An Overall Reaction Integrated with Highly Selective Oxidation of 5‐Hydroxymethylfurfural and Efficient Hydrogen Evolution

Abstract

Thermodynamically favorable electrooxidation reactions of biomass derivatives integrated with hydrogen evolution reaction (HER) can simultaneously provide value‐added chemicals and hydrogen, and eventually meeting the need for clean and sustainable energy development. Herein, the integration of a six‐electron involved anodic half‐reaction‐selective electrooxidation of 5‐hydroxymethylfurfural into 2,5‐furandicarboxylic acid (FDCA) on a hierarchically layered double hydroxide (CoFe@NiFe) with a cathodic HER in a two‐chamber system is reported. The overall reaction reaches 38 mA cm−2 at 1.40 V and exhibits 100% selectivity to yield FDCA and a nearly 100% Faraday efficiency with hydrogen production of 901 µmol cm−2. Several operando techniques confirm that the trivalent nickel species in the CoFe@NiFe catalyst are mainly responsible for this 100%‐selective oxidation reaction. This integrated overall reaction is thus a new strategy to utilize cheap catalysts and biomass derivatives to simultaneously produce value‐added chemicals and sustainable energy materials, and eventually to solve current challenges of energy depletion and environmental pollution.

Selective Electrosynthesis of 2,5‐Diformylfuran in a Continuous‐Flow System

“…As shown in the Figure 4b (blue curve), the overpotential was further reduced because the voltage was increased from À 1.6 to À 1.0 V, leading to less energy conservation. The reported cell voltages of paring HMF oxidation with HER by electrochemistry are 1.46 and 1.31 V at 10 mA cm À 2 in which FDCA rather DFF was produced, [13,39] which is higher than the value of 1.0 V at 14 mA cm À 2 in our continuous-flow system. Moreover, the calculated energy consumption (20 mA) is greatly reduced from 8.8 to 2.5 kJ to produce 1.56 g DFF (12.4 mmol) when CoS 2 /CoS and Pt were insitu loaded on the GF, which only consumed 28.4% energyof catalyst-free electrodes.…”

Efficient Electrooxidation of 5‐Hydroxymethylfurfural Using Co‐Doped Ni3S2 Catalyst: Promising for H2 Production under Industrial‐Level Current Density

“…[ 16 ] Thestandard electrooxidation potential of HMF (0.113 V) is much lower than the standard potential for OER (1.23 V). [ 17 , 18 ] Among the HMF oxidation products, 2,5‐furan dicarboxylic acid (FDCA) can serve as the major biobased alternative precursor to terephthalic acid, one of the petroleum‐derived monomers of various polyesters, for the productions of many commercialized polymers such as petroleum‐derived polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). The global market size of PET and PBT is approximately 18.76 million tons, which correspond to 7.4% and 0.25% of the global plastics production and primary energy consumption, respectively.…”

Earth‐Abundant Metal‐Based Electrocatalysts Promoted Anodic Reaction in Hybrid Water Electrolysis for Efficient Hydrogen Production: Recent Progress and Perspectives

“…A hierarchical composite comprising of NiFe LDH and CoFe LDH (named as CoFe@NiFe) was also fabricated by Zhao's group for the HMF oxidation. [59] The CoFe@NiFe composite integrates the merits of each bimetallic LDHs and shows better performance with a low onset potential of 1.28 V RHE and 100% FE toward FDCA at a potential of 1.4 V RHE in 1 m KOH (Figure 6d). In situ Raman and FTIR spectra (Figure 6e,f) indicate that the Ni 3+ species dominate the activity during the HMF electrooxidation reaction while Co 3+ species lower the onset potential and Fe 3+ species display negligible contribution, which is in line with previous reports.…”

“…Reproduced with permission. [59] Copyright 2021, Wiley-VCH. g) XPS spectra of Ni 2p and h) O 1s in NiCoBDC-NF and NiBDC-NF.…”

“…[30,45] Some works suggest the HMF oxidation is dependent on the applied potential and the HMF concentration during the electrooxidation. [50,59] While some others demonstrate the reaction pathway of the HMF oxidation is strongly affected by pH value. [31] No matter how many opinions were proposed, there are always exceptions as the HMF oxidation is a complex reaction with multi-steps electronic transfer and various products.…”