Hydrogenation versus hydrogenolysis during alkaline electrochemical valorization of 5-hydroxymethylfurfural over oxide-derived Cu-bimetallics

Abstract

The electrochemical conversion of 5-Hydroxymethylfurfural, especially its reduction, is an attractive green production pathway for carbonaceous e-chemicals. We demonstrate the reduction of 5-Hydroxymethylfurfural to 5-Methylfurfurylalcohol under strongly alkaline reaction environments over oxide-derived Cu bimetallic electrocatalysts. We investigate whether and how the surface catalysis of the MOx phases tune the catalytic selectivity of oxide-derived Cu with respect to the 2-electron hydrogenation to 2.5-Bishydroxymethylfuran and the (2 + 2)-electron hydrogenation/hydrogenolysis to 5-Methylfurfurylalcohol. We provide evidence for a kinetic competition between the evolution of H2 and the 2-electron hydrogenolysis of 2.5-Bishydroxymethylfuran to 5-Methylfurfurylalcohol and discuss its mechanistic implications. Finally, we demonstrate that the ability to conduct 5-Hydroxymethylfurfural reduction to 5-Methylfurfurylalcohol in alkaline conditions over oxide-derived Cu/MOx Cu foam electrodes enable an efficiently operating alkaline exchange membranes electrolyzer, in which the cathodic 5-Hydroxymethylfurfural valorization is coupled to either alkaline oxygen evolution anode or to oxidative 5-Hydroxymethylfurfural valorization.

Review and Perspective of Nickel and Its Derived Catalysts for Different Electrochemical Synthesis Reactions in Alkaline Media for Hydrogen Production

“…Most previous studies used electrocatalysts deposited on porous substrates (e.g., 3D Ni foam, , 3D Co foam, and carbon paper) with high surface areas to achieve high HMF oxidation performance. Some researchers also used precatalysts.…”

“…Furthermore, produced H 2 is the cleanest energy with very high calorific demand in the 21st century (Figure 11b). 211,212 Most previous studies used electrocatalysts deposited on porous substrates (e.g., 3D Ni foam, 213,214 3D Co foam, 215 and carbon paper 216 ) with high surface areas to achieve high HMF oxidation performance. Some researchers also used precatalysts.…”

Recent progress of heterogeneous catalysts for transfer hydrogenation under the background of carbon neutrality

“…Hydrogenation is one of the most critical and fundamental processes in the modern chemical industry, and can produce important chemical and pharmaceutical intermediates. 18–23 However, the use of high pressure hydrogen inevitably leads to some disadvantages such as safety, storage and transportation, and the selectivity of the desired product is difficult to control. 24–27 In this respect, the catalytic transfer hydrogenation using organic hydrogen donors is therefore considered as a good alternative to H 2 hydrogenation, which not only reduces the requirements of special equipment but also improves the desired product selectivity due to the diversity of organic hydrogen donors (Scheme 2).…”

Efficient integration of carbon dioxide reduction and 5-hydroxymethylfurfural oxidation at high current density

“…Some previous studies break down and convert HMF into formic acid (FA) and maleic acid (MA), 24 while HMF can also be converted into 2,5-furandicarboxylic acid (FDCA). 25,26 FDCA serves as a crucial precursor, capable of generating polyethylene 2,5-furandicarboxylate (PEF) as a monomer, which in turn, can be utilized in the production of polyethylene terephthalate (PET), a promising contender for biomass-based plastics. 27 Au, Pt, Pd and various precious metals as well as molecular-based electrocatalysts have been studied to produce FDCA at low potential with outstanding performance.…”