文献类型：期刊文献

英文题名：Probing the Energetics of Molecule-Material Interactions at Interfaces and in Nanopores

作者：Li, Gengnan[1,2];Sun, Hui[3];Xu, Hongwu[4];Guo, Xiaofeng[1,4,5];Wu, Di[1,2,6]

机构：[1]Washington State Univ, Alexandra Navrotsky Inst Expt Thermodynam, Pullman, WA 99163 USA;[2]Washington State Univ, Gene & Linda Voiland Sch Chem Engn & Bioengn, Pullman, WA 99163 USA;[3]East China Univ Sci & Technol, Petr Proc Res Ctr, Shanghai 200237, Peoples R China;[4]Los Alamos Natl Lab, Earth & Environm Sci Div, Los Alamos, NM 87545 USA;[5]Washington State Univ, Dept Chem, Pullman, WA 99163 USA;[6]Washington State Univ, Mat Sci & Engn, Pullman, WA 99163 USA

年份：2017

卷号：121

期号：47

起止页码：26141

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20174504369406);WOS:【SCI-EXPANDED(收录号:WOS:000417228500001)】；

基金：We sincerely thank Prof. Alexandra Navrotsky at University of California, Davis, for the inspiration, guidance, and generous support. We are also grateful to Dr. Renqin Zhang for his invaluable contributions and discussions and Dr. Yushen Han and his colleagues for their amazing graphics and cover art. We also thank Jiyuan Zhong for his high quality biographical photography. H.S. thanks the National Natural Science Foundation of China for financial support under the Training Program of the Major Research Plan (Grant 91634112) and the Natural Science Foundation of Shanghai for financial support under the Natural Science Fund for Young Scholar (Grant 16ZR1408100). This work was supported by the institutional funds from the Gene and Linda Voiland School of Chemical Engineering and Bioengineering at Washington State University.

语种：英文

外文关键词：Zeolites - Alumina - Calorimeters - Carbon dioxide - Chemical industry - Mesoporous materials - Calorimetry - Chemical bonds - Temperature - Silica - Aluminum oxide - Organometallics - Binding energy - Crystalline materials - Gas adsorption

摘要：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 past 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, near-room 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, and 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.