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Time-Dependent CO[subscript 2] Sorption Hysteresis in a One-Dimensional Microporous Octahedral Molecular Sieve

Journal Article · · J. Am. Chem. Soc.
DOI:https://doi.org/10.1021/ja3014133· OSTI ID:1040656

The development of sorbents for next-generation CO{sub 2} mitigation technologies will require better understanding of CO{sub 2}/sorbent interactions. Among the sorbents under consideration are shape-selective microporous molecular sieves with hierarchical pore morphologies of reduced dimensionality. We have characterized the non-equilibrium CO{sub 2} sorption of OMS-2, a well-known one-dimensional microporous octahedral molecular sieve with manganese oxide framework. Remarkably, we find that the degree of CO{sub 2} sorption hysteresis increases when the gas/sorbent system is allowed to equilibrate for longer times at each pressure step. Density functional theory calculations indicate a 'gate-keeping' role of the cation in the tunnel, only allowing CO{sub 2} molecules to enter fully into the tunnel via a highly unstable transient state when CO{sub 2} loadings exceed 0.75 mmol/g. The energy barrier associated with the gate-keeping effect suggests an adsorption mechanism in which kinetic trapping of CO{sub 2} is responsible for the observed hysteretic behavior.

Research Organization:
Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
Sponsoring Organization:
DOE - BASIC ENERGY SCIENCES
OSTI ID:
1040656
Journal Information:
J. Am. Chem. Soc., Journal Name: J. Am. Chem. Soc. Journal Issue: (18) ; 05, 2012 Vol. 134; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
ENGLISH

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