摘要
利用氮化碳光催化剂催化生物质选择性转化,不仅扩展了非金属催化剂的应用领域,而且能够缓解化工产品过度依赖于化石能源的现状。2,5-二甲酰基呋喃是生产多种化工产品的关键中间体,本研究将均苯四甲酸二酐引入氮化碳骨架,并利用H_(2)O_(2)进行处理,制备了含有氮羟基的改性氮化碳光催化剂,并探究其在可见光激发下将生物质平台分子5-羟甲基糠醛通过绿色化学的方法选择性地氧化为2,5-二甲酰基呋喃的性能。结果表明:经过H_(2)O_(2)改性的催化剂,在可见光激发下可以产生氮氧自由基,使得底物分子侧链上的羟基选择性地氧化为醛基,避免了在水相光催化条件下可能产生的多种活性氧物种引起的开环、矿化反应等副反应。特别是,当光催化剂前驱体中蜜勒胺与均苯四甲酸二酐的比例为1:2时,在400 nm LED光源激发下,目标产物的选择性可达到96.2%。
Using carbon nitride photocatalysts to catalyze the selective conversion of biomass platform molecules could not only expand the application fields of non-metallic catalysts but also alleviate the dependence on fossil energy in chemical manufacturing.2,5-diformylfuran is an indispensable intermediate for the production of value-added chemicals.In this study,pyromellitic dianhydride and melem were used as the precursors.The pyromellitic dianhydride monomer was incorporated into the carbon nitride skeleton by high-temperature heat-treatment,and the catalysts were further treated with H_(2)O_(2).Finally non-metallic carbon nitride photocatalysts containing nitrogen hydroxyl groups were prepared.Moreover,its performance in the selective oxidation of 5-hydroxymethylfurfural into2,5-diformylfuran under visible light excitation was investigated.The results showed that H_(2)O_(2)-treated samples could generate nitroxide radicals under light irradiation,resulting in the selective oxidation of hydroxyl groups on the side chains of 5-hydroxymethylfurfural molecules into aldehyde groups,avoiding undesired side-reactions (ring-opening,mineralization reactions,etc.) caused by various reactive oxygen species that may be generated in aqueous solutions.In particular,under the excitation of an LED light source with a specific wavelength (400 nm),when the ratio of melem to PMDA precursor was 1:2,the selectivity of 2,5-diformylfuran over the photocatalyst could reach 96.2%.
作者
刘雪晨
曾滴
周沅逸
王海鹏
张玲
王文中
LIU Xuechen;ZENG Di;ZHOU Yuanyi;WANG Haipeng;ZHANG Ling;WANG Wenzhong(Shanghai Institute of Ceramics,Chinese Academy of Sciences,Shanghai 200050,China;University of Chinese Academy of Sciences,Beijing 100049,China;Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,Hangzhou 310024,China)
出处
《无机材料学报》
SCIE
EI
CAS
CSCD
北大核心
2022年第1期38-44,I0001,I0002,共9页
Journal of Inorganic Materials
基金
国家自然科学基金(51972327,51972325)。
