Ligand vacancy channels in pillared inorganic-organic hybrids for electrocatalytic organic oxidation with enzyme-like activities.

Simultaneously achieving abundant and well-defined active sites with high selectivity has been one of the ultimate goals for heterogeneous catalysis. Herein, we construct a class of Ni hydroxychloride-based inorganic-organic hybrid electrocatalysts with the inorganic Ni hydroxychloride chains pillared by the bidentate N-N ligands. The precise evacuation of N-N ligands under ultrahigh-vacuum forms ligand vacancies while partially retaining some ligands as structural pillars. The high density of ligand vacancies forms the active vacancy channel with abundant and highly-accessible undercoordinated Ni sites, exhibiting 5-25 fold and 20-400 fold activity enhancement compared to the hybrid pre-catalyst and standard β-Ni(OH) for the electrochemical oxidation of 25 different organic substrates, respectively. The tunable N-N ligand can also tailor the sizes of the vacancy channels to significantly impact the substrate configuration leading to unprecedented substrate-dependent reactivities on hydroxide/oxide catalysts. This approach bridges heterogenous and homogeneous catalysis for creating efficient and functional catalysis with enzyme-like properties.