Atomic Ni Species Anchored N‐Doped Carbon Hollow Spheres as Nanoreactors for Efficient Electrochemical CO2 Reduction

Abstract Electrochemical CO2 reduction to value‐added chemicals is a critical and challenging process for research of sustainable energy. Herein, we synthesize new nickel single atom catalysts embedded in nitrogen doped hollow carbon spheres (Ni−N/C‐x) via thermal treatment of Ni salts and nitrogen doped hollow carbon spheres (N/C‐x). The state of Ni species on Ni−N/C‐x can be tuned by the nitrogen species of N/C‐x and pyrrolic‐N favors the formation of atomic Ni species. Two catalysts, namely, Ni−N/C‐1/4 contains more pyrrolic‐N and more amount of atomic Ni species than that on Ni−N/C‐3/2 have been prepared. During all the measurement potential range, Ni−N/C‐1/4 displays a much higher catalytic activity for CO2 reduction to CO than Ni−N/C‐3/2. Within the potential range of −0.63 V to −0.98 V versus reversible hydrogen electrode (RHE), the faradaic efficiencies of CO on Ni−N/C‐1/4 exceed 70 %. Furthermore, Ni−N/C‐1/4 exhibits high selectivity for CO and excellent stability during 4.5 h of CO2 reduction electrolysis at the potential of −0.78 V versus RHE.