Size effect of ruthenium nanoparticles on water cracking properties with different crystal planes for boosting electrocatalytic hydrogen evolution.

Small size ruthenium (Ru) nanoparticles have shown remarkable potential for electrocatalytic hydrogen evolution reaction (HER). Nevertheless, the complicated preparation and relatively low activity of small size Ru nanoparticles are two key challenges. In this work, carbon nanotubes supported Ru nanoparticles catalysts (cnts@NC-Ru t °C) with different sizes were prepared via using the combination of L-3,4-dihydroxyphenylalanine (l-dopa) self-polymerization oxidation reaction and different high temperature annealing to study the variation of particle activity with size. Electrochemical test results showed that the optimized cnts@NC-Ru 700 °C catalyst exhibited a very low overpotential at 10 mA/cm (21 mV) and tafel slope of 34.93 mV/dec when the mass loading of precious metal per unit area was merely 12.11 μg/cm that surpassed most recently reported high-performance Ru based catalyst. The results of density functional theory (DFT) calculation showed that small Ru nanoparticles had abundant active sites, and the HO dissociation on small Ru nanoparticles (110) surface is quite easy than other surfaces, while (111) surface of small Ru nanoparticles is beneficial for Tafel step of HER. The synergy between (110) and (111) surfaces on the Ru cluster contributes to its outstanding HER performance. This study provides a novel design idea in promoting the preparation method and uncovering the reason of high activity of small size Ru nanoparticles.