Sb对Pd基催化剂用于常压直接合成H2O2的促进效应

doi:10.1016/S1872-2067(18)63031-1

催化学报 ›› 2018, Vol. 39 ›› Issue (4): 673-681.DOI: 10.1016/S1872-2067(18)63031-1

Sb对Pd基催化剂用于常压直接合成H₂O₂的促进效应

丁豆豆^a, 徐兴妍^a, 田鹏飞^a, 刘向林^a, 徐晶^a, 韩一帆^a,b

a 华东理工大学化学工程联合国家重点实验室, 上海 200237;
b 郑州大学化工与能源学院多相催化工程科学研究中心, 河南郑州 450001

收稿日期:2017-11-30 修回日期:2018-01-10 出版日期:2018-04-18 发布日期:2018-04-08
通讯作者: 徐晶, 韩一帆
基金资助:
国家自然科学基金（91534127，U1463205）；河南省中原学者；"111"引智计划（B08021）.

Promotional effects of Sb on Pd-based catalysts for the direct synthesis of hydrogen peroxide at ambient pressure

Doudou Ding^a, Xingyan Xu^a, Pengfei Tian^a, Xianglin Liu^a, Jing Xu^a, Yifan Han^a,b

a State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
b Research Center of Heterogeneous Catalysis and Engineering Science, School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2017-11-30 Revised:2018-01-10 Online:2018-04-18 Published:2018-04-08
Contact: 10.1016/S1872-2067(18)63031-1
Supported by:
This work was supported by the National Natural Science Foundation of China (91534127, U1463205), the Innovation Scientists and Technicians Troop Construction Projects of Henan Province, and the Chinese Education Ministry 111 Project (B08021).

摘要/Abstract

摘要：

H₂O₂作为一种高效绿色氧化剂，广泛应用于造纸、纺织、水处理等工业领域.目前蒽醌法是工业上生产H₂O₂的主要方法，相比之下，利用H₂和O₂直接合成H₂O₂，能耗低，污染小，适合与下游工艺技术进行耦合.而缺乏高性能催化剂是制约直接法合成H₂O₂工业化的主要原因.本文通过浸渍法制备了一系列负载型Pd-Sb/TiO₂双金属催化剂，并用于常压下H₂O₂直接催化合成反应.利用透射电子显微镜（TEM），X射线光电子能谱（XPS），H₂/O₂程序升温脱附（H₂/O₂-TPD），X射线衍射（XRD），原位CO吸附的傅里叶变换漫反射红外光谱（CO-DRIFTS）等手段对催化剂的电子和几何结构进行解析，深入研究了助剂Sb对该体系的促进作用.
结果显示，与单金属Pd催化剂相比，适量金属Sb的加入有效提高了催化性能，抑制了副反应的发生.当Pd/Sb摩尔比为50/1（Pd₅₀Sb）时，H₂O₂的选择性高达73%；但是当Pd/Sb为2时，催化剂对生成H₂O₂几乎没有活性.TEM和XRD证明，Sb的加入显著促进了Pd颗粒在载体TiO₂上的分散.XPS和H₂-TPD实验，发现，Sb改变了催化剂表面Pd²⁺/Pd⁰的比例，抑制了金属Pd的氧化；同时，Sb主要以氧化态存在，在催化剂表面形成Sb₂O₃氧化层，覆盖表面的Pd活性位，从而抑制了反应中H₂在催化剂表面的活化以及H₂O₂加氢副反应的发生.O₂-TPD结果表明，随着Sb的加入，O₂的脱附峰明显减弱，表明Pd-Sb/TiO₂不利于O₂的解离吸附.此外，原位CO-DRIFTS实验结果表明，Sb均匀分布在Pd-Sb催化剂表面，致使有利于生成H₂O的连续Pd活性位明显减少，而有利于合成H₂O₂的单个Pd原子活性位明显增加.
总的来说，Sb对Pd表面起到了显著的修饰作用，提高了催化剂表面O₂的非解离活化，从而促进了H₂O₂的高选择性合成.但是过量Sb的加入会抑制催化剂对H₂的活化作用，致使催化剂活性下降，因此优选Pd/Sb的比例对于提高催化剂性能具有重要作用.

关键词: 双金属催化剂, 过氧化氢, 钯, 锑, 直接合成

Abstract:

TiO₂-supported Pd-Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H₂O₂ at ambient pressure. The addition of Sb to Pd significantly enhanced catalytic performance, and a Pd₅₀Sb catalyst showed the greatest selectivity of up to 73%. Sb promoted the dispersion of Pd on TiO₂, as evidenced by transmission electron microscopy and X-ray diffraction. X-ray photoelectron spectroscopy indicated that the oxidation of Pd was suppressed by Sb. In addition, Sb₂O₃ layers were formed and partially wrapped the surfaces of Pd catalysts, thus suppressing the activation of H₂ and subsequent hydrogenation of H₂O₂. In situ diffuse reflection infrared Fourier transform spectroscopy for CO adsorption suggested that Sb homogenously located on the surface of Pd-Sb catalysts and isolated contiguous Pd sites, resulting in the rise of the ratio of Pd monomer sites that are favorable for H₂O₂ formation. As a result, the Sb modified Pd surfaces significantly enhanced the non-dissociative activation of O₂ and H₂O₂ selectivity.

Key words: Bimetallic catalyst, Hydrogen peroxide, Palladium, Antimony, Direct synthesis

丁豆豆, 徐兴妍, 田鹏飞, 刘向林, 徐晶, 韩一帆. Sb对Pd基催化剂用于常压直接合成H₂O₂的促进效应[J]. 催化学报, 2018, 39(4): 673-681.

Doudou Ding, Xingyan Xu, Pengfei Tian, Xianglin Liu, Jing Xu, Yifan Han. Promotional effects of Sb on Pd-based catalysts for the direct synthesis of hydrogen peroxide at ambient pressure[J]. Chinese Journal of Catalysis, 2018, 39(4): 673-681.

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Sb对Pd基催化剂用于常压直接合成H₂O₂的促进效应

Promotional effects of Sb on Pd-based catalysts for the direct synthesis of hydrogen peroxide at ambient pressure

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