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Title: Probing the Energetics of Molecule–Material Interactions at Interfaces and in Nanopores

Abstract

During the past decades, advances in interfacial chemistries at the molecular level are shaping our world by playing crucial roles in balancing global scale energy crisis and critical environmental concerns. However, systematic investigations into the binding energies, site distribution and their correlation with the molecular-level surface assemblages and structures at interfaces and in nanopores are rarely documented. In this review, we summarize a set of systematic calorimetric studies on surface energetics we performed during the last decade. These studies demonstrate how thermochemistry can reveal crucial energetic insights into a series of molecule – material interactions relevant to a number of applications, including carbon capture and sequestration, energy production, sustainable chemical processing, catalysis, and nanogeoscience. Calorimetric methodologies developed and applied include direct gas adsorption calorimetry, nearroom temperature solvent immersion/solution calorimetry and high temperature oxide melt solution calorimetry. Using these highly unique techniques, we reveal the thermodynamic complexity of carbon dioxide capture on metal – organic framework (MOF) sorbents with built-in and grafted nucleophilic functional groups (-OH and -NH2). These studies suggest that carbon dioxide adsorption on functionalized MOFs is a complex process involving multiple thermodynamic factors, as reflected by changes in surface phase and structure, chemical bonding and degree of disordermore » with varying temperature and gas loading. The fundamental insights obtained may help optimize the design, synthesis and application of MOF-based carbon dioxide sorbents for carbon capture and sequestration. In parallel, we also explore the energetics of interaction and competition between small molecules (water, carbon dioxide, methane, simple and complex organics) and inorganic materials (calcite, silica, zirconia, zeolites, mesoporous frameworks, alumina, and uranium), at interfaces and in nanopores. Combined with spectroscopic, diffraction, electron microscopic and computational techniques, the energetics of gas/liquid – solid interactions can be correlated with specific bonds, molecular configurations and nanostructures. Although the energetics evolves continuously from weak association to strong bonding to classical capping, distinct regions of rapidly changing stepwise energetics often separate the different regimes. These phenomena are closely related to the properties of inorganic material surfaces (hydrophobicity and acidity/basicity), the framework architectures, and the chemical nature of adsorbate molecules. These direct thermodynamic insights reinforce our understanding of complex small molecule – inorganic material interactions important to multiple disciplines of chemical engineering, materials science, nanogeoscience and environmental technology, including heterogeneous catalysis, molecular separation, material design and synthesis, biomineralization, contaminant and nutrient transport, carbonate formation, and water – organic competitions on material/mineral surfaces.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5]
  1. Washington State Univ., Pullman, WA (United States). Alexandra Navrotsky Inst. for Experimental Thermodynamics, and Gene and Linda Voiland School of Chemical Engineering and Bioengineering
  2. East China Univ. of Science and Technology, Shanghai (China). Petroleum Processing Research Center
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Washington State Univ., Pullman, WA (United States). Alexandra Navrotsky Inst. for Experimental Thermodynamics; Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
  5. Washington State Univ., Pullman, WA (United States). Alexandra Navrotsky Inst. for Experimental Thermodynamics, and Gene and Linda Voiland School of Chemical Engineering and Bioengineering, and Dept. of Chemistry, Materials Science and Engineering
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE; National Natural Science Foundation of China (NNSFC); Natural Science Foundation of Shanghai
OSTI Identifier:
1479978
Report Number(s):
[LA-UR-17-26750]
[Journal ID: ISSN 1932-7447]
Grant/Contract Number:  
[AC52-06NA25396; 91634112; 16ZR1408100]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
[ Journal Volume: 121; Journal Issue: 47]; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Gengnan, Sun, Hui, Xu, Hongwu, Guo, Xiaofeng, and Wu, Di. Probing the Energetics of Molecule–Material Interactions at Interfaces and in Nanopores. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b07450.
Li, Gengnan, Sun, Hui, Xu, Hongwu, Guo, Xiaofeng, & Wu, Di. Probing the Energetics of Molecule–Material Interactions at Interfaces and in Nanopores. United States. doi:10.1021/acs.jpcc.7b07450.
Li, Gengnan, Sun, Hui, Xu, Hongwu, Guo, Xiaofeng, and Wu, Di. Wed . "Probing the Energetics of Molecule–Material Interactions at Interfaces and in Nanopores". United States. doi:10.1021/acs.jpcc.7b07450. https://www.osti.gov/servlets/purl/1479978.
@article{osti_1479978,
title = {Probing the Energetics of Molecule–Material Interactions at Interfaces and in Nanopores},
author = {Li, Gengnan and Sun, Hui and Xu, Hongwu and Guo, Xiaofeng and Wu, Di},
abstractNote = {During the past decades, advances in interfacial chemistries at the molecular level are shaping our world by playing crucial roles in balancing global scale energy crisis and critical environmental concerns. However, systematic investigations into the binding energies, site distribution and their correlation with the molecular-level surface assemblages and structures at interfaces and in nanopores are rarely documented. In this review, we summarize a set of systematic calorimetric studies on surface energetics we performed during the last decade. These studies demonstrate how thermochemistry can reveal crucial energetic insights into a series of molecule – material interactions relevant to a number of applications, including carbon capture and sequestration, energy production, sustainable chemical processing, catalysis, and nanogeoscience. Calorimetric methodologies developed and applied include direct gas adsorption calorimetry, nearroom temperature solvent immersion/solution calorimetry and high temperature oxide melt solution calorimetry. Using these highly unique techniques, we reveal the thermodynamic complexity of carbon dioxide capture on metal – organic framework (MOF) sorbents with built-in and grafted nucleophilic functional groups (-OH and -NH2). These studies suggest that carbon dioxide adsorption on functionalized MOFs is a complex process involving multiple thermodynamic factors, as reflected by changes in surface phase and structure, chemical bonding and degree of disorder with varying temperature and gas loading. The fundamental insights obtained may help optimize the design, synthesis and application of MOF-based carbon dioxide sorbents for carbon capture and sequestration. In parallel, we also explore the energetics of interaction and competition between small molecules (water, carbon dioxide, methane, simple and complex organics) and inorganic materials (calcite, silica, zirconia, zeolites, mesoporous frameworks, alumina, and uranium), at interfaces and in nanopores. Combined with spectroscopic, diffraction, electron microscopic and computational techniques, the energetics of gas/liquid – solid interactions can be correlated with specific bonds, molecular configurations and nanostructures. Although the energetics evolves continuously from weak association to strong bonding to classical capping, distinct regions of rapidly changing stepwise energetics often separate the different regimes. These phenomena are closely related to the properties of inorganic material surfaces (hydrophobicity and acidity/basicity), the framework architectures, and the chemical nature of adsorbate molecules. These direct thermodynamic insights reinforce our understanding of complex small molecule – inorganic material interactions important to multiple disciplines of chemical engineering, materials science, nanogeoscience and environmental technology, including heterogeneous catalysis, molecular separation, material design and synthesis, biomineralization, contaminant and nutrient transport, carbonate formation, and water – organic competitions on material/mineral surfaces.},
doi = {10.1021/acs.jpcc.7b07450},
journal = {Journal of Physical Chemistry. C},
number = [47],
volume = [121],
place = {United States},
year = {2017},
month = {10}
}

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