Pd-Au/1cTiO2/SiO2催化剂的制备及其烯烃的环氧化性能

doi:10.11949/0438-1157.20200778

摘要/Abstract

摘要：

使用沉淀沉积法及溶液浸渍法分别将Au和Pd纳米粒子负载在原子层沉积法制备的1cTiO₂/SiO₂载体上，制备出两种不同Pd负载量的Pd-Au双金属活性中心纳米催化剂。采用TEM、EDX、XPS对所制备的催化剂进行了详细的表征，确定了纳米粒子的形貌、Pd-Au元素的化学价态和组成。测试了该类催化剂在以氧气为氧源的环己烯环氧化反应中的活性和选择性，并对反应溶剂、共还原剂种类、反应温度等条件进行了筛选。在优化后的反应条件下考察了该催化剂对不同结构烯烃的适用性。对于环状烯烃，底物转化率均大于95%，环氧产物选择性均大于91%。催化剂在循环回收5次后，催化活性和反应选择性保持不变。

关键词: 催化剂, 纳米材料, 环氧化, 烯烃, 活性, 稳定性

Abstract:

Two kinds of Pd-Au bimetallic nanocatalysts (0.01% Pd-Au/1cTiO₂/SiO₂ and 0.05% Pd-Au/1cTiO₂/SiO₂) were prepared by using 1cTiO₂/SiO₂as support, which had a single layer TiO₂ thin film on SiO₂ substrate by atomic layer deposition (ALD) technique. Deposition of Au and Pd on 1cTiO₂/SiO₂ was carried out by means of deposition precipitation and impregnation. Au loading of the two catalysts was both 0.01%(mass), and the Pd loading were 0.01% and 0.05% respectively. The prepared catalysts were characterized by transmission electron microscopy (TEM), energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS), and the morphology of nanoparticles, the chemical valence state and composition of Pd and Au elements were determined. The Pd-Au bimetallic nanocatalysts were used in the selective epoxidation of cyclohexene using oxygen as oxidant, and the conditions such as the reaction solvent, the type of co-reductant and the reaction temperature were screened. The applicability of the catalyst to different structural olefins was investigated under the optimized reaction conditions. For cyclic olefins, the substrate conversion rate is greater than 95%, and the epoxy product selectivity is greater than 91%. After the catalyst is recycled 5 times, the catalytic activity and reaction selectivity remain unchanged.

Key words: catalyst, nanomaterials, epoxidation, olefin, reactivity, stability

中图分类号:

TQ 116.2⁺5

曾伟,刘甲,张德谨,杨国强,张志炳. Pd-Au/1cTiO₂/SiO₂催化剂的制备及其烯烃的环氧化性能[J]. 化工学报, 2020, 71(11): 4999-5006.

Wei ZENG,Jia LIU,Dejin ZHANG,Guoqiang YANG,Zhibing ZHANG. Preparation of catalyst Pd-Au/1cTiO₂/SiO₂ and epoxidation of olefins[J]. CIESC Journal, 2020, 71(11): 4999-5006.

图/表 11

图1 催化剂的TEM图

Fig.1 TEM images of catalysts

图2 催化剂的EDX能谱

Fig.2 EDX spectra of catalysts

图3 催化剂的XPS宽谱a—0.05% Pd-Au/1cTiO2/SiO2; b—0.01% Pd-Au/1cTiO2/SiO2

Fig.3 XPS wide scan spectra of catalysts

图4 催化剂的XPS高分辨谱

Fig.4 XPS core level spectra of catalysts

图5 环己烯环氧化反应

Fig.5 Epoxidation of cyclohexene

图6 不同催化剂反应活性的评价

Fig.6 Performance of different catalysts

图7 溶剂对环己烯环氧化反应的影响

Fig.7 Effect of solvent on epoxidation of cyclohexene

图8 共还原剂对环己烯环氧化反应的影响

Fig.8 Effect of co-reductant on epoxidation of cyclohexene

图9 反应温度对环己烯环氧化反应的影响

Fig.9 Effect of reaction temperature on epoxidation of cyclohexene

图10 0.05% Pd-Au/1cTiO2/SiO2催化剂的回收性能测试

Fig.10 Reusability of 0.05% Pd-Au/1cTiO2/SiO2 catalyst

表1 不同烯烃的环氧化反应

Table 1 Epoxidation of different olefins catalyzed by Pd-Au catalyst

底物	反应时间/h	底物转化率/%	环氧化产物选择性/%
环戊烯	3	99	97
环辛烯	4	96	95
1-甲基-1-环己烯	4	98	91
降冰片烯	4	98	96
α-蒎烯	6	98	96
2,3-二甲基-2-丁烯	10	52	96
1-己烯^①	10	48	98
1-辛烯^①	10	39	97
1-十二烯^①	10	35	98
苯乙烯^①	8	83	91

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Pd-Au/1cTiO₂/SiO₂催化剂的制备及其烯烃的环氧化性能

Preparation of catalyst Pd-Au/1cTiO₂/SiO₂ and epoxidation of olefins

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