Substituent-induced electronic localization of nickel phthalocyanine with enhanced electrocatalytic CO2 reduction

Abstract Designing efficient catalysts with high activity and selectivity is desirable and challenging for CO2 reduction reaction (CO2RR). Nickel phthalocyanine (NiPc) is a promising molecule catalyst for CO2RR. However, the pristine NiPc suffers from poor CO2 adsorption and activation due to its electron deficiency of Ni–N4 site, which leads to inferior activity and stability during CO2RR. Here, we develop a substituent-induced electronic localization strategy to improve CO2 adsorption and activation, and thus catalytic performance. Theoretic calculations and experimental results indicate that the electronic localization on the Ni site induced by electron-donating substituents (hydroxyl or amino) of NiPc greatly enhances the CO2 adsorption and activation, which is positively associated with the electron-donating abilities of substituents. Employing the optimal catalyst of amino-substituted NiPc to catalyze CO2 into CO in flow cell can achieve an ultrahigh activity and selectivity of 99.8% at the current densities up to 400 mA cm-2. This work offers a novel strategy to regulate the electronic structure of the active site by introducing substituents for highly efficient CO2RR.