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用于将5-羟甲基糠醛水相好氧氧化为2,5-呋喃二甲酸的钴-二氧化铈二元氧化物纳米结:界面的作用

Cobalt-Ceria Binary Oxide Nanojunctions for Aqueous-Phase Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid: The Role of Interfaces.

作者信息

Chen Aicheng, Li Tingting, Zhang Qian, Zhu Hu

机构信息

Fujian-Taiwan Science and Technology Cooperation Base of Biomedical Materials and Tissue Engineering, Engineering Research Center of Industrial Biocatalysis, Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, P. R. China.

出版信息

Langmuir. 2023 Aug 22;39(33):11750-11759. doi: 10.1021/acs.langmuir.3c01380. Epub 2023 Aug 9.

Abstract

Cobalt-ceria binary oxide nanojunctions were prepared by a sol-gel method with various chelating agents. The formed interfaces among CeO and CoO can promote the generation of nucleophilic O from O and then tune the catalytic oxidizability of the as-prepared CoCe nanojunctions. Given the results of HMF oxidations, malic acid as a complexing agent during the preparation process of the cobalt-ceria binary oxide nanojunctions can lead to a good catalytic performance on HMF oxidations to FDCA, and a remarkable FDCA selectivity of 92.3% and almost 100% HMF conversion were obtained at 110 °C under O and alkali conditions. By comparing the catalytic performance of the nanojunctions and physical mixing of cobalt-ceria binary oxide on oxidations of HMF, 5-hydroxymethyl-2-furancarboxylic acid (HFCA), and 5-formyl-2-furancarboxylic acid (FFCA), the interfaces intrinsically enhanced the FDCA yield dominantly via boosting the HMF oxidation to HFCA with O during the stepwise oxidation of HMF to FDCA. It can be enlightening that the introduction of the active sites for transforming O to O to promote the transformation of HMF into HFCA is the key to boosting the selective aerobic oxidation of HMF to FDCA.

摘要

采用溶胶-凝胶法并使用各种螯合剂制备了钴-二氧化铈二元氧化物纳米结。CeO和CoO之间形成的界面可促进从O生成亲核O,进而调节所制备的CoCe纳米结的催化氧化性能。根据HMF氧化的结果,在钴-二氧化铈二元氧化物纳米结制备过程中使用苹果酸作为络合剂,可对HMF氧化生成FDCA产生良好的催化性能,在O2和碱性条件下于110°C时可获得92.3%的显著FDCA选择性和几乎100%的HMF转化率。通过比较纳米结与钴-二氧化铈二元氧化物物理混合物对HMF、5-羟甲基-2-呋喃羧酸(HFCA)和5-甲酰基-2-呋喃羧酸(FFCA)氧化的催化性能,在HMF逐步氧化为FDCA的过程中,界面通过促进HMF与O2氧化生成HFCA,本质上主要提高了FDCA的产率。引入将O2转化为O的活性位点以促进HMF转化为HFCA是提高HMF选择性有氧氧化为FDCA的关键,这一点具有启发性。

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