Photoelectrochemical operation of a surface-bound, nickel-phosphine H2 evolution catalyst on p-Si(111): a molecular semiconductor|catalyst construct.

We demonstrate the covalent attachment and catalytic function of a nickel-phosphine H2 evolution catalyst to a p-Si(111) photoelectrode. The covalently assembled semiconductor|molecular construct achieves a synergistic improvement (ΔVonset = +200 mV) as compared to a solution of [(PNP)2Ni](2+) in contact with a p-Si(111)-CH3 photoelectrode.