Plasma-engineered bifunctional cobalt-metal organic framework derivatives for high-performance complete water...

Metal-organic framework (MOF) derivatives are among the most promising catalysts for the hydrogen evolution reaction (HER) for clean hydrogen energy production. Herein, we report the in situ synthesized MOF-derived CoPO hollow polyhedron nanostructures by simultaneous high temperature annealing and Ar-N₂ radio frequency plasma treatment in the presence of a P precursor and subsequent oxygen incorporation from open air at lower temperature. The optimum Ar-N₂ gas flow rates are used to precisely tune the P/O ratio, cut Co bonds within the MOFs and reconnect Co with P. Consequently, both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance are enhanced. Meanwhile, the filling of P elements can effectively change the electronic structure around the catalyst to ensure the uniform distribution of catalytically active sites. The resultant CoPO hollow nanocages with large specific surface areas show excellent bifunctional electrocatalytic activity towards both HER and OER with a low overpotential of 105 and 275 mV and a small Tafel slope of 48 and 52 mV dec^-1, respectively. Our results open a new avenue for precise plasma-assisted engineering of MOF-derived hybrid hetero-structured electrocatalysts with rich oxygen vacancies and P dopants to simultaneously boost both half reactions in water electrolysis.