铑/氧化锌单原子催化剂的优异CO氧化反应性能

引用本文: 韩冰, 郎睿, 唐海莲, 徐嘉, 顾向奎, 乔波涛, 刘景月. 铑/氧化锌单原子催化剂的优异CO氧化反应性能[J]. 催化学报, 2019, 40(12): 1847-1853. doi: S1872-2067(19)63411-X shu

Citation: Bing Han, Rui Lang, Hailian Tang, Jia Xu, Xiang-Kui Gu, Botao Qiao, Jingyue(Jimmy) Liu. Superior activity of Rh₁/ZnO single-atom catalyst for CO oxidation[J]. Chinese Journal of Catalysis, 2019, 40(12): 1847-1853. doi: S1872-2067(19)63411-X shu

铑/氧化锌单原子催化剂的优异CO氧化反应性能

韩冰 ^a,b, ,
郎睿 ^a, ,
唐海莲 ^a, ,
徐嘉 ^c, ,
顾向奎 ^d, ,
乔波涛 ^a,e, ,
刘景月 ^c,

a 中国科学院大连化学物理研究所中国科学院应用催化科学与技术重点实验室, 辽宁大连 116023, 中国;
b 中国科学院大学, 北京 100049, 中国;
c 亚利桑那州立大学物理系, 坦佩, 亚利桑那州 85287, 美国;
d 韦恩州立大学化学工程与材料科学系, 底特律, 密歇根州 48202, 美国;
e 大连洁净能源国家实验室, 辽宁大连 116023, 中国
基金项目:
国家自然科学基金（21606222，217776270）；辽宁省“兴辽英才计划”（XLYC1807068）；美国国家科学基金（CHE-1465057）；洁净能源研究室合作基金（180403）.

摘要: 一氧化碳（CO）低温氧化因其在基础研究和实际应用中的重要意义和价值，成为多相催化领域中研究最多的反应之一.特定氧化物和复合氧化物均具有优异的CO氧化活性，但其高温稳定性较差，且易被水和硫化物毒化，严重限制了其实际应用.贵金属具有较高的CO氧化活性，但是资源稀缺、价格较高.减小贵金属尺寸至纳米尺度能够提高反应活性并有效提高金属利用效率，但由于只有纳米粒子表面的原子能够提供吸附反应活性位，因此金属原子利用率仍有待提高.
单原子催化是多相催化领域的新概念.单原子催化剂的活性组分以原子级分散在载体上，能够实现原子利用率最大化，降低贵金属使用量.活性位点的高度非饱和配位环境使得单原子催化剂在多种反应中具有优异的反应性能，如CO氧化、水汽变换、选择性加氢和选择性氧化等反应.单原子催化剂具有相对简单和均一的化学环境，可以作为较好的系统来研究化学反应的本质，如反应活性位点和金属与载体的相互作用等.贵金属如金、铂、钯在CO氧化中具有较高活性，但是一般认为铑金属活性较差.最近几年研究表明，铑基单原子、亚纳米催化剂在CO氧化反应中可具有优异活性，表明负载型铑单原子催化剂可能是一种潜在的CO氧化高活性催化剂.
氧化锌作为CO反应催化剂载体的研究不多，因为其不可还原性使得催化剂活性不高.氧化锌纳米线（ZnO-nw）主要晶面为{10-10}，作为载体使得催化剂活性位点更为均一.本文在前期研究工作基础上成功制备了氧化锌纳米线负载的铑、金、铂单原子催化剂，并研究了其CO氧化性能.采用氧化锌载体一是因为其不可还原性，可以最大程度降低载体的影响，二是其单一暴露晶面{10-10}可以使催化剂均一程度最大化.研究发现，在所制备的催化剂中Rh₁/ZnO-nw具有最高反应活性和良好的反应稳定性.CO完全转化温度为210℃，明显低于其它氧化锌负载的单原子催化剂.进一步测定其反应速率，得到Rh₁/ZnO-nw在180℃时单位活性位点转化数（TOF）为0.63 s^-1，是已报道的单原子催化剂中最高值之一，为相同氧化锌负载Rh纳米粒子的3倍（0.21 s^-1）.密度泛函理论计算揭示了氧化锌负载Rh单原子催化剂上CO氧化的反应机理和高活性原因.计算表明反应机理为Mars-van Krevelen，氧气在表面氧空位的解离是速控步骤，计算得到的能垒为Rh₁/ZnO < Pt₁/ZnO < Au₁/ZnO，表明CO氧化活性顺序为Rh₁/ZnO > Pt₁/ZnO > Au₁/ZnO，与实验结果相符.此外，测试了两种反应条件下Rh₁/ZnO-nw单原子催化剂的稳定性.在300℃反应温度、反应气氛为CO/O₂和模拟汽车尾气的反应条件下，即反应气氛为1.6% CO、1% O₂、0.01%丙烯、0.0087%甲苯、10%水、He平衡，在100 h的测试中其活性保持稳定.高温循环测试中，经过800℃反应后，活性有所下降，但是在经过原位还原后，其反应活性可以基本恢复，表明Rh₁/ZnO-nw单原子催化剂不仅具有优异的高温抗烧结性能，同时在水分和碳氢化合物存在的条件下，具有优异的抗毒化能力，展现出在实际应用中的潜力.

关键词:

English

Superior activity of Rh₁/ZnO single-atom catalyst for CO oxidation

a CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c Department of Physics, Arizona State University, Tempe, Arizona 85287, United States;
d Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, MI 48202, United States;
e Dalian National Laboratory for Clean Energy, CAS, Dalian 116023, Liaoning, China
Received Date: 21 July 2019
Revised Date: 30 August 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21606222, 21776270), Liaoning Revitalization Talents Program (XLYC1807068), DNL Cooperation Fund, CAS (180403) and US National Science Foundation under CHE-1465057.

Abstract: CO oxidation is of great importance in both fundamental study and industrial application. Supported noble metal catalysts are highly active for CO oxidation but suffer from the scarcity and high cost. Single-atom catalysts (SACs) can maximize the metal atom efficiency. Herein, ZnO nanowire (ZnO-nw) supported Rh, Au, and Pt SACs were successfully developed to investigate their CO oxidation performance. Interestingly, it was found that Rh₁/ZnO-nw showed much higher activity than the other noble metals which are usually regarded as good candidates for CO oxidation. In addition, the Rh SAC possessed high stability in high-temperature CO oxidation under simulated conditions in the presence of water and hydrocarbons. The high activity and stability make Rh₁/ZnO-nw promising for practical applications, especially in the automotive exhaust emission control. Theoretical calculations indicate that the CO oxidation proceeds via the Mars-van Krevelen mechanism and the lowest barrier for the rate-limiting O₂ dissociation at a surface oxygen vacancy site is a key factor in determining the observed highest activity of Rh₁/ZnO-nw amongst the studied SACs.

Key words:

Single-atom catalysis
/ Carbon monoxide oxidation
/ Rhodium
/ Zinc oxide nanowire
/ Density functional theory calculations

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沈阳化工大学材料科学与工程学院沈阳 110142

铑/氧化锌单原子催化剂的优异CO氧化反应性能

English

Superior activity of Rh₁/ZnO single-atom catalyst for CO oxidation

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铑/氧化锌单原子催化剂的优异CO氧化反应性能

English

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