Abstract
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•Ru-cluster decorated P-vacancy-rich CoP is fabricated by a controllable method.•The Ru9.8/r-CoP catalyst exhibits high activity and reusability for NaBH4 hydrolysis.•Abundant P vacancies contribute to the formation of more uniform and smaller Ru clusters.•The superior performance attributed to the synergy of Ru clusters and CoP support.
NaBH4 is considered the best hydrogen storage material due to its high hydrogen content of 10.6 wt% and good stability. However, NaBH4 hydrolysis requires an efficient catalyst because of the sluggish reaction kinetics. In this work, we have demonstrated a process of preparing a cobalt phosphide-supported Ru particulate nanocatalyst with abundant phosphorus vacancies for the first time. Electron paramagnetic resonance and transmission electron microscopy revealed that the synthesized Ru9.8/r-CoP catalyst has ample phosphorus vacancies, and Ru species are small particles (~2.5 nm) with uniform dispersion, respectively. More importantly, the optimized Ru9.8/r-CoP catalyst has the lowest activation energy (45.3 kJ mol−1) and exhibits excellent catalytic performance for NaBH4 hydrolysis with a high hydrogen generation rate 9783.3 mLH2 min−1 gcat−1 at 25 °C, which is higher than most of the cobalt-based catalysts. Moreover, the Ru9.8/r-CoP catalyst also shows good reusability. For example, the catalytic performance only declined by ca. 14% after five cycles. The excellent catalytic performance of Ru9.8/r-CoP is attributed to the abundant phosphorus vacancies along with a large specific surface area of r-CoP, which makes the Ru particles smaller and more uniformly dispersed on the surface, thereby exposing more active sites to show improved performance.