Electrodeposition of hybrid nanosheet-structured NiCo₂O₄ on carbon fiber paper as a non-noble electrocatalyst for efficient electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

Abstract

Electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) has received increasing attention as it is an eco-friendly strategy for synthesizing the key monomer for the production of bio-based plastics....

Electrochemical Oxidation of Primary Alcohols Using a Co2NiO4 Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

“…There has been an increasing interest in the AOR as an alternative to the OER at the anode in fuel-forming electrochemical reactions. − The work presented in this study suggests that Co 2 NiO 4 is an efficient catalyst for oxidizing primary alcohols with high selectivity for carboxylic acid products at potentials less positive than the onset of the OER. This study was the measurement of the AOR of linear primary alcohols to establish trends in activity and product distribution with alcohol chain length and applied potential.…”

“…48−50 Co 2 NiO 4 has also shown promise as an electrocatalyst for the oxidation of 5-hydroxymethyl furfural (HMF), a biomass derivative, to 2,5-furandicarboxylic acid (FDCA), a useful polymerization feedstock. 20,51,52 While previous studies of AOR at Co 2 NiO 4 electrocatalysts highlight the versatility of this catalyst material, these studies have not necessarily quantified the potential dependence of product distribution. Many AOR studies at Co 2 NiO 4 electrocatalysts focus primarily on measured current densities and do not quantify product selectivity, 48−50 or quantify product selectivity at only a single or a few applied potentials.…”

“…In electrochemical reactors, the reduction of H 2 O to H 2 or CO 2 to C-containing products at the cathode is coupled to the oxygen evolution reaction (OER) at the anode. Thus, the slow electrode kinetics of the OER limit the maximum current densities, which can be achieved at the cathode. − One possible alternative to the OER is the alcohol oxidation reaction (AOR), which has been shown in some studies to achieve higher current densities at less-positive applied potentials compared to the OER. − In addition, the large number of possible alcohol substrates, including everything from straight-chain alcohols − to biomass-derived products, ,− increase the likelihood that the AOR will produce chemicals that can be further processed into value-added chemical feedstocks.…”

“…The long-term applicability of alcohol oxidation to replace the OER in electrochemical applications requires the development of precious-metal-free catalyst systems that show high activity and high product selectivity for single value-added products. , Cobalt-based materials have shown particular promise as active catalysts for the AOR. ,− Ni-doped cobalt oxide (Co 2 NiO 4 ) has been reported as a particularly highly active for alcohol oxidation that is much more active than its Co 3 O 4 and NiO parent materials. , Specifically, Co 2 NiO 4 has been shown to operate with high activity for methanol (MeOH) oxidation, achieving current densities ≥10 mA cm –2 at ∼1.4 V vs reversible hydrogen electrode (RHE), approximately 0.2 V less positive than the onset of OER. − Co 2 NiO 4 has also shown promise as an electrocatalyst for the oxidation of 5-hydroxymethyl furfural (HMF), a biomass derivative, to 2,5-furandicarboxylic acid (FDCA), a useful polymerization feedstock. ,, …”

“…While previous studies of AOR at Co 2 NiO 4 electrocatalysts highlight the versatility of this catalyst material, these studies have not necessarily quantified the potential dependence of product distribution. Many AOR studies at Co 2 NiO 4 electrocatalysts focus primarily on measured current densities and do not quantify product selectivity, − or quantify product selectivity at only a single or a few applied potentials. ,, The few studies that explore potential dependence for the AOR at Co 2 NiO 4 show changes in product selectivity as a function of applied potential, suggesting a complicated interrelationship between potential and the reaction mechanism and kinetics. Although previous studies of the AOR at Co 2 NiO 4 have been very informative as to the catalytic nature of Co 2 NiO 4 , the lack of product analysis, and particularly potential-dependent product analysis, hinders deeper understanding of reaction selectivity, product selectivity, and possible mechanistic pathways for the AOR.…”