The Intergovernmental Panel on Climate Change(IPCC)recognises the pivotal role of renewable energies in the future energy system and the achievement of the zero-emission target.The implementation of renewables should ...The Intergovernmental Panel on Climate Change(IPCC)recognises the pivotal role of renewable energies in the future energy system and the achievement of the zero-emission target.The implementation of renewables should provide major opportunities and enable a more secure and decentralised energy supply system.Renewable fuels provide long-term solutions for the transport sector,particularly for applications where fuels with high energy density are required.In addition,it helps reducing the carbon footprint of these sectors in the long-term.Information on biomass characteristics feedstock is essential for scaling-up gasification from the laboratory to industrial-scale.This review deals with the transformation biogenic residues into a valuable bioenergy carrier like biomethanol as the liquid sunshine based on the combination of modified mature technologies such as gasification with other innovative solutions such as membranes and microchannel reactors.Tar abatement is a critical process in product gas upgrading since tars compromise downstream processes and equipment,for this,membrane technology for upgrading syngas quality is discussed in this paper.Microchannel reactor technology with the design of state-of-the-art multifunctional catalysts provides a path to develop decentralised biomethanol synthesis from biogenic residues.Finally,the development of a process chain for the production of(i)methanol as an intermediate energy carrier,(ii)electricity and(iii)heat for decentralised applications based on biomass feedstock flexible gasification,gas upgrading and methanol synthesis is analysed.展开更多
Pd-based catalysts are extensively employed to catalyze CO oxidative coupling to generate DMO,while the expensive price and high usage of Pd hinder its massive application in industrial production.Designing Pd-based c...Pd-based catalysts are extensively employed to catalyze CO oxidative coupling to generate DMO,while the expensive price and high usage of Pd hinder its massive application in industrial production.Designing Pd-based catalysts with high efficiency and low Pd usage as well as expounding the catalytic mechanisms are significant for the reaction.In this study,we theoretically predict that Pd stripe doping Co(111)surface exhibits excellent performance than pure Pd(111),Pd monolayer supporting on Co(111)and Pd single atom doping Co(111)surface,and clearly expound the catalytic mechanisms through the density functional theory(DFT)calculation and micro-reaction kinetic model analysis.It is obtained that the favorable reaction pathway is COOCH_(3)-COOCH_(3)coupling pathway over these four catalysts,while the rate-controlling step is COOCH_(3)+CO+OCH_(3)→2COOCH_(3)on Pd stripe doping Co(111)surface,which is different from the case(2COOCH_(3)→DMO)on pure Pd(111),Pd monolayer supporting on Co(111)and Pd single atom doping Co(111)surface.This study can contribute a certain reference value for developing Pd-based catalysts with high efficiency and low Pd usage for CO oxidative coupling to DMO.展开更多
The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However,the explorat...The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However,the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea(TU) encapsulated in zeolitic imidazolate frameworks(TU@ZIF) composites,which delivered very good oxygen reduction reaction(ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode(RHE), good stability and methanol tolerance. Density functional theory(DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O_(2)adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.展开更多
The co-pyrolysis of natural gas and coal is a promising way for the production of acetylene due to its high efficiency for energy and hydrogen utilization.This work investigated the thermodynamics for the copyrolysis ...The co-pyrolysis of natural gas and coal is a promising way for the production of acetylene due to its high efficiency for energy and hydrogen utilization.This work investigated the thermodynamics for the copyrolysis reaction of natural gas and coal using density functional theory.The favorable reaction conditions are presented in the form of phase diagrams.The calculation results show that the extra amount of methane may benefit the production of acetylene in the co-pyrolysis reaction,and the C/H ratio of 1:1,temperature around 3000 K and pressure at 0.1 MPa are most favorable.The results would provide basic data for related industrial process for the production of acetylene.展开更多
Ammonia, primarily made with Haber-Bosch process developed in 1909 and winning two Nobel prizes, is a promising noncarbon fuel for preventing global warming of 1.5 °C above pre-industrial levels. However,the unde...Ammonia, primarily made with Haber-Bosch process developed in 1909 and winning two Nobel prizes, is a promising noncarbon fuel for preventing global warming of 1.5 °C above pre-industrial levels. However,the undesired characteristics of the process, including high carbon footprint, necessitate alternative ammonia synthesis methods, and among them is chemical looping ammonia production(CLAP) that uses nitrogen carrier materials and operates at atmospheric pressure with high product selectivity and energy efficiency. To date, neither a systematic review nor a perspective in nitrogen carriers and CLAP has been reported in the critical area. Thus, this work not only assesses the previous results of CLAP but also provides perspectives towards the future of CLAP. It classifies, characterizes, and holistically analyzes the fundamentally different CLAP pathways and discusses the ways of further improving the CLAP performance with the assistance of plasma technology and artificial intelligence(AI).展开更多
In heterogeneous catalysis,the precise placement of active components to perform unique functions in cooperation with each other is a tremendous challenge.The migration of matter on micro/nano-scale caused by diffusio...In heterogeneous catalysis,the precise placement of active components to perform unique functions in cooperation with each other is a tremendous challenge.The migration of matter on micro/nano-scale caused by diffusion is a promising pathway for design of catalytic nanoreactors with precise active sites location and controllable microenvironment through compartmentalization and confinement effects.Herein,we report two categories of mesoporous ZnCoSiOx hollow nanoreactors with different metal distributions and microenvironment engineered by the diffusion behavior of metal species in confined nanospace.Double-shelled hollow structures with well-distributed metal species were obtained by adopting core@shell structured ZnCo-zeolitic imidazolate framework(ZIF)@SiO2 as a template and employing three stages of hydrothermal treatment including the decomposition of ZIF,diffusion of metal species into the silica shell,and Ostwald ripening.Additionally,the formation of yolk@shell structure with a collective(Zn-Co)metal oxide as the yolk was achieved by direct pyrolysis of ZnCo-ZIF@SiO2.In CO_(2)hydrogenation,ZnCoSiOx with double-shelled hollow structures and yolk@shell structures respectively afford CO and CH_(4)as main product,which is related with different dispersion and location of active sites in the two catalysts.This study provides an efficient method for the synthesis of catalytic nanoreactors on the basis of insights of the atomic diffusion in confined space at the mesoscale.展开更多
基金support for this work has been obtained from the Junta de Andalucía projects with reference P20-00594 co-funded by the European Union FEDER。
文摘The Intergovernmental Panel on Climate Change(IPCC)recognises the pivotal role of renewable energies in the future energy system and the achievement of the zero-emission target.The implementation of renewables should provide major opportunities and enable a more secure and decentralised energy supply system.Renewable fuels provide long-term solutions for the transport sector,particularly for applications where fuels with high energy density are required.In addition,it helps reducing the carbon footprint of these sectors in the long-term.Information on biomass characteristics feedstock is essential for scaling-up gasification from the laboratory to industrial-scale.This review deals with the transformation biogenic residues into a valuable bioenergy carrier like biomethanol as the liquid sunshine based on the combination of modified mature technologies such as gasification with other innovative solutions such as membranes and microchannel reactors.Tar abatement is a critical process in product gas upgrading since tars compromise downstream processes and equipment,for this,membrane technology for upgrading syngas quality is discussed in this paper.Microchannel reactor technology with the design of state-of-the-art multifunctional catalysts provides a path to develop decentralised biomethanol synthesis from biogenic residues.Finally,the development of a process chain for the production of(i)methanol as an intermediate energy carrier,(ii)electricity and(iii)heat for decentralised applications based on biomass feedstock flexible gasification,gas upgrading and methanol synthesis is analysed.
基金financially supported by the National Key Research and Development Program of China(2021YFA1502804)the Regional Innovation and Development Joint Fund of the National Natural Science Foundation of China(U22A20430)+3 种基金the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2022SX-FR001)the Natural Science Foundation of Shanxi Province(202203021212201)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxithe Foundation of Taiyuan University of Technology(2022QN138)
文摘Pd-based catalysts are extensively employed to catalyze CO oxidative coupling to generate DMO,while the expensive price and high usage of Pd hinder its massive application in industrial production.Designing Pd-based catalysts with high efficiency and low Pd usage as well as expounding the catalytic mechanisms are significant for the reaction.In this study,we theoretically predict that Pd stripe doping Co(111)surface exhibits excellent performance than pure Pd(111),Pd monolayer supporting on Co(111)and Pd single atom doping Co(111)surface,and clearly expound the catalytic mechanisms through the density functional theory(DFT)calculation and micro-reaction kinetic model analysis.It is obtained that the favorable reaction pathway is COOCH_(3)-COOCH_(3)coupling pathway over these four catalysts,while the rate-controlling step is COOCH_(3)+CO+OCH_(3)→2COOCH_(3)on Pd stripe doping Co(111)surface,which is different from the case(2COOCH_(3)→DMO)on pure Pd(111),Pd monolayer supporting on Co(111)and Pd single atom doping Co(111)surface.This study can contribute a certain reference value for developing Pd-based catalysts with high efficiency and low Pd usage for CO oxidative coupling to DMO.
基金supported financially by the National Natural Science Foundation of China (No. 21905271)Liaoning Natural Science Foundation (No. 20180510029)the Dalian National Laboratory for Clean Energy (DNL), DNL Cooperation Fund, Chinese Academy of Sciences (No. DNL180402)。
文摘The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However,the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea(TU) encapsulated in zeolitic imidazolate frameworks(TU@ZIF) composites,which delivered very good oxygen reduction reaction(ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode(RHE), good stability and methanol tolerance. Density functional theory(DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O_(2)adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.
基金supported by the National Natural Science Foundation of China(21875096)the Natural Science Foundation of Jiangxi Province,China(20181BCD40004,No.20224BAB213015)。
文摘The co-pyrolysis of natural gas and coal is a promising way for the production of acetylene due to its high efficiency for energy and hydrogen utilization.This work investigated the thermodynamics for the copyrolysis reaction of natural gas and coal using density functional theory.The favorable reaction conditions are presented in the form of phase diagrams.The calculation results show that the extra amount of methane may benefit the production of acetylene in the co-pyrolysis reaction,and the C/H ratio of 1:1,temperature around 3000 K and pressure at 0.1 MPa are most favorable.The results would provide basic data for related industrial process for the production of acetylene.
基金supported by the DNL Cooperation Fund,CAS(DNL180402)the support from the University of Wyoming。
文摘Ammonia, primarily made with Haber-Bosch process developed in 1909 and winning two Nobel prizes, is a promising noncarbon fuel for preventing global warming of 1.5 °C above pre-industrial levels. However,the undesired characteristics of the process, including high carbon footprint, necessitate alternative ammonia synthesis methods, and among them is chemical looping ammonia production(CLAP) that uses nitrogen carrier materials and operates at atmospheric pressure with high product selectivity and energy efficiency. To date, neither a systematic review nor a perspective in nitrogen carriers and CLAP has been reported in the critical area. Thus, this work not only assesses the previous results of CLAP but also provides perspectives towards the future of CLAP. It classifies, characterizes, and holistically analyzes the fundamentally different CLAP pathways and discusses the ways of further improving the CLAP performance with the assistance of plasma technology and artificial intelligence(AI).
基金supported by the National Natural Science Foundation of China(No.22005296)the Natural Science Foundation of Liaoning Province,China(No.2020-YQ-01)the LiaoNing Revitalization Talents Program,China(No.XLYC1807077).
文摘In heterogeneous catalysis,the precise placement of active components to perform unique functions in cooperation with each other is a tremendous challenge.The migration of matter on micro/nano-scale caused by diffusion is a promising pathway for design of catalytic nanoreactors with precise active sites location and controllable microenvironment through compartmentalization and confinement effects.Herein,we report two categories of mesoporous ZnCoSiOx hollow nanoreactors with different metal distributions and microenvironment engineered by the diffusion behavior of metal species in confined nanospace.Double-shelled hollow structures with well-distributed metal species were obtained by adopting core@shell structured ZnCo-zeolitic imidazolate framework(ZIF)@SiO2 as a template and employing three stages of hydrothermal treatment including the decomposition of ZIF,diffusion of metal species into the silica shell,and Ostwald ripening.Additionally,the formation of yolk@shell structure with a collective(Zn-Co)metal oxide as the yolk was achieved by direct pyrolysis of ZnCo-ZIF@SiO2.In CO_(2)hydrogenation,ZnCoSiOx with double-shelled hollow structures and yolk@shell structures respectively afford CO and CH_(4)as main product,which is related with different dispersion and location of active sites in the two catalysts.This study provides an efficient method for the synthesis of catalytic nanoreactors on the basis of insights of the atomic diffusion in confined space at the mesoscale.
