Regulating Adsorption of Intermediates via the Sulfur Modulating Dual-Atomic Sites for Boosting CO<sub>2</sub>RR
Kai Huang, Ru Li, Haodong Qi, Shuai Yang, Shuhao An, Cheng Lian, Qing Xu, Honglai Liu, Jun Hu
Abstract
The formation of dual-atom catalysts or heteroatom ligand modulation is the most promising strategy for optimizing single–atom catalysts (SACs) for the more efficient conversion of CO 2 to valuable chemicals. However, heteroatom ligands introduced into the dual-atomic sites are expected but still under-explored. In this study, a dual-atom Fe–Ni pair electrocatalyst with N– and S–coordination in porous carbon nanosheets was conceptually predicted for electrocatalytic CO 2 reduction to CO (CO 2 RR). In contrast to SACs and traditional diatomic catalysts (DACs), joined S–coordination can balance the cooperative activities of Fe and Ni sites, making the CO 2 adsorption configuration bidentate at both Fe–Ni sites. This regulation leads to a substantial change in CO* adsorption from Fe to Ni sites, facilitating CO desorption and boosting the electrocatalytic CO 2 RR. Experimental results demonstrate that the obtained FeNi–NSC catalyst achieves high selectivity with the Faradaic efficiencies for CO of 96.1%, and a remarkable activity with the turnover frequency of 6526.9 h –1 at −1.0 V, which were over 4.5 and 2.5 times of those from the single Fe or Ni sites. This work gives us insight into designing highly effective catalysts guided by theoretical calculation.