载体相变下Pt-TiO2 SMSI研究及其对CO催化性能的影响

doi:10.6023/A22040162

摘要/Abstract

金属-载体强相互作用(SMSI)是多相催化中的一个重要概念, 对负载金属催化剂的稳定性和活性均有重要影响. 目前尽管有关Pt-TiO₂体系的SMSI已有阐述, 但主要围绕载体的结构敏感性(晶面效应)、贵金属的粒径尺寸(尺寸效应)对SMSI的影响进行研究, 而TiO₂的晶型对SMSI的形成是否存在影响目前尚未报道. 在本工作中, 选择青铜矿TiO₂(B)为载体, 通过浸渍法负载Pt得到Pt-TiO₂(B)催化剂, 并在H₂、H₂-O₂氛围对其进行热处理. 研究结果表明, 500 ℃ 高温下H₂处理不仅导致催化剂中载体由青铜矿变为锐钛矿, 而且引起载体迁移至Pt颗粒表面形成几何包覆. 当此催化剂再次经400 ℃ O₂处理, Pt颗粒表面的包覆层消失, 呈现典型的SMSI行为. 借助高分辨透射电子显微镜(HRTEM)以及CO漫反射傅立叶变换红外光谱(CO-DRIFTS)结果分析, TiO₂的晶型转变对SMSI的形成具有重要影响. 此外, 对不同气氛、温度下处理的Pt-TiO₂进行了催化CO氧化性能研究, 结果证明SMSI产生的几何包覆以及载体的氧缺陷对催化CO氧化性能提升发挥了重要作用. 显然, 该工作丰富了Pt-TiO₂体系的SMSI研究, 为其它载体晶相转变(或物相转变)可能诱导SMSI产生提供了参考意义.

关键词: 金属-载体强相互作用, 青铜矿, 晶相转变, 几何包覆, CO氧化

The strong metal-support interaction (SMSI) has long been studied in heterogonous catalysis on account of its importance in stabilizing active metals and tuning catalytic performance. So far, although there are many reports about SMSI in Pt-TiO₂ system, they are mainly focusing on support structure sensitivity (crystal plane effect) and the size of supported noble metals (size effect), it is still unclear whether the TiO₂ crystalline phase influences the creation of SMSI or not. In this study, we choose brookite TiO₂(TiO₂(B)) as support to prepare Pt-TiO₂(B) catalyst by means of traditional impregnation method. Then the as-prepared Pt_imp/TiO₂(B) was treated at different temperature under different atmosphere, specifically, 250 ℃ heat treatment under H₂ (the sample is labeled as Pt_imp/TiO₂(B)-H250), 500 ℃ heat treatment under H₂ (the sample is labeled as Pt_imp/TiO₂(B)-H500), and 400 ℃ heat treatment under O₂ followed by H₂ treatment at 500 ℃ (the sample is labeled as Pt_imp/TiO₂(B)-H500+O400). The experimental results show that the 500 ℃ heat treatment under H₂ atmosphere induces the crystalline phase transformation of TiO₂(B) into anatase, and more importantly, this transformation leads to the TiO_2-_x migration as a result of the encapsulation of Pt particles by TiO_2-_x. After further heat treatment at 400 ℃ under O₂ atmosphere, the TiO_2-_x shell coated on the Pt nanoparticle surfaces was removed, which displays a classical SMSI behavior. According to the high resolution transmission electron microscope (HRTEM) and CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS) results, we proposed that the crystalline phase transformation plays a great role in the creation of SMSI. In addition, we selected CO oxidation as a model reaction to compare the catalytic activity of Pt_imp/TiO₂(B) catalysts. The results demonstrate that the activity of the catalysts is simultaneously affected by the TiO_2-_x coating on Pt nanoparticles and the oxygen vacancy concentration within the support. More specifically, compared with TiO₂(B), anatase TiO₂ has abundant oxygen vacancies, which is of great importance to activate O₂. In the case of Pt_imp/TiO₂(B)-H500+O400 catalyst, the active sites of Pt nanoparticles are exposed due to the removal of TiO_2-_x coating, and the anatase TiO₂ has a certain amount of oxygen vacancies. Therefore, Pt_imp/TiO₂(B)-H500+O400 catalyst exhibits the best activity among all compared Pt/TiO₂(B) catalyst. Obviously, this work greatly enriches the SMSI for Pt/TiO₂ system, and provides an important reference value for the creation of SMSI, if any, when other crystalline phase transformation (or phase transformation) involved supports are suitably chosen.

Key words: strong metal-support interaction, TiO₂(B), phase change, physical coating, CO oxidation

引用此文

贾亚辉, 李春生, 徐忠震, 刘伟, 高道伟, 陈国柱. 载体相变下Pt-TiO₂ SMSI研究及其对CO催化性能的影响[J]. 化学学报, 2022, 80(9): 1289-1298.

Yahui Jia, Chunsheng Li, Zhongzhen Xu, Wei Liu, Daowei Gao, Guozhu Chen. The SMSI of Pt-TiO₂ During the Crystalline Phase Transformation and Its Effect on CO Oxidation Performance[J]. Acta Chimica Sinica, 2022, 80(9): 1289-1298.

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图/表 10

图1. Ptimp/TiO2(B)系列催化剂的XRD图谱

Figure 1. XRD patterns of Ptimp/TiO2(B)-H250, Ptimp/TiO2(B)-H500 and Ptimp/TiO2(B)-H500+O400

图2. Ptimp/TiO2(B)系列催化剂的Raman图谱(a)以及H2-TPR曲线(b)

Figure 2. Raman spectra (a) and H2-TPR (b) of Ptimp/TiO2(B)-H250, Ptimp/TiO2(B)-H500 and Ptimp/TiO2(B)-H500+O400

图3. Ptimp/TiO2(B)系列催化剂的HRTEM图以及相应的Pt纳米颗粒尺寸分布: (a, b) H250, (c, d) H500, (e, f) H500+O400

Figure 3. HRTEM images of Ptimp/TiO2(B) series catalysts and corresponding Pt nanoparticles size distribution: (a, b) H250, (c, d) H500, (e, f) H500+O400

图4. Ptimp/TiO2(B)系列催化剂的CO-DRIFTS图谱(a)以及1843 cm-1桥式吸附峰放大图(b)

Figure 4. CO-DRIFTS spectra (a) and enlarged 1843 cm-1 bridge adsorption peak (b) of Ptimp/TiO2(B) series catalysts

图5. TiO2(B)-H500/Pt系列催化剂的XRD谱图(a)以及CO-DRIFTS (b)

Figure 5. XRD patterns (a) and CO-DRIFTS spectra (b) of TiO2(B) -H500/Pt series catalysts

图6. Ptimp/TiO2(B)系列催化剂的CO氧化催化温度-转化率图

Figure 6. CO conversion as a function of temperature for Ptimp/TiO2(B) series catalysts

图7. Ptimp/TiO2(B)系列催化剂的XPS-Ti 2p (a)以及XPS-O 1s图谱(b)

Figure 7. XPS-Ti 2p (a) and XPS-O1s (b) spectra of Ptimp/TiO2(B) series catalysts

图8. Ptimp/TiO2(B)-H250催化剂的in-situ DRIFTS: (a)室温CO吸附; (b) 135 ℃下CO吸附; (c)室温下O2吹扫; (d) 135 ℃下O2吹扫

Figure 8. In-situ DRIFTS of Ptimp/TiO2(B)-H250 catalyst: (a) CO adsorption at room temperature; (b) CO adsorption at 135 ℃; (c) O2 purge at room temperature; (d) O2 purge at 135 ℃

图9. Ptimp/TiO2(B)-H500催化剂的in-situ DRIFTS: (a)室温CO吸附; (b) 135 ℃下CO吸附; (c)室温下O2吹扫; (d) 135 ℃下O2吹扫

Figure 9. In-situ DRIFTS of Ptimp/TiO2(B)-H500 catalyst: (a) CO adsorption at room temperature; (b) CO adsorption at 135 ℃; (c) O2 purge at room temperature; (d) O2 purge at 135 ℃

图10. Ptimp/TiO2(B)-H500+O400催化剂的in-situ DRIFTS: (a)室温CO吸附; (b) 135 ℃下CO吸附; (c)室温下O2吹扫; (d) 135 ℃下O2吹扫

Figure 10. In-situ DRIFTS of Ptimp/TiO2(B)-H500+O400 catalyst: (a) CO adsorption at room temperature; (b) CO adsorption at 135 ℃; (c) O2 purge at room temperature; (d) O2 purge at 135 ℃

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载体相变下Pt-TiO₂ SMSI研究及其对CO催化性能的影响

The SMSI of Pt-TiO₂ During the Crystalline Phase Transformation and Its Effect on CO Oxidation Performance

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