From atomic bonding to heterointerfaces: Co2P/WC constructed by lacunary polyoxometalates induced strategy as efficient hydrogen evolution electrocatalysts at all pH values

Herein, a novel in-situ "atomic binding to heterointerface" strategy is proposed to obtain Co2P/WC@NC/CNTs catalyst with abundant heterointerface between cobalt phosphide and tungsten carbide (Co2P/WC) by the pol-yoxometalates (POMs)-based metal-organic frameworks (MOFs) precursor. The natural quasi interfaces in K10[Co4(H2O)2(PW9O34)2] molecule crucially guide the abundant Co2P/WC heterointerfaces down to atomic level. Meanwhile, MOFs cages can effectively encapsulate nanosized POMs at molecular level to control the size and dispersion of Co2P/WC nanoparticle, while carbon nanotubes (CNTs) enhance conductivity at nanoscale level. The interfacial electronic modulation between Co2P and WC lowering the energy barrier of the rate determining step, thus Co2P/WC@NC/CNTs showed reasonable hydrogen evolution reaction (HER) activity and stability in all-pH media including sea water. This work provides a "bottom-up" synthetic strategy for confined heterostructures, thus offering the prospect for more efficient interfacial charge modulation.