Metal-Dependent Selectivity on the Reactions of Carbon Dioxide with Diatomic Hydride Anions MH<sup>–</sup> (M = Co, Ni, and Cu)
Li‐Xue Jiang, Xiao‐Na Li, Sheng‐Gui He
Abstract
A fundamental understanding of the selective hydrogenation of carbon dioxide (CO2) is of great importance to transform CO2 into value-added chemicals and provides a molecular-level guidance to encourage the design of improved catalysts. Herein, benefiting from the study of diatomic hydride anions MH– (M = Co, Ni, and Cu) with CO2 in the gas phase, we identified that the product selectivity is highly dependent on the nature of 3d metals. Note that gas-phase metal hydrides are ideal models of the active sites for CO2 hydrogenation in related condensed-phase systems. The experimental results showed that the CuH– anion can selectively transform CO2 into hydrogenation product HCO2– while NiH– can reduce CO2 into CO selectively, and both channels were observed on the reaction of CoH– with CO2. This 3d-metal-dependent selectivity on the reactions of MH– with CO2 was further rationalized by using quantum chemical calculations.