Journal
ADVANCED MATERIALS
Volume 34, Issue 36, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adma.202205767
Keywords
coordination symmetry; Cu-N; O-2; (2); electrocatalytic nitrate reduction to ammonia; long-term stability; single-atom catalysts
Categories
Funding
- National Key R&D Program of China [2020YFC1818401, 2017YFC0210906]
- National Natural Science Foundation of China [21938006, 21776190, 21978185]
- China Postdoctoral Science Foundation [2020M681714]
- Basic Research Project of Leading Technology in Jiangsu Province [BK20202012]
- Suzhou Science and Technology Bureau Project [SYG201935]
- Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
- Advanced Computing East China Sub-center
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Symmetry-broken Cusingle-atom catalysts with higher catalytic activity and long-term stability have been designed for nitrate electrocatalytic reduction, providing a new approach for industrial production of ammonia.
Nitrate electrocatalytic reduction (NO3RR) for ammonia production is a promising strategy to close the N-cycle from nitration contamination, as well as an alternative to the Haber-Bosch process with less energy consumption and carbon dioxide release. However, current long-term stability of NO3RR catalysts is usually tens of hours, far from the requirements for industrialization. Here, symmetry-broken Cusingle-atom catalysts are designed, and the catalytic activity is retained after operation for more than 2000 h, while an average ammonia production rate of 27.84 mg h(-1) cm(-2) at an industrial level current density of 366 mA cm(-2) is achieved, obtaining a good balance between catalytic activity and long-term stability. Coordination symmetry breaking is achieved by embedding one Cu atom in graphene nanosheets with two N and two O atoms in the cis-configuration, effectively lowering the coordination symmetry, rendering the active site more polar, and accumulating more NO3- near the electrocatalyst surface. Additionally, the cis-coordination splits the Cu 3d orbitals, which generates an orbital-symmetry-matched pi-complex of the key intermediate *ONH and reduces the energy barrier, compared with the sigma-complex generated with other catalysts. These results reveal the critical role of coordination symmetry in single-atom catalysts, prompting the design of more coordination-symmetry-broken electrocatalysts toward possible industrialization.
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