Selective electrooxidation of 5-hydroxymethylfurfural to 5-formyl-furan-2-formic acid on non-metallic polyaniline catalysts: structure-function relationships

在非金属聚苯胺催化剂上选择性电氧化5-羟甲基糠醛生成5-甲酰基呋喃-2-甲酸:结构-功能关系

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Abstract

The biomass-derived HMF oxidation reaction (HMFOR) holds great promise for sustainable production of fine chemicals. However, selective electrooxidation of HMF to high value-added intermediate product 5-formyl-furan-2-formic acid (FFCA) is still challenging. Herein, we report the electrocatalytic HMFOR to selectively produce FFCA using carbon paper (CP) supported polyaniline (PANI) as a catalyst. The PANI/CP non-metallic hybrid catalyst with moderate oxidation capacity exhibitsoptimized FFCA selectivity up to 76% in alkaline media, which has reached the best performance in reported literature studies. Identification and quantification of active sites for the HMFOR are further realized via linking the activity to structural compositions of PANI; both polaronic-type nitrogen (N3) and positively charged nitrogen (N4) species are proved responsible for adsorption and activation of HMF, and the intrinsic activity of N4 is higher than that of N3. The present work provides new physical-chemical insights into the mechanism of the HMFOR on non-metallic catalysts, paving the way for the establishment of structure-function relations and further development of novel electrochemical synthesis systems.

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