CO2 reduction reaction pathways on single-atom Co sites: Impacts of local coordination environment

doi:10.1016/S1872-2067(21)63893-7

Abstract

Abstract:

Single-atom catalysts have been proposed as promising electrocatalysts for CO₂ reduction reactions (CO₂RR). Co-N₄ active sites have attracted wide attention owing to their excellent CO selectivity and activity. However, the effect of the local coordination environment of Co sites on CO₂ reduction reaction pathways is still unclear. In this study, we investigated the CO₂ reduction reaction pathways on Co-N₄ sites supported on conjugated N₄-macrocyclic ligands with 1,10-phenanthroline subunits (Co-N₄-CPY) by density functional theory calculations. The local coordination environment of single-atom Co sites with N substituted by O (Co-N₃O-CPY) and C (Co-N₃C-CPY) was studied for comparison. The calculation results revealed that both C and O coordination break the symmetry of the primary CoN₄ ligand field and induce charge redistribution of the Co atom. For Co-N₄-CPY, CO was confirmed to be the main product of CO₂RR. HCOOH is the primary product of Co-N₃O-CPY because of the greatly increased energy barrier of CO₂ to *COOH. Although the energy barrier of CO₂ to *COOH is reduced on Co-N₃C-CPY, the desorption process of *CO becomes more difficult. CH₃OH (or CH₄) are obtained by further *CO hydrogenation reduction when using Co-N₃C-CPY. This work provides new insight into the effect of the local coordination environment of single-atom sites on CO₂ reduction reaction pathways.

Key words: Coordination environment, Product selectivity, Single-atom catalyst, CO₂ reduction reaction, DFT calculation

Haixia Gao, Kang Liu, Tao Luo, Yu Chen, Junhua Hu, Junwei Fu, Min Liu. CO₂ reduction reaction pathways on single-atom Co sites: Impacts of local coordination environment[J]. Chinese Journal of Catalysis, 2022, 43(3): 832-838.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63893-7

https://www.cjcatal.com/EN/Y2022/V43/I3/832

Figures/Tables 4

Fig. 1. Optimized structures of Co-N4-CPY (a), Co-N3O-CPY (b), and Co-N3C-CPY (c).

Fig. 2. Electronic structures. (a) Electronic projected densities of states (PDOS) of Co-N4-CPY, Co-N3O-CPY, and Co-N3C-CPY. (b) PDOS of Co atom in Co-N4-CPY, Co-N3O-CPY, and Co-N3C-CPY; (c) Charge density difference of Co-N4-CPY, Co-N3O-CPY, and Co-N3C-CPY, before and after Co is anchored onto the framework. Yellow and green regions represent positively and negatively charged regions, respectively, and the iso-surface value is 3 × 10-3 e/Bohr3.

Fig. 3. (a) Free energy diagrams of CO2 reduction pathway to CO and corresponding intermediates on Co-N4-CPY (at 0 V vs. RHE); (b) Free energy diagrams of CO2 reduction pathway to HCOOH and corresponding intermediates on Co-N3O-CPY (at 0 V vs. RHE); (c) Free energy diagrams of CO2 reduction pathway to CH4/CH3OH and corresponding intermediates on Co-N3C-CPY (at 0 V vs. RHE).

Fig. 4. (a) Electronic projected densities of states (PDOS) of C and O atoms; PDOS of Co, C-2p (bonded to Co on *COOH), and O-2p (bonded to Co on *OCHO) on Co-N4-CPY (b), Co-N3O-CPY (c), and Co-N3C-CPY (d).

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CO₂ reduction reaction pathways on single-atom Co sites: Impacts of local coordination environment

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