铂负载二氧化钛光催化剂在单波长下苯乙炔高选择性加氢

引用本文: 连菊红, 柴玉超, 祁育, 郭向阳, 关乃佳, 李兰冬, 章福祥. 铂负载二氧化钛光催化剂在单波长下苯乙炔高选择性加氢[J]. 催化学报, 2020, 41(4): 598-603. doi: S1872-2067(19)63453-4 shu

Citation: Juhong Lian, Yuchao Chai, Yu Qi, Xiangyang Guo, Naijia Guan, Landong Li, Fuxiang Zhang. Unexpectedly selective hydrogenation of phenylacetylene to styrene on titania supported platinum photocatalyst under 385 nm monochromatic light irradiation[J]. Chinese Journal of Catalysis, 2020, 41(4): 598-603. doi: S1872-2067(19)63453-4 shu

铂负载二氧化钛光催化剂在单波长下苯乙炔高选择性加氢

a 南开大学, 材料科学与工程学院, 国家新材料研究院, 天津 300350;
b 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 洁净能源国家实验室(筹), 能源材料化学协同创新中心, 辽宁大连 116023
基金项目:
国家自然科学基金（21633009）；大连市杰出青年科学基金项目（2017RJ02）；兴辽人才计划（XLYC1807241）.

摘要: 苯乙烯是一种非常重要的化工原料，它是工业上生产聚苯乙烯、树脂和丁苯橡胶的重要单体，而苯乙烯单体中经常含有苯乙炔杂质，影响苯乙烯的聚合性能，因此研究苯乙炔选择性加氢生成苯乙烯具有十分重要的工业意义.传统的热催化苯乙炔加氢反应会用到易燃易爆的氢气，引起操作的危险性，因此，开发具有环境友好型的加氢反应体系具有很重要的意义.光催化加氢反应利用光生电子强的还原能力，还原质子产生活性的氢物种加氢，相较于传统的热催化使用氢气作为加氢源加氢，能够在温和的条件下实现高选择性加氢.基于此，本文利用Pt/TiO₂作为光催化剂，甲醇作为加氢源实现了在385nm单波长光照下苯乙炔的高选择性加氢.
首先，我们利用光沉积的方法将Pt负载在TiO₂的表面，通过透射电子显微镜图像和紫外可见吸收光谱表征了负载在TiO₂表面Pt的颗粒分布和光学性质.结果表明负载的Pt的颗粒大约在5nm左右，Pt的负载改变了TiO₂在可见光区的吸收性能.XPS结果显示，通过光沉积得到的Pt的价态为金属态和氧化态共存.光催化苯乙炔加氢实验表明，Pt/TiO₂催化剂在室温常压条件下不仅具有高的苯乙炔光催化转化率，当光照达8h后，苯乙炔完全转化，而且在6h之内苯乙烯选择性保持在91.3%，具有高的苯乙烯选择性.通过对负载的Pt的含量进行了优化，筛选出当Pt的负载量为1wt%时，苯乙炔的转化率最高.为了对比，利用传统热催化的方法氢气作为加氢源进行了苯乙炔加氢实验，结果发现，使用氢气作为加氢源时，虽然苯乙炔的转化率为100%，但产物是过加氢的产物乙苯.这主要是因为在光催化反应过程中，TiO₂导带上的电子迁移至Pt颗粒上，导致Pt的电子密度增加，Pt颗粒表面高的电子密度有利于加氢中间产物苯乙烯的脱附，因此，在光催化加氢过程中不会发生过加氢反应，具有高的苯乙烯选择性.同时，扩展实验表明，Pt/TiO₂光催化剂对其他类型的炔烃加氢也具有高的选择性，表明Pt/TiO₂光催化炔烃加氢具有普适性.由此可见，光催化炔烃加氢未来将成为一种环境友好而高效的方法.

关键词:

English

Unexpectedly selective hydrogenation of phenylacetylene to styrene on titania supported platinum photocatalyst under 385 nm monochromatic light irradiation

a School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350, China;
b State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023, Liaoning, China
Received Date: 11 November 2019
Revised Date: 30 November 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21633009), Dalian Science Foundation for Distinguished Young Scholars (2017RJ02), and the Liaoning Revitalization Talents Program (XLYC1807241).

Abstract: Conversion of alkynes to alkenes by photocatalysis has inspired extensive interest, but it is still challenging to obtain both high conversion and selectivity. Here we first demonstrate the photocatalytic conversion of phenylacetylene (PLE) to styrene (STE) with both high conversion and selectivity by using the titania (TiO₂) supported platinum (Pt) as photocatalyst under 385 nm monochromatic light irradiation. It is demonstrated that the conversion rate of PLE is strongly dependent on the content of Pt cocatalyst loaded on the surface of TiO₂. Based on our optimization, the conversion of PLE and the selectivity towards STE on the 1 wt% Pt/TiO₂ photocatalyst can unexpectedly reach as high as 92.4% and 91.3%, respectively. The highly selective photocatalytic hydrogenation can well be extended to the conversion of other typical alkynes to alkenes, demonstrating the generality of selective hydrogenation of C≡C over the Pt/TiO₂ photocatalyst.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

铂负载二氧化钛光催化剂在单波长下苯乙炔高选择性加氢

English

Unexpectedly selective hydrogenation of phenylacetylene to styrene on titania supported platinum photocatalyst under 385 nm monochromatic light irradiation

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

铂负载二氧化钛光催化剂在单波长下苯乙炔高选择性加氢

English

Unexpectedly selective hydrogenation of phenylacetylene to styrene on titania supported platinum photocatalyst under 385 nm monochromatic light irradiation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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