Molybdenum, tungsten doped cobalt phosphides as efficient catalysts for coproduction of hydrogen and formate by glycerol electrolysis

H 2 and formate are important energy carriers in fuel-cells and feedstocks in chemical industry. The hydrogen evolution reaction (HER) coupling with electro-oxidative cleavage of thermodynamically favorable polyols is a promising way to coproduce H 2 and formate via electrochemical means, highly active catalysts for HER and electrooxidative cleavage of polycols are the key to achieve such a goal. Herein, molybdenum (Mo), tungsten (W) doped cobalt phosphides (Co 2 P) deposited onto nickel foam (NF) substrate, denoted as Mo-Co 2 P/NF and W-Co 2 P/NF, respectively, were investigated as catalytic electrodes for HER and electrochemical glycerol oxidation reaction (GOR) to yield H 2 and formate. The W-Co 2 P/NF electrode exhibited low overpotential ( η ) of 113 mV to attain a current density ( J ) of −100 mA cm −2 for HER, while the Mo-Co 2 P/NF electrode demonstrated high GOR efficiency for selective production of formate. In situ Raman and infrared spectroscopic characterizations revealed that the evolved CoO 2 from Co 2 P is the genuine catalytic sites for GOR. The asymmetric electrolyzer based on W-Co 2 P/NF cathode and Mo-Co 2 P/NF anode delivered a J  = 100 mA cm −2 at 1.8 V voltage for glycerol electrolysis, which led to 18.2 % reduced electricity consumption relative to water electrolysis. This work highlights the potential of heteroelement doped phosphide in catalytic performances for HER and GOR, and opens up new avenue to coproduce more widespread commodity chemicals via gentle and sustainable electrocatalytic means.