Bin Zhu,Qiuge Wang,Jinggang Wang,Xiao Yu,Jian Zhang,Chunlin Chen
Graphical The nitrogen-doped-carbon encapsulated cobalt (Co@NC) chainmail nanowires were synthetized for the electrocatalytic production of 2,5-furandicarboxylic acid (FDCA) from 2,5-bis(hydroxymethyl)furan (BHMF). The Co@NC on Ni foam achieved 97.9 % conversion of BHMF, yielding 93.3 % FDCA at 1.475 V vs. RHE. The superior electrochemical performance of Co@NC/NF can be attributed to its large electrochemically active surface area and excellent kinetic parameters. 2,5-Furandicarboxylic acid (FDCA) has emerged as an important bio-based furanic compound, which has broad application prospects in renewable energy and materials, especially in the preparation of polyethylene 2,5-furandicarboxylate (PEF). While the conventional synthesis of FDCA involves oxidation of 5-hydroxymethylfurfural (HMF) as a substitute, the thermal and chemical instability of HMF due to its aldehyde group poses challenges. A more favorable alternative is the utilization of 2,5-bis(hydroxymethyl)furan (BHMF), a non-aldehyde and more stable precursor. This study pioneeringly reports nitrogen-doped-carbon encapsulated cobalt (Co@NC) chainmail nanowires for the thermal and electrocatalytic oxidation of BHMF to FDCA. The Co@NC/NF achieved a 97.9 % conversion of BHMF with a 93.3 % yield of FDCA at 1.475 V vs. RHE, whereas thermal catalysis only obtained 14.9 % FDCA yield after 10 hours. Kinetic studies indicated that the large electrochemically active surface area and excellent kinetic parameters contribute its superior electrochemical performance. Mechanistic analysis revealed that the migration of inner electrons to the exterior modified the electronic properties of the carbon layer, thereby facilitating the oxidation of BHMF. Furthermore, the in-situ generation of high-valent cobalt species markedly accelerated the BHMF oxidation. This research underscores the potential of carbon-encapsulated metal chainmail catalysts in thermal and electrochemical biomass conversion.
2,5-Furandicarboxylic acid (FDCA), an important platform chemical, is often synthesized from hydroxymethylfurfural (HMF), while the energy efficiency of the reaction is limited by the slow hydroxymethyl oxidation, resulting in poor technoeconomy. In this study, a bimetallic Au–Pd microwave-responsive catalyst was designed to achieve high-efficiency synthesis of FDCA by coupling microwave-activated peroxyl radical formation from hydrogen peroxide (H2O2). Pd sites were responsible for dissociating H2O2 into peroxyl radicals (·OOH), and Au sites accepted peroxyl radicals and oxidized HMF into FDCA. The microwave-boosted reaction synergy on the bimetallic Au–Pd dual active centers enabled the reaction to occur at near-room temperature (45 °C) and reached the highest FDCA yield of 88 mol % at 65 °C. Experimental and electric-field DFT studies revealed that microwaves increased the rate constant of H2O2 decomposition by 1.6-fold compared to conventional heating methods, with an ultrahigh H2O2 utilization rate of 90%. This work provides a new platform for highly efficient peroxyl radical formation with microwave energy, which can be extended to a wider range of oxidation reactions with accelerated reaction kinetics and enhanced energy efficiency.
Lei Yang,Anbang Duan,Yuan Ding,Xiquan Song,Qianli Ma,Zhanyin Liu,Tingying Wei,Zhixing Wang,Chunzhao Liu
The growing demand for sustainable biomanufacturing has driven significant interest in 2,5-furandicarboxylic acid (FDCA), a bio-based platform chemical for producing renewable polymers. The eco-friendly oxidoreductase laccase exhibits promising FDCA biosynthesis capacity yet is hampered by pH-dependent activity decay and susceptibility to proteolytic degradation. Herein, we developed a bio-enabled synthesis approach to fabricate three-dimensional laccase-integrated copper hybrid nanoflowers (Lac-NFs) through enzyme–metal coordination-driven self-assembly. The engineered Lac-NFs displayed high enzyme encapsulation efficiency (89.28%) and enhanced environmental robustness compared to free laccase. Furthermore, the Lac-NFs maintained prolonged storage stability with well-preserved activity relative to the native enzyme. Elevated catalytic efficiency and refined enzymatic kinetics were achieved via copper-mediated electron transfer networks within the hybrid matrix. Remarkably, Lac-NFs demonstrate exceptional catalytic efficiency and selectivity in the conversion of HMF to FDCA, achieving complete substrate conversion under precisely controlled operational parameters. This nano–biohybrid design establishes a robust and efficient biocatalytic platform for biomass valorization into high-value-added chemicals, exhibiting promising scalability prospects for industrial implementation.
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