“自上而下”构筑TiO2与Pt纳米簇之间的活性界面II: 催化一氧化碳氧化反应性能和机理

doi:10.1016/S1872-2067(23)64598-X

催化学报 ›› 2024, Vol. 58: 247-254.DOI: 10.1016/S1872-2067(23)64598-X

• 论文 • 上一篇

“自上而下”构筑TiO₂与Pt纳米簇之间的活性界面II: 催化一氧化碳氧化反应性能和机理

杜晓蕊^a^,^b^,¹, 黄一珂^a^,^c^,¹, 潘晓丽^a, 江训柱^a^,^d, 苏杨^a, 杨静怡^a, 郭亚琳^a^,^e, 韩冰^a^,^f, 文承彦^b, 王晨光^b^,^g,*(), 乔波涛^a^,^d,*()

^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技重点实验室, 辽宁大连116023
^b中国科学院广州能源研究所, 广东广州510640
^c北京科学智能研究院, 北京100000
^d中国科学院大学, 北京100049
^e重庆大学化学化工学院多尺度多孔材料研究中心, 重庆400044
^f中国石化大连石油化工研究院, 辽宁大连116023
^g中国科学院可再生能源重点实验室, 广东广州510640

收稿日期:2023-12-09 接受日期:2024-01-04 出版日期:2024-03-18 发布日期:2024-03-28
通讯作者: *电子信箱: bqiao@dicp.ac.cn (乔波涛),wangcg@ms.giec.ac.cn (王晨光).
作者简介:¹共同第一作者.
基金资助:
中国科学院稳定支持基础研究领域青年团队计划(YSBR-022);中国科学院稳定支持基础研究领域青年团队计划(YSBR-044);国家自然科学基金(22309185);国家重点研发计划项目(2021YFA1500503);辽宁省自由探索基金(2023020351-JH6/1005);国家自然科学基金中日合作交流项目(21961142006);国家自然科学基金单原子催化基础研究中心(22388102)

Top-down fabrication of active interface between TiO₂ and Pt nanoclusters. Part 2: Catalytic performance and reaction mechanism in CO oxidation

Xiaorui Du^a^,^b^,¹, Yike Huang^a^,^c^,¹, Xiaoli Pan^a, Xunzhu Jiang^a^,^d, Yang Su^a, Jingyi Yang^a, Yalin Guo^a^,^e, Bing Han^a^,^f, Chengyan Wen^b, Chenguang Wang^b^,^g,*(), Botao Qiao^a^,^d,*()

^aCAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bGuangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^cArtificial Intelligence for Science Institute, Beijing 100000, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China
^eMulti-scale Porous Materials Center, Institute of Advanced Interdisciplinary Studies, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
^fSINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co., Ltd. Dalian 116023, Liaoning, China
^gCAS Key Laboratory of Renewable Energy, Guangzhou 510640, Guangdong, China

Received:2023-12-09 Accepted:2024-01-04 Online:2024-03-18 Published:2024-03-28
Contact: *E-mail: bqiao@dicp.ac.cn (B. Qiao),wangcg@ms.giec.ac.cn (C. Wang).
About author:¹Contributed equally to this work.
Supported by:
CAS Project for Young Scientists in Basic Research(YSBR-022);CAS Project for Young Scientists in Basic Research(YSBR-044);National Natural Science Foundation of China(22309185);National Key Project for Fundamental Research and Development of China(2021YFA1500503);Liaoning Province Free Exploration Fund(2023020351-JH6/1005);Natural Science Foundation of China and Japan Society for the Promotion of Science Cooperative Research Project(21961142006);National Natural Science Foundation of China(22388102)

摘要/Abstract

摘要：

CO氧化是工业生产和汽车尾气处理中的重要反应, 对控制环境污染具有重要意义. 同时, 作为结构敏感的常见探针反应, CO氧化对催化基础理论的发展和新型催化剂的开发都起到重要的推动作用, 如L-H、MvK机理的提出和发展、单原子催化剂的发现和相关理论的发展等. 深入研究催化剂上的CO氧化机理, 不仅能够深化我们对催化剂构效关系的理解, 而且可以为催化剂在其他化学反应中的应用提供有益的参考和启示. 在本工作的第一部分(Chin. J. Catal., 2024, 58, 237-246)中, 我们通过Pt纳米颗粒(NP)在TiO₂表面的再分散, 成功合成了Pt/TiO₂纳米簇(NC)催化剂, 随之以CO氧化为模型反应研究其催化性能.

本工作研究发现, Pt/TiO₂ NC对CO氧化具有较好的表观和本征活性, 其在100和20 °C下的表观反应速率为2.61和0.24 mol_CO g_Pt^‒1 h^‒1, 分别是Pt NP催化剂的7.2和12倍, 也是大部分文献报道的Pt基催化剂的3‒20倍; 相应地, Pt NC催化剂上的CO氧化在100和20 °C下的TOF值为0.18和0.016 s^‒1, 分别是Pt NP催化剂的2.7和4.4倍. 同时, Pt NC稳定性突出, 在经过五次循环或长达40 h的反应后, 其活性无明显降低. 随后, 详细研究了催化剂上的CO氧化反应机理. 动力学研究表明, Pt NP催化剂上的CO和O₂反应级数皆为正(0.15和0.45), 推测其上的CO氧化遵循MvK机制或非竞争的L-H机制. 而Pt NC催化剂上CO级数为‒0.019, O₂级数为0.33, 近零CO级数表明CO对反应没有影响, CO氧化的决速步为O₂的活化. 同位素¹⁸O标记实验结果表明, 在Pt NP催化剂上主要是晶格氧参与反应, 表明其反应路径主要遵循MvK机制. 而在Pt NC催化剂上, 参与反应的主要是活化的气相氧. 为了进一步研究Pt NC上CO氧化反应过程, 进行了¹⁸O₂参与的脉冲反应实验, 发现无论在常温或100 °C下, 当¹⁸O₂通过预吸附CO饱和的Pt NC样品时, 没有CO₂产生. 排除CO对O₂活化的影响(CO级数接近零), 这表明吸附在Pt NC上的CO并未发生反应. 相反, 当CO通过预吸附¹⁸O₂饱和的Pt NC样品时, 立即有CO₂产生, 表明是气相CO或者弱吸附在载体TiO₂表面的CO与催化剂上预吸附并活化的氧发生了反应. 低温原位红外光谱实验结果表明, 在‒160 °C下, 弱吸附在TiO₂表面的CO的确发生了反应, 而吸附在Pt NC上的CO没有反应. 由于在低温下, Pt被强吸附的CO覆盖, 而TiO₂对CO氧化是无活性的, 因此这也证实了Pt NC-TiO₂界面在低温下活化O₂的能力. 上述结果表明, Pt NC催化剂上的CO氧化反应机理为: CO吸附在TiO₂表面并与在界面处活化的氧发生反应.

综上, 本文深入研究了TiO₂负载的Pt纳米簇催化剂上的CO氧化反应机理, 有助于理解负载金属纳米簇催化剂高活性的起因, 同时可为高活性催化剂的设计和构筑提供借鉴.

关键词: 多相催化, 纳米簇, 再分散, 金属-氧化物界面, 一氧化碳氧化

Abstract:

In this work, following Part 1 that has found a redispersion process from Pt nanoparticles (NPs, about 3.4 nm) to nanoclusters (NCs, about 1 nm) on TiO₂ and elucidated its mechanism, we carefully investigated the catalytic performance of the obtained Pt NC catalyst in CO oxidation as well as the corresponding reaction mechanism. The Pt NC catalyst excels than its parent catalyst in terms of both intrinsic and apparent activity. Detailed studies by combining kinetic measurements, isotopic labeling reaction experiments, and low-temperature operando FT-IR unambiguously demonstrated that the Pt NCs deposited on TiO₂ can form unique interfacial sites that enable to active O₂ at very low temperature, thus the CO adsorbed on TiO₂ can diffuses to, and reacts with, the activated oxygen, rendering a high activity at low temperatures. This work is contributory in understanding the origin of the high activity of the supported metal cluster catalysts.

Key words: Heterogeneous catalysis, Nanocluster, Redispersion, Metal-oxide interface, CO oxidation

杜晓蕊, 黄一珂, 潘晓丽, 江训柱, 苏杨, 杨静怡, 郭亚琳, 韩冰, 文承彦, 王晨光, 乔波涛. “自上而下”构筑TiO₂与Pt纳米簇之间的活性界面II: 催化一氧化碳氧化反应性能和机理[J]. 催化学报, 2024, 58: 247-254.

Xiaorui Du, Yike Huang, Xiaoli Pan, Xunzhu Jiang, Yang Su, Jingyi Yang, Yalin Guo, Bing Han, Chengyan Wen, Chenguang Wang, Botao Qiao. Top-down fabrication of active interface between TiO₂ and Pt nanoclusters. Part 2: Catalytic performance and reaction mechanism in CO oxidation[J]. Chinese Journal of Catalysis, 2024, 58: 247-254.

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图/表 8

Fig. 1. DRIFT spectra of CO adsorption at the saturation coverage on freshly synthesized Pt/TiO2-400 and Pt/TiO2-550 and the in situ reduced samples.

Fig. 2. Pt 4f XPS of Pt/TiO2-400 and Pt/TiO2-550 samples that reduced at 200 and 500 °C, respectively, under 10 vol% H2/He for 1 h at a flow rate of 30 mL min?1. The green peak represents the Ti 3s energy loss.

Fig. 3. Representative HAADF-STEM images and corresponding Pt size distributions of Pt/TiO2-400-H200 (a,b) and Pt/TiO2-550-H500 (c,d).

Fig. 4. (a) CO conversion as a function of reaction temperature on samples. (b) Repeated light-off curves for CO oxidation on Pt/TiO2-550-H500. (c) CO conversion with time-on-stream over Pt/TiO2-550-H500. Reaction condition: 1 vol% CO, 1 vol% O2, and balance He, gas flow 30 mL min?1; 20 mg catalyst; weight hourly space velocity (WHSV): 90000 mL gcat?1 h?1.

Fig. 5. Reaction rates (rCO, molCO gPt?1 h?1) as a function of CO (a) or O2 (b) concentration over catalysts at 80 °C; reaction orders were determined from the slope of each line.

Fig. 6. Isotopic labeling reaction experiment results over Pt/TiO2-400-H200 (a) and Pt/TiO2-550-H500 (b) samples; In each experiment, the in situ reduced catalyst was heated to 100 °C under He purge, then CO and isotopic 18O2 balanced with He was allowed to pass through for about 10 min followed by He purging until all the signals decreased to baseline level; Afterwards, 16O2 and CO balanced with He was introduced.

Fig. 7. The isotopic oxygen involved pulse reaction experiment results over Pt/TiO2-550-H500 at 100 °C (a,c) and room temperature (b,d), respectively. (a,b) the sample was firstly saturated by CO, followed by He purging until all the signals decreased to baseline level, then pulse of 18O2 introduced, after which mixed reactant gas (CO + 18O2 +He) was allowed to flow past. (c,d) the sample was firstly treated by 18O2 and then purged by He, passed by CO pulse, and mixed reactant gas (CO + 18O2 +He) was flow past afterwards.

Fig. 8. Evolution of operando FT-IR spectra at ?160 °C after introducing O2 to the CO pre-adsorbed Pt/TiO2-550-H500.

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“自上而下”构筑TiO₂与Pt纳米簇之间的活性界面II: 催化一氧化碳氧化反应性能和机理

Top-down fabrication of active interface between TiO₂ and Pt nanoclusters. Part 2: Catalytic performance and reaction mechanism in CO oxidation

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