The catalytic oxidation of biomass-derived 5-(hydroxymethyl)­furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a promising route to produce bioplastic monomers. Developing budget non-noble-metal catalysts for the efficient air-oxidation of HMF to FDCA is highly demanded but challenging. In this contribution, we present a facile and green vitamin C (VC)-assisted solid-state grinding method for synthesizing mesoporous Mn–Co spinel oxides with improved oxygen vacancy (Ov) concentration, which could offer a satisfactory FDCA yield of 96% using air as the oxygen source (130 °C, 1.5 MPa air, 3 h). Remarkably, Mn3Co2O x –0.3VC offered an outstanding FDCA formation rate of 2611 μmolFDCA·gcat –1·h–1, which is the highest value achieved so far among ever-described Mn-based catalysts. Based on experimental studies, the catalytic performance of Mn–Co oxides for the oxidation of HMF corresponds well with their Mn–O bond intensities. The catalyst with a higher Ov concentration exhibits a weaker Mn–O bond intensity, which brings about a higher lattice oxygen (OL) reactivity. More importantly, density functional theory (DFT) calculations also demonstrate that increasing the Ov amount not only boosts the OL reactivity of the catalyst by reducing the formation energy of Ov but also contributes to the adsorption and activation of O2 over the catalyst by significantly cutting down the O2 adsorption energy, thus leading to an enhanced catalytic activity for the oxidation of HMF. Besides, the catalyst with a higher Ov concentration provides a stronger substrate adsorption ability, which may also promote the HMF oxidation reactions. This work provides insights into the role of Ov over Mn-based oxides in oxidation catalysis by a Mars–van Krevelen mechanism.

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The direct fabrication of furan‐2,5‐dimethylcarboxylate (FDMC), a promising renewable monomer, from biomass‐derived 5‐hydroxymethylfurfural (HMF) is a cutting‐edge process. In this contribution, an elaborately designed N‐doped carbon‐supported CoCu bimetallic catalyst (CoxCuy‐NC; x/y=9:1, 7:3, 4:6, which represents the designed molar ratio of Co and Cu in the catalyst), which could offer a desirable FDMC yield of 95 % under mild and base‐free conditions (Co7Cu3‐NC, 2 bar O2, 80 °C, 4 h) is described for the oxidative esterification of HMF. Notably, an FDMC formation rate of 6.1 molFDMC molCo−1 h−1 was achieved over Co7Cu3‐NC, which represents the highest catalytic efficiency so far among Co‐based catalytic systems. It has been demonstrated that Cu‐doping in Co7Cu3‐NC catalyst brings about more active sites (Co‐Nx species) with stronger molecular oxygen activation ability. The increase of surface N content of Co7Cu3‐NC also improves basicity of the catalyst, which favors the hydrogen abstraction process during the HMF oxidative esterification reaction. These findings may pave an efficient and green way for the synthesis of sustainable bio‐based polymer monomers.

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