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Title: Tuning Internal Strain in Metal–Organic Frameworks via Vapor Phase Infiltration for CO2 Reduction

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [3];  [1];  [1];  [4];  [5];  [6];  [7];  [6];  [2]; ORCiD logo [1]
  1. San Diego State Univ., CA (United States). Dept. of Chemistry and Biochemistry
  2. Marquette Univ., Milwaukee, WI (United States). Dept. of Chemistry
  3. The Molecular FoundryLawrence Berkeley National Laboratory Berkeley CA 94720 USA
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  5. Idaho National Lab. (INL), Idaho Falls, ID (United States). Nuclear Materials Dept.
  6. Univ. of California, San Diego, CA (United States). Materials Science and Engineering Program
  7. San Diego State Univ., CA (United States). Dept. of Chemistry and Biochemistry; Anhui Normal Univ., Wuhu (China). The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, College of Chemistry and Materials Science
+ Show Author Affiliations

Abstract A gas‐phase approach to form Zn coordination sites on metal–organic frameworks (MOFs) by vapor‐phase infiltration (VPI) was developed. Compared to Zn sites synthesized by the solution‐phase method, VPI samples revealed approximately 2.8 % internal strain. Faradaic efficiency towards conversion of CO 2 to CO was enhanced by up to a factor of four, and the initial potential was positively shifted by 200–300 mV. Using element‐specific X‐ray absorption spectroscopy, the local coordination environment of the Zn center was determined to have square‐pyramidal geometry with four Zn−N bonds in the equatorial plane and one Zn‐OH 2 bond in the axial plane. The fine‐tuned internal strain was further supported by monitoring changes in XRD and UV/Visible absorption spectra across a range of infiltration cycles. The ability to use internal strain to increase catalytic activity of MOFs suggests that applying this strategy will enhance intrinsic catalytic capabilities of a variety of porous materials.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231; DMR-1654140; CBET-1704992
OSTI ID:
1779238
Alternate ID(s):
OSTI ID: 1595851
Journal Information:
Angewandte Chemie (International Edition), Vol. 59, Issue 11; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

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36 MATERIALS SCIENCE
CO2 reduction
internal strain
metal-organic frameworks
vapor-phase infiltration