.This model achieved mean absolute errors of 0.08–0.15 eV for the free energies of C_(2)intermediates,enabling precise site activity quantification.Results indicated that increasing the concentration of Cu,Ag,and Al significantly boosts activity for CO and C_(2)formation,whereas Au,Pd,and Pt exhibit negative effects.By screening stable composition space,promising HEA bulk compositions for CO,HCOOH,and C_(2)products were predicted,offering superior catalytic activity compared to pure Cu catalysts.展开更多
Recycling of indium secondary resources to prepare indium-based electrocatalysts for efficient CO_(2)reduction has been a promising strategy to bridge the gap between indium recycling and utilization.Herein,the chemis...Recycling of indium secondary resources to prepare indium-based electrocatalysts for efficient CO_(2)reduction has been a promising strategy to bridge the gap between indium recycling and utilization.Herein,the chemisorption of metal cations in indium tin oxide(ITO)etching wastewater by iminodiacetic groups of commercial D401 resin successfully achieves nearly 100%indium recovery and also fulfills wastewater emission standards.Theoretical calculation unveils that metallic indium over In_(2)O_(3)support(In/In_(2)O_(3))possesses the lowest energy barrier for electrochemical reduction of CO_(2)to formate.Such an In/In_(2)O_(3)is hence constructed by air annealing the metal cation-adsorbed resin and post in situ electrochemical reconstruction upon CO_(2)reduction.The In/In_(2)O_(3)derived from the ITO etching wastewater exhibits exceptional electrocatalytic CO_(2)-to-formate performance as current efficiency is higher than 92%throughout 145 h galvanostatic electrolysis at-250 mA cm^(-2).The rational integration of metallurgy and material for indium recycling and utilization adds knowledge on designing In-based electrocatalysts,contributing to addressing indium scarcity and carbon-neutral challenge.展开更多
The use of fossil fuels significantly contributes to excess CO_(2) emissions.Catalytic hydrogenation of CO_(2) to dimethyl ether(DME)is an effective method for CO_(2) recycling,offering both environmental and economic...The use of fossil fuels significantly contributes to excess CO_(2) emissions.Catalytic hydrogenation of CO_(2) to dimethyl ether(DME)is an effective method for CO_(2) recycling,offering both environmental and economic benefits.Zeolites,known for their efficiency as solid catalysts,are widely utilized in the chemical industries.Bifunctional catalysts based on zeolites have gained attention for their applications in CO_(2) hydrogenation to DME.This review discusses key factors affecting the catalytic performance of zeolites,including topologies,Si/Al ratio,crystal size,and the proximity of metallic species to the zeolite catalysts.Although bifunctional catalytic systems enhance the conversion of CO_(2) to DME,they also lead to high CO selectivity at elevated temperatures,which can limit both DME yield and selectivity.We present recent advancements in the development of bifunctional catalysts for the direct hydrogenation of CO_(2) to DME,providing insights for designing optimized catalysts for tandem reaction systems.展开更多
Photocatalysis offers a sustainable solution to two pressing global issues:greenhouse gas mitigation and clean energy generation.By harnessing light energy,photocatalytic processes enable water splitting for hydrogen ...Photocatalysis offers a sustainable solution to two pressing global issues:greenhouse gas mitigation and clean energy generation.By harnessing light energy,photocatalytic processes enable water splitting for hydrogen production and CO_(2) conversion into value-added products.Among the materials explored for photocatalysis,nickel-based photocatalysts have emerged as highly promising due to their low cost,abundance,stability,and efficiency.This review summarizes recent advancements in Ni-based photocatalysts,highlighting their role in improving photocatalytic performance by enhancing light absorption,charge separation,and reducing charge recombination.Key challenges and future directions for optimizing these materials are also discussed,offering insights into their potential for advancing clean energy technologies.展开更多
The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kine...The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kinetics and competing reaction pathways present challenges in achieving high product selectivity and efficiency.Herein,we focus on the transformation of CO_(2)into C_(2)+products,particularly emphasizing advances in non-copper-based catalytic systems,which have emerged as promising alternatives that present unique electronic structures and adsorption properties.Unlike conventional copper catalysts,these systems offer distinct advantages in selectivity and stability,particularly through the modulation of surface defect engineering.We systematically analyze the main reaction pathways leading to C_(2)+products,including ethylene formation and higher hydrocarbon(C_(2)-4)alcohols and oxygenates,while critically assessing the mechanistic insights that differentiate non-copper catalysts from their Cu-based counterparts.By summarizing recent developments,the key challenges,and optimization strategies,we provide a comprehensive overview of how non-copper catalysts can enable efficient and scalable CO_(2)reduction reactions,with an aim of assisting researchers in their design of novel catalysts that may reach industrial applications.展开更多
Carbon-based materials have been widely applied for pollutant removal relying on their rich pore structure,functional groups,chemical stability,and expandability.However,the traditional manufacturing process of carbon...Carbon-based materials have been widely applied for pollutant removal relying on their rich pore structure,functional groups,chemical stability,and expandability.However,the traditional manufacturing process of carbon materials based on organic compounds pyrolysis is high energy-consuming and high-emission,which is not conducive to addressing the climate crisis and achieving the goal of carbon neutrality.Molten salt electrolysis technology enables the direct capture and reduction of CO_(2)to produce solid carbon,resulting in significant environmental benefits while achieving carbon emissions reduction.The molten salt also has a purification function,enabling the production of high-purity carbon materials.The kinetics of the electrochemical reduction process can be easily controlled,and the co-reduction of multiple elements provides convenience for the in-situ optimization of carbon material structure and the expansion of its applications.Therefore,this review focuses on the thermodynamics&kinetics processes of molten salt capture and electrochemical reduction of CO_(2)to prepare carbon materials.It further reviews the recent research progress on the preparation of carbon materials for pollutant removal based on molten salt electrochemical processes for the first time.Finally,we analyze the advantages and challenges of the current molten salt electrochemical processes and offers prospects for future research directions.展开更多
The study of the effects of supercritical CO_(2)(ScCO_(2))under high temperature and high pressure on the mechanical properties and fracturing potential of shale holds significant implications for advancing our unders...The study of the effects of supercritical CO_(2)(ScCO_(2))under high temperature and high pressure on the mechanical properties and fracturing potential of shale holds significant implications for advancing our understanding of enhanced shale gas extraction and reservoir exploration and development.This study examines the influence of three fluids,i.e.ScCO_(2),deionized water(DW),and ScCO_(2)tDW,on the mechanical properties and fracturability of shale at immersion pressures of 15 MPa and 45 MPa,with a constant temperature of 100C.The key findings are as follows:(1)Uniaxial compressive strength(UCS)of shale decreased by 10.72%,11.95%,and 23.67%at 15 MPa,and by 42.40%,46.84%,and 51.65%at 45 MPa after immersion in ScCO_(2),DW,and ScCO_(2)tDW,respectively,with the most pronounced effect observed in ScCO_(2)tDW;(2)Microstructural analysis revealed that while ScCO_(2)and DW do not significantly alter the microstructure,immersion in ScCO_(2)tDW results in a more complex surface morphology;(3)Acoustic emission(AE)analysis indicates a reduction in stress for crack damage,with a decreased fractal dimension of AE signals in different fluids.AE energy is primarily generated during the unstable crack propagation stage;(4)A quantitative method employing a multi-factor approach combined with the brittleness index(BI)effectively characterizes shale fracturability.Evaluation results show that ScCO_(2)tDW has a more significant effect on shale fracturability,with fracturability indices of 0.833%and 1.180%following soaking at 15 MPa and 45 MPa,respectively.Higher immersion pressure correlates positively with increased shale fracturability.展开更多
The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close atten...The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close attention is paid to the carbon capture,utilization,and storage concept.The key component of this concept is the catalytic conversion of CO_(2)into valuable chemical compounds and fuels.Light olefins are one of the most industrially important chemicals,and their sustainable production via CO_(2)hydrogenation could be a prospective way to reach carbon neutrality.Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost,high activity,and good stability.This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO_(2)hydrogenation into light olefins.Particular attention is paid to understanding the roles of catalyst composition,structural properties,and promoters in enhancing catalytic activity,selectivity,and stability.展开更多
Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies i...Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today.High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation,but it is a complicated and difficult task to precisely control their structures.The strategy of pore-space partition(PSP)is a powerful way to construct this type MOFs,which has the characteristic of isostructural relationship,and can be resulted in a similar performance for them.Therefore,it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers.Herein,three tetranuclear Cu(Ⅱ)cluster-based MOFs(FJU-112/113/114)with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units.With the highest microporosity and unique functional site,FJU-114 realized a good improvement in the adsorption and separation performance of C_(2)H_(2)/CO_(2).The gas adsorption and lab-scale C_(2)H_(2)/CO_(2)breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm^(3)/g for C_(2)H_(2),and shows the best separation factor of 4.2 among three MOFs.The GCMC simulation reveals that a stronger adsorption binding site of C_(2)H_(2)in FJU-114a located in the cage II near the unchanged tetranuclear copper node,combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C_(2)H_(2)adsorption and separation.展开更多
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supported by the National Natural Science Foundation of China (No. 52374292)China Baowu Low Carbon Metallurgy Innovation Foundation, China (No. BWLCF202309)the Natural Science Foundation of Changsha City, China (No. KQ2208271)。
文摘Some active metal oxides(Al_(2)O_(3),TiO_(2),and Cr_(2)O_(3))were selected as dopants to the Al_(2)O_(3)-based ceramic shells for investment casting of K417G superalloy.The effects of dopant types and contents(0,2,5,and 8 wt.%)on the wettability and interfacial reaction between the alloy and shell were investigated by a sessile-drop experiment.The results show that increasing the Al_(2)O_(3) doping contents(0−8 wt.%)reduces the porosity(21.74%−10.08%)and roughness(3.22−1.34μm)of the shell surface.The increase in Cr_(2)O_(3) dopant content(2−8 wt.%)further exacerbates the interfacial reaction,leading to an increase in the thickness of the reaction layer(2.6−3.1μm)and a decrease in the wetting angle(93.9°−91.0°).The addition of Al_(2)O_(3) and TiO_(2) dopants leads to the formation of Al_(2)TiO_(5) composite oxides in the reaction products,which effectively inhibits the interfacial reaction.The increase in TiO_(2) dopant contents(0−8 wt.%)further promotes the formation of Al_(2)TiO_(5),which decreases the thickness of the interfacial reaction layer(3.9−1.2μm)and increases the wetting angle(95.0°−103.8°).The introduced dopants enhance the packing density of the shell surface,while simultaneously suppress the diffusion of active metal elements from the alloy matrix to the interface.
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
基金supported by Shanxi Provincial Key Research and Development Project(202102090301026)Graduate Education Innovation Project of Taiyuan University of Science and Technology(SY2023024)。
文摘Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent materials were successfully synthesized by loading TEPA onto the pore MgO/ZrO_(2)carriers in the paper.The pore structure and surface characteristic of the samples were analyzed by using XRD,BET,FT-IR and SEM.The adsorbent materials exhibited microcrystalline state,and the crystallinity of all samples gradually decreased as the increase of TEPA content.The pore structure analysis indicated that the modification of MgO-ZrO_(2)adsorbents with TEPA led to the decrease of the specific surface areas,but the narrow micro-mesopore size distributions ranging from 1.8-12 nm in the adsorbents still were maintained.FT-IR spectrum results further verified the successful loading of TEPA.The adsorption capacity of the adsorbents for CO_(2)were tested by using an adsorption apparatus equipped with gas chromatography.The results indicated that when the TEPA loading reached 50%,the sample exhibited the maximum adsorption value for CO_(2),reaching 4.07 mmol/g under the operation condition of 75℃and atmospheric pressure.This result could be assigned to not only the base active sites but also the coexistence of both micropore and mesopore in the adsorbent.After three cycles tests for CO_(2)capture,the adsorption value of the sample for CO_(2)can also reached 95%of its original adsorption capacity,which verified the excellent cyclic operation stability.
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.
基金Project(52204378)supported by the National Natural Science Foundation of China。
文摘The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.
文摘High-entropy alloy(HEA)offer tunable composition and surface structures,enabling the creation of novel active sites that enhance catalytic performance in renewable energy application.However,the inherent surface complexity and tendency for elemental segregation,which results in discrepancies between bulk and surface compositions,pose challenges for direct investigation via density functional theory.To address this,Monte Carlo simulations combined with molecular dynamics were employed to model surface segregation across a broad range of elements,including Cu,Ag,Au,Pt,Pd,and Al.The analysis revealed a trend in surface segregation propensity following the order Ag>Au>Al>Cu>Pd>Pt.To capture the correlation between surface site characteristics and the free energy of multi-dentate CO_(2)reduction intermediates,a graph neural network was designed,where adsorbates were transformed into pseudo-atoms at their centers of mass.This model achieved mean absolute errors of 0.08–0.15 eV for the free energies of C_(2)intermediates,enabling precise site activity quantification.Results indicated that increasing the concentration of Cu,Ag,and Al significantly boosts activity for CO and C_(2)formation,whereas Au,Pd,and Pt exhibit negative effects.By screening stable composition space,promising HEA bulk compositions for CO,HCOOH,and C_(2)products were predicted,offering superior catalytic activity compared to pure Cu catalysts.
基金funding support from the National Key R&D Program of China(2023YFA1508001)the National Natural Science Foundation of China(22272120 and U2202251)+1 种基金the Hainan Province Science and Technology Special Fund(ZDYF2023SHFZ120)the Research Foundation of Marine Science and Technology Collaborative Innovation Center of Hainan University(XTCX2022HYB01)。
文摘Recycling of indium secondary resources to prepare indium-based electrocatalysts for efficient CO_(2)reduction has been a promising strategy to bridge the gap between indium recycling and utilization.Herein,the chemisorption of metal cations in indium tin oxide(ITO)etching wastewater by iminodiacetic groups of commercial D401 resin successfully achieves nearly 100%indium recovery and also fulfills wastewater emission standards.Theoretical calculation unveils that metallic indium over In_(2)O_(3)support(In/In_(2)O_(3))possesses the lowest energy barrier for electrochemical reduction of CO_(2)to formate.Such an In/In_(2)O_(3)is hence constructed by air annealing the metal cation-adsorbed resin and post in situ electrochemical reconstruction upon CO_(2)reduction.The In/In_(2)O_(3)derived from the ITO etching wastewater exhibits exceptional electrocatalytic CO_(2)-to-formate performance as current efficiency is higher than 92%throughout 145 h galvanostatic electrolysis at-250 mA cm^(-2).The rational integration of metallurgy and material for indium recycling and utilization adds knowledge on designing In-based electrocatalysts,contributing to addressing indium scarcity and carbon-neutral challenge.
基金the National Key Research and Development Program of China(2021YFA1500401)the National Natural Science Foundation of China(22288101)the‘111 Center’(B17020)for supporting this work.
文摘The use of fossil fuels significantly contributes to excess CO_(2) emissions.Catalytic hydrogenation of CO_(2) to dimethyl ether(DME)is an effective method for CO_(2) recycling,offering both environmental and economic benefits.Zeolites,known for their efficiency as solid catalysts,are widely utilized in the chemical industries.Bifunctional catalysts based on zeolites have gained attention for their applications in CO_(2) hydrogenation to DME.This review discusses key factors affecting the catalytic performance of zeolites,including topologies,Si/Al ratio,crystal size,and the proximity of metallic species to the zeolite catalysts.Although bifunctional catalytic systems enhance the conversion of CO_(2) to DME,they also lead to high CO selectivity at elevated temperatures,which can limit both DME yield and selectivity.We present recent advancements in the development of bifunctional catalysts for the direct hydrogenation of CO_(2) to DME,providing insights for designing optimized catalysts for tandem reaction systems.
文摘Photocatalysis offers a sustainable solution to two pressing global issues:greenhouse gas mitigation and clean energy generation.By harnessing light energy,photocatalytic processes enable water splitting for hydrogen production and CO_(2) conversion into value-added products.Among the materials explored for photocatalysis,nickel-based photocatalysts have emerged as highly promising due to their low cost,abundance,stability,and efficiency.This review summarizes recent advancements in Ni-based photocatalysts,highlighting their role in improving photocatalytic performance by enhancing light absorption,charge separation,and reducing charge recombination.Key challenges and future directions for optimizing these materials are also discussed,offering insights into their potential for advancing clean energy technologies.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U24B20201)National Natural Science Foundation of China(22372007 and 21972010).
文摘The need to secure environmentally sustainable sources of clean fuel has led to intensive research into the catalytic conversion of CO_(2)into valuable C_(2)+compounds.However,the intrinsically sluggish reduction kinetics and competing reaction pathways present challenges in achieving high product selectivity and efficiency.Herein,we focus on the transformation of CO_(2)into C_(2)+products,particularly emphasizing advances in non-copper-based catalytic systems,which have emerged as promising alternatives that present unique electronic structures and adsorption properties.Unlike conventional copper catalysts,these systems offer distinct advantages in selectivity and stability,particularly through the modulation of surface defect engineering.We systematically analyze the main reaction pathways leading to C_(2)+products,including ethylene formation and higher hydrocarbon(C_(2)-4)alcohols and oxygenates,while critically assessing the mechanistic insights that differentiate non-copper catalysts from their Cu-based counterparts.By summarizing recent developments,the key challenges,and optimization strategies,we provide a comprehensive overview of how non-copper catalysts can enable efficient and scalable CO_(2)reduction reactions,with an aim of assisting researchers in their design of novel catalysts that may reach industrial applications.
基金supported by the National Natural Science Foundation of China(Nos.52200143,51979011 and 52276208)the Natural Science Foundation of Hubei Province(No.2024AFB546)the Fundamental Research Funds for Central Public Welfare Research Institutes(Nos.CKSF2023302/CL and CKSF2023314/CL).
文摘Carbon-based materials have been widely applied for pollutant removal relying on their rich pore structure,functional groups,chemical stability,and expandability.However,the traditional manufacturing process of carbon materials based on organic compounds pyrolysis is high energy-consuming and high-emission,which is not conducive to addressing the climate crisis and achieving the goal of carbon neutrality.Molten salt electrolysis technology enables the direct capture and reduction of CO_(2)to produce solid carbon,resulting in significant environmental benefits while achieving carbon emissions reduction.The molten salt also has a purification function,enabling the production of high-purity carbon materials.The kinetics of the electrochemical reduction process can be easily controlled,and the co-reduction of multiple elements provides convenience for the in-situ optimization of carbon material structure and the expansion of its applications.Therefore,this review focuses on the thermodynamics&kinetics processes of molten salt capture and electrochemical reduction of CO_(2)to prepare carbon materials.It further reviews the recent research progress on the preparation of carbon materials for pollutant removal based on molten salt electrochemical processes for the first time.Finally,we analyze the advantages and challenges of the current molten salt electrochemical processes and offers prospects for future research directions.
基金financial support from the Science and Technology Innovation Program of Hunan Province(Grant No.2023RC1021)the National Natural Science Foundation of China(Grant No.52231012)+1 种基金the Natural Science Foundation of Hainan Province(Grant No.424QN213)the Scientific Research Foundation of Hainan University.
文摘The study of the effects of supercritical CO_(2)(ScCO_(2))under high temperature and high pressure on the mechanical properties and fracturing potential of shale holds significant implications for advancing our understanding of enhanced shale gas extraction and reservoir exploration and development.This study examines the influence of three fluids,i.e.ScCO_(2),deionized water(DW),and ScCO_(2)tDW,on the mechanical properties and fracturability of shale at immersion pressures of 15 MPa and 45 MPa,with a constant temperature of 100C.The key findings are as follows:(1)Uniaxial compressive strength(UCS)of shale decreased by 10.72%,11.95%,and 23.67%at 15 MPa,and by 42.40%,46.84%,and 51.65%at 45 MPa after immersion in ScCO_(2),DW,and ScCO_(2)tDW,respectively,with the most pronounced effect observed in ScCO_(2)tDW;(2)Microstructural analysis revealed that while ScCO_(2)and DW do not significantly alter the microstructure,immersion in ScCO_(2)tDW results in a more complex surface morphology;(3)Acoustic emission(AE)analysis indicates a reduction in stress for crack damage,with a decreased fractal dimension of AE signals in different fluids.AE energy is primarily generated during the unstable crack propagation stage;(4)A quantitative method employing a multi-factor approach combined with the brittleness index(BI)effectively characterizes shale fracturability.Evaluation results show that ScCO_(2)tDW has a more significant effect on shale fracturability,with fracturability indices of 0.833%and 1.180%following soaking at 15 MPa and 45 MPa,respectively.Higher immersion pressure correlates positively with increased shale fracturability.
基金supported by the Ministry of Higher Education,Science and Innovation,and the Slovenian Research Agency(ARIS)throughresearch grants J7-4638 and J2-4441.
文摘The development of human industry inevitably leads to excessive carbon dioxide(CO_(2))emissions.It can cause critical ecological consequences,primarily global warming and ocean acidification.In this regard,close attention is paid to the carbon capture,utilization,and storage concept.The key component of this concept is the catalytic conversion of CO_(2)into valuable chemical compounds and fuels.Light olefins are one of the most industrially important chemicals,and their sustainable production via CO_(2)hydrogenation could be a prospective way to reach carbon neutrality.Fe-based materials are widely recognized as effective thermocatalysts and photothermal catalysts for that process thanks to their low cost,high activity,and good stability.This review critically examines the most recent progress in the development and optimization of Fe-based catalysts for CO_(2)hydrogenation into light olefins.Particular attention is paid to understanding the roles of catalyst composition,structural properties,and promoters in enhancing catalytic activity,selectivity,and stability.
基金financially supported by the National Natural Science Foundation of China(Nos.21975044,21971038,21922810 and 22271046)the Fujian Provincial Department of Science and Technology(Nos.2023J01355,2023J011106 and 2022R1022001).
文摘Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today.High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation,but it is a complicated and difficult task to precisely control their structures.The strategy of pore-space partition(PSP)is a powerful way to construct this type MOFs,which has the characteristic of isostructural relationship,and can be resulted in a similar performance for them.Therefore,it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers.Herein,three tetranuclear Cu(Ⅱ)cluster-based MOFs(FJU-112/113/114)with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units.With the highest microporosity and unique functional site,FJU-114 realized a good improvement in the adsorption and separation performance of C_(2)H_(2)/CO_(2).The gas adsorption and lab-scale C_(2)H_(2)/CO_(2)breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm^(3)/g for C_(2)H_(2),and shows the best separation factor of 4.2 among three MOFs.The GCMC simulation reveals that a stronger adsorption binding site of C_(2)H_(2)in FJU-114a located in the cage II near the unchanged tetranuclear copper node,combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C_(2)H_(2)adsorption and separation.
