物理化学学报2024,Vol.40Issue(1) :26-27.DOI:10.3866/PKU.WHXB202303003

WO3-TiO2负载的Pt单原子催化剂光热协同催化丙烷和丙烯氧化

Photo-Thermo Catalytic Oxidation of C3H8 and C3H6 over the WO3-TiO2 Supported Pt Single-Atom Catalyst

朱锐杰 康磊磊 李林 潘晓丽 王华 苏杨 李广亿 程鸿魁 李仁贵 刘晓艳 王爱琴
物理化学学报2024,Vol.40Issue(1) :26-27.DOI:10.3866/PKU.WHXB202303003

WO3-TiO2负载的Pt单原子催化剂光热协同催化丙烷和丙烯氧化

Photo-Thermo Catalytic Oxidation of C3H8 and C3H6 over the WO3-TiO2 Supported Pt Single-Atom Catalyst

朱锐杰 1康磊磊 2李林 2潘晓丽 2王华 2苏杨 2李广亿 2程鸿魁 3李仁贵 4刘晓艳 5王爱琴1
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作者信息

  • 1. 中国科学院大连化学物理研究所,中国科学院航天催化材料重点实验室,能源材料化学协同创新中心,辽宁 大连 116023;中国科学院大学,北京 100049
  • 2. 中国科学院大连化学物理研究所,中国科学院航天催化材料重点实验室,能源材料化学协同创新中心,辽宁 大连 116023
  • 3. 正大能源材料(大连)有限公司,辽宁 大连 116021
  • 4. 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,辽宁 大连 116023;大连洁净能源国家实验室,辽宁 大连 116023
  • 5. 中国科学院大连化学物理研究所,中国科学院航天催化材料重点实验室,能源材料化学协同创新中心,辽宁 大连 116023;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,辽宁 大连 116023
  • 折叠

摘要

单原子催化剂(single-atom catalyst,SAC)可以最大化金属原子利用率,并具有独特的电子特性,已经在各种催化反应中进行了广泛的探索.然而,与纳米催化剂相比,贵金属SAC在烃类氧化反应中通常被认为是不活泼的.在本文中,证明了WO3-TiO2负载的Pt SAC(Pt1/WO3-TiO2)在光热协同催化氧化C3H8和C3H6这两种典型的挥发性有机化合物(VOCs)中表现出比相应的纳米催化剂(PtNP/WO3-TiO2)高得多的活性.研究发现,Pt1/WO3-TiO2和PtNP/WO3-TiO2都可以通过克服氧中毒来提高光热协同催化C3H8氧化的活性.值得注意的是,Pt1/WO3-TiO2的反应速率达到了3792 µmol∙gPt-1∙s-1,这对C3H8氧化是一个新的突破.更有趣的是,由于C3H6在PtNP/WO3-TiO2上的强吸附导致催化剂C3H6中毒,因此PtNP/WO3-TiO2上的光热协同催化C3H6氧化无法进行.但是,得益于C3H6和Pt单原子之间适中的相互作用,Pt1/WO3-TiO2上的C3H6中毒在光照下可以被克服.因此,Pt1/WO3-TiO2在光热协同催化C3H6氧化中显示出更高的活性.这项工作表明,SAC的优势不仅在于节约贵金属,还在于可以根据其独特的电子特性发现新的催化反应.

Abstract

Catalytic oxidation is a commonly employed technology in the industry for removing volatile organic compounds(VOCs)due to its exceptional efficiency under mild operating conditions.Although supported Pt-based nano-catalysts are recognized widely as one of the most promising and extensively used industrial catalysts for VOC abatement,their practical application,and development are restricted by their exorbitant cost.Single-atom catalyst(SAC)with maximized metal utilization and exclusive electronic character has been explored extensively in various catalytic reactions.However,Pt SAC is usually deemed to be inactive in hydrocarbon oxidation reactions in thermal catalysis,compared with its nanoparticle counterpart.Here,we demonstrate that the WO3-TiO2 supported Pt SAC(Pt1/WO3-TiO2)exhibits much higher activities than the corresponding nanoparticle catalyst(PtNP/WO3-TiO2)in photo-thermo catalytic oxidation of C3H8 and C3H6,which represent different kinds of typical VOCs.A key finding is that the activities of Pt1/WO3-TiO2 and PtNP/WO3-TiO2 can be accelerated in photo-thermo catalytic C3H8 oxidation by overcoming oxygen poisoning.Upon the light irradiation,the apparent active energy(Ea)of the Pt1/WO3-TiO2 and PtNP/WO3-TiO2 decline from 116 to 60 kJ·mol-1 and from 103 to 30 kJ·mol-1,respectively,substantiating their effectiveness in photo-thermo catalysis.Notably,a substantially higher reaction rate of 3792 µmol∙gPt-1∙s-1 on the Pt1/WO3-TiO2 is achieved,which should be a benchmark for C3H8 oxidation.More intriguingly,photo-thermo catalytic C3H6 oxidation on the PtNP/WO3-TiO2 is prohibited due to the strong adsorption-induced C3H6 poisoning on the Pt nanoparticles,for which the Ea of the PtNP/WO3-TiO2 catalyst for C3H6 oxidation is maintained at approximately 55 kJ·mol-1,regardless of the light irradiation.In comparison,the C3H6 poisoning on the Pt1/WO3-TiO2 can be mitigated by light illumination,where the Ea of the Pt1/WO3-TiO2 catalyst for C3H6 oxidation dramatically reduced from 49 to 16 kJ·mol-1,signifying that the high energy barrier of C3H6 oxidation can be mediated by the light.Profiting from the apt affinity between C3H6 and Pt single atoms,the photogenerated electrons accumulated on the Pt single atoms produce repulsive force towards the electron-rich C3H6 molecules,which is conducive to the C3H6 desorption from the Pt1/WO3-TiO2.Therefore,the Pt1/WO3-TiO2 exhibits enhanced activity in photo-thermo catalytic C3H6 oxidation.This study exemplifies that the advantages of SAC are not only saving the consumption of precious metals but also discovering new catalytic reactions on the account of the specific electronic characteristic.

关键词

单原子催化剂/光热协同催化/氧化反应/氧中毒/丙烯中毒

Key words

Single-atom catalyst/Photo-thermo catalysis/Oxidation reaction/Oxygen poisoning/Propylene poisoning

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基金项目

国家自然科学基金(22102180)

辽宁省兴辽英才计划(XLYC2007070)

中国科学院洁净能源创新研究院合作基金(DNL202002)

中央高校基本科研业务费专项资金(20720220009)

出版年

2024
物理化学学报
中国化学会

物理化学学报

CSTPCD北大核心
影响因子:0.951
ISSN:1000-6818
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