The electrocatalysis of CO.sub.2 reduction to formic acid (HCOOH) as a useful chemical fuel has attracted much attention, but is facing the dilemma of low conversion efficiency. Herein, a series of transition elements were intentionally implanted into layered Bi.sub.2SeO.sub.2 surface to act as bimetallic reactive sites for decreasing the rate-limiting barriers. The calculations disclose that the doped 3d-metals can partially changes the electronic state distribution of 6 s lone pair electrons in Bi.sup.3+cation, in which this particular orbital hybridization leads to an intriguing bonding interaction between dopants and neighboring Se/O atomic layers. This interlayer electronic state coupling makes the half-filled dopants demonstrate the spin-resolved charge transfer and orbital interaction between bimetallic sites and reactants, because of the localized atomic distortion and electronic reconfiguration. This work provides a new insight into engineering surficial electronic structure and catalytic activity.