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Title: Catalysis on Singly Dispersed Rh Atoms Anchored on an Inert Support

Abstract

A metal catalyst supported on an inert substrate could consist of both metal nanoparticles and singly dispersed metal atoms. Whether these singly dispersed metal atoms are active and how different their catalytic mechanism could be in contrast to a supported metal catalyst are fundamentally important for understanding catalysis on a supported metal or oxide. In this study, by taking reduction of NO with CO on singly dispersed Rh atoms anchored on an inert support SiO 2 as a probe system (Rh 1/SiO 2), we demonstrated how singly dispersed metal atoms on an inert support could perform a complex multi-step catalytic cycle through a mechanism distinctly different from that for a supported metal nanoparticle with continuously packed metal sites. These singly dispersed Rh 1 atoms anchored on SiO 2 are active in reducing nitric oxide with carbon monoxide through two reaction pathways that are different from those of Rh nanoparticles. In situ IR studies show that a CO molecule and a NO molecule coadsorb on a singly dispersed Rh atom, Rh 1 anchored on SiO 2, and couple to form an N atom to adsorb on the surface and a CO 2 molecule to desorb. The adsorbed N atom further couplesmore » with another CO molecule in the gas phase to form an intermediate -NCO on Rh 1; this intermediate can directly couple with an NO molecule adsorbed on the same Rh1 to form N 2 and CO 2. In another pathway, the adsorbed N atom can couple with a coadsorbed NO on the same Rh 1 to form N 2O; N 2O further reacts with adsorbed CO on the same Rh 1 to form N 2 and CO 2 through a high activation barrier that can be overcome at a high temperature. Our studies show that the singly dispersed metal atoms on an inert support have great potential to perform selective transformation of chemicals. Lastly, the confirmed catalysis with a singly dispersed Rh 1 on SiO 2 through a mechanism different from a metal nanoparticle supported on the same substrate suggests the significance of taking the single-atom catalysis (SAC) into fundamental studies of catalysis of a supported metal catalyst, since metal nanoparticles and singly dispersed metal atoms likely coexist on the inert support of many supported catalysts.« less

Authors:
 [1];  [2];  [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [6];  [1]; ORCiD logo [4]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Kansas, Lawrence, KS (United States). Department of Chemical and Petroleum Engineering and Department of Chemistry
  2. Tsinghua University, Beijing (China). Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Chemical Science Division
  4. Iowa State Univ., Ames, IA (United States). Department of Chemistry
  5. Arizona State Univ., Tempe, AZ (United States). Department of Physics
  6. Yeshiva Univ., New York, NY (United States). Department of Physics
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1468066
Grant/Contract Number:  
[AC05-00OR22725; SC0014561; FG02-03ER15476; SC0012335]
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
[ Journal Volume: 8; Journal Issue: 1]; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; in situ; infrared spectroscopy; insert support; operando; reduction of nitric oxide; rhodium; single-atom catalysis; singly dispersed metal atom

Citation Formats

Zhang, Shiran, Tang, Yan, Nguyen, Luan, Zhao, Ya-Fan, Wu, Zili, Goh, Tian-Wei, Liu, Jimmy Jingyue, Li, Yuanyuan, Zhu, Tong, Huang, Wenyu, Frenkel, Anatoly I., Li, Jun, and Tao, Franklin Feng. Catalysis on Singly Dispersed Rh Atoms Anchored on an Inert Support. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b01788.
Zhang, Shiran, Tang, Yan, Nguyen, Luan, Zhao, Ya-Fan, Wu, Zili, Goh, Tian-Wei, Liu, Jimmy Jingyue, Li, Yuanyuan, Zhu, Tong, Huang, Wenyu, Frenkel, Anatoly I., Li, Jun, & Tao, Franklin Feng. Catalysis on Singly Dispersed Rh Atoms Anchored on an Inert Support. United States. doi:10.1021/acscatal.7b01788.
Zhang, Shiran, Tang, Yan, Nguyen, Luan, Zhao, Ya-Fan, Wu, Zili, Goh, Tian-Wei, Liu, Jimmy Jingyue, Li, Yuanyuan, Zhu, Tong, Huang, Wenyu, Frenkel, Anatoly I., Li, Jun, and Tao, Franklin Feng. Thu . "Catalysis on Singly Dispersed Rh Atoms Anchored on an Inert Support". United States. doi:10.1021/acscatal.7b01788. https://www.osti.gov/servlets/purl/1468066.
@article{osti_1468066,
title = {Catalysis on Singly Dispersed Rh Atoms Anchored on an Inert Support},
author = {Zhang, Shiran and Tang, Yan and Nguyen, Luan and Zhao, Ya-Fan and Wu, Zili and Goh, Tian-Wei and Liu, Jimmy Jingyue and Li, Yuanyuan and Zhu, Tong and Huang, Wenyu and Frenkel, Anatoly I. and Li, Jun and Tao, Franklin Feng},
abstractNote = {A metal catalyst supported on an inert substrate could consist of both metal nanoparticles and singly dispersed metal atoms. Whether these singly dispersed metal atoms are active and how different their catalytic mechanism could be in contrast to a supported metal catalyst are fundamentally important for understanding catalysis on a supported metal or oxide. In this study, by taking reduction of NO with CO on singly dispersed Rh atoms anchored on an inert support SiO2 as a probe system (Rh1/SiO2), we demonstrated how singly dispersed metal atoms on an inert support could perform a complex multi-step catalytic cycle through a mechanism distinctly different from that for a supported metal nanoparticle with continuously packed metal sites. These singly dispersed Rh1 atoms anchored on SiO2 are active in reducing nitric oxide with carbon monoxide through two reaction pathways that are different from those of Rh nanoparticles. In situ IR studies show that a CO molecule and a NO molecule coadsorb on a singly dispersed Rh atom, Rh1 anchored on SiO2, and couple to form an N atom to adsorb on the surface and a CO2 molecule to desorb. The adsorbed N atom further couples with another CO molecule in the gas phase to form an intermediate -NCO on Rh1; this intermediate can directly couple with an NO molecule adsorbed on the same Rh1 to form N2 and CO2. In another pathway, the adsorbed N atom can couple with a coadsorbed NO on the same Rh1 to form N2O; N2O further reacts with adsorbed CO on the same Rh1 to form N2 and CO2 through a high activation barrier that can be overcome at a high temperature. Our studies show that the singly dispersed metal atoms on an inert support have great potential to perform selective transformation of chemicals. Lastly, the confirmed catalysis with a singly dispersed Rh1 on SiO2 through a mechanism different from a metal nanoparticle supported on the same substrate suggests the significance of taking the single-atom catalysis (SAC) into fundamental studies of catalysis of a supported metal catalyst, since metal nanoparticles and singly dispersed metal atoms likely coexist on the inert support of many supported catalysts.},
doi = {10.1021/acscatal.7b01788},
journal = {ACS Catalysis},
number = [1],
volume = [8],
place = {United States},
year = {2017},
month = {10}
}

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