Journal article
Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
Nature (London), Vol.519(7543), pp.303-308
03/19/2015
DOI: 10.1038/nature14327
PMID: 25762144
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 withstate-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
Details
- Title: Subtitle
- Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
- Creators
- Thomas M. Mcdonald - School of Environmental SciencesJarad A. Mason - Durham UniversityXueqian Kong - School of Materials Science and EngineeringEric D. Bloch - Laboratoire d’Electrochimie et de Physico-chimie des Matériaux et des InterfacesDavid Gygi - University of California, BerkeleyAlessandro Dani - University of TurinValentina Crocellà - University of TurinFilippo Giordanino - University of TurinSamuel O. Odoh - University of MinnesotaWalter S. Drisdell - Lawrence Berkeley National LaboratoryBess Vlaisavljevich - University of California, BerkeleyAllison L. Dzubak - University of MinnesotaRoberta Poloni - Science et Ingénierie des Matériaux et ProcédésSondre K. Schnell - La Trobe UniversityNora Planas - Centre d’histoire de Sciences PoKyuho Lee - University of OuluTod Pascal - Génétique et amélioration des fruits et légumesLiwen F. Wan - State Key Joint Laboratory of Environment Simulation and Pollution ControlDavid Prendergast - Central Veterinary Research LaboratoryJeffrey B. Neaton - Lawrence Berkeley National LaboratoryBerend Smit - Lawrence Berkeley National LaboratoryJeffrey B. Kortright - Lawrence Berkeley National LaboratoryLaura Gagliardi - University of Minnesota SystemSilvia Bordiga - University of TurinJeffrey A. Reimer - Lawrence Berkeley National LaboratoryJeffrey R. Long - School of Chemistry, Centre for Biomolecular Sciences
- Resource Type
- Journal article
- Publication Details
- Nature (London), Vol.519(7543), pp.303-308
- DOI
- 10.1038/nature14327
- PMID
- 25762144
- NLM abbreviation
- Nature
- ISSN
- 0028-0836
- eISSN
- 1476-4687
- Publisher
- Nature Publishing Group
- Language
- English
- Date published
- 03/19/2015
- Academic Unit
- Chemistry
- Record Identifier
- 9984618524102771
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