Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production
We present self-supporting W-doped Ni2P nanosheet arrays,serving as bifunctional catalysts for selective electrooxidation of benzylamine(BA)to high-value benzonitrile(BN),while simultane-ously promoting hydrogen production.The assembled W-Ni2P/NF||W-Ni2P/NF(NF:nickel foam)electrolyzer requires a voltage of only 1.41 V to achieve a current density of 10 mA cm-2 in alkaline solution containing 25 mmol L-1 BA,exhibiting an impressive Faradaic efficiency 95％for benzo-nitrile synthesis.In-situ Raman and FTIR spectroscopies identify catalytically active NiOOH centers and key catalytic intermediates.X-ray absorption spectroscopy(XAS)and theoretical calculations suggest that W acts as electron attractors on adjacent Ni atoms,forming an electron-deficient Ni domain that promotes the adsorption and activation of-NH2 group,leading to efficient dehydro-genation into C≡N bonds.The doped W also optimizes the adsorption of hydrogen(ΔGH*)on Ni2P,thus promote the hydrogen evolution.This work highlights the electronic modification of Ni active sites as a key factor for bifunctional electrocatalysis in selective nitrile electrosynthesis and concur-rent hydrogen evolution.
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