### CoMn@NC催化5-羟甲基糠醛常压氧化为2, 5-呋喃二甲酸二甲酯

1. 1 中国科学技术大学, 中国科学院城市污染物转化重点实验室, 安徽省生物质洁净能源重点实验室, 合肥 230026
2 合肥综合性国家科学中心, 能源研究所, 合肥 230031
• 收稿日期:2022-04-18 录用日期:2022-05-06 发布日期:2022-05-16
• 通讯作者: 傅尧 E-mail:fuyao@ustc.edu.cn
• 作者简介:第一联系人：

These authors contributed equally to this work.

• 基金资助:
国家重点研发项目(2018YFB1501604);中国科学院战略重点研究项目(XDA21060101);国家自然科学基金(21875239);国家自然科学基金(51821006);国家自然科学基金(51961135104);国家自然科学基金(21905266);中央高校基本科研业务费专项资金(WK3530000013)

### Aerobic Oxidation of 5-Hydroxymethylfurfural to Dimethyl Furan-2, 5-dicarboxylate over CoMn@NC Catalysts Using Atmospheric Oxygen

Jianan Teng1,2, Guangyue Xu1,2, Yao Fu1,2,*()

1. 1 Anhui Province Key Laboratory of Biomass Clean Energy, CAS Key Laboratory of Urban Pollutant Conversion, University of Science and Technology of China, Hefei 230026, China
2 Institute of Energy, Hefei Comprehensive National Science Center, Hefei 230031, China
• Received:2022-04-18 Accepted:2022-05-06 Published:2022-05-16
• Contact: Yao Fu E-mail:fuyao@ustc.edu.cn
• About author:Yao Fu, Email: fuyao@ustc.edu.cn; Tel.: +86-551-63607476
• Supported by:
the National Key R & D Program of China(2018YFB1501604);the Strategic Priority Research Program of the CAS(XDA21060101);the National Natural Science Foundation of China(21875239);the National Natural Science Foundation of China(51821006);the National Natural Science Foundation of China(51961135104);the National Natural Science Foundation of China(21905266);the Fundamental Research Funds for the Central Universities(WK3530000013)

2, 5-呋喃二甲酸二甲酯(DMFDCA)这一生物质衍生的增值化学品是石油基聚合物单体对苯二甲酸(TPA)的理想替代品。本研究采用一步共热解法合成了两种廉价金属修饰的氮掺杂多孔碳催化剂CoMn@NC，并将其用于5-羟甲基糠醛(HMF)在温和条件下的需氧氧化。由Co3Mn2@NC-800催化HMF在50 ℃和常压氧气的条件下反应12 h后，得到产率为85%的DMFDCA。多孔催化剂的高比表面积提高了传质效率。Co纳米粒子(NPs)和呈原子级分散的Mn与掺杂在碳中的氮配位形成M―Nx。富含吡啶氮的碳基体中的缺电子金属位点有利于HMF和氧的活化。氧形成的超氧自由基阴离子的存在确保了半缩醛中间体和5-(羟基甲基)-2-糠酸甲酯(HMMF)的羟甲基的脱氢氧化，从而高选择性得到DMFDCA。该催化剂性能稳定，可适用于各种取代芳醇。该催化体系具有用于生产聚合物单体羧基酯的应用潜力。

Abstract:

Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co3Mn2@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―Nx (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.

MSC2000:

• O643