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Cooperative insertion of CO_2 in diamine-appended metal-organic frameworks

机译:CO_2在二胺附加的金属有机骨架中的协同插入

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摘要

人们正在研究先进的固体吸附剂,将其作为高效气体分离技术的潜在试剂,这些技术可帮助使碳收集技术更为经济。这篇论文对一个以前没有被报告过的、附加有二胺的金属有机框架的二氧化碳吸附机制进行了研究。该材料显示了异乎寻常的、可能有潜在实用价值的吸附性能。作者发现,二氧化碳通过向该金属有机框架的高度稳定的金属—胺键内插入来吸附。正如该框架的拓扑所表明的那样,胺具有均匀的、完美的间隔,因此单一二氧化碳分子的插入会诱导相邻的点在一个前所未有的链式反应过程中也去吸附二氧化碳。%The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO_2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended Metal-organic frameworks can behave as 'phase-change' adsorbents, with unusual step-shaped CO_2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a Metal-dependent threshold pressure, CO_2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO_2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO_2 from various gas mixtures, and yield insights into the conservation of Mg~(2+) within the ribulose-l,5-bisphosphate carboxylase/oxygenase family of enzymes.
机译:人们正在研究先进的固体吸附剂,将其作为高效气体分离技术的潜在试剂,这些技术可帮助使碳收集技术更为经济。这篇论文对一个以前没有被报告过的、附加有二胺的金属有机框架的二氧化碳吸附机制进行了研究。该材料显示了异乎寻常的、可能有潜在实用价值的吸附性能。作者发现,二氧化碳通过向该金属有机框架的高度稳定的金属—胺键内插入来吸附。正如该框架的拓扑所表明的那样,胺具有均匀的、完美的间隔,因此单一二氧化碳分子的插入会诱导相邻的点在一个前所未有的链式反应过程中也去吸附二氧化碳。%The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO_2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended Metal-organic frameworks can behave as 'phase-change' adsorbents, with unusual step-shaped CO_2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a Metal-dependent threshold pressure, CO_2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO_2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO_2 from various gas mixtures, and yield insights into the conservation of Mg~(2+) within the ribulose-l,5-bisphosphate carboxylase/oxygenase family of enzymes.

著录项

  • 来源
    《Nature》 |2015年第7543期|303-308A1|共7页
  • 作者单位

    Department of Chemistry, University of California, Berkeley, California 94720, USA;

    Department of Chemistry, University of California, Berkeley, California 94720, USA;

    Department of Chemical and Biological Engineering, University of California, Berkeley, California 94720, USA,Department of Chemistry, Zhejiang University, Hangzhou 310027, China;

    Department of Chemistry, University of California, Berkeley, California 94720, USA;

    Department of Chemistry, University of California, Berkeley, California 94720, USA;

    Chemistry Department, NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15,I-10135 Torino, Italy;

    Chemistry Department, NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15,I-10135 Torino, Italy;

    Chemistry Department, NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15,I-10135 Torino, Italy;

    Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA;

    Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA;

    Department of Chemical and Biological Engineering, University of California, Berkeley, California 94720, USA;

    Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA;

    Universite Grenoble Alpes, Science et Ingenierie des Materiaux et Precedes (SIMAP), F-38000 Grenoble, France,Centre National de la Recherche Scientifique, SIMAP, F-38000, Grenoble, France;

    Department of Chemical and Biological Engineering, University of California, Berkeley, California 94720, USA,Department of Chemistry, Norwegian University of Science and Technology, Hogskoleringen 5, 7491 Trondheim, Norway;

    Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA;

    Department of Chemical and Biological Engineering, University of California, Berkeley, California 94720, USA,Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA;

    Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA;

    Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA;

    Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA;

    Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA,Department of Physics, University of California, Berkeley, California 94720, USA,Kavli Energy Nanosciences Institute, University of California, Berkeley, California 94720, USA;

    Department of Chemical and Biological Engineering, University of California, Berkeley, California 94720, USA,Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA,Institut des Sciences et Ingenierie Chimiques, Valais, Ecole Polytechnique Federale de Lausanne (EPFL), Rue de l'Industrie 17, CH-1950 Sion, Switzerland;

    Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA;

    Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA;

    Chemistry Department, NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15,I-10135 Torino, Italy;

    Department of Chemical and Biological Engineering, University of California, Berkeley, California 94720, USA,Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA;

    Department of Chemistry, University of California, Berkeley, California 94720, USA,Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA;

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