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Title: Critical Factors Driving the High Volumetric Uptake of Methane in Cu3(btc)2

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b06657· OSTI ID:1386971
 [1];  [2];  [2];  [3];  [4];  [2];  [3];  [5];  [3];  [6]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Georgetown Univ., Washington, DC (United States)
  5. Univ. of California, Berkeley, CA (United States); Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
+ Show Author Affiliations

We report a thorough experimental and computational study has been carried out to elucidate the mechanistic reasons for the high volumetric uptake of methane in the metal–organic framework Cu3(btc)2 (btc3– = 1,3,5-benzenetricarboxylate; HKUST-1). Methane adsorption data measured at several temperatures for Cu3(btc)2, and its isostructural analogue Cr3(btc)2, show that there is little difference in volumetric adsorption capacity when the metal center is changed. In situ neutron powder diffraction data obtained for both materials were used to locate four CD4 adsorption sites that fill sequentially. This data unequivocally shows that primary adsorption sites around, and within, the small octahedral cage in the structure are favored over the exposed Cu2+ or Cr2+ cations. These results are supported by an exhaustive parallel computational study, and contradict results recently reported using a time-resolved diffraction structure envelope (TRDSE) method. Moreover, the computational study reveals that strong methane binding at the open metal sites is largely due to methane–methane interactions with adjacent molecules adsorbed at the primary sites instead of an electronic interaction with the metal center. Simulated methane adsorption isotherms for Cu3(btc)2 are shown to exhibit excellent agreement with experimental isotherms, allowing for additional simulations that show that modifications to the metal center, ligand, or even tuning the overall binding enthalpy would not improve the working capacity for methane storage over that measured for Cu3(btc)2 itself.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations (CGS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institute of Standards and Technology (NIST); National Science Foundation (NSF)
Grant/Contract Number:
SC0001015; FG02-12ER16362; AC02-05CH11231
OSTI ID:
1386971
Journal Information:
Journal of the American Chemical Society, Vol. 137, Issue 33; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 59 works
Citation information provided by
Web of Science

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Cited By (13)

Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry journal January 2019
Tailoring the pore geometry and chemistry in microporous metal–organic frameworks for high methane storage working capacity journal January 2019
Insights into Selective Gas Sorbent Functionality Gained by Using Time-Resolved Neutron Diffraction journal May 2018
Strategies for Overcoming Defects of HKUST‐1 and Its Relevant Applications journal April 2019
A Metal-Organic Framework with Optimized Porosity and Functional Sites for High Gravimetric and Volumetric Methane Storage Working Capacities journal March 2018
Preparation of a Composite Material AC/Cu-BTC with Improved Water Stability and n-Hexane Vapor Adsorption journal September 2019
Defect Creation in HKUST-1 via Molecular Imprinting: Attaining Anionic Framework Property and Mesoporosity for Cation Exchange Applications journal September 2017
High-pressure methane storage and selective gas adsorption in a cyclohexane-functionalised porous organic cage journal June 2019
Hydrogen Storage and Selective, Reversible O 2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites journal June 2016
A Metal-Organic Framework with a Pore Size/Shape Suitable for Strong Binding and Close Packing of Methane journal March 2016
High-pressure methane storage and selective gas adsorption in a cyclohexane-functionalised porous organic cage text January 2019
High-pressure methane storage and selective gas adsorption in a cyclohexane-functionalised porous organic cage text January 2019
A Metal-Organic Framework with a Pore Size/Shape Suitable for Strong Binding and Close Packing of Methane journal March 2016

Figures / Tables (12)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
membrane
carbon capture
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)
metals
adsorption
molecules
screening assays
materials