金属载体强相互作用增强Au/TiO2催化剂在3-硝基苯乙烯选择性加氢反应的活性

doi:10.1016/S1872-2067(20)63763-9

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1530-1537.DOI: 10.1016/S1872-2067(20)63763-9

金属载体强相互作用增强Au/TiO₂催化剂在3-硝基苯乙烯选择性加氢反应的活性

洪峰^a^,^b, 王升扬^a^,^c, 张军营^a, 付俊红^a, 蒋齐可^a, 孙科举^d^,^#(), 黄家辉^a^,^*()

^a中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 辽宁大连116023
^b中国科学院大学, 北京100049
^c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
^d燕山大学环境与化学工程学院, 应用化学重点实验室, 河北秦皇岛066004

收稿日期:2020-11-25 接受日期:2021-01-15 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 孙科举,黄家辉
基金资助:
洁净能源示范变革性技术-中科院战略先导专项(XDA21030900);国家重点研发计划(2019YFC1905300);自然科学基金国际交流合作计划(21961142006);中国科学院创新研究院合作基金(DNL201903);国家自然科学基金(51701201)

Strong metal-support interaction boosting the catalytic activity of Au/TiO₂ in chemoselective hydrogenation

Feng Hong^a^,^b, Shengyang Wang^a^,^c, Junying Zhang^a, Junhong Fu^a, Qike Jiang^a, Keju Sun^d^,^#(), Jiahui Huang^a^,^*()

^aDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^dKey Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China

Received:2020-11-25 Accepted:2021-01-15 Online:2021-09-18 Published:2021-05-16
Contact: Keju Sun,Jiahui Huang
About author:^# E-mail: kjsun@ysu.edu.cn
^* Tel: +86-411-82463012; E-mail: jiahuihuang@dicp.ac.cn;
Supported by:
“Transformational Technologies for Clean Energy and Demonstration”, Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21030900);National Key R&D Program of China(2019YFC1905300);Projects of International Cooperation and Exchanges NSFC(21961142006);DNL Cooperation Fund, CAS(DNL201903);National Natural Science Foundation of China(51701201)

摘要/Abstract

摘要：

自Haruta与Hutchings于上世纪八十年代末发现金纳米催化剂优异的反应活性以来, 科研人员对金催化的应用领域进行了广泛而深入地研究. 对金催化科学和应用领域的研究一直在进行. 大量的研究表明, 金催化剂在各种选择性氧化反应中具有优异的催化性能(高活性和高选择性). 然而, 在催化加氢反应中, 尽管金催化剂相比于铂族金属显示出优越的选择性, 但是由于金催化剂选择性加氢反应的活性较差, 使其在选择性催化加氢反应中的应用受到了极大的限制. 研究表明, 金催化剂较弱的活化氢气能力是其催化加氢反应活性低的主要原因.
研究发现, 氢气活化的活性中心可能是界面、负价金、低配位的金原子等. 金催化剂具有明显的载体效应, 金属-载体之间的相互作用能够显著地改变金催化剂的催化性能. Tauster等研究发现, 铂族金属与还原性载体之间存在强相互作用, 能够引发载体包覆金属表面, 并且使得电子从载体向金属迁移, 导致金属带负电. 受金属-载体强相互作用(SMSI) 效应的启发, 本文探究了Au/TiO₂催化剂中SMSI对金催化剂加氢性能的影响. 在H₂或O₂气氛下高温焙烧Au/TiO₂, 获得一系列金催化剂(Au/TiO₂-TA, T为焙烧温度(°C): 300、400、500和600; A为气氛: H₂或O₂).
对比在3-硝基苯乙烯(3-NS)选择性加氢反应中的活性发现, Au/TiO₂-500H的TOF值是Au/TiO₂-500O的3.3倍; 动力学测试表明, Au/TiO₂-500H和Au/TiO₂-500O的反应表观活化能分别为79.5和105.1 kJ/mol. 这表明两类催化剂催化活性中心的结构存在差异. X射线光电子能谱测试结果表明, Au/TiO₂-H样品中Au带部分负电, 而Au/TiO₂-O中Au显示为金属态. HAADF-STEM和EELS显示, Au/TiO₂-H中Au NPs的表面有TiO_x物种, 增加了Au-TiO₂的界面. EPR结果表明, Au/TiO₂-H中存在表面Ti³⁺物种, 而Au/TiO₂-O样品中则没有. 为确认加氢反应的活性中心到底是界面还是负价金物种, 本文探究了不同温度下氢气处理的Au/TiO₂的结构与性能的关系, 发现Au/TiO₂-300H/400H/500H催化剂都显示出较好的催化3-NS加氢活性, 而Au/TiO₂-600H虽然具有更多的负价金物种, 但是3-NS选择性加氢反应的活性反而降低, 因此, 负价金不是活性中心. 这是因为不同温度处理的Au/TiO₂-H样品中, SMSI的强弱不同, 在300、400、500°C下, SMSI能够增加Au-TiO₂的界面长度, 从而增强了3-NS加氢反应的活性; 而温度达到600°C, SMSI效应太强, Au NPs被包覆更密实, 导致Au/TiO₂-600H的3-NS选择性加氢反应的活性下降. 密度泛函理论计算表明, Au/TiO₂-H样品具有更低的H₂解离活化能以及氢转移活化能. 氢氘交换反应也进一步验证了SMSI有利于H₂的活化.

关键词: 金催化, 金属-载体强相互作用, 界面, 3-硝基苯乙烯选择性加氢, 增强活性

Abstract:

Gold catalysts have been reported as highly effective catalysts in various oxidation reactions. However, for chemoselective hydrogenation reactions, gold-based catalysts normally show much lower catalytic activity than platinum group metals, even though their selectivities are excellent. Here, we report that the chemoselective hydrogenation activity of 3-nitrostyrene to 3-vinylaniline over Au/TiO₂ can be enhanced up to 3.3 times through the hydrogen reduction strategy. It is revealed that strong metal-support interaction, between gold nanoparticles (NPs) and TiO₂ support, is introduced through hydrogen reduction, resulting in partial dispersion of reduced TiO_x on the Au surface. The partially covered Au not only increases the perimeter of the interface between the gold NPs and the support, but also benefits H₂ activation. Reaction kinetic analysis and H₂-D₂ exchange reaction show that H₂ activation is the critical step in the hydrogenation of 3-nitrostyrene to 3-vinylaniline. Density functional theory calculations verify that hydrogen dissociation and hydrogen transfer are favored at the interface of gold NPs and TiO₂ over the hydrogen-reduced Au/TiO₂. This study provides insights for fabricating highly active gold-based catalysts for chemoselective hydrogenation reactions.

Key words: Gold catalysis, Strong metal support interaction, Interface, 3-Nitrostyrene chemoselective hydrogenation, Boosting activity

洪峰, 王升扬, 张军营, 付俊红, 蒋齐可, 孙科举, 黄家辉. 金属载体强相互作用增强Au/TiO₂催化剂在3-硝基苯乙烯选择性加氢反应的活性[J]. 催化学报, 2021, 42(9): 1530-1537.

Feng Hong, Shengyang Wang, Junying Zhang, Junhong Fu, Qike Jiang, Keju Sun, Jiahui Huang. Strong metal-support interaction boosting the catalytic activity of Au/TiO₂ in chemoselective hydrogenation[J]. Chinese Journal of Catalysis, 2021, 42(9): 1530-1537.

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图/表 4

Fig. 1. Conversion of 3-NS and selectivity of 3-VA versus time over Au/TiO2 catalysts calcined under different conditions. Gold catalysts were calcined at (a) 400 or (b) 500 °C. Reaction conditions: 3-NS (1.2 mmol); Au catalyst (6 × 10-3 mmol Au); H2 pressure (2 MPa); stirring rate: 1200 rpm, temperature: 60 °C.

Fig. 2. (a) TOF values of 3-NS hydrogenation over Au/TiO2-500H and Au/TiO2-500O. Conditions: 3-NS (1.2 mmol); Au catalyst (6 × 10-3 mmol Au). (b) Arrhenius plots for 3-NS chemoselective hydrogenation over Au/TiO2-500H and Au/TiO2-500O. Conversion of 3-NS is in the range 10%-20%. Reaction conditions: 3-NS (0.2 mmol); Au catalyst (1 × 10-3 mmol Au); H2 pressure (2 MPa); stirring rate: 1200 rpm; temperature: 40, 50, 60 and 70 °C.

Fig. 3. (a) 3-NS conversion versus time over Au/TiO2 catalyst calcined under different gaseous atmospheres; (b) EPR spectra of the gold catalysts calcined at 500 °C under different gases; HAADF-STEM images and EELS spectra of (c,d) Au/TiO2-500O and (e,f) Au/TiO2-500H.

Fig. 4. H2-D2 exchange reaction over Au/TiO2-500H (a) and Au/TiO2-500O (b). This reaction was performed in a fixed bed at a temperature range of 30-200 °C. Conditions: 30 mL·min of 50% H2 and 50% D2 (space velocity = 36000 mL·gcat-1·h-1); temperature range: 30-200 °C; pressure: 0.1 MPa. (c) The reaction paths for the H2-D2 exchange reaction on Au/TiO2-x (representing Au/TiO2-500H) and Au/TiO2 (on behalf of Au/TiO2-500O). (d) The energy changes of hydrogen transfer on Au/TiO2 and Au/TiO2-x. The red, blue, yellow, and pink balls represent oxygen, titanium, gold, and hydrogen or deuterium, respectively.

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金属载体强相互作用增强Au/TiO₂催化剂在3-硝基苯乙烯选择性加氢反应的活性

Strong metal-support interaction boosting the catalytic activity of Au/TiO₂ in chemoselective hydrogenation

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