Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High-Efficient Atomically Dispersed CoN4 Active Sites

He, Yanghua; Shi, Qiurong; Shan, Weitao; Li, Xing; Kropf, A. Jeremy; Wegener, Evan C.; Wright, Joshua; Karakalos, Stavros; Su, Dong; Cullen, David A.; Wang, Guofeng; Myers, Deborah J.; Wu, Gang

doi:10.1002/anie.202017288

Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High-Efficient Atomically Dispersed CoN₄ Active Sites

Journal Article · Sun Jan 24 23:00:00 EST 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202017288· OSTI ID:1787932

He, Yanghua ^[1]; Shi, Qiurong ^[1]; Shan, Weitao ^[2]; Li, Xing ^[3]; Kropf, A. Jeremy ^[4]; Wegener, Evan C. ^[4]; Wright, Joshua ^[5]; Karakalos, Stavros ^[6]; Su, Dong ^[3]; ^[7]; Wang, Guofeng ^[2]; Myers, Deborah J. ^[4]; ^[1]

State Univ. of New York (SUNY), Buffalo, NY (United States)
Univ. of Pittsburgh, PA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Illinois Inst. of Technology, Chicago, IL (United States)
Univ. of South Carolina, Columbia, SC (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We elucidate the structural evolution of CoN₄ sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)-8-derived carbon host as an ideal model for Co²⁺ ion adsorption. Subsequent in situ X-ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co-OH and Co-O species into active CoN₄ sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four-electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal-induced compressive strain of Co-N bonds in CoN₄ active sites formed at 900 °C. Further, we developed a two-step (i.e., Co ion doping and adsorption) Co-N-C catalyst with increased CoN₄ site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office

Grant/Contract Number:: AC05-00OR22725; AC02-06CH11357

OSTI ID:: 1787932

Alternate ID(s):: OSTI ID: 1786224
OSTI ID: 1798135

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 17 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High-Efficient Atomically Dispersed CoN4 Active Sites

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