A Molecular Copper Catalyst for Electrochemical Water Reduction with a Large Hydrogen-Generation Rate Constant in Aqueous Solution

The copper complex [(bztpen)Cu](BF4)(2) (bztpen=N-benzyl-N,N,N-tris(pyridin-2-ylmethyl)ethylenediamine) displays high catalytic activity for electrochemical proton reduction in acidic aqueous solutions, with a calculated hydrogen-generation rate constant (k(obs)) of over 10000s(-1). A turnover frequency (TOF) of 7000h(-1)cm(-2) and a Faradaic efficiency of 96% were obtained from a controlled potential electrolysis (CPE) experiment with [(bztpen)Cu](2+) in pH2.5 buffer solution at -0.90V versus the standard hydrogen electrode (SHE) over two hours using a glassy carbon electrode. A mechanism involving two proton-coupled reduction steps was proposed for the dihydrogen generation reaction catalyzed by [(bztpen)Cu](2+).