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

呋喃 5-羟甲基糠醛 催化作用 氧气 化学 有机化学 无机化学
作者
Jia‐nan Teng,Guangyue Xu,Yao Fu
出处
期刊:Acta Physico-chimica Sinica [Acta Physico-Chimica Sinica & University Chemistry Editorial Office, Peking University]
卷期号:: 2204031- 被引量:1
标识
DOI:10.3866/pku.whxb202204031
摘要

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 °C 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.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
大幅提高文件上传限制,最高150M (2024-4-1)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
qiaokizhang完成签到,获得积分10
刚刚
Azur1完成签到 ,获得积分10
刚刚
coco完成签到,获得积分20
刚刚
浅眸流年完成签到,获得积分10
1秒前
326503177完成签到,获得积分10
2秒前
goldNAN完成签到,获得积分10
2秒前
kim应助经竺采纳,获得10
2秒前
勇往直前完成签到,获得积分10
2秒前
菜菜鱼发布了新的文献求助10
3秒前
从容芮应助温眼张采纳,获得10
3秒前
李健的小迷弟应助是微微采纳,获得30
4秒前
精明寒松完成签到 ,获得积分10
5秒前
科研通AI2S应助连世开采纳,获得10
5秒前
聪明夏天完成签到,获得积分10
6秒前
tetrakis完成签到,获得积分10
6秒前
今夕何夕完成签到,获得积分10
7秒前
沧海一兰完成签到,获得积分10
8秒前
幸福大碗完成签到,获得积分10
9秒前
小庄完成签到 ,获得积分10
9秒前
jtksbf完成签到 ,获得积分10
9秒前
谨慎寻冬完成签到,获得积分10
9秒前
10秒前
TUTU应助李高宗采纳,获得20
11秒前
Owen应助啦啦啦采纳,获得10
11秒前
SYC完成签到,获得积分10
12秒前
Tim完成签到 ,获得积分10
12秒前
陈陈完成签到,获得积分10
15秒前
tesla发布了新的文献求助20
15秒前
big ben完成签到 ,获得积分10
15秒前
典雅的太阳完成签到,获得积分10
15秒前
杠赛来完成签到,获得积分10
16秒前
DJ完成签到,获得积分10
16秒前
scienceljk完成签到,获得积分10
18秒前
ning完成签到,获得积分10
18秒前
pl完成签到 ,获得积分10
18秒前
万能图书馆应助fdpb采纳,获得10
18秒前
啊呜完成签到,获得积分10
19秒前
不甜完成签到 ,获得积分10
19秒前
Simmy完成签到,获得积分10
19秒前
11完成签到,获得积分10
20秒前
高分求助中
Sustainability in Tides Chemistry 2000
Microlepidoptera Palaearctica, Volumes 1 and 3 - 13 (12-Volume Set) [German] 1122
Дружба 友好报 (1957-1958) 1000
The Data Economy: Tools and Applications 1000
Mantiden - Faszinierende Lauerjäger – Buch gebraucht kaufen 700
PraxisRatgeber Mantiden., faszinierende Lauerjäger. – Buch gebraucht kaufe 700
A Dissection Guide & Atlas to the Rabbit 600
热门求助领域 (近24小时)
化学 医学 生物 材料科学 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 基因 遗传学 催化作用 物理化学 免疫学 量子力学 细胞生物学
热门帖子
关注 科研通微信公众号,转发送积分 3099895
求助须知:如何正确求助?哪些是违规求助? 2751334
关于积分的说明 7613172
捐赠科研通 2403314
什么是DOI,文献DOI怎么找? 1275235
科研通“疑难数据库(出版商)”最低求助积分说明 616318
版权声明 599053