Cooperative insertion of CO2 in diamine-appended metal-organic frameworks

Thomas M. McDonald, Jarad A. Mason, Xueqian Kong, Eric D. Bloch, David Gygi, Alessandro Dani, Valentina Crocellà, Filippo Giordanino, Samuel O. Odoh, Walter S. Drisdell, Bess Vlaisavljevich, Allison L. Dzubak, Roberta Poloni, Sondre K. Schnell, Nora Planas, Kyuho Lee, Tod Pascal, Liwen F. Wan, David Prendergast, Jeffrey B. Neaton, Berend Smit, Jeffrey B. Kortright, Laura Gagliardi, Silvia Bordiga, Jeffrey A. Reimer and Jeffrey R. Long ()
Additional contact information
Thomas M. McDonald: University of California, Berkeley, California 94720, USA
Jarad A. Mason: University of California, Berkeley, California 94720, USA
Xueqian Kong: University of California, Berkeley, California 94720, USA
Eric D. Bloch: University of California, Berkeley, California 94720, USA
David Gygi: University of California, Berkeley, California 94720, USA
Alessandro Dani: NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15, I-10135 Torino, Italy
Valentina Crocellà: NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15, I-10135 Torino, Italy
Filippo Giordanino: NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15, I-10135 Torino, Italy
Samuel O. Odoh: Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA
Walter S. Drisdell: Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
Bess Vlaisavljevich: University of California, Berkeley, California 94720, USA
Allison L. Dzubak: Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA
Roberta Poloni: Université Grenoble Alpes, Science et Ingénierie des Matériaux et Procédés (SIMAP), F-38000 Grenoble, France
Sondre K. Schnell: University of California, Berkeley, California 94720, USA
Nora Planas: Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA
Kyuho Lee: University of California, Berkeley, California 94720, USA
Tod Pascal: Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA
Liwen F. Wan: Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA
David Prendergast: Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA
Jeffrey B. Neaton: Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, California 94720, USA
Berend Smit: University of California, Berkeley, California 94720, USA
Jeffrey B. Kortright: Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
Laura Gagliardi: Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA
Silvia Bordiga: NIS and INSTM Centre of Reference, University of Turin, Via Quarello 15, I-10135 Torino, Italy
Jeffrey A. Reimer: University of California, Berkeley, California 94720, USA
Jeffrey R. Long: University of California, Berkeley, California 94720, USA

Nature, 2015, vol. 519, issue 7543, 303-308

Abstract: Abstract 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 CO2 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 CO2 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, CO2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO2 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 CO2 from various gas mixtures, and yield insights into the conservation of Mg2+ within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.

Date: 2015
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DOI: 10.1038/nature14327

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