The development of efficient hydrogen storage materials is one of the biggest technical challenges for the coming ＂hydrogen economy＂. The liquid organic hydrogen carriers （LOHCs） with high hydrogen contents, rever...The development of efficient hydrogen storage materials is one of the biggest technical challenges for the coming ＂hydrogen economy＂. The liquid organic hydrogen carriers （LOHCs） with high hydrogen contents, reversibilities and moderate dehydrogenation kinetics have been considered as an alternative option supplementing the extensively investigated inorganic hydride systems. In this review, LOHCs for long distance H2 transport and for onboard application will be discussed with the focuses of the design and development of LOHCs and their hydrogenation ＆ dehydrogenation catalyses.展开更多
Ammonia(NH3)is a cornerstone widely used in the modern agriculture and industry,the annual global production gradually increases to almost 200 million tons.Nearly 80%of the produced NH3 is used in the fertilizer indus...Ammonia(NH3)is a cornerstone widely used in the modern agriculture and industry,the annual global production gradually increases to almost 200 million tons.Nearly 80%of the produced NH3 is used in the fertilizer industry and is essential for the development of global agriculture and consequently for maintaining population growth.Furthermore,NH3 can power hydrogen(H2)fueled devices,such as H2 fuel cells(FC),to use the interconversion between chemical energy and electric energy of nitrogen(N2)cycle,which can effectively alleviate the intermittent problems of renewable energy.However,the problems faced by NH3 in storage and release still restrict its development.Herein,this review introduces the latest research and development of electrochemical NH3 synthesis and direct NH3 FC,as well as outlines the technical challenges,possible improvement measures and development perspectives.N2 reduction reaction(NRR)and nitrate reduction reaction(NO3RR)are two potential approaches for electrochemical NH3 synthesis.However,the existing research foundation still faces challenges in achieving high selectivity and efficiency.Direct NH3 FC are easy to transport and are expected to be widely used in mobile energy consuming equipment,but also limited by the lack of highly active and stable NH3 oxidation electrocatalysts.The perspectives of ammonia fuel cells as an alternative green energy are discussed.展开更多
The intermittent nature of renewable resources requires for most applications the development of efficient and cost-effective technologies for steady supply of electrical energy.The storage of energy in the form of hy...The intermittent nature of renewable resources requires for most applications the development of efficient and cost-effective technologies for steady supply of electrical energy.The storage of energy in the form of hydrogen chemically bound within organic molecules(rather than physically as compressed gas or cooled liquid)represents an alternative approach that is attracting great research interest.Compared to other liquid organic hydrogen carriers(LOHCs),dimethyl ether(DME)appears to have the largest potential impact on society,especially if inserted in technological chains of CO_(2) sequestration and utilization,so to determine an effective mitigation of environmental issues,without any net effect on the carbon footprint.Specifically,the steps of H2 storage and H2 release can take place in two coupled chemical processes,constituted by the exothermic synthesis of DME via CO_(2) hydrogenation and the endothermic steam reforming of DME,respectively.Herein,the latest advances in the development of heterogeneous bifunctional and hybrid catalysts for the direct hydrogenation of CO_(2) to DME are thoroughly reviewed,with special emphasis on thermodynamics,catalyst design and process feasibility.Despite many aspects behind the mechanism of DME synthesis from H2-CO_(2) streams are still to be uncovered,the recent progress in the research on H2 release by DME steam reforming is increasing the interest for effectively closing this binary H2 loop,in view of future green deals and sustainable research developments.展开更多
Hydrogen has been deemed as one of the most efficient energy carriers for a broad variety of industrial applications[1,2].Large-scale,low-cost hydrogen production,safe storage and delivery represent a tremendous techn...Hydrogen has been deemed as one of the most efficient energy carriers for a broad variety of industrial applications[1,2].Large-scale,low-cost hydrogen production,safe storage and delivery represent a tremendous technological challenge and have become a subject of intense research and development activities in the past few decades[3–5].展开更多
Hydrogen has attracted widespread attention as a carbon-neutral energy source,but developing efficient and safe hydrogen storage technologies remains a huge challenge.Recently,liquid organic hydrogen carriers(LOHCs)te...Hydrogen has attracted widespread attention as a carbon-neutral energy source,but developing efficient and safe hydrogen storage technologies remains a huge challenge.Recently,liquid organic hydrogen carriers(LOHCs)technology has shown great potential for efficient and stable hydrogen storage and transport.This technology allows for safe and economical large-scale transoceanic transportation and long-cycle hydrogen storage.In particular,traditional organic hydrogen storage liquids are derived from nonrenewable fossil fuels through costly refining procedures,resulting in unavoidable environmental contamination.Biomass holds great promise for the preparation of LOHCs due to its unique carbon-balance properties and feasibility to manufacture aromatic and nitrogen-doped compounds.According to recent studies,almost 100%conversion and 92% yield of benzene could be obtained through advanced biomass conversion technologies,showing great potential in preparing biomass-based LOHCs.Overall,the present LOHCs systems and their unique applications are introduced in this review,and the technical paths are summarized.Furthermore,this paper provides an outlook on the future development of LOHCs technology,focusing on biomass-derived aromatic and N-doped compounds and their applications in hydrogen storage.展开更多
N-Ethylcarbazole(NEC)is one of the most promising liquid organic hydrogen carriers(LOHCs),but its application is limited by sluggish kinetics due to lack of high-efficiency,low-cost catalysts.This work reports a cobal...N-Ethylcarbazole(NEC)is one of the most promising liquid organic hydrogen carriers(LOHCs),but its application is limited by sluggish kinetics due to lack of high-efficiency,low-cost catalysts.This work reports a cobalt(Co)-based catalyst promoted by nonstoichiometric yttrium hydride(YH_(3−x))to achieve high-efficiency,reversible hydrogen storage in NEC,with>5.5 wt%reversible hydrogen storage capacity could be achieved below 473 K,and with good kinetics.The YH_(3−x)-promoted Co-based catalyst is the first non-noble metal catalyst with high activity for NEC hydrogenation and 12H-NEC dehydrogenation reactions.A mechanistic study suggests that YH_(3−x)facilitates the reversible hydrogen transfer both in the hydrogenation and the dehydrogenation reactions.The nonstoichiometric YH_(3−x)contained both lattice H and H vacancies with tunable H chemical potential serve as the H donor and H acceptor for reversible hydrogen transfer.Our results support the practical application of LOHCs and inspire new approaches for the utilization of conventional metal hydrides to promote versatile H transfer reactions.展开更多
Hydrogenation of N-ethylcarbazole(NEC),the hydrogen lean form of a liquid organic hydrogen carrier,on TiO2 supported Ru-Ni bimetallic catalysts is investigated.Crystal structure of TiO2 plays a critical role on the hy...Hydrogenation of N-ethylcarbazole(NEC),the hydrogen lean form of a liquid organic hydrogen carrier,on TiO2 supported Ru-Ni bimetallic catalysts is investigated.Crystal structure of TiO2 plays a critical role on the hydrogenation activity and selectivity towards fully hydrogenated product.Ru/anatase catalyst exhibits higher selectivity but lower reactivity compared to Ru/rutile catalyst.Ni addition significantly promotes the performance of Ru/anatase catalyst while causes severe performance deterioration of Ru/rutile catalyst.Commercial P25,a mixture of anatase and rutile phases in approximate ratio A/R1/4,is found to be the best TiO2 support for NEC hydrogenation.Ru/P25 catalyst outperforms both Ru/rutile and Ru/anatase and its activity can be further slightly improved by Ni addition.The unexpected synergism between the two different TiO2 phases for Ru based NEC hydrogenation catalysts is related to metal-support interaction and Ru-Ni interaction.展开更多
基金supported by the Project of the National Natural Science Funds for Distinguished Young Scholar(51225206)Projects of the National Natural Science Foundation of China(grant nos.U1232120,51301161,21473181 and 51472237)
文摘The development of efficient hydrogen storage materials is one of the biggest technical challenges for the coming ＂hydrogen economy＂. The liquid organic hydrogen carriers （LOHCs） with high hydrogen contents, reversibilities and moderate dehydrogenation kinetics have been considered as an alternative option supplementing the extensively investigated inorganic hydride systems. In this review, LOHCs for long distance H2 transport and for onboard application will be discussed with the focuses of the design and development of LOHCs and their hydrogenation ＆ dehydrogenation catalyses.
基金support from Suzhou Foreign Academician Workstation(SWY2021002)National Natural Science Foundation of China(No.22202144)Collaborative Innovation Center of Water Treatment Technology and Material,and Innovation Platform for Academicians of Hainan Province.
文摘Ammonia(NH3)is a cornerstone widely used in the modern agriculture and industry,the annual global production gradually increases to almost 200 million tons.Nearly 80%of the produced NH3 is used in the fertilizer industry and is essential for the development of global agriculture and consequently for maintaining population growth.Furthermore,NH3 can power hydrogen(H2)fueled devices,such as H2 fuel cells(FC),to use the interconversion between chemical energy and electric energy of nitrogen(N2)cycle,which can effectively alleviate the intermittent problems of renewable energy.However,the problems faced by NH3 in storage and release still restrict its development.Herein,this review introduces the latest research and development of electrochemical NH3 synthesis and direct NH3 FC,as well as outlines the technical challenges,possible improvement measures and development perspectives.N2 reduction reaction(NRR)and nitrate reduction reaction(NO3RR)are two potential approaches for electrochemical NH3 synthesis.However,the existing research foundation still faces challenges in achieving high selectivity and efficiency.Direct NH3 FC are easy to transport and are expected to be widely used in mobile energy consuming equipment,but also limited by the lack of highly active and stable NH3 oxidation electrocatalysts.The perspectives of ammonia fuel cells as an alternative green energy are discussed.
文摘The intermittent nature of renewable resources requires for most applications the development of efficient and cost-effective technologies for steady supply of electrical energy.The storage of energy in the form of hydrogen chemically bound within organic molecules(rather than physically as compressed gas or cooled liquid)represents an alternative approach that is attracting great research interest.Compared to other liquid organic hydrogen carriers(LOHCs),dimethyl ether(DME)appears to have the largest potential impact on society,especially if inserted in technological chains of CO_(2) sequestration and utilization,so to determine an effective mitigation of environmental issues,without any net effect on the carbon footprint.Specifically,the steps of H2 storage and H2 release can take place in two coupled chemical processes,constituted by the exothermic synthesis of DME via CO_(2) hydrogenation and the endothermic steam reforming of DME,respectively.Herein,the latest advances in the development of heterogeneous bifunctional and hybrid catalysts for the direct hydrogenation of CO_(2) to DME are thoroughly reviewed,with special emphasis on thermodynamics,catalyst design and process feasibility.Despite many aspects behind the mechanism of DME synthesis from H2-CO_(2) streams are still to be uncovered,the recent progress in the research on H2 release by DME steam reforming is increasing the interest for effectively closing this binary H2 loop,in view of future green deals and sustainable research developments.
基金the financial support from the National Natural Science Foundation of China(Nos.21473164,21603195 and 21875225)Major project of Technical Innovation of Hubei Province(No.2017AAA126)the Fundamental Research Funds for Central Universities,China University of Geosciences(Wuhan)(Nos.CUGL170405 and CUG180604)。
文摘Hydrogen has been deemed as one of the most efficient energy carriers for a broad variety of industrial applications[1,2].Large-scale,low-cost hydrogen production,safe storage and delivery represent a tremendous technological challenge and have become a subject of intense research and development activities in the past few decades[3–5].
基金supported by the National Natural Science Fund for Excellent Young Scholars(China)(Grant No.51822604).
文摘Hydrogen has attracted widespread attention as a carbon-neutral energy source,but developing efficient and safe hydrogen storage technologies remains a huge challenge.Recently,liquid organic hydrogen carriers(LOHCs)technology has shown great potential for efficient and stable hydrogen storage and transport.This technology allows for safe and economical large-scale transoceanic transportation and long-cycle hydrogen storage.In particular,traditional organic hydrogen storage liquids are derived from nonrenewable fossil fuels through costly refining procedures,resulting in unavoidable environmental contamination.Biomass holds great promise for the preparation of LOHCs due to its unique carbon-balance properties and feasibility to manufacture aromatic and nitrogen-doped compounds.According to recent studies,almost 100%conversion and 92% yield of benzene could be obtained through advanced biomass conversion technologies,showing great potential in preparing biomass-based LOHCs.Overall,the present LOHCs systems and their unique applications are introduced in this review,and the technical paths are summarized.Furthermore,this paper provides an outlook on the future development of LOHCs technology,focusing on biomass-derived aromatic and N-doped compounds and their applications in hydrogen storage.
基金This research was made possible as a result of a generous grant from MOST of China(no.2018YFB1502102)NSFC(nos.21771006,51771002,and 51971004).
文摘N-Ethylcarbazole(NEC)is one of the most promising liquid organic hydrogen carriers(LOHCs),but its application is limited by sluggish kinetics due to lack of high-efficiency,low-cost catalysts.This work reports a cobalt(Co)-based catalyst promoted by nonstoichiometric yttrium hydride(YH_(3−x))to achieve high-efficiency,reversible hydrogen storage in NEC,with>5.5 wt%reversible hydrogen storage capacity could be achieved below 473 K,and with good kinetics.The YH_(3−x)-promoted Co-based catalyst is the first non-noble metal catalyst with high activity for NEC hydrogenation and 12H-NEC dehydrogenation reactions.A mechanistic study suggests that YH_(3−x)facilitates the reversible hydrogen transfer both in the hydrogenation and the dehydrogenation reactions.The nonstoichiometric YH_(3−x)contained both lattice H and H vacancies with tunable H chemical potential serve as the H donor and H acceptor for reversible hydrogen transfer.Our results support the practical application of LOHCs and inspire new approaches for the utilization of conventional metal hydrides to promote versatile H transfer reactions.
基金国家自然科学基金资助项目(22072172)国家杰出青年科学基金资助项目(21825204)+2 种基金中国科学院青年创新促进会资助项目(Y2021056)榆林学院与大连清洁能源国家实验室合作基金资助项目(YLU-DNL Fund 2022007)山西省科技创新团队专项资金资助项目(202304051001007)。
基金NSFC (Nos. 21771006, U1607126 and 51771002)MOST of China (No. 2017YFB0405902)Beijing Municipal Commission of Science and Technology (Z17110000091702)
文摘Hydrogenation of N-ethylcarbazole(NEC),the hydrogen lean form of a liquid organic hydrogen carrier,on TiO2 supported Ru-Ni bimetallic catalysts is investigated.Crystal structure of TiO2 plays a critical role on the hydrogenation activity and selectivity towards fully hydrogenated product.Ru/anatase catalyst exhibits higher selectivity but lower reactivity compared to Ru/rutile catalyst.Ni addition significantly promotes the performance of Ru/anatase catalyst while causes severe performance deterioration of Ru/rutile catalyst.Commercial P25,a mixture of anatase and rutile phases in approximate ratio A/R1/4,is found to be the best TiO2 support for NEC hydrogenation.Ru/P25 catalyst outperforms both Ru/rutile and Ru/anatase and its activity can be further slightly improved by Ni addition.The unexpected synergism between the two different TiO2 phases for Ru based NEC hydrogenation catalysts is related to metal-support interaction and Ru-Ni interaction.
