Interface engineering is a significance strategy to afford efficient selective oxidation for supported catalysts. Herein, constructing of frustrated Lewis pairs (FLPs) sites on CeO 2 and supporting Au-Pd nanoparticles to provide a highly selective production of 2,5-furandicarboxylic acid (FDCA) from 2,5-bis(hydroxymethyl)furan (BHMF). Mechanism investigations illustrate that the FLPs active sites enhance the adsorption and activation of catalyst for BHMF, decreasing the activation energy of rate-determining step. Simultaneously, the FLPs sites induce the electron transfer of the catalyst, generating a novel Au-Pd-CeO 2 interface that promotes the adsorption of molecule oxygen and the formation of the superoxide radical. Thereby, the Au x Pd y /P T -CeO 2 catalysts enable superior catalytic performance, achieving a satisfactory turnover frequency of 55.29 h −1 and a highly FDCA yield of 94.0 %. Such interfacial FLPs sites exhibit the great potentials for the selective oxidation of various unsaturated compounds.
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.
Electrocatalysis using 5-hydroxylmethylfurfural (HMF) as a substrate to produce 2,5-furandicarboxylic (FDCA) is a potentially sustainable and mild route to harvest both value-added chemicals and clean energy hydrogen. However, the poor chemical and thermal stability of HMF has impeded its storage and industrialization. Additionally, the uncontrollability, scalability, and cost of catalyst preparation methods are rarely considered in this field. Herein, we capitalize on the spontaneous and harmful corrosion phenomenon occurring under natural conditions to prepare efficient Co-based catalysts for the electrooxidation 2,5-bis(hydroxymethyl)furan (BHMF) with more stable dihydroxy groups, coupled with hydrogen evolution. The preparation of electrocatalysts through corrosion engineering is a straightforward, cost-effective, highly feasible, and scalable approach, requiring minimal equipment. In the optimal concentration of 200 mM BHMF, an ultrahigh current density of 1981.7 mA cm −2 was achieved at 2.293 V vs. RHE, contributed by both BHMF oxidation and oxygen evolution reaction (OER). Chronoamperometric electrolysis realized efficient FDCA production with 95.4% yield and 96.5% faradaic efficiency (FE) at an ultralow potential of 1.4 V vs. RHE. Since it is etched and grown on the substrate itself, the catalyst prepared by corrosion engineering is very stable and undergoes ten successive chronoamperometric electrolysis without significant structural or performance failure. Moreover, kinetic analyses are investigated to explore the origin of catalytic activity and reaction energy barrier. Finally, to further realize the potential of FDCA and H 2 production in practical application, we innovatively designed a device with a two-electrode electrolyzer and a solar cell in series to drive BHMF electrooxidation with outdoor sunlight. The complete conversion of BHMF only takes 90 min, achieving a 93.5% FDCA yield and nearly theoretical hydrogen evolution.
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