SiO2负载的Au-Ni双金属催化剂在乙炔选择加氢反应中的应用

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1338-1346.

SiO₂负载的Au-Ni双金属催化剂在乙炔选择加氢反应中的应用

柴梦倩^a,b, 刘晓艳^a, 李林^a, 裴广贤^a,b, 任煜京^a,b, 苏杨^a, 程鸿魁^c, 王爱琴^a, 张涛^a

a 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;
b 中国科学院大学, 北京 100049;
c 正大能源材料(大连)股份有限公司, 辽宁大连 116021

收稿日期:2017-04-14 修回日期:2017-06-06 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 刘晓艳
基金资助:
国家自然科学基金（21303194，21476227，21522608，21573232，21690084）；中国科学院青年促进会（2014163）；国家重点研发计划“纳米科技”重点专项（2016YFA0202801）；中国科学院战略性先导科技专项（XDB17020100）；辽宁省科技厅（2015020086-101）.

SiO₂-supported Au-Ni bimetallic catalyst for the selective hydrogenation of acetylene

Mengqian Chai^a,b, Xiaoyan Liu^a, Lin Li^a, Guangxian Pei^a,b, Yujing Ren^a,b, Yang Su^a, Hongkui Cheng^c, Aiqin Wang^a, Tao Zhang^a

a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c Chia Tai Energy Materials(Dalian) Co., Ltd., Dalian 116021, Liaoning, China

Received:2017-04-14 Revised:2017-06-06 Online:2017-08-18 Published:2017-08-04
Supported by:
This work was supported by the National Natural Science Foundation of China (21303194, 21476227, 21522608, 21573232, 21690084), Youth Innovation Promotion Association of the Chinese Academy of Sciences (2014163), the National Key Projects for Fundamental Research and Development of China (2016YFA0202801), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), and the Department of Science and Technology of Liaoning Province (2015020086-101).

摘要/Abstract

摘要：

负载型Au催化剂在乙炔选择加氢反应中表现出很高的乙烯选择性，但其转化率相对较低.通过添加第二种金属如Pd，Fe，Ag和Cu等，制备双金属催化剂是提高其在加氢反应中催化活性的一种非常有效的手段.其中Au-Pd双金属催化剂是最受关注的体系之一，Pd的加入可以非常显著地提高其催化乙炔选择加氢反应的活性.据文献报道，与Pd同一主族的Ni也具有较好的加氢活性.尽管与Pd相比，Ni很难与Au形成合金，但目前已有Au-Ni双金属催化剂在多种反应中表现出协同效应的报道，如水气变换、CO氧化以及芳香硝基化合物选择加氢等.因此，向Au催化剂中添加Ni也可能提高催化剂在乙炔选择加氢反应中的催化活性.
因此，我们采用两步法制备了一系列SiO₂负载的具有不同Ni：Au原子比的Au-Ni双金属催化剂，并将其用于乙炔选择加氢反应，发现Au-Ni双金属催化剂在该反应中表现出了显著的协同效应，其活性明显优于相应单金属催化剂的活性.尽管其乙烯选择性略低于单金属Au催化剂，但明显高于单金属Ni催化剂.通过调节还原温度和/或Ni：Au的比例，对催化剂的性能进行了优化.结果显示，当Ni：Au=0.5时，催化剂表现出最优的综合性能，即兼具较高的乙炔转化率和乙烯选择性.
为了研究Au-Ni双金属催化剂中金属纳米粒子的结构、组成以及Au-Ni之间的相互作用，我们对催化剂进行了X射线衍射（XRD）、高分辨透射电镜（HRTEM）、能量散射谱（EDS）以及原位红外光谱（DRIFTS）表征.XRD和TEM结果显示，催化剂中的Au-Ni双金属纳米粒子都具有高分散和粒径均匀的特点.通过EDS分析，发现在Au-Ni双金属催化剂中的单个金属纳米粒子同时含有Au和Ni两种元素，尽管每个纳米粒子中Ni：Au的比例有差异.HRTEM结果发现，Au-Ni双金属纳米粒子的晶格间距介于Au（111）和Ni（111）的晶面间距之间，说明在Au-Ni双金属催化剂中有Au-Ni合金形成.原位DRIFTS结果显示，在Au-Ni双金属催化剂中，Au的存在促进了Ni的还原，说明Au与Ni之间存在紧密的相互作用.综上可见，Au和Ni在乙炔选择加氢反应中所表现出的协同效应主要归功于Au-Ni合金的形成，其中金属态Ni起主要的活性作用，而Au的存在则提高了催化剂的乙烯选择性.

关键词: 金, 镍, 双金属催化剂, 协同效应, 乙炔加氢

Abstract:

Supported Au catalysts have been reported to exhibit high ethylene selectivity in the hydrogenation of acetylene, but the conversion is relatively low. Adding a second metal to Au has proven to be a promising approach to enhance its catalytic performance in acetylene hydrogenation. In this work, SiO₂-supported Au-Ni bimetallic catalysts were synthesized and investigated in the selective hydrogenation of acetylene. The Au-Ni bimetallic catalysts exhibited much higher catalytic performance than that of the corresponding monometallic Au or Ni catalysts. By tuning the reduction temperature and/or Ni loading, we obtained an Au-Ni/SiO₂ catalyst with optimal performance. The results of transmission electron microscopy imaging revealed that the Au-Ni bimetallic particles were highly dispersed on the SiO₂ support. Meanwhile, analysis of the bimetallic catalyst by energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrated the formation of Au-Ni alloy, which contributed to the synergistic effect between Au and Ni in the hydrogenation of acetylene.

Key words: Gold, Nickel, Bimetallic catalyst, Synergistic effect, Acetylene hydrogenation

柴梦倩, 刘晓艳, 李林, 裴广贤, 任煜京, 苏杨, 程鸿魁, 王爱琴, 张涛. SiO₂负载的Au-Ni双金属催化剂在乙炔选择加氢反应中的应用[J]. 催化学报, 2017, 38(8): 1338-1346.

Mengqian Chai, Xiaoyan Liu, Lin Li, Guangxian Pei, Yujing Ren, Yang Su, Hongkui Cheng, Aiqin Wang, Tao Zhang. SiO₂-supported Au-Ni bimetallic catalyst for the selective hydrogenation of acetylene[J]. Chinese Journal of Catalysis, 2017, 38(8): 1338-1346.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/

https://www.cjcatal.com/CN/Y2017/V38/I8/1338

参考文献

[1] B. M. Collins, US Patent 4126645, 1978.
[2] A. Borodzinski, G. C. Bond, Catal. Rev. Sci. Eng., 2006, 48, 91-144.
[3] A. Borodzinski, G. C. Bond, Catal. Rev. Sci. Eng., 2008, 50, 379-469.
[4] B. Yang, R. Burch, C. Hardacre, G. Headdock, P. Hu, ACS Catal., 2012, 2, 1027-1032.
[5] A. Borodzinski, A. Cybulski, Appl. Catal. A, 2000, 198, 51-66.
[6] J. Osswald, K. Kovnir, M. Armbruster, R. Giedigkeit, R. E. Jentoft, U. Wild, Y. Grin, R. Schlogl, J. Catal., 2008, 258, 219-227.
[7] T. V. Choudhary, C. Sivadinarayana, A. K. Datye, D. Kumar, D. W. Goodman, Catal. Lett., 2003, 86, 1-8.
[8] Y. H. Park, G. L. Price, Ind. Eng. Chem. Res., 1992, 31, 469-474.
[9] J. Panpranot, K. Kontapakdee, P. Praserthdam, J. Phys. Chem. B, 2006, 110, 8019-8024.
[10] I. Y. Ahn, H. L. Ji, S. S. Kum, S. H. Moon, Catal. Today, 2007, 123, 151-157.
[11] Q. W. Zhang, J. Li, X. X. Liu, Q. M. Zhu, Appl. Catal. A, 2000, 197, 221-228.
[12] M. Haruta, T. Kobayashi, H. Sano, N. Yamada, Chem. Lett., 1987, 405-408.
[13] Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Science, 2003, 301, 935-938.
[14] C. Della Pina, E. Falletta, M. Rossi, Chem. Soc. Rev., 2012, 41, 350-369.
[15] H. S. Wei, X. F. Wei, X. Yang, G. Z. Yin, A. Q. Wang, X. Y. Liu, Y. Q. Huang, T. Zhang, Chin. J. Catal., 2015, 36, 160-167.
[16] Y. Tan, X. Y. Liu, L. L. Zhang, A. Q. Wang, L. Li, X. L. Pan, S. Miao, M. Haruta, H. S. Wei, H. Wang, F. J. Wang, X. D. Wang, T. Zhang, An-gew. Chem. Int. Ed., 2017, 56, 2709-2713.
[17] C. Aprile, A. Corma, M. E. Domine, H. Garcia, C. Mitchell, J. Catal., 2009, 264, 44-53.
[18] A. C. Gluhoi, J. W. Bakker, B. E. Nieuwenhuys, Catal. Today, 2010, 154, 13-20.
[19] X. Y. Liu, C. Y. Mou, S. Lee, Y. N. Li, J. Secrest, B. W. L. Jang, J. Catal., 2012, 285, 152-159.
[20] X. L. Yan, J. H. Bao, C. Yuan, J. Wheeler, W. Y. Lin, R. F. Li, B. W. L. Jang, J. Catal., 2016, 344, 194-201.
[21] A. Sarkany, A. Horvath, A. Beck, Appl. Catal. A, 2002, 229, 117-125.
[22] A. Sarkany, Z. Schay, K. Frey, E. Szeles, I. Sajo, Appl. Catal. A, 2010, 380, 133-141.
[23] X. Y. Liu, Y. N. Li, J. W. Lee, C. Y. Hong, C. Y. Mou, B. W. Jang, Appl. Catal. A, 2012, 439, 8-14.
[24] J. W. Lee, X. Y. Liu, C. Y. Mou, J. Chin. Chem. Soc., 2013, 60, 907-914.
[25] A. Sarkany, O. Geszti, G. Safran, Appl. Catal. A, 2008, 350, 157-163.
[26] A. J. McCue, R. T. Baker, J. A. Anderson, Faraday Discuss., 2016, 188, 499-523.
[27] G. Kyriakou, M. B. Boucher, A. D. Jewell, E. A. Lewis, T. J. Lawton, A. E. Baber, H. L. Tierney, M. Flytzani-Stephanopoulos, E. H. Sykes, Science, 2012, 335, 1209-1212.
[28] G. X. Pei, X. Y. Liu, A. Q. Wang, L. Li, Y. Q. Huang, T. Zhang, J. W. Lee, B. W. L. Jang, C. Y. Mou, New J. Chem., 2014, 38, 2043-2051.
[29] S. Hwang, J. Lee, U. G. Hong, J. C. Jung, J. H. Baik, D. J. Koh, H. Lim, I. K. Song, J. Nanosci. Nanotechnol., 2012, 12, 6051-6057.
[30] H. Ozay, Sci. Adv. Mater., 2013, 5, 575-582.
[31] H. Nishikawa, D. Kawamoto, Y. Yamamoto, T. Ishida, H. Ohashi, T. Akita, T. Honma, H. Oji, Y. Kobayashi, A. Hamasaki, T. Yokoyama, M. Tokunaga, J. Catal., 2013, 307, 254-264.
[32] S. A. Nikolaev, E. V. Golubina, L. M. Kustov, A. L. Tarasov, O. P. Tkachenko, Kinet. Catal., 2014, 55, 311-318.
[33] A. V. Chistyakov, P. A. Zharova, M. V. Tsodikov, S. A. Nikolaev, I. N. Krotova, D. I. Ezzhelenko, Kinet. Catal., 2016, 57, 803-811.
[34] A. Aguilar-Tapia, L. Delannoy, C. Louis, C. W. Han, V. Ortalan, R. Zanella, J. Catal., 2016, 344, 515-523.
[35] Y. Azizi, C. Petit, V. Pitchon, J. Catal., 2008, 256, 338-334.
[36] G. X. Pei, X. Y. Liu, A. Q. Wang, A. F. Lee, M. A. Isaacs, L. Li, X. L. Pan, X. F. Yang, X. D. Wang, Z. J. Tai, K. Wilson, T. Zhang, ACS Catal., 2015, 5, 3717-3725.
[37] G. X. Pei, X. Y. Liu, X. F. Yang, L. L. Zhang, A. Q. Wang, L. Li, H. Wang, X. D. Wang, T. Zhang, ACS Catal., 2017, 7, 1491-1500.
[38] S. Labat, F. Bocquet, B. Gilles, O. Thomas, Scripta Mater., 2004, 50, 717-721.
[39] M. Tsuji, D. Yamaguchi, M. Matsunaga, K. Ikedo, Cryst. Growth Des., 2011, 11, 1995-2005.
[40] S. H. Zhou, Z. Ma, H. F. Yin, Z. L. Wu, B. Eichhorn, S. H. Overbury, S. Dai, J. Phys. Chem. C, 2009, 113, 5758-5765.
[41] X. Y. Liu, A. Q. Wang, X. D. Wang, C. Y. Mou, T. Zhang, Chem. Com-mun., 2008, 3187-3189.
[42] X. Wei, X. F. Yang, A. Q. Wang, L. Li, X. Y. Liu, T. Zhang, C. Y. Mou, J. Li, J. Phys. Chem. C, 2012, 116, 6222-6232.
[43] A. Q. Wang, X. Y. Liu, C. Y. Mou, T. Zhang, J. Catal., 2013, 308, 258-271.
[44] D. S. Wang,Y. D. Li, J. Am. Chem. Soc., 2010, 132, 6280-6281.
[45] X. Y. Liu, M. H. Liu, Y. C. Luo, C. Y. Mou, S. D. Lin, H. K. Cheng, J. M. Chen, J. F. Lee, T. S. Lin, J. Am. Chem. Soc., 2012, 134, 10251-10258.
[46] M. Mihaylov, H. Knoezinger, K. Hadjiivanov, B. C. Gates, Chem. Ing. Tech., 2007, 79, 795-806.
[47] K. I. Hadjiivanov, G. N. Vayssilov, Adv. Catal., 2002, 47, 307-511.
[48] S. A. Nikolaev, D. A. Pichugina, D. F. Mukhamedzyanova, Gold Bull., 2012, 45, 221-231.
[49] X. Y. Liu, C. Y. Mou, S. Lee, Y. N. Li, J. Secrest, B. W. L. Jang, J. Catal., 2012, 285, 152-159.
[50] M. Boronat, P. Concepción, A. Corma, J. Phys. Chem. C, 2009, 113, 16772-16784.
[51] J. H. Xu, Y. Q. Huang, X. F. Yang, L. He, H. R. Zhou, Q. Q. Lin, T. Zhang, H. R. Geng, J. Nanosci. Nanotechnol., 2014, 14, 6894-6899.

SiO₂负载的Au-Ni双金属催化剂在乙炔选择加氢反应中的应用

SiO₂-supported Au-Ni bimetallic catalyst for the selective hydrogenation of acetylene

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[2]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[3]	李世杰, 王春春, 董珂欣, 张鹏, 陈晓波, 李鑫. 新型MIL-101(Fe)/BiOBr S型异质催化剂用于高效光催化降解抗生素和还原六价铬: 光催化性能分析和光催化机理研究[J]. 催化学报, 2023, 51(8): 101-112.
[4]	尹春, 杨甫林, 王书莉, 冯立纲. 异质结构NiSe₂/MoSe₂用于高效尿素辅助电解水制氢[J]. 催化学报, 2023, 51(8): 225-236.
[5]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[6]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[7]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.
[8]	周波, 石建巧, 姜一民, 肖磊, 逯宇轩, 董帆, 陈晨, 王特华, 王双印, 邹雨芹. 强化脱氢动力学实现超低电池电压和大电流密度下抗坏血酸电氧化[J]. 催化学报, 2023, 50(7): 372-380.
[9]	李慧杰, 池漫洲, 辛兴, 王瑞杰, 刘天府, 吕红金, 杨国昱. 异金属取代的多金属氧酸盐@光响应型金属-有机框架用于高选择性光催化CO₂还原[J]. 催化学报, 2023, 50(7): 343-351.
[10]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. 用于电化学能量转换反应的非贵金属单原子催化剂[J]. 催化学报, 2023, 50(7): 195-214.
[11]	刘德法, 孙彬, 白硕杰, 高婷婷, 周国伟. 双助催化剂Ag/Ti₃C₂/TiO₂分层花状微球用于增强光催化产氢活性[J]. 催化学报, 2023, 50(7): 273-283.
[12]	刘诗瑶, 巩玉同, 杨晓, 张楠楠, 刘会斌, 梁长海, 陈霄. 具有富电子镍位点的耐酸金属间化合物CaNi₂Si₂催化剂用于不饱和有机酸酐/酸的水相加氢[J]. 催化学报, 2023, 50(7): 260-272.
[13]	韩璟怡, 管景奇. 通过限域-热解策略可控合成双原子催化剂[J]. 催化学报, 2023, 49(6): 1-4.
[14]	张功, 张炜松, 王小雨, 杨洋, 季定纬, 万伯顺, 陈庆安. 镍催化杂芳烃的非天然戊烯基化及环状单萜化反应[J]. 催化学报, 2023, 49(6): 123-131.
[15]	娄向西, 高璇, 刘钰, 褚名宇, 张丛洋, 邱盈华, 杨文秀, 曹暮寒, 王贵领, 张桥, 陈金星. 高效光热催化废旧聚酯塑料升级回收[J]. 催化学报, 2023, 49(6): 113-122.