铜基非贵金属异相催化剂在环境修复中的应用

doi:10.1016/S1872-2067(17)62996-6

催化学报 ›› 2018, Vol. 39 ›› Issue (4): 566-582.DOI: 10.1016/S1872-2067(17)62996-6

铜基非贵金属异相催化剂在环境修复中的应用

方亚蓉, 郭彦炳

华中师范大学化学学院环境与应用化学研究所, 农药与化学生物学教育部重点实验室, 湖北武汉 430079

收稿日期:2017-11-30 修回日期:2017-12-31 出版日期:2018-04-18 发布日期:2018-04-08
通讯作者: 郭彦炳
基金资助:
国家"千人计划青年人才"启动基金；高等学校学科创新引智计划（111计划，B17019）；国家自然科学基金（21777051）.

Copper-based non-precious metal heterogeneous catalysts for environmental remediation

Yarong Fang, Yanbing Guo

Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental and Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, Hubei, China

Received:2017-11-30 Revised:2017-12-31 Online:2018-04-18 Published:2018-04-08
Contact: 10.1016/S1872-2067(17)62996-6
Supported by:
The authors are grateful for the financial support from the Recruitment Program of Global Young Experts start-up funds, the Program of Introducing Talents of Discipline to Universities of China (111 Program, B17019), and the National Natural Sci-ence Foundation of China (21777051).

摘要/Abstract

摘要：

近年来，全球经济和工业高速发展带来的环境问题，不仅严重影响着经济社会的可持续发展，更极大地危害着人类健康.石油化工、医药生产和交通运输等过程产生的气、液、固相污染物可直接或间接造成臭氧层空洞、光化学烟雾及水体污染等重大环境问题.气相污染物中，CO和可挥发性有机物（VOCs）不仅具有生物毒性，更是形成光化学烟雾等大气污染的主要前驱体.NO_x和SO₂会造成酸雨的形成，极大地破坏生态系统.工业废水中难分解的有机污染物可对环境造成持续性破坏.而不完全燃烧产生的碳烟颗粒物不仅影响气候和大气环境，同时可导致心血管疾病高发，危害人体健康.源头控制是环境污染治理的关键，而催化净化是当前污染物源头控制最有效的技术之一.因此，设计和开发稳定、高效的环境修复催化剂是科学家们面临的一个关键问题.传统贵金属（Pt，Rh，Pd）催化剂虽然催化活性高，但是存在价格昂贵且易中毒等不足.而过渡金属及其氧化物因具有高活性、价格低廉和高储量等特点有望成为贵金属的替代催化剂.
铜是具有3d轨道的过渡金属，有活泼的物理化学性质，是工业中大量应用的有色金属.铜基氧化物因高氧化还原电势和低环境危害被广泛应用于热催化、电催化和光催化.基于文献报道，铜基催化剂主要分为三类：铜氧化物（CuO_x），负载型铜氧化物（CuO_x/support）和固溶体铜氧化物（CuO_x-X）.本篇综述首先探讨了铜氧化物的价态、晶体结构、形貌、暴露晶面以及载体与催化剂活性之间的内在联系，阐明铜基催化剂结构与性能的构效关系及高效催化剂的设计原则；继而全面总结了近年来不同类型的铜基材料在催化净化环境污染物中的应用，主要介绍了以下5类反应：CO的催化氧化，NO_x的选择性催化还原（SCR），VOCs的完全燃烧，废水中有机污染物降解，以及碳烟颗粒物催化燃烧.我们深入阐述铜氧化物的催化活性位点和催化机制；分析负载型铜基催化剂的比表面积、分散度、协同作用和界面作用对催化剂的活性和稳定性的影响；阐明固溶体催化剂的独特原子组成设计与性能关系，为高效催化剂设计提供思路.此外，本综述对铜基催化剂在环境催化中的研究现状以及尚未解决的问题进行了剖析与展望.通过铜氧化物表面调控，复合催化剂的界面调控，具有更高稳定性和抗中毒性的高效催化剂有望开发成功，而团簇及单原子铜催化剂也有望在此领域有所突破.

关键词: 铜基催化剂, 异相催化, CO催化氧化, 选择性催化还原, 可挥发性有机物氧化, 有机污染物降解, 碳烟颗粒物催化燃烧

Abstract:

This paper presents a detailed review of copper-based catalysts used in wide-ranging environmental remediation, including gas, liquid and solid phase pollutant elimination. Latest advances in the remarkable catalytic activity of copper-based catalysts, including bulk CuO_x, supported CuO_x, and solid solution CuO_x-X are emphasized. The structure-activity relationships among the crystal structure, morphology, catalyst support, and catalytic performance in specific catalytic reactions for environmental remediation are discussed. Furthermore, current obstacles faced by Cu-based catalysts and potential strategies to address them have been proposed, which may aid the future research and development of highly efficient Cu-based non-precious metal catalysts.

Key words: Copper-based catalyst, Heterogeneous reaction, CO oxidation, Selective catalytic reduction, Volatile organic compounds oxidation, Organic pollutant degradation, Soot combustion

方亚蓉, 郭彦炳. 铜基非贵金属异相催化剂在环境修复中的应用[J]. 催化学报, 2018, 39(4): 566-582.

Yarong Fang, Yanbing Guo. Copper-based non-precious metal heterogeneous catalysts for environmental remediation[J]. Chinese Journal of Catalysis, 2018, 39(4): 566-582.

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铜基非贵金属异相催化剂在环境修复中的应用

Copper-based non-precious metal heterogeneous catalysts for environmental remediation

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