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Title: Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions

Ammonia interactions and competition with water at the interface of nanoporous metal organic framework thin films of HKUST-1 (Cu 3Btc 2 , Btc = 1,3,5-benzenedicarboxylate) are investigated with ambient pressure X-ray photoelectron spectroscopy (APXPS). In the absence of water, ammonia adsorption at the Cu 2+ metal center weakens the metal-linker bond of the framework. In the presence of water, due to the higher binding energy (adsorption strength) of ammonia compared to water, ammonia replaces water at the unsaturated Cu 2+ metal centers. The water molecules remaining in the pores are stabilized by hydrogen bonding to ammonia. Hydrogen bonding between the water and ammonia strengthens the metal-ammonia interaction due to cooperative interactions. Cooperative interactions result in a reduction in the metal center oxidation state facilitating linker replacement by other species explaining the previously reported structure degradation.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 44; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1378633

Nijem, Nour, Fürsich, Katrin, Bluhm, Hendrik, Leone, Stephen R., and Gilles, Mary K.. Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions. United States: N. p., Web. doi:10.1021/acs.jpcc.5b05716.
Nijem, Nour, Fürsich, Katrin, Bluhm, Hendrik, Leone, Stephen R., & Gilles, Mary K.. Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions. United States. doi:10.1021/acs.jpcc.5b05716.
Nijem, Nour, Fürsich, Katrin, Bluhm, Hendrik, Leone, Stephen R., and Gilles, Mary K.. 2015. "Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions". United States. doi:10.1021/acs.jpcc.5b05716. https://www.osti.gov/servlets/purl/1378633.
@article{osti_1378633,
title = {Ammonia Adsorption and Co-adsorption with Water in HKUST-1: Spectroscopic Evidence for Cooperative Interactions},
author = {Nijem, Nour and Fürsich, Katrin and Bluhm, Hendrik and Leone, Stephen R. and Gilles, Mary K.},
abstractNote = {Ammonia interactions and competition with water at the interface of nanoporous metal organic framework thin films of HKUST-1 (Cu3Btc2 , Btc = 1,3,5-benzenedicarboxylate) are investigated with ambient pressure X-ray photoelectron spectroscopy (APXPS). In the absence of water, ammonia adsorption at the Cu2+ metal center weakens the metal-linker bond of the framework. In the presence of water, due to the higher binding energy (adsorption strength) of ammonia compared to water, ammonia replaces water at the unsaturated Cu2+ metal centers. The water molecules remaining in the pores are stabilized by hydrogen bonding to ammonia. Hydrogen bonding between the water and ammonia strengthens the metal-ammonia interaction due to cooperative interactions. Cooperative interactions result in a reduction in the metal center oxidation state facilitating linker replacement by other species explaining the previously reported structure degradation.},
doi = {10.1021/acs.jpcc.5b05716},
journal = {Journal of Physical Chemistry. C},
number = 44,
volume = 119,
place = {United States},
year = {2015},
month = {10}
}