Mechanistic Studies into the Selective Production of 2,5-furandicarboxylic Acid from 2,5-bis(hydroxymethyl)furan Using Au-Pd Bimetallic Catalyst Supported on Nitrated Carbon Material

Abstract

Aerobic oxidation of bio-sourced 2,5-bis(hydroxymethyl)furan (BHMF) to 2, 5-furandicarboxylic acid (FDCA), a renewable and green alternative to petroleum-derived terephthalic acid (TPA), is of great significance in green chemicals production. Herein, hierarchical porous bowl-like nitrogen-rich (nitrated) carbon-supported bimetallic Au-Pd nanocatalysts (AumPdn/ N-BNxC) with different nitrogen content and bimetal nanoparticle sizes were developed and employed for the highly efficient aerobic oxidation of BHMF to FDCA in sodium carbonate aqueous solution. The reaction pathway for catalytic oxidation of BHMF went through the steps of BHMF→HMF→HMFCA→FFCA→FDCA. Kinetics studies showed that the activation energies of BHMF, HMF, HMFCA, and FFCA were 58.1 kJ·moL−1, 39.1 kJ·moL−1, 129.2 kJ·moL−1, and 56.3 kJ·moL−1, respectively, indicating that the oxidation of intermediate HMFCA to FFCA was the rate-determining step. ESR tests proved that the active species was a superoxide radical. Owing to the synergy between the nitrogen-rich carbon support and bimetallic Au-Pd nanoparticles, the Au1Pd1/N-BN2C nanocatalysts exhibited BHMF conversion of 100% and FDCA yield of 95.8% under optimal reaction conditions. Furthermore, the nanocatalysts showed good stability and reusability. This work provides a versatile strategy for the design of heterogeneous catalysts for the highly efficient production of FDCA from BHMF.

Interaction between copper and nickel species for electrooxidation of 2,5-bis(hydroxymethyl)furan

“…4e). To the best of our knowledge, this catalytic performance, especially the yield of FDCA, surpasses that of all catalysts reported in the literature for the oxidation of BHMF, including electrocatalysts such as NiCo/CF(95.4%), 44 Co 3 O 4 /CF (95.8%), 45 CoOOH/Ni (90.2%), 33 and Pt/Pb (7%), 46 and thermal catalysts such as Au m Pd n /N–BN x C (95.8%), 47 Pd/ o -CNT (93.0%), 48 Ru–Acr( i Pr) (81%), 49 and Au 1 Pd 1 /pBNC–30%HNO 3 (35.6%). 50 A detailed comparison is presented in Table S2 †.…”

A perspective on nitrogen-doped carbon in 5-hydroxymethylfurfural oxidation

“…21 The synergistic interaction between the metal and the nitrogen-doped carbon material improves the activity of catalysts. 22–25 Graphite nitrogen can activate oxygen molecules, and pyridine nitrogen can provide bases. 26 Appropriate doping of graphite nitrogen and pyridine nitrogen can increase the electron mobility and active site, accelerate the electron transfer rate between the nitrogen-doped carbon shell and metal particles, and improve the catalytic activity.…”

Strongly Electron-Interacting Ru–Ce Pair Sites in RuOx/CeO2–HAP for Efficient Oxidation of MMF to FDCA

“…However, the high reactivity of hydroxymethyl and aldehyde groups on HMF makes it not only versatile but also prone to undesired reactions with byproducts such as humins and levulinic acid, leading to an energy-intensive process and elevated costs for HMF . These challenges hinder the low-cost industrial production of FDCA. − Due to these issues, researchers are turning to derivatives of HMF, such as 1,3-propanediol (PD-HMF), , [5-(hydroxymethyl)­furan-2-yl]­methanol (HMFO), 2,5-bis­(hydroxymethyl)­furan (BHMF), and 5-methoxymethylfurfural (MMF), , as alternative reactants to produce FDCA. Among them, MMF is gaining increasing attention for better storage stability and accessible through fructose dehydration in the presence of methanol .…”