摘要
A radical C−C-coupling reaction of acetonitrile into succinonitrile over hydrophobic TiO_(2) photocatalyst with enhanced catalytic activity was developed.In addition,the usage of a flow reactor further improved the photon utilization efficiency for succinonitrile synthesis at room temperature.The space time yield of succinonitrile reached 55.59μmol/(g·h)over hydrophobic TiO_(2) catalyst,which was much higher than that of pristine TiO_(2)(4.23μmol/(g·h)).Mechanistic studies revealed that the hydrophobic modification of TiO_(2) promoted the separation and transfer of photogenerated carriers,as well as suppressed their recombination.Hydrophobic TiO_(2) also enhanced the adsorption of−CH3 of acetonitrile,thus facilitating the activation of C−H bond and the utilization efficiency of photocarriers.
丁二腈作为重要精细化工中间体,在医药、日化、工业纤维等领域应用广泛。光催化为在温和条件下乙腈高选择性生成C-C偶联化学品提供了新途径,但受限于光子效率低,催化性能有待提升。本研究采用水热法制备了疏水性TiO_(2)基光催化剂,在流动反应器中实现了乙腈向丁二腈的选择性转化。疏水性TiO_(2)光催化剂因光吸收能力增强,显著提升了丁二腈的时空产率,丁二腈时空产率高达55.59μmol/(g·h),明显高于未改性TiO_(2)催化剂(丁二腈时空产率仅为4.23μmol/(g·h))。实验研究表明,疏水性TiO_(2)表面增强了对乙腈-CH3基团的吸附,促进了光生载流子消耗,进而实现·CH2CN的C-C偶联生成丁二腈。同时,疏水改性促进了光生载流子分离与转移,提升了光催化活性。本工作基于流动相光催化反应器,通过疏水性改性增强C-C偶联反应活性,实现高附加值化学品的合成,为高效光催化丁二腈合成提供一种新思路。
出处
《燃料化学学报(中英文)》
2025年第12期1807-1816,共10页
Journal of Fuel Chemistry and Technology
基金
supported by the National Key R&D Program of China(2021YFF0500703)
Natural Science Foundation of Shanghai(22JC1404200)
Program of Shanghai Academic/Technology Research Leader(20XD1404000)
Natural Science Foundation of China(U22B20136,22293023)
Science and Technology Major Project of Inner Mongolia(2021ZD0042)
the Youth Innovation Promotion Association of CAS。
作者简介
Corresponding author:代元元(1990),博士,内蒙古鄂尔多斯电力冶金集团股份有限公司工业技术研究院研究员,主要研究领域聚焦工业催化剂研发及多能耦合利用,E-mail:daiyuanyuan@chinaerdos.com;Corresponding author:钟良枢.E-mail:niuqiang@chinaerdos.com;龚坤(1995),博士,研究方向为多能互补催化碳基分子制清洁燃料和高附加值化学品,gongkun@chinaerdos.com;牛强(1984),博士,内蒙古鄂尔多斯电力冶金集团股份有限公司工业技术研究院院长,研究方向涵盖催化剂工业应用、碳捕集利用与封存(CCUS)技术以及固体废物回收利用等领域,niuqiang@chinaerdos.com。
