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Nickel and nitrogen co-doped carbon (Ni–N–C) has emerged as a promising catalyst for the CO 2 reduction reaction (CO 2 RR); however, the chemical nature of its active sites has remained elusive. Herein, we report the exploration of the reactivity and active sites of Ni–N–C for the CO 2 RR. Single atom Ni coordinated with N confined in a carbon matrix was prepared through thermal activation of chemically Ni-doped zeolitic imidazolate frameworks (ZIFs) and directly visualized by aberration-corrected scanning transmission electron microscopy. Electrochemical results show the enhanced intrinsic reactivity and selectivity of Ni–N sites for the reduction of CO 2 to CO, delivering a maximum CO faradaic efficiency of 96% at a low overpotential of 570 mV. Density functional theory (DFT) calculations predict that the edge-located Ni–N 2+2 sites with dangling bond-containing carbon atoms are the active sites facilitating the dissociation of the C–O bond of the *COOH intermediate, while bulk-hosted Ni–N 4 is kinetically inactive. Furthermore, the high capability of edge-located Ni–N 4 being able to thermodynamically suppress the competitive hydrogen evolution is also explained. The proposal of edge-hosed Ni–N 2+2 sites provides new insight into designing high-efficiency Ni–N–C for CO 2 reduction.
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Atomically dispersed single Ni site catalysts for high-efficiency CO 2 electroreduction at industrial-level current densities
Atomically dispersed and nitrogen-coordinated single Ni sites ( i.e. , NiN x moieties) embedded in partially graphitized carbon have emerged as effective catalysts for CO 2 electroreduction to CO. However, much mystery remains behind the extrinsic and intrinsic factors that govern the overall catalytic CO 2 electrolysis performance. Here, we designed a high-performance single Ni site catalyst through elucidating the structural evolution of NiN x sites during thermal activation and other critical external factors ( e.g. , carbon particle sizes and Ni content) by using Ni–N–C model catalysts derived from nitrogen-doped carbon carbonized from a zeolitic imidazolate framework (ZIF)-8. The N coordination, metal–N bond length, and thermal wrinkling of carbon planes in Ni–N–C catalysts significantly depend on thermal temperatures. Density functional theory (DFT) calculations reveal that the shortening Ni–N bonds in compressively strained NiN 4 sites could intrinsically enhance the CO 2 RR activity and selectivity of the Ni–N–C catalyst. Notably, the NiN 3 active sites with optimal local structures formed at higher temperatures ( e.g. , 1200 °C) are intrinsically more active and CO selective than NiN 4 , providing a new opportunity to design a highly active catalyst via populating NiN 3 sites with increased density. We also studied how morphological factors such as the carbon host particle size and Ni loading alter the final catalyst structure and performance. The implementation of this catalyst in an industrial flow-cell electrolyzer demonstrated an impressive performance for CO generation, achieving a current density of CO up to 726 mA cm −2 with faradaic efficiency of CO above 90%, representing one of the best catalysts for CO 2 reduction to CO.
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- Award ID(s):
- 1804326
- PAR ID:
- 10345300
- Date Published:
- Journal Name:
- Energy & Environmental Science
- Volume:
- 15
- Issue:
- 5
- ISSN:
- 1754-5692
- Page Range / eLocation ID:
- 2108 to 2119
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1039/D2EE00318J
