Controlled One‐pot Synthesis of Nickel Single Atoms Embedded in Carbon Nanotube and Graphene Supports with High Loading

Abstract

Single-atom catalysts (SACs) have attracted much attentions due to the advantages of high catalysis efficiency and selectivity. However, the controllable and efficient synthesis of SACs remains a significant challenge. Herein, we report a controlled one-pot synthesis of nickel single atoms embedded on nitrogen-doped carbon nanotubes (NiSA N CNT) and nitrogen-doped graphene (NiSA N G). The formation of NiSA N CNT is due to the solid-to-solid rolling up mechanism during the high temperature pyrolysis at 800°C from the stacked and layered Ni-doped g-C3N4, gC3N4 Ni structure to a tubular CNT structure. Addition of citric acid introduces an amorphous carbon source on the layered g-C3N4 Ni and after annealing at the same temperature of 800°C, instead of formation of NiSA N CNT, Ni single atoms embedded in planar graphene type supports, NiSA N G were obtained. The density functional theory (DFT) calculation indicates the introduction of amorphous carbon source substantially reduces the structure fluctuation or curvature of layered g-C3N4-Ni intermediate products, thus interrupting the solid-to-solid rolling process and leading to the formation of planar graphene type supports for Ni single atoms. The assynthesized NiSA N G with Ni atomic loading of ~6 wt% catalysts shows a better activity and stability for the CO2 reduction reaction (CO2RR) than NiSA N CNT with Ni atomic loading of ~15 wt% due to the open and exposed Ni single atom active sites in NiSA N G. This study demonstrates for the first time the feasibility in the control of the microstructure of carbon supports in the synthesis of SACs.