Cage-Confinement Pyrolysis Route to Ultrasmall Tungsten Carbide Nanoparticles for Efficient Electrocatalytic Hydrogen Evolution.

The size-controlled synthesis of ultrasmall metal-based catalysts is of vital importance for chemical conversion technologies. Here, a cage-confinement pyrolysis strategy is presented for the synthesis of ultrasmall tungsten carbide nanoclusters/nanoparticles. An RHO type zeolitic metal azolate framework MAF-6, possessing large nanocages and small apertures, is selected to confine the metal source W(CO)6. High temperature pyrolysis gives tungsten carbide nanoclusters/nanoparticles with sizes ca. 2 nm, which can serve as an excellent electrocatalyst for the hydrogen evolution reaction. In 0.5 M H2SO4, it exhibits very low overpotential of 51 mV at 10 mA cm-2 and Tafel slope of 49 mV per decade, as well as the highest exchange current density of 2.4 mA cm-2 among all tungsten/molybdenum-based catalysts. Moreover, it also shows excellent stability and antiaggregation behavior after long-term electrolytic process.