To unravel the structure and composition sensitivity of transition metal phosphides (M_xP_y) to C₂H₂ semi-hydrogenation catalytic performance, a series of M_xP_y (M = Mo, W, Fe, Co, Ni and Pd) with different crystal facet, exposed termination, and M: P ratio are fully examined. DFT calculations and microkinetic modeling show that C₂H₄ selectivity and activity over M_xP_y catalysts are sensitive to surface atomic structure and composition, attributing to different electronic properties. C₂H₂ adsorption energy is verified as good descriptor to evaluate C₂H₄ formation rate. FeP(1 0 1)-I catalyst is screened out to present Pd-like performance with higher C₂H₄ formation rate, higher C₂H₄ selectivity and greater stability against green oil formation than the Pd and other M_xP_y catalysts, which is still superior to the previously reported catalysts, such as the metal oxide, metal alloy and M_xS_y, as well as comparable to intermetallic compound. The results could supply a valuable clue for designing and optimizing M_xP_y catalysts in C₂H₂ semi-hydrogenation.

为了揭示过渡金属磷化物 (M _x P _y ) 对 C ₂ H ₂半加氢催化性能的结构和成分敏感性，一系列 M _x P _y (M = Mo、W、Fe、Co、Ni 和 Pd)具有不同晶面、暴露端接和 M:P 比的全面检查。DFT 计算和微动力学模型表明，C ₂ H ₄对 M _x P _y催化剂的选择性和活性对表面原子结构和组成很敏感，这归因于不同的电子特性。C ₂ H ₂吸附能被证实是评价C ₂ H ₄形成率的良好描述符。筛选出FeP(1  0  1)-I 催化剂，与 Pd 和其他 M _x P _y催化剂相比，具有更高的 C ₂ H ₄形成率、更高的 C ₂ H ₄选择性和对绿油形成的稳定性更高的类 Pd 性能, 这仍然优于先前报道的催化剂, 如金属氧化物、金属合金和 M _x S _y , 以及可与金属间化合物相媲美。该结果可为设计和优化 M _x P提供有价值的线索_y催化剂在C ₂ H ₂半加氢反应中。