Nitrogen- and phosphorus-codoped carbon-based catalyst for acetylene hydrochlorination
Nitrogen- and phosphorus-codoped carbon-based catalyst for acetylene hydrochlorination
复制标题
氮磷共掺杂碳基乙炔氢氯化催化剂
DOI：
10.1016/j.jcat.2019.03.044
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发表时间：
2019-05-01
影响因子：
7.3
通讯作者：
Li, Xiaonian
中科院分区：
文献类型：
--
作者：
Zhao, Jia;Wang, Bolin;Li, Xiaonian
催化乙炔氢氯化法生产氯乙烯单体（VCM）具有重要的工业意义，因为VCM是聚氯乙烯的前体。最近有人提出用碳基材料替代目前用于氯乙烯单体生产的剧毒氯化汞催化剂，这种材料既环保又具有成本效益。然而，由于缺乏有效的活性位点，它们的反应性相对较低，因此它们的实际应用受到限制。碳基材料的结构工程已被证明是调整其物理和化学性质的有力策略，这些性质与其催化性能直接相关。本论文以1-乙基磺酸盐-3-甲基咪唑磷酸二氢盐[ESO（3）HMim（+）H（2）PO（4）（-）]为磷源，1-乙基-3-甲基咪唑双氰胺[EMim]N+（CN）（2）（-）]为氮源，其显示出出乎意料的高乙炔氢氯化活性，时空产率可与一些开发良好的Au基催化剂的时空产率相比。结合密度泛函理论计算的实验观察表明，与吡啶结构中的氮键合的磷原子是性能最好的NP-C600催化剂的活性位点。本工作为碳基无金属材料的结构调整提供了一种有前途的方法，以有效地优化其催化机理和应用。(C)2019爱思唯尔公司All rights reserved.
Catalyzed acetylene hydrochlorination for vinyl chloride monomer (VCM) production is of great industrial importance, as VCM is the precursor for polyvinyl chloride. Carbon-based materials have recently been proposed as environmentally friendly and cost-efficient substitutes for highly toxic mercuric chloride catalyst, which is currently used for VCM manufacture. However, their practical application has been limited because of their relatively low reactivity, due to the lack of efficient active sites. Structural engineering of carbon-based materials has been proved a powerful strategy for tuning their physical and chemical properties, which are directly related to their catalytic properties. Here we present a novel and highly active nitrogen- and phosphorus-codoped carbon-based catalyst prepared using 1-ethylsulfo nate-3-methylimidazolium dihydrogen phosphate [ESO(3)HMim(+)H(2)PO(4)(-)] as a phosphorus source and 1-ethyl-3-methylimidazolium dicyanamide [EMim]N+(CN)(2)(-)] as a nitrogen source, which has shown unexpectedly high acetylene hydrochlorination activity with space-time yield comparable to that of some well-developed Au-based catalysts. Experimental observations in combination with density functional theory calculations demonstrated that phosphorus atoms bonded with nitrogen in the pyridine structure are the active sites for the best-performing NP-C600 catalyst. This work provides a promising method of structure tuning of carbon-based metal-free materials to effectively optimize their catalytic mechanism and applications. (C) 2019 Elsevier Inc. All rights reserved.