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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 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 phasemore » 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.« 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). Chemical Sciences, Geosciences, and 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. https://doi.org/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. https://doi.org/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. https://doi.org/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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Works referenced in this record:

Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003


Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013

  • Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300361m

Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

Atomically Dispersed Supported Metal Catalysts
journal, July 2012


Catalytically Active Single-Atom Sites Fabricated from Silver Particles
journal, March 2012


Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY
journal, March 2012

  • Lu, Jing; Aydin, Ceren; Browning, Nigel D.
  • Angewandte Chemie International Edition, Vol. 51, Issue 24
  • DOI: 10.1002/anie.201107391

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition
journal, May 2013

  • Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01775

Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction
journal, November 2013

  • Flytzani-Stephanopoulos, Maria
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar4001845

Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen
journal, May 2014


A Single-Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms
journal, July 2014

  • Kistler, Joseph D.; Chotigkrai, Nutchapon; Xu, Pinghong
  • Angewandte Chemie International Edition, Vol. 53, Issue 34
  • DOI: 10.1002/anie.201403353

CO Oxidation on Supported Single Pt Atoms: Experimental and ab Initio Density Functional Studies of CO Interaction with Pt Atom on θ-Al 2 O 3 (010) Surface
journal, August 2013

  • Moses-DeBusk, Melanie; Yoon, Mina; Allard, Lawrence F.
  • Journal of the American Chemical Society, Vol. 135, Issue 34
  • DOI: 10.1021/ja401847c

Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina
journal, September 2014

  • Peterson, Eric J.; DeLaRiva, Andrew T.; Lin, Sen
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5885

Theoretical and Experimental Investigations on Single-Atom Catalysis: Ir 1 /FeO x for CO Oxidation
journal, September 2014

  • Liang, Jin-Xia; Lin, Jian; Yang, Xiao-Feng
  • The Journal of Physical Chemistry C, Vol. 118, Issue 38
  • DOI: 10.1021/jp503769d

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit
journal, October 2015

  • Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9550

Highly Efficient Catalysis of Preferential Oxidation of CO in H 2 -Rich Stream by Gold Single-Atom Catalysts
journal, September 2015


FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes
journal, December 2014

  • Wei, Haisheng; Liu, Xiaoyan; Wang, Aiqin
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6634

Catalysis on singly dispersed bimetallic sites
journal, August 2015

  • Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8938

Thermally stable single-atom platinum-on-ceria catalysts via atom trapping
journal, July 2016


Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes
journal, January 2016

  • Liu, Wengang; Zhang, Leilei; Yan, Wensheng
  • Chemical Science, Vol. 7, Issue 9
  • DOI: 10.1039/C6SC02105K

Reduction of Nitric Oxide with Hydrogen on Catalysts of Singly Dispersed Bimetallic Sites Pt 1 Co m and Pd 1 Co n
journal, January 2016


Catalysis and In Situ Studies of Rh 1 /Co 3 O 4 Nanorods in Reduction of NO with H 2
journal, April 2013

  • Wang, Lei; Zhang, Shiran; Zhu, Yuan
  • ACS Catalysis, Vol. 3, Issue 5
  • DOI: 10.1021/cs300816u

Theoretical Investigations of Pt 1 @CeO 2 Single-Atom Catalyst for CO Oxidation
journal, May 2017

  • Tang, Yan; Wang, Yang-Gang; Li, Jun
  • The Journal of Physical Chemistry C, Vol. 121, Issue 21
  • DOI: 10.1021/acs.jpcc.7b00313

Visualizing reacting single atoms in chemical reactions: Advancing the frontiers of materials research
journal, July 2015


Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts
journal, January 2016

  • Cao, Shaowen; Tao, Franklin (Feng); Tang, Yu
  • Chemical Society Reviews, Vol. 45, Issue 17
  • DOI: 10.1039/C6CS00094K

High-Pressure (1 Torr) Scanning Tunneling Microscopy (STM) Study of the Coadsorption and Exchange of CO and NO on the Rh(111) Crystal Face
journal, May 2002

  • Rider, Keith B.; Hwang, Kevin S.; Salmeron, Miquel
  • Journal of the American Chemical Society, Vol. 124, Issue 19
  • DOI: 10.1021/ja020055w

Inhomogeneous Electron Gas
journal, November 1964


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


A Detailed Model of Local Structure and Silanol Hydrogen Bonding of Silica Gel Surfaces
journal, April 1997

  • Chuang, I-Ssuer; Maciel, Gary E.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 16
  • DOI: 10.1021/jp9629046

Silicon-29 NMR study of dehydrated/rehydrated silica gel using cross polarization and magic-angle spinning
journal, March 1983

  • Sindorf, Dean W.; Maciel, Gary E.
  • Journal of the American Chemical Society, Vol. 105, Issue 6
  • DOI: 10.1021/ja00344a012

The structures of the β-cristobalite phases of SiO 2 and AlPO 4
journal, June 1975


Small but Strong Lessons from Chemistry for Nanoscience
journal, December 2012


Structure of Isolated Molybdenum(VI) and Molybdenum(IV) Oxide Species on Silica: Periodic and Cluster DFT Studies
journal, February 2012

  • Handzlik, Jarosław; Ogonowski, Jan
  • The Journal of Physical Chemistry C, Vol. 116, Issue 9
  • DOI: 10.1021/jp207385h

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A hybrid Gaussian and plane wave density functional scheme
journal, October 1997


Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Separable dual-space Gaussian pseudopotentials
journal, July 1996


A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 111, Issue 15
  • DOI: 10.1063/1.480097

Comparison of methods for finding saddle points without knowledge of the final states
journal, November 2004

  • Olsen, R. A.; Kroes, G. J.; Henkelman, G.
  • The Journal of Chemical Physics, Vol. 121, Issue 20
  • DOI: 10.1063/1.1809574

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
journal, December 2005

  • Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J.
  • The Journal of Chemical Physics, Vol. 123, Issue 22
  • DOI: 10.1063/1.2104507

Superlinearly converging dimer method for transition state search
journal, January 2008

  • Kästner, Johannes; Sherwood, Paul
  • The Journal of Chemical Physics, Vol. 128, Issue 1
  • DOI: 10.1063/1.2815812

Recent developments and applications of electron microscopy to heterogeneous catalysis
journal, January 2012

  • Yang, Judith C.; Small, Matthew W.; Grieshaber, Ross V.
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35371g

Understanding complete oxidation of methane on spinel oxides at a molecular level
journal, August 2015

  • Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8798

Infrared Characterization of Rh Surface States and Their Adsorbates during the NO−CO Reaction
journal, March 2000

  • Almusaiteer, Khalid A.; Chuang, Steven S. C.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 10
  • DOI: 10.1021/jp9922155

An in Situ Infrared Study of the Reactivity of Adsorbed NO and CO on Rh Catalysts
journal, August 1994

  • Srinivas, G.; Chuang, S. S. C.; Debnath, S.
  • Journal of Catalysis, Vol. 148, Issue 2
  • DOI: 10.1006/jcat.1994.1261

How to Conceptualize Catalytic Cycles? The Energetic Span Model
journal, February 2011

  • Kozuch, Sebastian; Shaik, Sason
  • Accounts of Chemical Research, Vol. 44, Issue 2
  • DOI: 10.1021/ar1000956

Explore the Catalytic Reaction Mechanism in the Reduction of NO by CO on the Rh 7 + Cluster: A Quantum Chemical Study
journal, March 2012

  • Xie, Hujun; Ren, Meng; Lei, Qunfang
  • The Journal of Physical Chemistry C, Vol. 116, Issue 14
  • DOI: 10.1021/jp2118357

    Works referencing / citing this record:

    Atomic (single, double, and triple atoms) catalysis: frontiers, opportunities, and challenges
    journal, January 2019

    • Chen, Z. W.; Chen, L. X.; Yang, C. C.
    • Journal of Materials Chemistry A, Vol. 7, Issue 8
    • DOI: 10.1039/c8ta11416a

    Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site
    journal, October 2019


    Highlights of Major Progress on Single-Atom Catalysis in 2017
    journal, February 2019


    Harnessing the Wisdom in Colloidal Chemistry to Make Stable Single-Atom Catalysts
    journal, July 2018

    • Hülsey, Max J.; Zhang, Jiaguang; Yan, Ning
    • Advanced Materials, Vol. 30, Issue 47
    • DOI: 10.1002/adma.201802304