Electrocatalytic oxidation of 5‐hydroxymethylfurfural for sustainable 2,5‐furandicarboxylic acid production—From mechanism to catalysts design

Abstract

Catalytic conversion of biomass-based platform chemicals is one of the significant approaches to utilize renewable biomass resources. 2,5-Furandicarboxylic acid (FDCA), obtained by an electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), has attracted extensive attention due to the potential of replacing terephthalic acid to synthesize high-performance polymeric materials for commercialization. In the present work, the pHdependent reaction pathways and factors influencing the degree of functional group oxidation are first discussed. Then the reaction mechanism of HMF oxidation is further elucidated using the representative examples. In addition, the emerging catalyst design strategies (defects, interface engineering) used in HMF oxidation are generalized, and structure-activity relationships between the abovementioned strategies and catalysts performance are analyzed. Furthermore, cathode pairing reactions, such as hydrogen evolution reaction, CO 2 reduction reaction (CO 2 RR), oxygen reduction reaction, and thermodynamically favorable organic reactions to lower the cell voltage of the electrolysis system, are discussed. Finally, the challenges and prospects of the electrochemical oxidation of HMF for FDCA are presented, focusing on deeply investigated reaction mechanism, coupling reaction, reactor design, and downstream product separation/purification.

Carbon Nanotubes Deposited on Mordenite Zeolite/NiAl-Layered Double Hydroxide Composites as Electrocatalysts for 2,5-Furandicarboxylic Acid Production from 5-Hydroxymethylfurfural

“…The higher ratio of DFF to HMFCA indicates that path I was predominant at a lower concentration of KOH, which is consistent with the previous works reporting that path I is preferable in a non-strong alkaline environment, while path II is the main route under a strong alkaline condition. , However, the higher selectivity of DFF compared with HMFCA during the initial period implied that the reaction pathway via DFF was more favorable . These results are consistent with the previous work reported by Wang and co-workers, revealing that the adsorption energies calculated from the DFT method of the hydroxy group of HMF (−1.15 eV) on the surface of the NiO catalyst was stronger than that of the aldehyde group (−0.86 V), leading to the preferential oxidation of HMF via the DFF pathway. , …”

“…43 These results are consistent with the previous work reported by Wang and coworkers, revealing that the adsorption energies calculated from the DFT method of the hydroxy group of HMF (−1.15 eV) on the surface of the NiO catalyst was stronger than that of the aldehyde group (−0.86 V), leading to the preferential oxidation of HMF via the DFF pathway. 52,53 To compare the catalytic activity among different catalysts, the NiAl-LDH-MOR exhibited a low conversion of HMF at 31% with a very low selectivity of FDCA at 2% due to the lack of conductivity of the material. Moreover, the commercial CNT as the electrode cannot achieve a high FDCA production of only 52.5% FDCA selectivity (Figure 8A) because of the absence of nickel catalytic active species.…”

Design of earth‐abundant amorphous transition metal‐based catalysts for electrooxidation of small molecules: Advances and perspectives

“…Moreover, coupling UOR/HzOR with hydrogen evolution reaction (HER) is suggested to realize energy‐saving hydrogen production 4 . Similarly, the electrochemical oxidation of methanol, glycerol, sulfion, formic acid, and 5‑hydroxymethylfurfural (HMF) also has been investigated to replace OER for producing hydrogen with lower energy consumption and obtaining value‐added chemicals 5,6 . Overall, the oxidative transformation of these small molecules in an electrochemical way would significantly benefit the sustainable energy system and green environment.…”

Cu2P7‐CoP Heterostructure Nanosheets Enable High‐Performance of 5‐Hydroxymethylfurfural Electrooxidation

“…Cobalt phosphide catalysts (Co-P, [24] Ce-CoP [25] and CoP-CoOOH [26] ) have been reported for the HMF electrooxidation, demonstrating their promising application potential. [27] However, their intrinsic electroactivity for HMF conversion is still unsatisfactory. Recently, Cu-based materials have gradually attracted attention in HMF electrooxidation because their activity to water oxidation (competitive reaction of HMF oxidation) is usually lower than that of Ni/Co-based materials.…”