Ce-Zr 复合氧化物负载 Au 纳米粒子催化甲醇氧化反应中的载体效应

doi:10.3724/SP.J.1088.2012.20543

摘要/Abstract

摘要： 采用沉积-沉淀法制备了不同 Ce/Zr 比的 Au/Ce_1-xZr_xO₂ (x = 0, 0.2, 0.4, 0.6, 0.8) 催化剂, 研究了其催化甲醇完全氧化反应和选择氧化反应中的载体效应. 通过 X 射线衍射、拉曼光谱、X 射线光电子能谱、高分辨透射电镜、CO₂ 和 NH₃ 程序升温脱附以及 CO 吸附红外光谱等手段表征了催化剂的结构、组成和酸碱性. 结果表明, 这些催化剂具有相似的载体粒径和晶相结构、Au 担载量、Au 粒径和价态以及相似的表面酸碱性等. 在甲醇完全氧化和甲醇选择氧化反应中, Au/Ce_1-xZr_xO₂ 催化剂活性均随载体中 Ce/Zr 比的减小而降低. 与催化剂储氧量, 即表面活性氧浓度下降一致. 对于甲醇选择氧化反应, 甲酸甲酯选择性则随 Ce/Zr 比减小而升高. 这不是由于催化剂表面酸碱性差异所致, 而是与催化剂载体中 Ce 含量降低导致的表面活性氧浓度减小和催化剂的氧化能力减弱密切相关. Au 催化剂载体效应本质的认识将有助于为目标氧化反应设计具有更高活性或选择性的催化剂体系.

关键词: 氧化铈, 氧化锆, 复合氧化物, 纳米金, 甲醇氧化, 载体效应, 储氧量, 甲酸甲酯

Abstract: Ce-Zr oxide-supported nano-sized Au catalysts Au/Ce_1-xZr_xO₂ (x = 0, 0.2, 0.4, 0.6, 0.8) were prepared by a deposition-precipitation method. Their catalytic properties were examined in both the combustion of methanol and the selective oxidation of methanol to methyl formate. The composition and structure of the catalysts were characterized by complementary methods including nitrogen physisorption, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and high resolution transmission electron microscopy. Their acidity and basicity were probed by CO₂ and NH₃ temperature-programmed desorption and also Fourier transform infrared spectroscopy for CO adsorption. The characterization results showed that the catalysts possessed similar particle size and phase of the Ce_1-xZr_xO₂supports, and their Au nanoparticles were of around 3.0 nm mainly in the state of Au⁰. In the CH₃OH combustion reaction (1% CH₃OH + 14% O₂), the activity of the Au/Ce_1-xZr_xO₂ catalysts decreased with decreasing the Ce contents in the Ce_1-xZr_xO₂ supports. Similar change was also found in the methanol selective oxidation (6% CH₃OH + 3% O₂), while the selectivity to methyl formate increased with decreasing the Ce contents. Such changes in the catalytic activity of the Au/Ce_1-xZr_xO₂ catalysts were in positive parallel with their oxygen storage capacity values, which reflect the number of the lattice oxygen atoms active for the methanol oxidation. The support effects on the selectivity for methyl formate were clear not due to effects of the supports on the acid-base properties of the catalysts but to the effects on the active lattice oxygen atoms on catalyst surfaces and consequently their reducibility. Such understanding on the support effects provides useful information for design of oxide-supported Au catalysts with improved activity or selectivity for the targeted oxidation reactions.

Key words: ceria, zirconia, mixed oxide, nano-gold, methanol oxidation, support effect, oxygen storage capacity, methyl formate

张鸿鹏, 刘海超. Ce-Zr 复合氧化物负载 Au 纳米粒子催化甲醇氧化反应中的载体效应[J]. 催化学报, 2013, 34(1): 235-242.

ZHANG Hong-Peng, LIU Hai-Chao. Support Effects on Properties of Ce-Zr Mixed Oxide-Supported Gold Catalysts in Oxidation of Methanol[J]. Chinese Journal of Catalysis, 2013, 34(1): 235-242.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.3724/SP.J.1088.2012.20543

https://www.cjcatal.com/CN/Y2013/V34/I1/235

参考文献

1 Bond G C, Thompson D T. Catal Rev-Sci Eng, 1999, 41: 319
2 Haruta M, Daté M. Appl Catal A, 2001, 222: 427
3 Choudhary T V, Goodman D W. Top Catal, 2002, 21: 25
4 Kung H H, Kung M C, Costello C K. J Catal, 2003, 216: 425
5 Stephen A, Hashmi K, Hutchings G J. Angew Chem, Int Ed, 2006, 45: 7896
6 Grzybowska-Swierkosz B. Catal Today, 2006, 112: 3
7 Kung M C, Davis R J, Kung H H. J Phys Chem C, 2007, 111: 11767
8 Della Pina C, Falletta E, Prati L, Rossi M. Chem Soc Rev, 2008, 37: 2077
9 Corma A, Garcia H. Chem Soc Rev, 2008, 37: 2096
10 Ma Zh, Dai Sh. Nano Res, 2011, 4: 3
11 Wei Y Ch, Liu J, Zhao Zh, Duan A J, Jiang G Y. J Catal, 2012, 287: 13
12 Lopez N, Janssens T V W, Clausen B S, Xu Y, Mavrikakis M, Bligaard T, Nørskov J K. J Catal, 2004, 223: 232
13 Choudhary T V, Goodman D W. Appl Catal A, 2005, 291: 32
14 Grunwaldt J-D, Maciejewski M, Becker O S, Fabrizioli P, Baiker A. J Catal, 1999, 186: 458
15 Bond G C, Thompson D T. Gold Bull, 2000, 33: 41
16 Haruta M. Gold Bull, 2004, 37: 27
17 Weiher N, Bus E, Delannoy L, Louis C, Ramaker D E, Miller J T, van Bokhoven J A. J Catal, 2006, 240: 100
18 Carrettin S, Concepción P, Corma A, Lopez-Nieto J M, Puntes V F. Angew Chem, Int Ed, 2004, 43: 2538
19 Zhang X, Wang H, Xu B Q. J Phys Chem B, 2005, 109: 9678
20 Schubert M M, Hackenberg S, van Veen A C, Muhler M, Plzak V, Behm R J. J Catal, 2001, 197: 113
21 Janssens T V W, Carlsson A, Puig-Molina A, Clausen B S. J Catal, 2006, 240: 108
22 Kotobuki M, Leppelt R, Hansgen D A, Widmann D, Behm R J. J Catal, 2009, 264: 67
23 Dobrosz-Gomez I, Kocemba I, Rynkowski J M. Appl Catal B, 2008, 83: 240
24 Dobrosz-Gomez I, Kocemba I, Rynkowski J M. Appl Catal B, 2009, 88: 83
25 Dobrosz-Gomez I, Kocemba I, Rynkowski J M. Catal Lett, 2009, 128: 297
26 Dobrosz-Gomez I, Gomez-Garcia M A, Rynkowski J M. Pol J Environ Stud, 2009, 18: 587
27 Dobrosz-Gomez I, Gomez-Garcia M A, Rynkowski J M. Kinet Catal, 2010, 51: 823
28 Si R, Zhang Y W, Li Sh J, Lin B X, Yan Ch H. J Phys Chem B, 2004, 108: 12481
29 Zhang H P, Liu H Ch. J Nat Gas Chem, 2012, in press.
30 Tatibouët J M. Appl Catal A, 1997, 148: 213
31 Xu B J, Liu X Y, Haubrich J, Madix R J, Friend C M. Angew Chem, Int Ed, 2009, 48: 4206
32 Wittstock A, Zielasek V, Biener J, Friend C M, Bäumer M. Science, 2010, 327: 319
33 Han M M, Wang X J, Shen Y N, Tang Ch H, Li G Sh, Smith R L Jr. J Phys Chem C, 2010, 114: 793
34 Liu H, Iglesia E. J Phys Chem B, 2005, 109: 2155
35 Manzoli M, Boccuzzi F, Chiorino A, Vindigni F, Deng W L, Flytzani-Stephanopoulos M. J Catal, 2007, 245: 308

编辑推荐

Metrics

阅读次数

全文

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	0	0	0	30

来源	本网站	其他网站

次数	29	1
比例	97%	3%

摘要

最新录用	在线预览	正式出版

0	0	89

	来源	本网站

	次数	89
	比例	100%

[1]	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.
[2]	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.
[3]	刘华, 康磊磊, 王华, 蒋齐可, 刘晓艳, 王爱琴. 硫酸化氧化锆负载的Ru单原子催化甲烷直接转化制甲醇[J]. 催化学报, 2023, 46(3): 64-71.
[4]	魏英聪, 张琪琪, 周颖, 马雄风, 王乐乐, 王严杰, 洒荣建, 龙金林, 付贤智, 员汝胜. 非贵金属等离子共振增强MoO_3-_x基S型异质结光催化苯甲醇氧化同步产氢和苯甲醛[J]. 催化学报, 2022, 43(10): 2665-2677.
[5]	陈军伟, 欧祖翘, 陈海鑫, 宋树芹, 王昆, 王毅. 电催化剂纳米碳基载体的研究进展[J]. 催化学报, 2021, 42(8): 1297-1326.
[6]	钟静萍, 黄科薪, 许文涛, 唐华果, Muhammad Waqas, 樊友军, 王睿翔, 陈卫, 王沂轩. 导电共聚物衍化新策略制备硫、氮共掺杂碳纳米管及其对改善PtCu纳米晶分散性与甲醇电催化氧化的促进作用[J]. 催化学报, 2021, 42(7): 1205-1215.
[7]	李石波, 田植群, 刘洋, 蒋政, 哈森, 陈兴发, 帕纳斯, 沈培康. 分级骨架和多层的Pt-Ni纳米晶体用于高效氧还原和甲醇氧化反应[J]. 催化学报, 2021, 42(4): 648-657.
[8]	谭媛, 刘晓艳, 张磊磊, 刘菲, 王爱琴, 张涛. 纳米金催化肉桂醛选择加氢制肉桂醇[J]. 催化学报, 2021, 42(3): 470-481.
[9]	刘建芳, 冉真真, 曹琪岩, 季生福. MIL-88B(Fe_x, Co_1‒_x)催化剂制备及甲醇液相H₂O₂氧化一步合成甲酸甲酯[J]. 催化学报, 2021, 42(12): 2254-2264.
[10]	董春燕, 周燕, 塔娜, 刘雯璐, 李名润, 申文杰. 氧化铈形貌对Pd纳米粒子分散的影响[J]. 催化学报, 2021, 42(12): 2234-2241.
[11]	王翔, 李美俊, 吴自力. 二氧化铈催化剂的氧化还原和酸碱性质的原位光谱表征[J]. 催化学报, 2021, 42(12): 2122-2140.
[12]	林炳裕, 吴玉远, 方笔耘, 李春艳, 倪军, 王秀云, 林建新, 江莉龙. 氧化铈负载钌催化剂中钌表面密度对氨合成活性和氢中毒的影响[J]. 催化学报, 2021, 42(10): 1712-1723.
[13]	杨彬, 邓威, 郭利民, 石原逹己. 铜-氧化铈固溶体催化剂用于二氧化碳催化加氢制甲醇[J]. 催化学报, 2020, 41(9): 1348-1359.
[14]	Sara Colussi, Paolo Fornasiero, Alessandro Trovarelli. Pd/CeO₂甲烷氧化催化剂的构效关系[J]. 催化学报, 2020, 41(6): 938-950.
[15]	James Kammert, Jisue Moon, Zili Wu. 二氧化铈与氢气之间相互作用及其在炔烃选择加氢中的应用[J]. 催化学报, 2020, 41(6): 901-914.