TEM与HAADF法表征Ru/C催化剂活性中心
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摘要
采用TEM与HAADF法研究表征了Ni-Ru/C催化剂的活性中心。由于成像衬度较弱,TEM能够辨别Ru纳米粒子而遗漏Ni纳米粒子,HAADF则可以同时实现辨识C载体上的Ru与Ni金属纳米颗粒。Ni-Ru/C催化剂活性中心包含孤立型及拱月型两种,其数量比例约为1/2。Ru与Ni纳米颗粒平均尺寸分别为2.58、0.88nm,其中Ru纳米晶粒以(010)晶面暴露为主。通过联用TEM及HAADF法表征炭基贵金属催化剂得到相对于单纯使用TEM或化学吸附法更为全面的活性中心分散状态、粒径尺寸及与助剂的相互关系等信息,从而在高性能催化剂的研发中发挥技术支撑作用。
Activity centers of Ni-Ru/C were characterized by TEM and HAADF Methods. Ru nanoparticles can be distinguished by TEM, while a large number of Ni particles were omitted due to the weak mass thickness contrast of the sample.HAADF can identify the Ru and Ni nanoparticles on the C carrier. Active centers of the catalyst included two types, isolated type and arched type, with the ratio of approximately 1/2. The average sizes of Ru and Ni nanoparticles were 2.58 nm and 0.88 nm, respectively. Ru nanocrystals were mainly exposed by(010) crystal planes.The dispersion state, particle size and relationship of the carbon-based noble meta catalysts were comprehensively presented by combining TEM and HAADF method, which could play an important technical support role in the development of high performance catalysts.
Activity centers of Ni-Ru/C were characterized by TEM and HAADF Methods. Ru nanoparticles can be distinguished by TEM, while a large number of Ni particles were omitted due to the weak mass thickness contrast of the sample.HAADF can identify the Ru and Ni nanoparticles on the C carrier. Active centers of the catalyst included two types, isolated type and arched type, with the ratio of approximately 1/2. The average sizes of Ru and Ni nanoparticles were 2.58 nm and 0.88 nm, respectively. Ru nanocrystals were mainly exposed by(010) crystal planes.The dispersion state, particle size and relationship of the carbon-based noble meta catalysts were comprehensively presented by combining TEM and HAADF method, which could play an important technical support role in the development of high performance catalysts.
引文
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[19]Rossetti I., Pernicone N., Forni L.. Characterisation of Ru/C catalysts for ammonia synthesis by oxygen chemisorption[J]. Applied Catalysis A:General, 2003,248(1):97-103.
[20]陈高升,王筱喃,王学海.不同载体和金属助剂负载Pt催化剂对丙烷催化氧化活性研究[J].当代化工,2016,45(8):1735-1739.
[2]施天伟,严新焕,王骏鹏,等. Ru/C催化剂的制备及催化喹啉加氢性能研究[J].精细化工, 2015,32(12):1382-1387.
[3]王骏鹏,姚健龙,施天伟,等. Ru/C催化剂的制备及其催化双酚A加氢的研究[J].现代化工, 2016,36(5):61-64.
[4]李建修,杜啸岚. Ru/C催化剂在苯选择加氢反应中的催化性能[J].合成纤维工业, 2011,34(5):33-35.
[5]沈亚峰,雷远进,沈善问,等.以醋酸钌为前驱体的Ru/C催化剂在葡萄糖加氢制取山梨醇反应中活性的研究J].贵金属, 2009,30(1):40-44+52.
[6]郭方,王越吕连海.高分散度Ru/C选择性催化对氯硝基苯加氢制备对氯苯胺[J].精细化工, 2007,24(3):252-256.
[7]L. Roiban, L. Sorbier, C. Pichon, et al. 3D-TEM investigation of the nanostructure of aδ-Al2O3 catalyst support decorated with Pd nanoparticles[J]. Nanoscale, 2012,4(3):946-954.
[8]L. Kovarik, A. Genc, C. Wang, et al. Tomography and High-Resolution Electron Microscopy Study of Surfaces and Porosity in a Plate-likeγ-Al2O3[J]. The Journal of Physical Chemistry C, 2012,117(1):179-186.
[9]满毅,黄文氢.测试条件对Ni催化剂的金属分散度的影响[J].石油化工, 2014,43(9):1087-1090.
[10]杨卫亚,凌凤香,沈智奇,等.超薄切片与高角环形暗场像联用表征Pd/Al2O3催化剂贵金属的分散性[J].精细石油化工,2017,34(4):1-4.
[11]杨卫亚,凌凤香,沈智奇,等. Pd/Al2O3催化剂贵金属分散性质的表征[J].石油化工, 2017,46(8):985-989.
[12]杨卫亚,沈智奇,王丽华,等.透射电子显微镜及相关技术在多相催化研究中的应用[J].分析测试学报, 2010,29(7):755-760.
[13]贾志宏,丁立鹏,陈厚文.高分辨扫描透射电子显微镜原理及其应用[J].物理, 2015,44(7):446-452.
[14]Wang H., Dong J., L. Allard,F. et al. Single-site Pt/La-Al2O3 stabilized by barium as an active and stable catalyst in purifying CO and C3H6emissions[J]. Applied Catalysis B:Environmental, 2019,244:327-339.
[15]Zhang H., Jin M., Xiong Y., et al. Shape-Controlled Synthesis of Pd Nanocrystals and Their Catalytic Applications[J]. Accounts of chemical research, 2013,46(8):1783-1794.
[16]Chen Q., Jia Y., Xie S., et al. Well-faceted noble-metal nanocrystals with nonconvex polyhedral shapes[J]. Chemical Society Reviews,2016,45(11):3207-3220.
[17]Fang G., Li W., Shen X., et al. Differential Pd-nanocrystal facets demonstrate distinct antibacterial activity against Gram-positive and Gram-negative bacteria[J]. Nature Communications, 2018,9(1):129.
[18]Jin M., Liu H., Zhang H., et al. Synthesis of Pd nanocrystals enclosed by{100}facets and with sizes <10 nm for application in CO oxidation[J].Nano Research, 2011,4(1):83-91.
[19]Rossetti I., Pernicone N., Forni L.. Characterisation of Ru/C catalysts for ammonia synthesis by oxygen chemisorption[J]. Applied Catalysis A:General, 2003,248(1):97-103.
[20]陈高升,王筱喃,王学海.不同载体和金属助剂负载Pt催化剂对丙烷催化氧化活性研究[J].当代化工,2016,45(8):1735-1739.