Emerging dual-atomic-site catalysts for electrocatalytic CO_(2)reduction

The electrochemical CO_(2)reduction reaction(CO_(2)RR)to yield high-value added fuels and chemicals provides a promising approach towards global carbon neutrality.Constant endeavors have been devoted to the exploration of high-efficiency catalyst with rapid reaction kinetics,low energy input,and high selectivity.In addition to the maximum metal atomic utilization and unique catalytic performance of single-atom catalyst(SAC),dual-atomic-site catalysts(DASCs)offer more sophisticated and tunable atomic structure through the modulations of another adjacent metal atom,which can bring new opportunities for CO_(2)RR as a deeper extension of SACs and have recently aroused surging interest.In this review,we highlight the recent advances on DASCs for enhancing CO_(2)RR.First,the classification,synthesis,and identification of DASCs are provided according to the geometric structure and electronic configuration of dual-atomic active sites.Then,the catalytic applications of DASCs in CO_(2)RR are categorized based on marriage-type,hetero-nuclear,and homo-nuclear dual-atomic sites.Particularly,the structure-activity relationship of DASCs in CO_(2)RR is elaborately summarized through systematically analyzing the reaction pathways and the atom structures.Finally,the opportunities and challenges are proposed for inspiring the design of future DASCs with high structural accuracy and high CO_(2)RR activity and selectivity.

Structural and Interaction Properties of Porphyrin Layers — A Quantum Chemical Study

This paper is proposed to understand the interaction of porphyrin layers with diatomic molecules interacting at their interior regions by applying ab initio and density functional theory （DFT） methods. We have used NO, GO, and O2 diatomic molecules to interact with the porphyrin layers. The most common Fe-centered metalloporphyrin structure with tetra-pyrrlic rings having N4 core is chosen for the study. The optimization of Porphyrin-Porphyrin （PI-PII） and Porphyrin-Diatomic molecule-Porphyrin （P1-AB-P11） （AB = NO, CO, and 02） complexes are performed using HF method. In order to understand the planarity and appropriate stacking size of porphyrins and also to infer the separation of diatomic molecules between porphyrin layers the behavior of PI-AB-PH complexes （where AB = NO, CO, and 02） are analyzed using structural properties and molecular electrostatic potentials （MEP）. The MEPs are caiculated using hybrid exchange correlation functional B3PW91 of DFT Mong with 6-31＋G basis set for the PI-PH and PI-AB-Pzz complexes obtained from HF method.