Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Abstract

Electrochemical valorization of biomass waste (e.g., glycerol) for production of value‐added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost‐effective, and highly efficient electrocatalysts for producing value‐added products at the anode and high‐purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm−2 is 1.105 V at 60 °C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high‐performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward CC cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

In Situ Derived Porous CoNi@Mo2C-CNT Composites for Excellent Electromagnetic Wave Absorption Properties

“…As well, carbon nanotubes can be detected encircling the surface of the porous nanorods. As can be seen in Figure a, the X-ray diffraction (XRD) pattern shows the precursor nanorods were CoMoO 4 , Co 0.5 Ni 0.5 MoO 4 , and NiMoO 4 . Following calcination, the diffraction peaks of the three samples agree with the Mo 2 C (JCPDS No.…”

Facile surface reconstructions of cobalt–copper phosphide heterostructures enable efficient electrocatalytic glycerol oxidation for energy-saving hydrogen evolution

“…31,32 The most effective electrocatalysts for the GOR reported so far are often based on noble metals 33 such as Au, Pd, Pt and their alloys (PtBi and PdBi), 34,35 which suffer from high cost and poor stability against poisoning, making them less competitive for economically feasible hydrogen production. In recent reports, transition metal-based catalysts have shown great promise as alternatives to noble metals for the GOR in alkaline media, including transition metal oxides, [36][37][38][39] hydroxides, [40][41][42][43][44] and nitrides. 12,45,46 In particular, metal oxides and hydroxides containing both Co and Cu have demonstrated good activity toward the GOR.…”

Nanofibrillar hydrogels outperform Pt/C for hydrogen evolution reactions under high-current conditions

“…4 In this regard, researchers have attempted to develop electrocatalysts with minimal use of noble metal elements [5][6][7][8] or with earth-abundant elements. [9][10][11][12][13][14][15][16][17][18][19] For example, the former electrocatalyst category includes Pt nanoparticles supported on carbon nanomaterials 5,6 and Pt-and Ru-based single-atom catalysts. 7,8 The latter category includes earth-abundant transition metal-based compounds, such as oxides, 9,10 phosphides, 11-13 nitrides [14][15][16] and chalcogenides.…”

“…9–19 For example, the former electrocatalyst category includes Pt nanoparticles supported on carbon nanomaterials 5,6 and Pt- and Ru-based single-atom catalysts. 7,8 The latter category includes earth-abundant transition metal-based compounds, such as oxides, 9,10 phosphides, 11–13 nitrides 14–16 and chalcogenides. 17,18 While most transition metals are relatively abundant, there is a high possibility that key electrocatalytic transition metal elements, particularly Co, have limited availability due to mass consumption in the rapidly growing Li-ion battery industry.…”