When used as electrocatalysts for the reduction of CO₂, p-block metals (e.g., Bi, Sb, Tl, Pb, In, and Sn) are known to exhibit high selectivity toward the production of formic acid (HCOOH). Nonetheless, the current knowledge on the two key intermediates, namely COOH and OCHO, is lacking, which hinders the mechanistic understanding and development of efficient p-block metal catalysts. In this study, the molecular adsorption phenomena related to the electrocatalytic reduction of CO₂ (ERC) on p-block metal surfaces are investigated using dispersion-corrected density functional theory (DFT-D) calculations. It is demonstrated that the surfaces of p-block metals display low chemical reactivity toward CO₂. The adsorbates of OCHO with Ometal bonds are consistently more stable than those of COOH with Cmetal bonds. Consequently, the adsorption of OCHO is favored over COOH adsorption, leading to the selective formation of HCOOH instead of CO. Structural, vibrational, and electronic properties of these two adsorbates are discussed to facilitate future experimental mechanistic studies.

已知当p-嵌段金属（例如Bi，Sb，Tl，Pb，In和Sn）用作还原CO _2的电催化剂时，对甲酸（HCOOH）的生产显示出高选择性。但是，目前缺乏关于两个关键中间体（即COOH和OCHO）的知识，这阻碍了对有效的p嵌段金属催化剂的机械理解和开发。在这项研究中，使用分散校正的密度泛函理论（DFT-D）计算来研究与p嵌段金属表面上的CO ₂（ERC）电催化还原有关的分子吸附现象。已经证明，p-嵌段金属的表面显示出对CO _2的低化学反应性。的吸附物具有O金属键的OCHO始终比具有C金属键的COOH稳定。因此，OCHO的吸附比COOH的吸附更受青睐，从而导致选择性地形成HCOOH而不是CO。讨论了这两种吸附物的结构，振动和电子性质，以利于将来的实验机理研究。