Devices and methods for electrocatalytic hydrogen production

A photoelectrochemical device for hydrogen generation, comprising:

• at least one electrochemical cell comprising an anode compartment, a cathode compartment, an anion exchange membrane separating the anode compartment and the cathode compartment, an anode electrode placed in the anode compartment, and a cathode electrode placed in the cathode compartment, wherein the anode electrode comprises a substrate and a metal-based electrocatalyst formed on the substrate, wherein the metal-based electrocatalyst is a layered Au—Pt—Bi electrocatalyst comprising an Au—Pt base layer and a Bi layer deposited on the Au—Pt base layer, and wherein the anode compartment contains an electrolyte comprising glycerol, and a Bi-containing salt comprising Bi(NO3)3 added in the electrolyte;
• and
• a photovoltaic module integrated with the at least one electrochemical cell such that the cathode electrode of the at least one electrochemical cell is a photocathode and adapted for converting energy of photons to electrical energy for driving the at least one electrochemical cell to facilitate redox reactions therein,
• wherein the at least one electrochemical cell is configured to
• generate hydrogen from glycerol oxidation at a cell potential driven from the photovoltaic module under illumination, the cell potential being as low as 0.4 V and smaller than 1.7 V that is a minimal practical potential required for water splitting;
• and
• in-situ restore electrocatalytic activity of the anode electrode via a periodic cathodic reverse step to re-deposit Bi from the Bi-containing salt added to the electrolyte, thereby maintaining performance for an extended duration.