Quasi-Covalently Coupled Ni-Cu Atomic Pair for Synergistic Electroreduction of CO2

Developing highly active, selective, and stable electrocatalysts for the carbon dioxide reduction reaction (CO2RR) is crucial to establish a CO2 conversion system for industrial implementation and, therefore, to realize an artificially closed carbon loop. This can only be achieved through the rational material design based upon the knowledge of the operational active site at the molecular scale. Enlightened by theoretical screening, herein, we for the first time manipulate a novel Ni-Cu atomic pair configuration toward improved CO2RR performance. Systematic characterizations and theoretical modeling reveal that the secondary Cu metal incorporation positively shifts the Ni 3d orbital energy to the Fermi level and thus accelerates the rate-determining step, *COOH formation. In addition, the intrinsic inactivity of Cu toward the competing hydrogen evolution reaction causes a considerable reaction barrier for water dissociation on the Ni-Cu moiety. Due to these attributes, the as-developed Ni/Cu-N-C catalyst exhibits excellent catalytic activity and selectivity, with a record-high turnover frequency of 20,695 h(-1) at -0.6 V (vs RHE) and a maximum Faradaic efficiency of 97.7% for CO production. Furthermore, the dynamic structure evolution monitored by operando X-ray absorption fine-structure spectroscopy unveils the interaction between the Ni center and CO2 molecules and the synergistic effect of the Ni-Cu atomic pair on CO2RR activity.

Automated summary

Through theoretical screening, researchers successfully improved the catalytic performance of CO2RR by utilizing a novel Ni-Cu atomic pair configuration for the first time, achieving high efficiency in converting CO2 into carbon. Systematic characterizations and theoretical modeling revealed the inactivity of Cu towards the competing hydrogen evolution reaction and the promoting effect of Ni-Cu atomic pair on CO2RR activity.