Coupling Cu⁺ Species and Zr Single Atoms for Synergetic Catalytic Transfer Hydrodeoxygenation of 5-Hydroxymethylfurfural

The formation and stabilization of Cu+ species are important to develop efficient Cu-based catalysts for the catalytic transfer hydrodeoxygenation (CTHDO) of renewable biomass to value-added products but challenging. Herein, we demonstrate that the introduction of atomically dispersed Zr species into a CuOx matrix (Cu10Zr0.39Ox) greatly promoted its catalytic activity and stability for the CTHDO of 5-hydroxymethylfurfural (HMF) into 2,5-dimethylfuran (DMF). In particular, almost quantitative DMF yield could be implemented over Cu10Zr0.39Ox accompanied by an impressive DMF formation rate of 8.1 mmolDMF·gcat–1·h–1, which outperforms the existing works for the CTHDO of HMF to DMF. Experimental and theoretical observations revealed that the electronic interactions between the doped Zr atom species and CuOx enabled the generation of ample and stable Cu+ species. The single-atom Zr species also promoted the adsorption and activation of the substrates and worked synergistically with Cu+ species to boost the CTHDO of HMF by reducing the reaction energy barriers.