Thermodynamics of Water-Cationic Species-Framework Guest- Host Interactions within Transition Metal Ion-Exchanged Mordenite Relevant to Selective Anaerobic Oxidation of Methane to Methanol

被引：9

作者：

Zhang, Xianghui ^{[3
,6
]}

Cockreham, Cody B. ^{[3
,6
,7
]}

Huang, Zhiyang ^{[3
,6
]}

Sun, Hui ^{[1
,2
]}

Yang, Chen ^{[3
,6
]}

Marin-Flores, Oscar G. ^{[6
]}

Wang, Baodong ^{[8
]}

Guo, Xiaofeng ^{[9
,10
]}

Ha, Su ^{[6
]}

Xu, Hongwu ^{[7
]}

Wu, Di ^{[3
,4
,5
]}

机构：

[1] East China Univ Sci & Technol, Petr Proc Res Ctr, Shanghai 200237, Peoples R China

[2] East China Univ Sci & Technol, Int Joint Res Ctr Green Energy Chem Engn, Shanghai 200237, Peoples R China

[3] Washington State Univ, Alexandra Navrotsky Inst Expt Thermodynam, Pullman, WA 99163 USA

[4] Washington State Univ, Gene & Linda Voiland Sch Chem Engn & Bioengn, Dept Chem, Pullman, WA 99163 USA

[5] Washington State Univ, Gene & Linda Voiland Sch Chem Engn & Bioengn, Mat Sci & Engn, Pullman, WA 99163 USA

[6] Washington State Univ, Gene & Linda Voiland Sch Chem Engn & Bioengn, Pullman, WA 99163 USA

[7] Los Alamos Natl Lab, Earth & Environm Sci Div, Los Alamos, NM 87545 USA

[8] Natl Inst Clean & Low Carbon Energy, Beijing 102211, Peoples R China

[9] Washington State Univ, Alexandra Navrotsky Inst Expt Thermodynam, Dept Chem, Pullman, WA 99163 USA

[10] Washington State Univ, Alexandra Navrotsky Inst Expt Thermodynam, Mat Sci & Engn, Pullman, WA 99163 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2020年 / 11卷 / 12期

基金：

中国国家自然科学基金; 上海市自然科学基金;

关键词：

CRYSTALLIZATION ENERGETICS; THERMAL-DECOMPOSITION; ENZYMATIC OXIDATION; CORROSION PRODUCT; N2O DECOMPOSITION; DIRECT CONVERSION; FAST PYROLYSIS; LIGHT OLEFINS; TO-METHANOL; ZEOLITES;

D O I：

10.1021/acs.jpclett.0c01331

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Low-temperature anaerobic methane conversion to methanol (MTM) using copper ion-exchanged mordenite (Cu-MOR) as the catalyst and water as the sole source of oxygen is promising for sustainable utilization of methane. Integrating in situ calorimetric, spectroscopic, and structural methodologies, we report a systematic study on energetics of water-cationic species-framework guest-host interactions as a function of water loading for several mordenites relevant to low-temperature MTM. Notably, the near-zero coverage hydration enthalpy on Cu-MOR is -133.1 +/- 6.0 kJ/mol water, which is related to Cu-MOR regeneration using water as oxidant. The copper oxo sites are thermally stable up to 915 degrees C and remain chemically intact as an oxygen source after complete hydration and dehydration. This study underscores the importance of manipulating the oxidation state and coordination chemistry of transition metal guest species in zeolites by fine-tuning the partial pressure of water as a strategy for rational design, synthesis, and modification of catalysts.

引用

页码：4774 / 4784

页数：11