Journal
ACS CATALYSIS
Volume 12, Issue 14, Pages 8676-8686Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c01885
Keywords
volcanic selectivity; electrochemical CO2 reduction reaction; operando X-ray absorption fine structure spectroscopy; dynamic structural changes; atomically dispersed Ni catalyst
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Funding
- National Natural Science Foundation of China [U1732267]
- Shanghai Science and Technology Development Funds [22YF1454500]
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Potential-dependent selectivity changes are widely observed in electrocatalysis, but a detailed understanding of these changes at an atomic level is still lacking. In this study, we use a model atomically dispersed nickel catalyst to obtain a comprehensive view of potential-induced structure changes during the CO2 reduction reaction. Our findings show that the catalyst exhibits volcano-like selectivity changes that are dependent on the distance between the nickel atom and the carbon basal plane. Theoretical calculations suggest that local dynamic behaviors play a crucial role in regulating the distribution of the d band center of nickel.
Potential-dependent selectivity changes exist widely in electrocatalysis. However, an atomistic view of such changes remains a vital missing piece of the puzzle. Here, we employ a model atomically dispersed nickel catalyst to obtain the first full view of potential-induced structure changes at an atomic level during the electrochemical CO2 reduction reaction. The model catalyst consists of a single Ni site coordinated with pyrrole nitrogen in the form of Ni-N-4, as confirmed by comprehensive X-ray absorption spectroscopy (XAS) analyses. The catalyst exhibits typical potential-dependent volcanolike selectivity changes. Operando XAS revealed that the peak similar to 99% CO selectivity is achieved when the distance between the Ni atom and the carbon basal plane reaches an optimal distance of similar to 0.1 angstrom in the potential range of -0.5 to -0.8 V (vs RHE). The selectivity drops as the distance changes, induced by a potential shift. Theoretical calculations suggested that local dynamic behaviors directly regulate the distribution of the d band center of Ni. Our work provides a clear quantitative correlation between the dynamic configuration and the catalytic properties, which should benefit the future design of atomically dispersed catalysts.
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