Laser Derived Co1Ni1@MOF with Efficient Charge Exchanges Boosting Selective Catalytic Hydrogenation

Abstract

Metal–organic framework (MOF) catalysts promise selective hydrogenation of C═O bonds, a process that is thermodynamically unfavorable because of the presence of C─O, C═C, and C─C bonds within furan rings. However, the reactivity and stability of MOF are often impeded in catalytic reactions by structural collapse or phase transition stemming from commonly employed strategies such as defect engineering. The present work investigates a novel strategy for designing highly active Co₁Ni₁@UiO-66-NH₂ catalysts by embedding Co₁Ni₁ within the UiO-66-NH₂ framework. This approach facilitates efficient charge transfer between the reactants and the catalysts, thereby preserving both reactivity and structural integrity. The turnover frequency of Co₁Ni₁@UiO-66-NH₂ is 430 h⁻¹, in contrast to 18 h⁻¹ of UiO-66-NH₂, demonstrating that the transfer hydrogenation activity of Co₁Ni₁@UiO-66-NH₂ is 24 times greater than that of UiO-66-NH₂. More importantly, the reaction rate achieves 7.27 mol g⁻¹ h⁻¹, with a furfuryl alcohol (FOL) yield of 100%, and the Co₁Ni₁@UiO-66-NH₂ catalyst retains its excellent catalytic activity even after eight cycles of applications. Density functional theory calculations indicate that, in comparison to UiO-66-NH₂, Co- and Ni@UiO-66-NH₂, Co₁Ni₁@UiO-66-NH₂ exhibits relatively strong interactions and significant charge exchanges between reactants and catalysts. These interactions not only facilitate the dehydrogenation of isopropanol but also enhance the hydrogenation of furfural. Furthermore, the density of states reveals a greater number of states near the Fermi level in Co₁Ni₁@UiO-66-NH₂ compared to Co- and Ni@UiO-66-NH₂, and thereby facilitates the substantial charge exchanges and efficient catalytic performance of Co₁Ni₁@UiO-66-NH₂.