Polar O–Co–P Surface for Bimolecular Activation in Catalytic Hydrogen Generation

Boron hydrides release an abundant amount of hydrogen in the presence of a suitable catalyst. Accelerating bimolecular activation kinetics is the key to designing cost‐effective catalysts for borohydride hydrolysis. In this study, the bimolecular activation of a polar O–Co–P site demonstrated superior hydrogen‐generation kinetics (turnover frequency, TOF = 37 min −1 , 298 K) and low activation energy (41.0 kJ mol −1 ) close to that of noble‐metal‐based catalysts. Through a combination of experiments and theoretical calculations, it was revealed that the activated dangling oxygen atom in the Co–O precursor effectively replaced via surface‐phosphorization because of strong electronic interactions between the dangling oxygen and P atoms. This substitution modulated the local coordination environment and electronegativity around the surface Co sites and formed a new polar O–Co–P active site for optimizing the activation kinetics of ammonia borane and water. This strategy based on bimolecular activation may create new avenues in the field of catalysis.