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 (Co_xCu_y‐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 mol_FDMC mol_Co⁻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‐N_x 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.

中文翻译：

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N掺杂碳载CoCu双金属催化剂对5-羟甲基糠醛的氧化酯化反应

由生物质衍生的5-羟甲基糠醛（HMF）直接制备呋喃-2,5-二甲基羧酸酯（FDMC）是一种很有前途的可再生单体。在此贡献中，精心设计的N掺杂碳载CoCu双金属催化剂（Co _x Cu _y -NC; x / y = 9：1、7：3、4：6，代表了Co和Cu的设计摩尔比在催化剂），它可以提供95％的期望的产率FDMC轻度和无碱基的条件下（共₇的Cu ₃ -NC，2巴Ô ₂，80℃，4小时），用于HMF的氧化酯化描述。值得注意的是，FDMC形成速率为6.1 mol _FDMC  mol _Co ^-1在Co ₇ Cu ₃ -NC上达到 h ^-1，这是迄今为止Co基催化体系中最高的催化效率。已经证明，在Co ₇ Cu ₃ -NC催化剂中掺杂铜会带来更多的活性位点（Co-N _x物种），并且具有更强的分子氧活化能力。Co ₇ Cu ₃ -NC表面N含量的增加也提高了催化剂的碱度，这有利于HMF氧化酯化反应过程中的氢提取过程。这些发现可能为合成可持续的生物基聚合物单体铺平了有效而绿色的道路。