Nanoporous Ni₃P Evolutionarily Structured onto a Ni Foam for Highly Selective Hydrogenation of Dimethyl Oxalate to Methyl Glycolate

Methyl glycolate (MG) is a versatile platform molecule to produce numerous important chemicals and materials, especially new-generation biocompatible and biodegradable poly(glycolic acid). In principle, it can be massively produced from syngas (CO + H₂) via gas-phase hydrogenation of CO-derived dimethyl oxalate (DMO), but the groundbreaking catalyst represents a grand challenge. Here, we report the discovery of a Ni-foam-structured nanoporous Ni₃P catalyst, evolutionarily transformed from a Ni₂P/Ni-foam engineered from nano-to macro-scale, being capable of nearly fully converting DMO into MG at >95% selectivity and stable for at least 1000 h without any sign of deactivation. As revealed by kinetic experiments and theoretical calculations, in comparison with Ni₂P, Ni₃P achieves a higher surface electron density that is favorable for MG adsorption in a molecular manner rather than in a dissociative manner and has much higher activation energy for MG hydrogenation to ethylene glycol (EG), thereby markedly suppressing its overhydrogenation to EG.