skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation

Abstract

To meet the requirements of potential applications, it is of great importance to explore new catalysts for formic acid oxidation that have both ultra-high mass activity and CO resistance. In this work, we successfully synthesize atomically dispersed Rh on N-doped carbon (SA-Rh/CN) and discover that SA-Rh/CN exhibits promising electrocatalytic properties for formic acid oxidation. The mass activity shows 28- and 67-fold enhancements compared with state-of-the-art Pd/C and Pt/C, respectively, despite the low activity of Rh/C. Interestingly, SA-Rh/CN exhibits greatly enhanced tolerance to CO poisoning, and Rh atoms in SA-Rh/CN resist sintering after long-term testing, resulting in excellent catalytic stability. Density functional theory calculations suggest that the formate route is more favourable on SA-Rh/CN. According to calculations, the high barrier to produce CO, together with the relatively unfavourable binding with CO, contribute to its CO tolerance.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [4]; ORCiD logo [5];  [4];  [6];  [6];  [7]; ORCiD logo [8];  [9]; ORCiD logo [10];  [11];  [8]; ORCiD logo [9];  [12];  [12];  [4];  [4] more »; ORCiD logo [3]; ORCiD logo [4];  [4] « less
  1. Tsinghua Univ., Beijing (China); Central South Univ., Changsha (China)
  2. Chinese Academy of Sciences (CAS), Beijing (China). Inst. of High Energy Physics, Beijing Synchrotron Radiation Facility
  3. Xi’an Jiaotong Univ. (China)
  4. Tsinghua Univ., Beijing (China)
  5. Chinese Academy of Science (CAS), Shanghai (China). Shanghai Inst. of Applied Physics, Shanghai Synchrotron Radiation Facilities
  6. Chinese Academy of Sciences, Changchun (China). Changchun Inst. of Applied Chemistry; Jilin Province Key Lab. of Low Carbon Chemical Power Sources, Changchun (China)
  7. Beijing Univ. of Chemical Technology (China)
  8. Xiamen Univ. (China)
  9. Wuhan Univ. (China)
  10. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  11. Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics,
  12. Central South Univ., Changsha (China)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
National Key R&D Program of China; National Natural Science Foundation of China (NNSFC); China Postdoctoral Science Foundation; Jilin Province Science and Technology Development Program; USDOE Laboratory Directed Research and Development (LDRD) Program; Youth Innovation Promotion Association CAS
OSTI Identifier:
1616956
Grant/Contract Number:  
AC02-76SF00515; 21671117; 21871159; 21890383
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 15; Journal Issue: 5; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrocatalysis; Materials science

Citation Formats

Xiong, Yu, Dong, Juncai, Huang, Zheng-Qing, Xin, Pingyu, Chen, Wenxing, Wang, Yu, Li, Zhi, Jin, Zhao, Xing, Wei, Zhuang, Zhongbin, Ye, Jinyu, Wei, Xing, Cao, Rui, Gu, Lin, Sun, Shigang, Zhuang, Lin, Chen, Xiaoqing, Yang, Hua, Chen, Chen, Peng, Qing, Chang, Chun-Ran, Wang, Dingsheng, and Li, Yadong. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. United States: N. p., 2020. Web. doi:10.1038/s41565-020-0665-x.
Xiong, Yu, Dong, Juncai, Huang, Zheng-Qing, Xin, Pingyu, Chen, Wenxing, Wang, Yu, Li, Zhi, Jin, Zhao, Xing, Wei, Zhuang, Zhongbin, Ye, Jinyu, Wei, Xing, Cao, Rui, Gu, Lin, Sun, Shigang, Zhuang, Lin, Chen, Xiaoqing, Yang, Hua, Chen, Chen, Peng, Qing, Chang, Chun-Ran, Wang, Dingsheng, & Li, Yadong. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. United States. doi:https://doi.org/10.1038/s41565-020-0665-x
Xiong, Yu, Dong, Juncai, Huang, Zheng-Qing, Xin, Pingyu, Chen, Wenxing, Wang, Yu, Li, Zhi, Jin, Zhao, Xing, Wei, Zhuang, Zhongbin, Ye, Jinyu, Wei, Xing, Cao, Rui, Gu, Lin, Sun, Shigang, Zhuang, Lin, Chen, Xiaoqing, Yang, Hua, Chen, Chen, Peng, Qing, Chang, Chun-Ran, Wang, Dingsheng, and Li, Yadong. Mon . "Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation". United States. doi:https://doi.org/10.1038/s41565-020-0665-x. https://www.osti.gov/servlets/purl/1616956.
@article{osti_1616956,
title = {Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation},
author = {Xiong, Yu and Dong, Juncai and Huang, Zheng-Qing and Xin, Pingyu and Chen, Wenxing and Wang, Yu and Li, Zhi and Jin, Zhao and Xing, Wei and Zhuang, Zhongbin and Ye, Jinyu and Wei, Xing and Cao, Rui and Gu, Lin and Sun, Shigang and Zhuang, Lin and Chen, Xiaoqing and Yang, Hua and Chen, Chen and Peng, Qing and Chang, Chun-Ran and Wang, Dingsheng and Li, Yadong},
abstractNote = {To meet the requirements of potential applications, it is of great importance to explore new catalysts for formic acid oxidation that have both ultra-high mass activity and CO resistance. In this work, we successfully synthesize atomically dispersed Rh on N-doped carbon (SA-Rh/CN) and discover that SA-Rh/CN exhibits promising electrocatalytic properties for formic acid oxidation. The mass activity shows 28- and 67-fold enhancements compared with state-of-the-art Pd/C and Pt/C, respectively, despite the low activity of Rh/C. Interestingly, SA-Rh/CN exhibits greatly enhanced tolerance to CO poisoning, and Rh atoms in SA-Rh/CN resist sintering after long-term testing, resulting in excellent catalytic stability. Density functional theory calculations suggest that the formate route is more favourable on SA-Rh/CN. According to calculations, the high barrier to produce CO, together with the relatively unfavourable binding with CO, contribute to its CO tolerance.},
doi = {10.1038/s41565-020-0665-x},
journal = {Nature Nanotechnology},
number = 5,
volume = 15,
place = {United States},
year = {2020},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Surfactant-Directed Synthesis of Mesoporous Pd Films with Perpendicular Mesochannels as Efficient Electrocatalysts
journal, September 2015

  • Li, Cuiling; Jiang, Bo; Miyamoto, Nobuyoshi
  • Journal of the American Chemical Society, Vol. 137, Issue 36
  • DOI: 10.1021/jacs.5b06278

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


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

An Effective Pd-Ni 2 P/C Anode Catalyst for Direct Formic Acid Fuel Cells
journal, November 2013

  • Chang, Jinfa; Feng, Ligang; Liu, Changpeng
  • Angewandte Chemie International Edition, Vol. 53, Issue 1
  • DOI: 10.1002/anie.201308620

Size-Controlled Synthesis of Platinum-Copper Hierarchical Trigonal Bipyramid Nanoframes
journal, October 2014

  • Chen, Sheng; Su, Hongyang; Wang, Youcheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 1
  • DOI: 10.1002/anie.201408399

Shape-Controlled Synthesis of Surface-Clean Ultrathin Palladium Nanosheets by Simply Mixing a Dinuclear Pd I Carbonyl Chloride Complex with H 2 O
journal, June 2013

  • Li, Huan; Chen, Guangxu; Yang, Huayan
  • Angewandte Chemie International Edition, Vol. 52, Issue 32
  • DOI: 10.1002/anie.201303772

XAS and DFT Investigation of Mononuclear Cobalt(III) Peroxo Complexes: Electronic Control of the Geometric Structure in CoO 2 versus NiO 2 Systems
journal, January 2011

  • Sarangi, Ritimukta; Cho, Jaeheung; Nam, Wonwoo
  • Inorganic Chemistry, Vol. 50, Issue 2
  • DOI: 10.1021/ic101730r

Concave and duck web-like platinum nanopentagons with enhanced electrocatalytic properties for formic acid oxidation
journal, January 2016

  • Lai, Jianping; Niu, Wenxin; Li, Suping
  • Journal of Materials Chemistry A, Vol. 4, Issue 3
  • DOI: 10.1039/C5TA08882H

Catalysis by Supported Single Metal Atoms
journal, November 2016


An ab Initio Molecular Dynamics Study on the Solvation of Formate ion and Formic acid in Water
journal, October 2012

  • Chen, Qiubo; Liu, Zhifeng; Wong, Chee How
  • Journal of Theoretical and Computational Chemistry, Vol. 11, Issue 05
  • DOI: 10.1142/S021963361250068X

A first principles comparison of the mechanism and site requirements for the electrocatalytic oxidation of methanol and formic acid over Pt
journal, January 2009

  • Neurock, Matthew; Janik, Michael; Wieckowski, Andrzej
  • Faraday Discuss., Vol. 140
  • DOI: 10.1039/B804591G

Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation
journal, March 2016


Multimetallic nanosheets: synthesis and applications in fuel cells
journal, January 2018

  • Zeb Gul Sial, Muhammad Aurang; Ud Din, Muhammad Aizaz; Wang, Xun
  • Chemical Society Reviews, Vol. 47, Issue 16
  • DOI: 10.1039/C8CS00113H

One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation
journal, March 2014

  • Yang, Sudong; Dong, Jing; Yao, Zhaohui
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep04501

Inflating hollow nanocrystals through a repeated Kirkendall cavitation process
journal, November 2017


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Towards More Active and Stable Electrocatalysts for Formic Acid Electrooxidation: Antimony-Decorated Octahedral Platinum Nanoparticles
journal, November 2012

  • Vidal-Iglesias, Francisco J.; López-Cudero, Ana; Solla-Gullón, José
  • Angewandte Chemie International Edition, Vol. 52, Issue 3
  • DOI: 10.1002/anie.201207517

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

Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory study
journal, August 2011


Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction
journal, October 2017

  • Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-01100-7

Photochemical route for synthesizing atomically dispersed palladium catalysts
journal, May 2016


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

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


Catalytic activities of Pt thin films electrodeposited onto Bi coated glassy carbon substrate toward formic acid electrooxidation
journal, December 2014


A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Atomic-Level Insight into Optimizing the Hydrogen Evolution Pathway over a Co 1 -N 4 Single-Site Photocatalyst
journal, August 2017

  • Cao, Yuanjie; Chen, Si; Luo, Qiquan
  • Angewandte Chemie International Edition, Vol. 56, Issue 40
  • DOI: 10.1002/anie.201706467

A stepwise-designed Rh-Au-Si nanocomposite that surpasses Pt/C hydrogen evolution activity at high overpotentials
journal, February 2017


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Ultrathin and Ultralong Single-Crystal Platinum Nanowire Assemblies with Highly Stable Electrocatalytic Activity
journal, June 2013

  • Xia, Bao Yu; Wu, Hao Bin; Yan, Ya
  • Journal of the American Chemical Society, Vol. 135, Issue 25
  • DOI: 10.1021/ja402955t

Single Atom (Pd/Pt) Supported on Graphitic Carbon Nitride as an Efficient Photocatalyst for Visible-Light Reduction of Carbon Dioxide
journal, May 2016

  • Gao, Guoping; Jiao, Yan; Waclawik, Eric R.
  • Journal of the American Chemical Society, Vol. 138, Issue 19
  • DOI: 10.1021/jacs.6b02692

Dendritic defect-rich palladium–copper–cobalt nanoalloys as robust multifunctional non-platinum electrocatalysts for fuel cells
journal, September 2018


Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014

  • Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4865107

Highly doped and exposed Cu( i )–N active sites within graphene towards efficient oxygen reduction for zinc–air batteries
journal, January 2016

  • Wu, Haihua; Li, Haobo; Zhao, Xinfei
  • Energy & Environmental Science, Vol. 9, Issue 12
  • DOI: 10.1039/C6EE01867J

Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials
journal, August 2015

  • Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa
  • Nature Materials, Vol. 14, Issue 9
  • DOI: 10.1038/nmat4367

Wavelet analysis of extended x-ray absorption fine structure data
journal, March 2005


Self-consistent aspects of x-ray absorption calculations
journal, August 2009


Direct observation of noble metal nanoparticles transforming to thermally stable single atoms
journal, July 2018


Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst
journal, December 2016

  • Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms14036

Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
journal, March 2011

  • Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico
  • ChemCatChem, Vol. 3, Issue 7
  • DOI: 10.1002/cctc.201000397

Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications
journal, July 2018


Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes
journal, February 2010

  • Ji, Xiulei; Lee, Kyu Tae; Holden, Reanne
  • Nature Chemistry, Vol. 2, Issue 4, p. 286-293
  • DOI: 10.1038/nchem.553

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

A mixed-solvent route to unique PtAuCu ternary nanotubes templated from Cu nanowires as efficient dual electrocatalysts
journal, February 2016


Single-Site Active Cobalt-Based Photocatalyst with a Long Carrier Lifetime for Spontaneous Overall Water Splitting
journal, June 2017

  • Liu, Wei; Cao, Linlin; Cheng, Weiren
  • Angewandte Chemie International Edition, Vol. 56, Issue 32
  • DOI: 10.1002/anie.201704358

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Bridge-Bonded Formate:  Active Intermediate or Spectator Species in Formic Acid Oxidation on a Pt Film Electrode?
journal, December 2006

  • Chen, Y. -X.; Heinen, M.; Jusys, Z.
  • Langmuir, Vol. 22, Issue 25
  • DOI: 10.1021/la060928q

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
journal, November 2014

  • Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs500737p

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Spatially Resolved Quantification of the Surface Reactivity of Solid Catalysts
journal, April 2016

  • Huang, Bing; Xiao, Li; Lu, Juntao
  • Angewandte Chemie International Edition, Vol. 55, Issue 21
  • DOI: 10.1002/anie.201601824

The facile synthesis of single crystalline palladium arrow-headed tripods and their application in formic acid electro-oxidation
journal, January 2015

  • Su, Na; Chen, Xueying; Ren, Yuanhang
  • Chemical Communications, Vol. 51, Issue 33
  • DOI: 10.1039/C5CC00353A

Ultra-uniform PdBi nanodots with high activity towards formic acid oxidation
journal, July 2017


Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst
journal, January 2017

  • Vaughan, Benjamin A.; Khani, Sarah K.; Gary, J. Brannon
  • Journal of the American Chemical Society, Vol. 139, Issue 4
  • DOI: 10.1021/jacs.6b10658

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005

  • Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
  • Nature Materials, Vol. 4, Issue 5, p. 366-377
  • DOI: 10.1038/nmat1368

Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization
journal, July 2018


“Raisin Bun”-Like Nanocomposites of Palladium Clusters and Porphyrin for Superior Formic Acid Oxidation
journal, April 2013


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


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

General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities
journal, January 2018


Deprotonation of Solvated Formic Acid:  Car−Parrinello and Metadynamics Simulations
journal, February 2006

  • Lee, Jung-Goo; Asciutto, Eliana; Babin, Volodymyr
  • The Journal of Physical Chemistry B, Vol. 110, Issue 5
  • DOI: 10.1021/jp055809i

Freestanding palladium nanosheets with plasmonic and catalytic properties
journal, December 2010

  • Huang, Xiaoqing; Tang, Shaoheng; Mu, Xiaoliang
  • Nature Nanotechnology, Vol. 6, Issue 1
  • DOI: 10.1038/nnano.2010.235