Preparation of catalyst Pd-Au/1cTiO<sub>2</sub>/SiO<sub>2</sub> and epoxidation of olefins

ZENG Wei; LIU Jia; ZHANG Dejin; YANG Guoqiang; ZHANG Zhibing

doi:10.11949/0438-1157.20200778

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

Celebration Column for School of Chemistry and Chemical Engineering\, Nanjing University | 更新时间：2026-07-24

- Preparation of catalyst Pd-Au/1cTiO₂/SiO₂ and epoxidation of olefins
- CIESC Journal Vol. 71, Issue 11, Pages: 4999-5006(2020)
- 作者机构：
  
  南京大学化学化工学院，江苏南京 210023
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200778
  CLC： TQ 116.2⁺5
- Received：20 June 2020，
  
  Revised：2020-07-13，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
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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 DOI: 10.11949/0438-1157.20200778.

ZENG Wei, LIU Jia, ZHANG Dejin, YANG Guoqiang, ZHANG Zhibing. Preparation of catalyst Pd-Au/1cTiO₂/SiO₂ and epoxidation of olefins[J]. CIESC Journal, 2020, 71(11): 4999-5006 DOI: 10.11949/0438-1157.20200778.
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 DOI: 10.11949/0438-1157.20200778. DOI：

ZENG Wei, LIU Jia, ZHANG Dejin, YANG Guoqiang, ZHANG Zhibing. Preparation of catalyst Pd-Au/1cTiO₂/SiO₂ and epoxidation of olefins[J]. CIESC Journal, 2020, 71(11): 4999-5006 DOI: 10.11949/0438-1157.20200778. DOI：

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1cTiO

/SiO

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。

Abstract

Two kinds of Pd-Au bimetallic nanocatalysts (0.01% Pd-Au/1cTiO

/SiO

and 0.05% Pd-Au/1cTiO

/SiO

) were prepared by using 1cTiO

/SiO

as support

which had a single layer TiO

thin film on SiO

substrate by atomic layer deposition (ALD) technique. Deposition of Au and Pd on 1cTiO

/SiO

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.

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references

Lane B S , Burgess K . Metal-catalyzed epoxidations of alkenes with hydrogen peroxide [J ] . Chemical Reviews , 2003 , 103 ( 7 ): 2457 - 2473 .

Vaughan O P H , Kyriakou G , Macleod N , et al . Copper as a selective catalyst for the epoxidation of propene [J ] . Journal of Catalysis , 2005 , 236 ( 2 ): 401 - 404 .

Blanckenberg A , Malgas-Enus R . Olefin epoxidation with metal-based nanocatalysts [J ] . Catalysis Reviews , 2019 , 61 ( 1 ): 27 - 83 .

Andrus M B , Poehlein B W . Epoxidation of olefins with peracid at low temperature with copper catalysis [J ] . Tetrahedron Letters , 2000 , 41 ( 7 ): 1013 - 1014 .

Woods K W , Beak P . The endocyclic restriction test: an experimental evaluation of the geometry at oxygen in the transition structure for epoxidation of an alkene by a peroxy acid [J ] . Journal of the American Chemical Society , 1991 , 113 ( 16 ): 6281 - 6283 .

Sharpless K B , Michaelson R C . High stereo- and regioselectivities in the transition metal catalyzed epoxidations of olefinic alcohols by tert-butyl hydroperoxide [J ] . Journal of the American Chemical Society , 1973 , 95 ( 18 ): 6136 - 6137 .

Banerjee D , Jagadeesh R V , Junge K , et al . Convenient and mild epoxidation of alkenes using heterogeneous cobalt oxide catalysts [J ] . Angewandte Chemie International Edition , 2014 , 53 ( 17 ): 4359 - 4363 .

Wang C , Yamamoto H . Tungsten-catalyzed asymmetric epoxidation of allylic and homoallylic alcohols with hydrogen peroxide [J ] . Journal of the American Chemical Society , 2014 , 136 ( 4 ): 1222 - 1225 .

Kamata K , Yonehara K , Sumida Y , et al . Efficient epoxidation of olefins with ≥99% selectivity and use of hydrogen peroxide [J ] . Science , 2003 , 300 ( 5621 ): 964 - 966 .

Zhou M D , Liu M J , Huang L L , et al . Olefin epoxidation with hydrogen peroxide using octamolybdate-based self-separating catalysts [J ] . Green Chemistry , 2015 , 17 ( 2 ): 1186 - 1193 .

刘颖 , 刘甲 , 杨国强 , 等 . 相转移催化H 2 O 2 氧化环己烯合成环氧环己烷的工艺研究 [J ] . 南京大学学报 , 2019 , 55 ( 5 ): 850 - 858 .

Liu Y , Liu J , Yang G Q , et al . Study on phase transfer catalytic synthesis of epoxycyclohexene by H 2 O 2 oxidation of cyclohexene [J ] . Journal of Nanjing University , 2019 , 55 ( 5 ): 850 - 858 .

Yang G Q , Huff M D , Du H Y , et al . Increased selectivity for allylic oxidation of cyclohexene using TiO 2 modified V 2 O 5 /MoO 3 catalysts [J ] . Catalysis Communications , 2017 , 99 : 43 - 48 .

Ji L , Wang Y N , Qian C , et al . Nitrile-promoted alkene epoxidation with urea–hydrogen peroxide (UHP) [J ] . Synthetic Communications , 2013 , 43 ( 16 ): 2256 - 2264 .

马晓雪 , 梁坤豪 , 魏杰 , 等 . 醚基高铼酸盐离子液体的催化性能研究 [J ] . 化工学报 , 2020 , 71 ( 1 ): 314 - 319 .

Ma X X , Liang K H , Wei J , et al . Study on catalytic properties of novel ether-based peerhenate ionic liquids [J ] . CIESC Journal , 2020 , 71 ( 1 ): 314 - 319 .

Yang G Q , Du H Y , Liu J , et al . Oxidation of olefins using molecular oxygen catalyzed by a part per million level of recyclable copper catalyst under mild conditions [J ] . Green Chemistry , 2017 , 19 ( 3 ): 675 - 681 .

Dou J , Tang Y , Nguyen L , et al . Oxidation of cyclohexene catalyzed by nanoporous Au(Ag) in liquid phase [J ] . Catalysis Letters , 2017 , 147 ( 2 ): 442 - 452 .

Zhu Y , Qian H , Drake B , et al . Atomically precise Au25(SR)18 nanoparticles as catalysts for the selective hydrogenation of α,β-unsaturated ketones and aldehydes [J ] . Angewandte Chemie International Edition , 2010 , 49 ( 7 ): 1295 - 1298 .

Fu Q , Saltsburg H , Flytzani-Stephanopoulos M . Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts [J ] . Science , 2003 , 301 ( 5635 ): 935 - 938 .

Wang L , Wang H , Hapala P , et al . Superior catalytic properties in aerobic oxidation of olefins over Au nanoparticles on pyrrolidone-modified SBA-15 [J ] . Journal of Catalysis , 2011 , 281 ( 1 ): 30 - 39 .

Gniewek A , Trzeciak A M , Ziółkowski J J , et al . Pd-PVP colloid as catalyst for Heck and carbonylation reactions: TEM and XPS studies [J ] . Journal of Catalysis , 2005 , 229 ( 2 ): 332 - 343 .

Liu H , Jiang T , Han B , et al . Selective phenol hydrogenation to cyclohexanone over a dual supported Pd-Lewis acid catalyst [J ] . Science , 2009 , 326 ( 5957 ): 1250 - 1252 .

Enache D I , Edwards J K , Landon P , et al . Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO 2 catalysts [J ] . Science , 2006 , 311 ( 5759 ): 362 - 365 .

Gao F , Goodman D W . Pd-Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles [J ] . Chemical Society Reviews , 2012 , 41 ( 24 ): 8009 - 8020 .

Nomura Y , Ishihara T , Hata Y , et al . Nanocolloidal Pd-Au as catalyst for the direct synthesis of hydrogen peroxide from H 2 and O 2 [J ] . ChemSusChem , 2008 , 1 ( 7 ): 619 - 621 .

Pritchard J , Kesavan L , Piccinini M , et al . Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au-Pd catalysts prepared by sol immobilization [J ] . Langmuir , 2010 , 26 ( 21 ): 16568 - 16577 .

Du J , Qi J , Wang D , et al . Facile synthesis of Au@TiO 2 core-shell hollow spheres for dye-sensitized solar cells with remarkably improved efficiency [J ] . Energy & Environmental Science , 2012 , 5 ( 5 ): 6914 - 6918 .

Park J Y , Lee H , Renzas J R , et al . Probing hot electron flow generated on Pt nanoparticles with Au/TiO 2 Schottky diodes during catalytic CO oxidation [J ] . Nano Letters , 2008 , 8 ( 8 ): 2388 - 2392 .

Furube A , Du L , Hara K , et al . Ultrafast plasmon-induced electron transfer from gold nanodots into TiO 2 nanoparticles [J ] . Journal of the American Chemical Society , 2007 , 129 ( 48 ): 14852 - 14853 .

Hadian D L , Hosseini M H . Enantioselective aerobic oxidation of olefins by magnetite nanoparticles at room temperature: a chiral carboxylic acid strategy [J ] . Green Chemistry , 2016 , 18 ( 2 ): 497 - 507 .

Liu Y Y , Leus K , Bogaerts T , et al . Bimetallic-organic framework as a zero-leaching catalyst in the aerobic oxidation of cyclohexene [J ] . ChemCatChem , 2013 , 5 ( 12 ): 3657 - 3664 .

Serra A C , Rocha G , António M . Mild oxygen activation with isobutyraldehyde promoted by simple salts [J ] . Tetrahedron Letters , 2011 , 52 ( 27 ): 3489 - 3491 .

Payne G B , Deming P H , Williams P H . Reactions of hydrogen peroxide(Ⅶ): Alkali-catalyzed epoxidation and oxidation using a nitrile as co-reactant [J ] . The Journal of Organic Chemistry , 1961 , 26 ( 3 ): 659 - 663 .

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

DOI：10.11949/0438-1157.20200778

摘要

Abstract

关键词

Keywords

references

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