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Title: Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions

Abstract

Catalytic transformation of CH 4 under a mild condition is significant for efficient utilization of shale gas under the circumstance of switching raw materials of chemical industries to shale gas. Here, we report the transformation of CH 4 to acetic acid and methanol through coupling of CH 4, CO and O 2 on single-site Rh 1O 5 anchored in microporous aluminosilicates in solution at ≤150 °C. The activity of these singly dispersed precious metal sites for production of organic oxygenates can reach about 0.10 acetic acid molecules on a Rh 1O 5 site per second at 150 °C with a selectivity of ~70% for production of acetic acid. It is higher than the activity of free Rh cations by >1000 times. Computational studies suggest that the first C–H bond of CH 4 is activated by Rh 1O 5 anchored on the wall of micropores of ZSM-5; the formed CH 3 then couples with CO and OH, to produce acetic acid over a low activation barrier.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [2];  [3];  [3];  [4];  [4];  [3];  [5];  [6]; ORCiD logo [3]
  1. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry
  2. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  3. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
  4. Univ. of Electro-Communications, Chofu (Japan). Innovation Research Center for Fuel Cells. Graduate School of Informatics and Engineering
  5. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry; Fuzhou Univ. (China). State Key Lab. of Photocatalysis on Energy and Environment. College of Chemistry
  6. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
Publication Date:
Research Org.:
Univ. of Kansas, Lawrence, KS (United States); Stony Brook Univ., NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1499949
Grant/Contract Number:  
FG02-03ER15476; SC0014561
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon capture and storage; catalytic mechanisms; heterogeneous catalysis

Citation Formats

Tang, Yu, Li, Yuting, Fung, Victor, Jiang, De-en, Huang, Weixin, Zhang, Shiran, Iwasawa, Yasuhiro, Sakata, Tomohiro, Nguyen, Luan, Zhang, Xiaoyan, Frenkel, Anatoly I., and Tao, Franklin. Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions. United States: N. p., 2018. Web. doi:10.1038/s41467-018-03235-7.
Tang, Yu, Li, Yuting, Fung, Victor, Jiang, De-en, Huang, Weixin, Zhang, Shiran, Iwasawa, Yasuhiro, Sakata, Tomohiro, Nguyen, Luan, Zhang, Xiaoyan, Frenkel, Anatoly I., & Tao, Franklin. Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions. United States. doi:10.1038/s41467-018-03235-7.
Tang, Yu, Li, Yuting, Fung, Victor, Jiang, De-en, Huang, Weixin, Zhang, Shiran, Iwasawa, Yasuhiro, Sakata, Tomohiro, Nguyen, Luan, Zhang, Xiaoyan, Frenkel, Anatoly I., and Tao, Franklin. Mon . "Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions". United States. doi:10.1038/s41467-018-03235-7. https://www.osti.gov/servlets/purl/1499949.
@article{osti_1499949,
title = {Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions},
author = {Tang, Yu and Li, Yuting and Fung, Victor and Jiang, De-en and Huang, Weixin and Zhang, Shiran and Iwasawa, Yasuhiro and Sakata, Tomohiro and Nguyen, Luan and Zhang, Xiaoyan and Frenkel, Anatoly I. and Tao, Franklin},
abstractNote = {Catalytic transformation of CH4 under a mild condition is significant for efficient utilization of shale gas under the circumstance of switching raw materials of chemical industries to shale gas. Here, we report the transformation of CH4 to acetic acid and methanol through coupling of CH4, CO and O2 on single-site Rh1O5 anchored in microporous aluminosilicates in solution at ≤150 °C. The activity of these singly dispersed precious metal sites for production of organic oxygenates can reach about 0.10 acetic acid molecules on a Rh1O5 site per second at 150 °C with a selectivity of ~70% for production of acetic acid. It is higher than the activity of free Rh cations by >1000 times. Computational studies suggest that the first C–H bond of CH4 is activated by Rh1O5 anchored on the wall of micropores of ZSM-5; the formed CH3 then couples with CO and OH, to produce acetic acid over a low activation barrier.},
doi = {10.1038/s41467-018-03235-7},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {2018},
month = {3}
}

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Works referenced in this record:

The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
journal, April 2012