Title: Tuning the Performance of Single-Atom Electrocatalysts: Support-Induced Structural Reconstruction

Journal Article · · Chemistry of Materials
 [1]; ORCiD logo [2];  [2];  [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [4]
  1. Chinese Academy of Sciences (CAS), Shanghai (China); Chinese Academy of Sciences (CAS), Beijing (China)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Northern Illinois Univ., DeKalb, IL (United States)
  4. Chinese Academy of Sciences (CAS), Shanghai (China)
+ Show Author Affiliations

We present that creating active and stable electrocatalysts remains a highly desirable and critical goal in the fields of catalysis and clean energy conversion. Single-atom catalyst (SAC), as a new research frontier in heterogeneous catalysis, has demonstrated emerging prospects for many electrocatalytic reactions. Support assisted pyrolysis approaches are widely used in the synthesis of single-atom electrocatalysts. While extensive efforts have been devoted to increase the loading of the atomically dispersed metal sites, the role of the support in creating these active metal sites remains largely unexplored. Herein, we compare catalysts created by support-free and support-assisted pyrolysis of vitamin B12 and cobalt tetramethoxyphenylporphyrin, respectively, and demonstrate an important effect of support-induced structural reconstruction that directly controls the activation of SAC. Electrochemical studies show support-free catalysts are inactive for oxygen reduction reaction whereas the support-assisted pyrolysis yields highly active catalysts using the same molecular precursors. X-ray absorption spectroscopy experiments reveal that both the metal-nitrogen coordination and the type of nitrogen species are different in these two types of samples, which leads to a difference in the d-band of the cobalt metal center and ultimately controls the catalytic activity and stability. In conclusion, this new insight provides a unique perspective on how to tune the electrocatalytic performances of SAC at the molecular level.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Key Basic Research Program of China; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1556073
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 21 Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single‐Site Catalysts Made of 3d Transition Metals journal November 2019
Modulating the Electronic Structure of Single‐Atom Catalysts on 2D Nanomaterials for Enhanced Electrocatalytic Performance journal March 2019
Single-atom catalysts templated by metal–organic frameworks for electrochemical nitrogen reduction journal January 2019

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30 DIRECT ENERGY CONVERSION
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Oxygen reduction
Single-atom electrocatalyst
Stability
Structural reconstruction
Support-assisted pyrolysis