Methanol,a crucial C1 intermediate,bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO_(2)and an active ...Methanol,a crucial C1 intermediate,bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO_(2)and an active intermediate for hydrocarbon synthesis.Despite significant progress in methanol-to-hydrocarbon(MTH)conversion,a comprehensive understanding of reaction mechanisms remains essential to enhance catalyst design and industrial applicability.This review critically synthesizes recent advances in mechanistic insights related to methanol conversion and methanol-mediated catalytic processes.Firstly,we systematically outline key reaction pathways involved in initial carbon–carbon(C–C)bond formation through direct and indirect mechanisms,emphasizing significant breakthroughs from spectroscopic analyses and theoretical calculations.Subsequently,we highlight the autocatalytic characteristics and dual-cycle mechanisms underlying MTH processes,critically evaluating the roles of zeolite structures,pore sizes,topology,and acidity in governing product selectivity and catalyst stability.Additionally,we discuss cutting-edge developments in tandem catalytic systems employing methanol as a pivotal intermediate for CO_(x)hydrogenation,emphasizing the transferable mechanistic principles and catalytic insights.Finally,we identify future research directions,including elucidating precise hydrocarbon pool(HCP)intermediates,optimizing zeolite structures through computational-guided design,and developing robust catalytic systems leveraging advanced characterization methods and artificial intelligence.By integrating multidisciplinary approaches from catalytic science,materials engineering,and reaction engineering,this review provides actionable guidance towards rational design and optimization of advanced catalytic systems for efficient methanol conversion processes.展开更多
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
A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and character...A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.展开更多
The success of catalytic schemes for the large-scale valorization of CO_(2) does not only depend on the development of active,selective and stable catalytic materials but also on the overall process design.Here we pre...The success of catalytic schemes for the large-scale valorization of CO_(2) does not only depend on the development of active,selective and stable catalytic materials but also on the overall process design.Here we present a multidisciplinary study(from catalyst to plant and techno-economic/lifecycle analysis)for the production of green methanol from renewable H2 and CO_(2).We combine an in-depth kinetic analysis of one of the most promising recently reported methanol-synthesis catalysts(InCo)with a thorough process simulation and techno-economic assessment.We then perform a life cycle assessment of the simulated process to gauge the real environmental impact of green methanol production from CO_(2).Our results indicate that up to 1.75 ton of CO_(2) can be abated per ton of produced methanol only if renewable energy is used to run the process,while the sensitivity analysis suggest that either rock-bottom H2 prices(1.5$kg1)or severe CO_(2) taxation(300$per ton)are needed for a profitable methanol plant.Besides,we herein highlight and analyze some critical bottlenecks of the process.Especial attention has been paid to the contribution of H2 to the overall plant costs,CH4 trace formation,and purity and costs of raw gases.In addition to providing important information for policy makers and industrialists,directions for catalyst(and therefore process)improvements are outlined.展开更多
The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synt...The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.展开更多
The electrochemical conversion of carbon dioxide into valuable products is pivotal for maintaining the global carbon cycle and mitigating global warming.This review explores the advancements in electrochemical CO_(2) ...The electrochemical conversion of carbon dioxide into valuable products is pivotal for maintaining the global carbon cycle and mitigating global warming.This review explores the advancements in electrochemical CO_(2) conversion,particularly focusing on producing methanol,ethanol,and n-propanol using various catalysts such as metals,metal oxides,metal alloys,and metal organic frameworks.Additionally,it covers the photoelectrochemical(PEC)conversion of CO_(2) into alcohols.The primary objective is to identify efficient electrocatalysts for ethanol,methanol,and n-propanol production,prioritizing selectivity,stability,Faradaic efficiency(FE),and current density.Notable catalysts include PtxZn nanoalloys,which exhibit an FE of~81.4% for methanol production,and trimetallic Pt/Pb/Zn nanoalloys,aimed at reducing Pt costs while enhancing catalyst stability and durability.Metal oxide catalysts like thin film Cu_(2)O/CuO on nickel foam and Cu_(2)O/ZnO achieve FE values of~38% and~16.6% for methanol production,respectively.Copper-based metal-organic frameworks,such as Cu@Cu_(2)O,demonstrate an FE of~45% for methanol production.Similarly,Ag_(0.14)/Cu_(0.86) and Cu-Zn alloys exhibit FEs of~63% and~46.6%,respectively,for ethanol production.Notably,n-propanol production via Pd–Cu alloy and graphene/ZnO/Cu_(2)O yields FEs of~13.7% and~23%,respectively.Furthermore,the review discusses recent advancements in PEC reactor design,photoelectrodes,reaction mechanisms,and catalyst durability.By evaluating the efficiency of these devices in liquid fuel production,the review addresses challenges and prospects in CO_(2) conversion for obtaining various valuable products.展开更多
The development of a highly efficient catalyst for CO_(2) activation and selective conversion to methanol is critical to address the issues associated with the high thermal stability of CO_(2) and controllable synthes...The development of a highly efficient catalyst for CO_(2) activation and selective conversion to methanol is critical to address the issues associated with the high thermal stability of CO_(2) and controllable synthesis of methanol.Cu-based catalysts have been widely studied because of the low cost and excellent performance in mild conditions.However,the improvement of catalytic activity and selectivity remains challenging.Herein,we prepared hollow Cu@ZrO_(2) catalysts through pyrolysis of Cu-loaded Zr-MOF for CO_(2) hydrogenation to methanol.Low-temperature pyrolysis generated highly dispersed Cu nanoparticles with balanced Cu^(0)/Cu^(+)sites,larger amounts of surface basic sites and abundant Cu-ZrO_(2) interface in the hollow structure,contributing to enhanced catalytic capacity for adsorption/activation of CO_(2) and selective hydrogenation to methanol.In situ Fourier Transform Infrared Spectroscopy revealed the methanol formation followed the formate-intermediated pathway.This work would provide a guideline for the design of high-performance catalysts and the understanding of the mechanism and active sites for CO_(2) hydrogenation to methanol.展开更多
In the context of peak carbon and carbon neutrality,the utilization of CO_(2)has attracted attention with the aim of reducing carbon emissions by converting CO_(2)into high-value chemicals or energy.Methanol(MeOH),whi...In the context of peak carbon and carbon neutrality,the utilization of CO_(2)has attracted attention with the aim of reducing carbon emissions by converting CO_(2)into high-value chemicals or energy.Methanol(MeOH),which is both a hydrogen and a carbon carrier,is considered the most promising among the CO_(2)-conversion products.This paper focus on routes for electrochemical conversion of CO_(2)to MeOH using green power and green hydrogen to achieve negative CO_(2)emissions.Three feasible technical routes for electrochemical conversion of CO_(2)to MeOH are proposed in this paper:Route 1,electrolysis of water to H_(2)and hydrogenation of CO_(2)to MeOH;Route 2,electrochemical reduction of CO_(2)to MeOH;and Route 3,co-electrolysis of CO_(2)-H_(2)O to syngas and synthesis of MeOH from syngas.Techno-economic assessments of the three routes are conducted using technical maturity surveys,system simulations and cost analyses to provide reference data for route selection for CO_(2)conversion to MeOH in China.Compared with the other routes,Route 1 is advantageous in terms of technical maturity and commercial application prospects.Although Route 1 is presently economically unviable,it is expected to achieve profitability and commercial application in the future with decreases in the cost of renewable power and continuous development of water-electrolysis technology.展开更多
MoS_(2) is a highly promising material for application in lithium-ion battery anodes due to its high theoretical capacity and low cost.However,problems with a fast capacity decay over cycling,especially at the first c...MoS_(2) is a highly promising material for application in lithium-ion battery anodes due to its high theoretical capacity and low cost.However,problems with a fast capacity decay over cycling,especially at the first cycles,and poor rate performance have deterred its practical implementation.Herein,electrodes comprised solely of few-layers 2D MoS_(2) nanosheets have been manufactured by scalable liquid-phase exfoliation and spray deposition methods.The long-standing controversy questioning the reversibility of conversion processes of MoS_(2)-based electrodes was addressed.Raman studies revealed that,in 2D MoS_(2) electrodes,conversion processes are indeed reversible,where nanostructure played a key role.Cycling of the electrodes at high current rates revealed an intriguing phenomenon consisting of a continuously increasing capacity after ca.100-200 cycles.This phenomenon was comprehensively addressed by a variety of electrochemical and microscopy methods that revealed underlying physical activation mechanisms that involved a range of profound electrode structural changes.Activation mechanisms delivered a capacitive electrode of a superior rate performance and cycling stability,as compared to the corresponding pristine electrodes,and to MoS_(2) electrodes previously reported.Herein,we have devised a methodology to overcome the problem of cycling stability of 2D MoS_(2) electrodes.Moreover,activation of electrodes constitutes a methodology that could be applied to enhance the energy storage performance of electrodes based on other 2D nanomaterials,or combinations thereof,strategically combining chemistries to engineer electrodes of superior energy storage properties.展开更多
The accelerating global transition toward carbon neutrality calls for transformative technologies capable of tightly coupling renewable energy with carbon reduction.Among next-generation approaches,solar-driven calciu...The accelerating global transition toward carbon neutrality calls for transformative technologies capable of tightly coupling renewable energy with carbon reduction.Among next-generation approaches,solar-driven calcium-based CO_(2)capture(SCa-CC)and thermochemical conversion(TC)constitutes a promising pathway by utilizing solar energy to directly facilitate the conversion of CO_(2)into value-added hydrocarbon fuels.This approach addresses the high energy consumption associated with conventional CO_(2)capture technologies,thereby mitigating the critical efficiency bottleneck and enhancing economic viability.However,the practical deployment of SCa-CC-TC remains constrained by a series of scientific and engineering challenges.These include the progressive degradation of functional material,the complex coupling of irradiation,thermal,flow,and reaction fields,the dynamic match of solar flux,particle transport,and reaction kinetics,and the constraints of techno-economic feasibility.Breakthroughs in both theoretical insight and practical inquiry are urgently required to enable reliable scale-up.This review offers a comprehensive analysis of full technical framework,encompassing solar energy harvesting,CO_(2)capture,and coupled heat-mass conversion.Recent advances are discussed in the of solar concentrator development,multifunctional materials modification,photothermal reactor configurations,coupling characteristics,and techno-economic assessments.Emerging multimodal activation strategies,including plasmonic,pyroelectric,and piezoelectric effects,are highlighted for their potential to improve reaction kinetics and product selectivity.Key scientific and engineering bottlenecks are analyzed,and strategic directions are proposed to accelerate the transition from laboratory-scale concepts to pilotand industrial-scale demonstrations.These insights are expected to promote the continued development of SCa-CCTC and facilitate the construction of a sustainable energy system with deep coupling of sunlight and carbon cycle.展开更多
Steam methane reforming(SMR)-based methanol synthesis plants utilizing a single CO2 feed represent one of the predominant technologies for improving methanol yield and CO2 utilization.However,SMR alone cannot achieve ...Steam methane reforming(SMR)-based methanol synthesis plants utilizing a single CO2 feed represent one of the predominant technologies for improving methanol yield and CO2 utilization.However,SMR alone cannot achieve full CO2 utilization,and a high water content accumulates if CO2 is only fed into the methanol reactor.In this study,a process integrating SMR with dry methane reforming to improve the conversion of both methane and CO2 is proposed.We also propose an innovative methanol production approach in which captured CO2 is introduced into both the SMR process and the recycle gas of the methanol synthesis loop.This dual CO2 feed approach aims to optimize the stoichio-metric ratio of the reactants.Comparative evaluations are carried out from a techno-economic point of view,and the proposed process is demonstrated to be more efficient in terms of both methanol productivity and CO2 utilization than the existing stand-alone natural gas-based methanol process.展开更多
Global warming caused by excess carbon dioxide(CO_(2))emission has been a focus of the world.The development of neutral carbon technologies becomes a strategic choice for the sustainable human society.Integrating CO_(...Global warming caused by excess carbon dioxide(CO_(2))emission has been a focus of the world.The development of neutral carbon technologies becomes a strategic choice for the sustainable human society.Integrating CO_(2) capture and conversion(iCCC)technology can simultaneously convert the captured CO_(2) from flue gas into value-added chemicals,which saves great energies and expenses incurred in CO_(2) compression and transportation processes of conventional carbon capture,utilization,and storage(CCUS)technology.The present review criti-cally discusses the dual-function materials(DFMs)and the iCCC technology at intermediate temperature for methane production and high temperature for syngas production.The design of reactor and optimization of operation conditions are emphasized from the perspective of industrial applications.The dual-fixed-bed reactors mode by switching the flue gas and reactant gases,and the dual-fluidized-bed reactors mode by the circulation of DFMs particles are comparatively reviewed.We hope this review can stimulate further studies including designing and fabricating feasible DFMs,exploring realistic catalytic process for CO_(2) conversion to high value-added chemicals,developing workable reactor modes and optimizing operation conditions,and establishing industrial demonstration for real applications of iCCC technology in the future.展开更多
Microalgae have piqued renewed interest as a sustainable biofuel feedstock owing to their high CO_(2)conversion efficiency.However,the major limitation of microalga-based biofuel production is low productivity.In this...Microalgae have piqued renewed interest as a sustainable biofuel feedstock owing to their high CO_(2)conversion efficiency.However,the major limitation of microalga-based biofuel production is low productivity.In this study,CO_(2)in flue gas emitted from the coal-fired power plants was fixed through mass microalgal cultivation using only sunlight as an energy source.To minimize the cost and energy required to supply the flue gas and efficiently utilize the microalgal biomass,a polycarbonate(PC)greenhouse and polymeric photobioreactors were installed near the power plant stack.Four different microalgal strains(Chlamydomonas reinhardtii,Chlorella sorokiniana,Neochloris oleoabundans,and Neochloris oleoabundans#13)were subjected to semi-continuous culturing for 1 month.The maximum biomass productivity was achieved by the N.oleoabun-dans#13 strain(0.703 g L^(−1)day^(−1)).Additionally,polymerase chain reaction analysis revealed that the individual microalgal culture was not cross-contaminated with other microalgal cultures in this cultivation system,owing to the structural proper-ties of photobioreactor comprising individual modules.The lipid content and calorific productivity of N.oleoabundans#13 biomass were 45.70%and 3.553 kJ L^(−1)day^(−1),respectively,which indicate satisfactory performance of biomass as a direct combustion fuel.The CO_(2)fixation rate,which was calculated based on the carbon content in the biomass,was 0.309 g CO_(2)L^(−1)day^(−1).Therefore,large amounts of CO_(2)can be reduced using the large-scale microalgal cultivation system,which enables efficient biological CO_(2)conversion and maximizes microalgal biomass utilization.展开更多
With advantages of low costs and high energy density,Li–S batteries are considered as one of the most promising energy storage devices.However,Li_(2)S_(2) with a high dissociation energy and insulative properties is ...With advantages of low costs and high energy density,Li–S batteries are considered as one of the most promising energy storage devices.However,Li_(2)S_(2) with a high dissociation energy and insulative properties is hard to convert into Li_(2)S,resulting in underutilization of sulfur capacity.Herein,Co-Mo_(2)C@C yolk–shell spheres as nanoreactors were designed to confront this challenge rationally.The Co-Mo_(2)C@C-induced Li_(2)S_(1/2) nucleation and growth in the three-dimensional process and the cathode produced more Li_(2)S after full discharge.Experimental studies and theoretical calculations reveal that the conversion barrier from Li_(2)S_(2) into Li_(2)S was lowered while the diffusion of lithium ions and electron transfer accelerated when using the Co-Mo_(2)C@C catalyst.Based on the above advantages,the Co-Mo_(2)C@C/S cathode exhibits a high reversible capacity and excellent cyclic stability,such as an initial specific capacity of 1200 mAh g^(−1) at 0.1 C with 709 mAh g^(−1) at 1.0 C after 1000 cycles with a low capacity fading rate of 0.04%per cycle.Even at high densities of 3.0 C and 5.0 C,the specific capacities are 647.6 and 557.7 mAh g^(−1) after 400 cycles,respectively.Impressively,it also shows ca.770 and 900 mAh g^(−1) at 0.2 C after 50 cycles with high sulfur loadings of 4.2 and 5.1 mg cm−2,respectively.The present work may provide new insights into the design of nanoreactors to promote Li_(2)S_(1/2) growth in a three-dimensional process and accelerate conversion from solid Li_(2)S_(2) to solid Li_(2)S in high performance Li–S batteries.展开更多
Hydrogen as a clean energy carrier has attracted great interests world-wide for substitution of fossil fuels and for abatement of the climate change concerns.However,green hydrogen from renewable resources is less tha...Hydrogen as a clean energy carrier has attracted great interests world-wide for substitution of fossil fuels and for abatement of the climate change concerns.However,green hydrogen from renewable resources is less than 0.1%at present in the world hydrogen production and this is largely from water electrolysis which is beneficial only when renewable electricity is used.Hydrogen production from diverse renewable resources is desirable.This review presents recent advances in hydrogen production from woody biomass through biomass steam gasification,producer gas processing and H_(2)/CO_(2)separation.The producer gas processing includes steam-methane reforming(SMR)and water-gas shift(WGS)reactions to convert CH_(4)and CO in the producer gas to H_(2)and CO_(2).The H_(2)storage discussed using liquid carrier through hydrogenation is also discussed.The CO_(2)capture prior to the SMR is investigated to enhance H_(2)yield in the SMR and the WGS reactions.展开更多
基金the Inner Mongolia Natural Science Foundation(2023ZD05,2025JQ028,2025MS02001)the National Natural Science Foundation of China(22278238,22238004)+3 种基金the National Key Research and Development Program of China(2024YFE0211400)the Major Science and Technology Program of Inner Mongolia Autonomous Region(20212120326)the“Elite Talents Revitalize Inner Mongolia”Initiative–Tier-1 Talent Team(202410)the Ordos Science and Technology Breakthrough(JBGS2024003),and Ordos Laboratory for their financial support.
文摘Methanol,a crucial C1 intermediate,bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO_(2)and an active intermediate for hydrocarbon synthesis.Despite significant progress in methanol-to-hydrocarbon(MTH)conversion,a comprehensive understanding of reaction mechanisms remains essential to enhance catalyst design and industrial applicability.This review critically synthesizes recent advances in mechanistic insights related to methanol conversion and methanol-mediated catalytic processes.Firstly,we systematically outline key reaction pathways involved in initial carbon–carbon(C–C)bond formation through direct and indirect mechanisms,emphasizing significant breakthroughs from spectroscopic analyses and theoretical calculations.Subsequently,we highlight the autocatalytic characteristics and dual-cycle mechanisms underlying MTH processes,critically evaluating the roles of zeolite structures,pore sizes,topology,and acidity in governing product selectivity and catalyst stability.Additionally,we discuss cutting-edge developments in tandem catalytic systems employing methanol as a pivotal intermediate for CO_(x)hydrogenation,emphasizing the transferable mechanistic principles and catalytic insights.Finally,we identify future research directions,including elucidating precise hydrocarbon pool(HCP)intermediates,optimizing zeolite structures through computational-guided design,and developing robust catalytic systems leveraging advanced characterization methods and artificial intelligence.By integrating multidisciplinary approaches from catalytic science,materials engineering,and reaction engineering,this review provides actionable guidance towards rational design and optimization of advanced catalytic systems for efficient methanol conversion processes.
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the Ministry of Higher Education Malaysia for providing financial support to this work via FRGS No:FRGS/1/2011/SG/UTP/02/13Universiti Teknologi PETRONAS
文摘A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.
基金support from the King Abdullah University of Science and Technology(KAUST).T.Cordero-Lanzac and A.T.Aguayo acknowledge the financial support received from the Spanish Ministry of Science and Innovation with some ERDF funds(CTQ2016-77812-R)the Basque Government(IT1218-19)+2 种基金T.Cordero-Lanzac also acknowledges the Spanish Ministry of Education,Culture and Sport for the award of his FPU grant(FPU15-01666)A.Navajas and L.M.Gandía gratefully acknowledge the financial support from Spanish Ministerio de Ciencia,Innovación y Universidades,and the European Regional Development Fund(ERDF/FEDER)(grant RTI2018-096294-B-C31)L.M.Gandía also thanks Banco de Santander and Universidad Pública de Navarra for their financial support under“Programa de Intensificación de la Investigación 2018”initiative.
文摘The success of catalytic schemes for the large-scale valorization of CO_(2) does not only depend on the development of active,selective and stable catalytic materials but also on the overall process design.Here we present a multidisciplinary study(from catalyst to plant and techno-economic/lifecycle analysis)for the production of green methanol from renewable H2 and CO_(2).We combine an in-depth kinetic analysis of one of the most promising recently reported methanol-synthesis catalysts(InCo)with a thorough process simulation and techno-economic assessment.We then perform a life cycle assessment of the simulated process to gauge the real environmental impact of green methanol production from CO_(2).Our results indicate that up to 1.75 ton of CO_(2) can be abated per ton of produced methanol only if renewable energy is used to run the process,while the sensitivity analysis suggest that either rock-bottom H2 prices(1.5$kg1)or severe CO_(2) taxation(300$per ton)are needed for a profitable methanol plant.Besides,we herein highlight and analyze some critical bottlenecks of the process.Especial attention has been paid to the contribution of H2 to the overall plant costs,CH4 trace formation,and purity and costs of raw gases.In addition to providing important information for policy makers and industrialists,directions for catalyst(and therefore process)improvements are outlined.
基金supported by the Ningbo Yongjiang Science and Technology Programme(2023A-161-C)。
文摘The robustness of single-atom catalysts(SACs)is a critical concern for practical applications,especially for thermal catalysis at elevated temperatures under reductive conditions.In this study,a laser solid-phase synthesis technique is reported to fabricate atom-nanoisland-sea structured SACs for the first time.The resultant catalysts are constructed by Pt single atoms on In_(2)O_(3)supported by Co3O4nanoislands uniformly dispersed in the sea of reduced graphene oxide.The laser process,with a maximum temperature of 2349 K within~100μs,produced abundant oxygen vacancies(up to 70.8%)and strong interactions between the Pt single atoms and In_(2)O_(3).The laser-synthesized catalysts exhibited a remarkable catalytic performance towards CO_(2)hydrogenation to methanol at 300°C with a CO_(2)conversion of 30.3%,methanol selectivity of 90.6%and exceptional stability over 48 h without any deactivation,outperforming most of the relevant catalysts reported in the literature.Characterization of the spent catalysts after testing for 48 h reveals that the Pt single atoms were retained and the oxygen vacancies remained almost unchanged.In situ diffuse reflectance infrared Fourier transform spectrum was conducted to establish the reaction mechanism supported by the density functional theory simulations.It is believed that this laser synthesis strategy opens a new avenue towards rapidly manufacturing highly active and robust thermal SACs.
基金the financial support from National Science Centre Poland(NCN)based on the decision number UMO-2021/43/D/ST5/00824financial support of research project supported by the program“Excellence Initiative-Research University”for the AGH University of Krakow.
文摘The electrochemical conversion of carbon dioxide into valuable products is pivotal for maintaining the global carbon cycle and mitigating global warming.This review explores the advancements in electrochemical CO_(2) conversion,particularly focusing on producing methanol,ethanol,and n-propanol using various catalysts such as metals,metal oxides,metal alloys,and metal organic frameworks.Additionally,it covers the photoelectrochemical(PEC)conversion of CO_(2) into alcohols.The primary objective is to identify efficient electrocatalysts for ethanol,methanol,and n-propanol production,prioritizing selectivity,stability,Faradaic efficiency(FE),and current density.Notable catalysts include PtxZn nanoalloys,which exhibit an FE of~81.4% for methanol production,and trimetallic Pt/Pb/Zn nanoalloys,aimed at reducing Pt costs while enhancing catalyst stability and durability.Metal oxide catalysts like thin film Cu_(2)O/CuO on nickel foam and Cu_(2)O/ZnO achieve FE values of~38% and~16.6% for methanol production,respectively.Copper-based metal-organic frameworks,such as Cu@Cu_(2)O,demonstrate an FE of~45% for methanol production.Similarly,Ag_(0.14)/Cu_(0.86) and Cu-Zn alloys exhibit FEs of~63% and~46.6%,respectively,for ethanol production.Notably,n-propanol production via Pd–Cu alloy and graphene/ZnO/Cu_(2)O yields FEs of~13.7% and~23%,respectively.Furthermore,the review discusses recent advancements in PEC reactor design,photoelectrodes,reaction mechanisms,and catalyst durability.By evaluating the efficiency of these devices in liquid fuel production,the review addresses challenges and prospects in CO_(2) conversion for obtaining various valuable products.
基金the financial support by the National Natural Science Foundation of China(22178265,U21B2096,21938008)the Tianjin Key Science and Technology Project(19ZXNCGX00030)。
文摘The development of a highly efficient catalyst for CO_(2) activation and selective conversion to methanol is critical to address the issues associated with the high thermal stability of CO_(2) and controllable synthesis of methanol.Cu-based catalysts have been widely studied because of the low cost and excellent performance in mild conditions.However,the improvement of catalytic activity and selectivity remains challenging.Herein,we prepared hollow Cu@ZrO_(2) catalysts through pyrolysis of Cu-loaded Zr-MOF for CO_(2) hydrogenation to methanol.Low-temperature pyrolysis generated highly dispersed Cu nanoparticles with balanced Cu^(0)/Cu^(+)sites,larger amounts of surface basic sites and abundant Cu-ZrO_(2) interface in the hollow structure,contributing to enhanced catalytic capacity for adsorption/activation of CO_(2) and selective hydrogenation to methanol.In situ Fourier Transform Infrared Spectroscopy revealed the methanol formation followed the formate-intermediated pathway.This work would provide a guideline for the design of high-performance catalysts and the understanding of the mechanism and active sites for CO_(2) hydrogenation to methanol.
基金supported by National Key R&D Program of China(2017YFB0601900)。
文摘In the context of peak carbon and carbon neutrality,the utilization of CO_(2)has attracted attention with the aim of reducing carbon emissions by converting CO_(2)into high-value chemicals or energy.Methanol(MeOH),which is both a hydrogen and a carbon carrier,is considered the most promising among the CO_(2)-conversion products.This paper focus on routes for electrochemical conversion of CO_(2)to MeOH using green power and green hydrogen to achieve negative CO_(2)emissions.Three feasible technical routes for electrochemical conversion of CO_(2)to MeOH are proposed in this paper:Route 1,electrolysis of water to H_(2)and hydrogenation of CO_(2)to MeOH;Route 2,electrochemical reduction of CO_(2)to MeOH;and Route 3,co-electrolysis of CO_(2)-H_(2)O to syngas and synthesis of MeOH from syngas.Techno-economic assessments of the three routes are conducted using technical maturity surveys,system simulations and cost analyses to provide reference data for route selection for CO_(2)conversion to MeOH in China.Compared with the other routes,Route 1 is advantageous in terms of technical maturity and commercial application prospects.Although Route 1 is presently economically unviable,it is expected to achieve profitability and commercial application in the future with decreases in the cost of renewable power and continuous development of water-electrolysis technology.
基金financial support from the China Scholarship Council(CSC grant.201808330389)。
文摘MoS_(2) is a highly promising material for application in lithium-ion battery anodes due to its high theoretical capacity and low cost.However,problems with a fast capacity decay over cycling,especially at the first cycles,and poor rate performance have deterred its practical implementation.Herein,electrodes comprised solely of few-layers 2D MoS_(2) nanosheets have been manufactured by scalable liquid-phase exfoliation and spray deposition methods.The long-standing controversy questioning the reversibility of conversion processes of MoS_(2)-based electrodes was addressed.Raman studies revealed that,in 2D MoS_(2) electrodes,conversion processes are indeed reversible,where nanostructure played a key role.Cycling of the electrodes at high current rates revealed an intriguing phenomenon consisting of a continuously increasing capacity after ca.100-200 cycles.This phenomenon was comprehensively addressed by a variety of electrochemical and microscopy methods that revealed underlying physical activation mechanisms that involved a range of profound electrode structural changes.Activation mechanisms delivered a capacitive electrode of a superior rate performance and cycling stability,as compared to the corresponding pristine electrodes,and to MoS_(2) electrodes previously reported.Herein,we have devised a methodology to overcome the problem of cycling stability of 2D MoS_(2) electrodes.Moreover,activation of electrodes constitutes a methodology that could be applied to enhance the energy storage performance of electrodes based on other 2D nanomaterials,or combinations thereof,strategically combining chemistries to engineer electrodes of superior energy storage properties.
基金supported by the National Natural Science Foundation of China(No.52488201)the Natural Science Foundation of Jiangsu Province(No.BK20232022)+3 种基金Science and Technology Support Program of Jiangsu Province(BT2024009)the National Natural Science Foundation of China(No.52406249)China Postdoctoral Innovative Talent Support Program(BX20240483)Jiangsu Funding Program for Excellent Postdoctoral Talent(2024ZB839).
文摘The accelerating global transition toward carbon neutrality calls for transformative technologies capable of tightly coupling renewable energy with carbon reduction.Among next-generation approaches,solar-driven calcium-based CO_(2)capture(SCa-CC)and thermochemical conversion(TC)constitutes a promising pathway by utilizing solar energy to directly facilitate the conversion of CO_(2)into value-added hydrocarbon fuels.This approach addresses the high energy consumption associated with conventional CO_(2)capture technologies,thereby mitigating the critical efficiency bottleneck and enhancing economic viability.However,the practical deployment of SCa-CC-TC remains constrained by a series of scientific and engineering challenges.These include the progressive degradation of functional material,the complex coupling of irradiation,thermal,flow,and reaction fields,the dynamic match of solar flux,particle transport,and reaction kinetics,and the constraints of techno-economic feasibility.Breakthroughs in both theoretical insight and practical inquiry are urgently required to enable reliable scale-up.This review offers a comprehensive analysis of full technical framework,encompassing solar energy harvesting,CO_(2)capture,and coupled heat-mass conversion.Recent advances are discussed in the of solar concentrator development,multifunctional materials modification,photothermal reactor configurations,coupling characteristics,and techno-economic assessments.Emerging multimodal activation strategies,including plasmonic,pyroelectric,and piezoelectric effects,are highlighted for their potential to improve reaction kinetics and product selectivity.Key scientific and engineering bottlenecks are analyzed,and strategic directions are proposed to accelerate the transition from laboratory-scale concepts to pilotand industrial-scale demonstrations.These insights are expected to promote the continued development of SCa-CCTC and facilitate the construction of a sustainable energy system with deep coupling of sunlight and carbon cycle.
基金the National Natural Science Foundation of China(Grant Nos.21878028,21606026)the Chongqing Social Livelihood Technological Innovation and Application Demonstration(No.CSTC2018JSCX-MSYBXX0336).
文摘Steam methane reforming(SMR)-based methanol synthesis plants utilizing a single CO2 feed represent one of the predominant technologies for improving methanol yield and CO2 utilization.However,SMR alone cannot achieve full CO2 utilization,and a high water content accumulates if CO2 is only fed into the methanol reactor.In this study,a process integrating SMR with dry methane reforming to improve the conversion of both methane and CO2 is proposed.We also propose an innovative methanol production approach in which captured CO2 is introduced into both the SMR process and the recycle gas of the methanol synthesis loop.This dual CO2 feed approach aims to optimize the stoichio-metric ratio of the reactants.Comparative evaluations are carried out from a techno-economic point of view,and the proposed process is demonstrated to be more efficient in terms of both methanol productivity and CO2 utilization than the existing stand-alone natural gas-based methanol process.
基金The authors are grateful to the financial support from Shanghai Science and Technology Committee(No.19160712100)National Natural Science Foundation of China(No.21878076).
文摘Global warming caused by excess carbon dioxide(CO_(2))emission has been a focus of the world.The development of neutral carbon technologies becomes a strategic choice for the sustainable human society.Integrating CO_(2) capture and conversion(iCCC)technology can simultaneously convert the captured CO_(2) from flue gas into value-added chemicals,which saves great energies and expenses incurred in CO_(2) compression and transportation processes of conventional carbon capture,utilization,and storage(CCUS)technology.The present review criti-cally discusses the dual-function materials(DFMs)and the iCCC technology at intermediate temperature for methane production and high temperature for syngas production.The design of reactor and optimization of operation conditions are emphasized from the perspective of industrial applications.The dual-fixed-bed reactors mode by switching the flue gas and reactant gases,and the dual-fluidized-bed reactors mode by the circulation of DFMs particles are comparatively reviewed.We hope this review can stimulate further studies including designing and fabricating feasible DFMs,exploring realistic catalytic process for CO_(2) conversion to high value-added chemicals,developing workable reactor modes and optimizing operation conditions,and establishing industrial demonstration for real applications of iCCC technology in the future.
基金This work was supported by the Korea CCS R&D Center(Korea CCS 2020 Project)of the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT of Korea[Grant number 2014M1A8A1049278]the Korea Institute of Energy Technology Evaluation and Planning(KETEP)Grant funded by the Korean government(Ministry of Trade,Industry and Energy)[Grant number 20172010202050].
文摘Microalgae have piqued renewed interest as a sustainable biofuel feedstock owing to their high CO_(2)conversion efficiency.However,the major limitation of microalga-based biofuel production is low productivity.In this study,CO_(2)in flue gas emitted from the coal-fired power plants was fixed through mass microalgal cultivation using only sunlight as an energy source.To minimize the cost and energy required to supply the flue gas and efficiently utilize the microalgal biomass,a polycarbonate(PC)greenhouse and polymeric photobioreactors were installed near the power plant stack.Four different microalgal strains(Chlamydomonas reinhardtii,Chlorella sorokiniana,Neochloris oleoabundans,and Neochloris oleoabundans#13)were subjected to semi-continuous culturing for 1 month.The maximum biomass productivity was achieved by the N.oleoabun-dans#13 strain(0.703 g L^(−1)day^(−1)).Additionally,polymerase chain reaction analysis revealed that the individual microalgal culture was not cross-contaminated with other microalgal cultures in this cultivation system,owing to the structural proper-ties of photobioreactor comprising individual modules.The lipid content and calorific productivity of N.oleoabundans#13 biomass were 45.70%and 3.553 kJ L^(−1)day^(−1),respectively,which indicate satisfactory performance of biomass as a direct combustion fuel.The CO_(2)fixation rate,which was calculated based on the carbon content in the biomass,was 0.309 g CO_(2)L^(−1)day^(−1).Therefore,large amounts of CO_(2)can be reduced using the large-scale microalgal cultivation system,which enables efficient biological CO_(2)conversion and maximizes microalgal biomass utilization.
基金supported by the Key-Area Research and Development Program of Guangdong Province(grant no.2020B0909-19005)the National Natural Science Foundation of China(grant nos.21975056 and 22179025)+1 种基金The Major and Special Project in the Field of Intelligent Manufacturing of the Universities in Guangdong Province(grant no.2020ZDZX2067)the Natural Science Foundation of Huizhou University(grant no.HZU202004).
文摘With advantages of low costs and high energy density,Li–S batteries are considered as one of the most promising energy storage devices.However,Li_(2)S_(2) with a high dissociation energy and insulative properties is hard to convert into Li_(2)S,resulting in underutilization of sulfur capacity.Herein,Co-Mo_(2)C@C yolk–shell spheres as nanoreactors were designed to confront this challenge rationally.The Co-Mo_(2)C@C-induced Li_(2)S_(1/2) nucleation and growth in the three-dimensional process and the cathode produced more Li_(2)S after full discharge.Experimental studies and theoretical calculations reveal that the conversion barrier from Li_(2)S_(2) into Li_(2)S was lowered while the diffusion of lithium ions and electron transfer accelerated when using the Co-Mo_(2)C@C catalyst.Based on the above advantages,the Co-Mo_(2)C@C/S cathode exhibits a high reversible capacity and excellent cyclic stability,such as an initial specific capacity of 1200 mAh g^(−1) at 0.1 C with 709 mAh g^(−1) at 1.0 C after 1000 cycles with a low capacity fading rate of 0.04%per cycle.Even at high densities of 3.0 C and 5.0 C,the specific capacities are 647.6 and 557.7 mAh g^(−1) after 400 cycles,respectively.Impressively,it also shows ca.770 and 900 mAh g^(−1) at 0.2 C after 50 cycles with high sulfur loadings of 4.2 and 5.1 mg cm−2,respectively.The present work may provide new insights into the design of nanoreactors to promote Li_(2)S_(1/2) growth in a three-dimensional process and accelerate conversion from solid Li_(2)S_(2) to solid Li_(2)S in high performance Li–S batteries.
文摘Hydrogen as a clean energy carrier has attracted great interests world-wide for substitution of fossil fuels and for abatement of the climate change concerns.However,green hydrogen from renewable resources is less than 0.1%at present in the world hydrogen production and this is largely from water electrolysis which is beneficial only when renewable electricity is used.Hydrogen production from diverse renewable resources is desirable.This review presents recent advances in hydrogen production from woody biomass through biomass steam gasification,producer gas processing and H_(2)/CO_(2)separation.The producer gas processing includes steam-methane reforming(SMR)and water-gas shift(WGS)reactions to convert CH_(4)and CO in the producer gas to H_(2)and CO_(2).The H_(2)storage discussed using liquid carrier through hydrogenation is also discussed.The CO_(2)capture prior to the SMR is investigated to enhance H_(2)yield in the SMR and the WGS reactions.
