抗烧结Rh-Sm2O3/SiO2催化剂的制备和表征及其甲烷部分氧化制合成气性能

doi:10.3866/PKU.WHXB201704243

物理化学学报 >> 2017, Vol. 33 >> Issue (8): 1689-1698.doi: 10.3866/PKU.WHXB201704243

抗烧结Rh-Sm₂O₃/SiO₂催化剂的制备和表征及其甲烷部分氧化制合成气性能

郑芳芳,李倩,张宏,翁维正*(),伊晓东,郑燕萍,黄传敬,万惠霖*()

厦门大学化学化工学院,固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室,福建厦门361005

收稿日期:2017-02-21 发布日期:2017-06-14
通讯作者: 翁维正,万惠霖 E-mail:wzweng@xmu.edu.cn;hlwan@xmu.edu.cn
基金资助:
国家重点基础研究发展规划项目(2013CB933102);国家自然科学基金(21473144);国家自然科学基金(21373168);国家基础科学人才培养基金项目(J1310024);教育部创新研究团队项目(IRT_14R31)

Preparation and Characterization of Sinter-Resistant Rh-Sm₂O₃/SiO₂ Catalyst and Its Performance for Partial Oxidation of Methane to Syngas

Fang-Fang ZHENG,Qian LI,Hong ZHANG,Wei-Zheng WENG*(),Xiao-Dong YI,Yan-Ping ZHENG,Chuan-Jing HUANG,Hui-Lin WAN*()

State Key Laboratory of Physical Chemistry of Solid State Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China

Received:2017-02-21 Published:2017-06-14
Contact: Wei-Zheng WENG,Hui-Lin WAN E-mail:wzweng@xmu.edu.cn;hlwan@xmu.edu.cn
Supported by:
The project was supported by the National Key Basic Research Program of China(2013CB933102);National Natural Science Foundation of China(21473144);National Natural Science Foundation of China(21373168);National Talent Development of Basic Research Program of China(J1310024);Program for Innovative Research Team in University, China(IRT_14R31)

摘要/Abstract

摘要：

以乙酰丙酮铑（Rh（acac）₃）和乙酰丙酮钐（Sm（acac）₃）为前驱体，用浸渍法制备了Rh/SiO₂和Rh-Sm₂O₃/SiO₂催化剂。采用原位红外光谱、热重分析、低温N₂吸附、X射线粉末衍射、高分辨透射电子显微镜、H₂-程序升温还原和X射线光电子能谱等实验技术对催化剂的制备过程，比表面积和物相以及Rh与Sm₂O₃间的相互作用进行了表征，并以甲烷部分氧化制合成气为目标反应对催化剂的稳定性进行了考察。研究表明：以Rh（acac）₃和Sm（acac）₃为前驱体采用简单的浸渍法即可制备出Rh平均粒径为2.3 nm且具有良好抗烧结性能的Rh-Sm₂O₃/SiO₂催化剂。在浸渍过程中乙酰丙酮化合物通过与SiO₂表面羟基形成氢键而负载于载体表面。Sm（acac）₃在SiO₂表面的单层负载量（质量分数）约为31%，对应于Sm₂O₃的质量分数约为15%，只要Sm（acac）₃的质量分数低于这一阈值，均可保证分解后生成的Sm₂O₃以高分散形式负载于SiO₂上，且不会因高温（800℃）焙烧而团聚。高分散于SiO₂表面的Sm₂O₃与Rh之间存在强的相互作用，可显著提高Rh的分散度，防止其在高温反应条件下烧结，进而使低Rh负载量的催化剂表现出良好的甲烷部分氧化制合成气反应活性和稳定性。

关键词: Rh-Sm₂O₃/SiO₂, 乙酰丙酮铑, 乙酰丙酮钐, 抗烧结, 甲烷部分氧化, 合成气

Abstract:

Rh/SiO₂ and Rh-Sm₂O₃/SiO₂ catalysts were synthesized by the conventional impregnation method using rhodium acetylacetonate (Rh(acac)₃) and samarium acetylacetonate (Sm(acac)₃) as precursors. The preparation and catalytic properties, as well as the interaction between Rh and Sm₂O₃, were characterized in detail by in situ infrared spectroscopy (IR), thermogravimetric analysis (TG), N₂ physisorption (Brunauer-Emmett-Teller (BET) method), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). The performance of the catalysts for the partial oxidation of methane (POM) to syngas was also investigated. The results showed that a sinter-resistant Rh-Sm₂O₃/SiO₂ catalyst with an average Rh particle size of ~2.3 nm could be synthesized using the conventional impregnation method with Rh(acac)₃ and Sm(acac)₃ as precursors. The surface silanol groups of SiO₂ acted as the centers to interact with M(acac)₃ (M=Rh, Sm) molecules when SiO₂ was impregnated in the M(acac)₃ solution, leading to the formation of a hydrogen-bonded M(acac)₃ layer on the SiO₂ surface. In this experiment, the monolayer coverage of Sm(acac)₃ on the SiO₂ surface was equal to a Sm(acac)₃ loading (mass fraction) of approximately 31%, which in turn corresponded to a Sm₂O₃ loading of approximately 15%. When a Sm(acac)₃/SiO₂ sample with Sm(acac)₃ loading below 31% was heated in air to approximately 360℃, the monolayer Sm(acac)₃ species decomposed into highly dispersed Sm₂O₃ species on the SiO₂ surface, which displayed superior stability against sintering at high temperature. No aggregation of the Sm₂O₃ species was observed even when the sample was heated to 800℃ in air. The strong interaction between the highly dispersed Sm₂O₃ and Rh plays a key role in increasing the dispersion of Rh species in the catalyst and preventing the Rh species from sintering under high temperature conditions. This factor should also be responsible for the superior activity and stability of the Rh-Sm₂O₃/SiO₂ catalyst with extremely low Rh loading for the catalytic partial oxidation of methane to syngas.

Key words: Rh-Sm₂O₃/SiO₂, Rh(acac)₃, Sm(acac)₃, Sinter-resistant, Partial oxidation of methane, Syngas

郑芳芳,李倩,张宏,翁维正,伊晓东,郑燕萍,黄传敬,万惠霖. 抗烧结Rh-Sm₂O₃/SiO₂催化剂的制备和表征及其甲烷部分氧化制合成气性能[J]. 物理化学学报, 2017, 33(8), 1689-1698. doi: 10.3866/PKU.WHXB201704243

Fang-Fang ZHENG,Qian LI,Hong ZHANG,Wei-Zheng WENG,Xiao-Dong YI,Yan-Ping ZHENG,Chuan-Jing HUANG,Hui-Lin WAN. Preparation and Characterization of Sinter-Resistant Rh-Sm₂O₃/SiO₂ Catalyst and Its Performance for Partial Oxidation of Methane to Syngas[J]. Acta Phys. -Chim. Sin. 2017, 33(8), 1689-1698. doi: 10.3866/PKU.WHXB201704243

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201704243

https://www.whxb.pku.edu.cn/CN/Y2017/V33/I8/1689

参考文献

1	Ashcroft A. T. ; Cheetham A. K. ; Green M. L. H. ; Vernon P. D. F. Nature 1991, 352, 225.
2	Hickman D. A. ; Schmidt L. D. Science 1993, 259, 343.
3	York A. P. ; Xiao T. ; Green M. L. Top. Catal. 2003, 22, 345.
4	Hu H. ; Ruckenstein E. Adv. Catal. 2004, 48, 297.
5	Liu H. ; He D. Catal. Surv. Asia 2012, 16, 53.
6	Al-Sayari S. A. Open Catal. J. 2013, 6, 17.
7	Enger B. C. ; L?deng R. ; Holmen A. Appl. Catal. A: Gen. 2008, 346, 1.
8	Kondratenko V. A. ; Berger-Karin C. ; Kondratenko E. V. ACS Catal. 2014, 4, 3136.
9	Ding C. ; Wang J. ; Jia Y. ; Ai G. ; Liu S. ; Liu P. ; Zhang K. ; Han Y. ; Ma X. Int. J. Hydrogen Energy 2016, 41, 10707.
10	Wang S. ; Zhao Q. F. ; Wei H. M. ; Wang J. Q. ; Cho M. Y. ; Cho H. S. ; Terasaki O. ; Wan Y. J. Am. Chem. Soc. 2013, 135, 11849.
11	Sun J. M. ; Ma D. ; Zhang H. ; Liu X. M. ; Han X. W. ; Bao X. H. ; Weinberg G. ; Pf?nder N. ; Su D. S. J. Am. Chem. Soc. 2006, 128, 15756.
12	Jin, Y. X.; Liu, Z. J.; Chen, W. X.; Xu, Z. D. Acta Phys. -Chim. Sin. 2002, 18, 459.
12	金亚旭,刘宗健.物理化学学报, 2002, 18, 459. doi:10.3866/PKU.WHXB20020516
13	Ungureanu A. ; Dragoi B. ; Chirieac A. ; Royer S. ; Duprez D. ; Dumitriu E. J. Mater. Chem. 2011, 21, 12529.
14	Zhao P. J. ; Wu R. ; Hou J. ; Chang A. M. ; Guan F. ; Zhang B. Acta Phys. -Chim. Sin. 2012, 28, 1971.
14	赵鹏君; 吴荣; 侯娟; 常爱民; 关芳; 张博. 物理化学学报, 2012, 28, 1971.
15	Zhu H. G. ; Lee B. ; Dai S. ; Overbury S. H. Langmuir 2003, 19, 3974.
16	De Rogatis L. ; Cargnello M. ; Gombac V. ; Lorenzut B. ; Montini T. ; Fornasiero P. ChemSusChem 2010, 3, 24.
17	Yang X. Y. ; Sun S. ; Ding J. J. ; Zhang Y. ; Zhang M. M. ; Gao C. ; Bao J. Acta Phys. -Chim. Sin. 2012, 28, 1957.
17	杨晓艳; 孙松; 丁建军; 张义; 张曼曼; 高琛; 鲍骏. 物理化学学报, 2012, 28, 1957.
18	Lu J. L. ; Fu B. S. ; Kung M. C. ; Xiao G. M. ; Elam J. W. ; Kung H. H. ; Stair P. C. Science 2012, 335, 1205.
19	Joo S. H. ; Park J. Y. ; Tsung C. K. ; Yamada Y. ; Yang P. D. ; Somorjai G. A. Nat. Mater. 2009, 8, 126.
20	Forman A. J. ; Park J. N. ; Tang W. ; Hu Y. S. ; Stucky G. D. ; McFarland E. W. ChemCatChem 2010, 2, 1318.
21	Arnal P. M. ; Comotti M. ; Schüth F. Angew. Chem. Int. Ed. 2006, 118, 8404.
22	Radloff C. ; Halas N. J. Appl. Phys. Lett. 2001, 79, 674.
23	Xu Y. ; Ma J. Q. ; Xu Y. F. ; Xu L. ; Xu L. ; Li H. X. ; Li H. RSC Adv. 2013, 3, 851.
24	Ruckenstein E. ; Hu Y. H. Appl. Catal. A: Gen. 1999, 183, 85.
25	Chu W. ; Yan Q. ; Liu S. ; Xiong G. Stud. Surf. Sci. Catal. 2000, 130, 3573.
26	Djinovi? P. ; Batista J. ; Pintar A. Int. J. Hydrogen Energy 2012, 37, 2699.
27	Miyazawa T. ; Okumura K. ; Kunimori K. ; Tomishige K. J. Phys. Chem. C. 2008, 112, 2574.
28	Fu Q. ; Saltsburg H. ; Flytzani-Stephanopoulos M. Science 2003, 301, 935.
29	Bera P. ; Priolkar K. R. ; Gayen A. ; Sarode P. R. ; Hegde M.S. ; Emura S. ; Kumashiro R. ; Jayaram V. ; Subbanna G. N. Chem Mater. 2003, 15, 2049.
30	Matolínová I. ; Fiala R. ; Khalakhan I. ; Vorokhta M. ; Sofer Z. ; Yoshikawa H. ; Kobayashi K. ; Matolín V. Appl. Surf. Sci. 2012, 258, 2161.
31	Matolín V. ; Matolínová I. ; Václav? M. ; Khalakhan I. ; Vorokhta M. ; Fiala R. ; Pi? I. ; Sofer Z. ; Poltierová-Vejpravová J. ; Mori T. ; Potin V. ; Yoshikawa H. ; Ueda S. ; Kobayashi K. Langmuir 2010, 26, 12824.
32	Miyazawa T. ; Okumura K. ; Kunimori K. ; Tomishige K. J. Phys. Chem. C. 2008, 112, 2574.
33	Choudhary V. R. ; Prabhakar B. ; Rajput A. M. ; Mamman A. S. Fuel 1998, 77, 1477.
34	Duarte R. B. ; Nachtegaal M. ; Bueno J. M. C. ; VanBokhoven J. A. J. Catal. 2012, 296, 86.
35	Bernal S. ; Calvino J. J. ; Cauqui M. A. ; Gatica J. M. ; Larese C. ; Omil J. A. P. ; Pintado J. M. Catal. Today 1999, 50, 175.
36	Wang R. ; Xu H. ; Liu X. ; Ge Q. ; Li W. Appl. Catal. A: Gen. 2006, 305, 204.
37	Li B. ; Weng W. Z. ; Zhang Q. ; Wang Z. W. ; Wan H. L. ChemCatChem 2011, 3, 1277.
38	Weng W. Z. ; Chen M. S. ; Yan Q. G. ; Wu T. H. ; Chao Z. S. ; Liao Y. Y. ; Wan H. L. Catal. Today. 2000, 63, 317.
39	Liu Y. ; Huang F. Y. ; Li J. M. ; Weng W. Z. ; Luo C. R. ; Wang M. L. ; Xia W. S. ; Huang C. J. ; Wan H. L. J. Catal. 2008, 256, 192.
40	McDonald R. S. J. Phys. Chem. 1958, 62, 1168.
41	Davydov V. Y. ; Kiselev A. V. ; Zhuravlev L. T. Trans. Faraday Soc. 1964, 60, 2254.
42	Gorbunov B. Z. ; Safatov A. S. J. Appl. Spectrosc. 1982, 36, 328.
43	Basila M. R. J. Chem. Phys. 1961, 35, 1151.
44	Xie Y. H. ; Li B. ; Weng W. Z. ; Zheng Y. P. ; Zhu K. T. ; Zhang N. W. ; Huang C. J. ; Wan H. L. Appl. Catal. A: Gen. 2015, 504, 179.
45	Mikami M. ; Nakagawa I. ; Shimanouchi T. Spectrochim. Acta Part A 1967, 23, 1037.
46	Mitchell M. B. ; Chakravarthy V. R. ; White M. G. Langmuir 1994, 10, 4523.
47	Kenvint J. C. ; White M. G. ; Mitchell M. B. Langmuir 1991, 7, 1198.
48	Van Der Voort P. ; White M. G. ; Vansant E. F. Langmuir 1998, 14, 106.
49	Babich I. V. ; Plyuto Y. V. ; Van Der Voort P. ; Vansant E. F. J. Colloid Interface Sci. 1997, 189, 144.
50	Nakamoto K. ; Martell A. E. J. Chem. Phys. 1960, 32, 588.
51	Kiselev, A. V.; Lygin, V. I. Infrared Spectra of Surface Compounds; John Wiley and Sons: New York, 1975; p 211
52	Zhuravlev L. T. Colloids Surf. A. 2000, 173, 1.
53	Trovarelli A. ; De Leitenburg C. ; Dolcetti G. ; Lorca J. L. J. Catal. 1995, 151, 111.
54	Krause K. R. ; Schabes-Retchkiman P. ; Schmidt L. D. J. Catal. 1992, 134, 204.
55	Li B. ; Li H. ; Weng W. Z. ; Zhang Q. ; Huang C. J. ; Wan H. L. Fuel 2013, 103, 1032.

[1]	叶成玉, 郁晓菲, 李文翠, 贺雷, 郝广平, 陆安慧. 磷化镍@镍-氮-碳双功能催化剂电还原CO₂-H₂O制合成气[J]. 物理化学学报, 2022, 38(4): 2004054 - .
[2]	邵自龙, 刘晓放, 张书南, 王慧, 孙予罕. 负载型Rh基催化剂上的CO加氢制乙醇反应：载体效应[J]. 物理化学学报, 2021, 37(10): 1911053 - .
[3]	连孟水,王雅莉,赵明全,李倩倩,翁维正,夏文生,万惠霖. Ni/SiO₂在甲烷部分氧化反应中的稳定性：W修饰的影响[J]. 物理化学学报, 2019, 35(6): 607 -615 .
[4]	宁红岩,杨其磊,杨晓,李鹰霞,宋兆钰,鲁逸人,张立红,刘源. 碳纤维负载Rh-Mn紧密接触的催化剂及其合成气制乙醇催化性能[J]. 物理化学学报, 2017, 33(9): 1865 -1874 .
[5]	廖珮懿,张辰,张丽君,杨彦章,钟良枢,郭晓亚,王慧,孙予罕. Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响[J]. 物理化学学报, 2017, 33(8): 1672 -1680 .
[6]	薛飞,何纪敏,陈维苗,宋宪根,程显波,丁云杰. 载体焙烧温度对Rh-Mn-Li/SBA-15催化CO加氢性能的影响[J]. 物理化学学报, 2016, 32(11): 2769 -2775 .
[7]	王雅莉,李琪,翁维正,夏文生,万惠霖. Y₂O₃修饰Ni/SiO₂催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性[J]. 物理化学学报, 2016, 32(11): 2776 -2784 .
[8]	陈维苗, 丁云杰, 薛飞, 宋宪根. CO加氢制C₂含氧化合物Rh基催化剂中常见助剂的作用[J]. 物理化学学报, 2015, 31(1): 1 -10 .
[9]	武应全, 王思晨, 解红娟, 高俊文, 田少鹏, 韩怡卓, 谭猗生. Cu对K-LaZrO₂异丁醇合成催化剂的影响[J]. 物理化学学报, 2015, 31(1): 166 -172 .
[10]	董文达, 朱何俊, 丁云杰, 裴彦鹏, 杜虹, 王涛. 微量Li助剂对Co/AC催化剂合成高碳醇性能的影响[J]. 物理化学学报, 2014, 30(9): 1745 -1751 .
[11]	任秀彬, 周安宁, 章结兵. 甲烷部分氧化过程中强制振荡的动力学Monte Carlo模拟[J]. 物理化学学报, 2014, 30(11): 2009 -2014 .
[12]	韩涛, 黄伟, 王晓东, 唐钰, 刘双强, 游向轩. Ce-Cu-Co/CNTs催化剂催化合成气制低碳醇及乙醇的研究[J]. 物理化学学报, 2014, 30(11): 2127 -2133 .
[13]	李琪, 侯玉慧, 董玲玉, 黄铭湘, 翁维正, 夏文生, 万惠霖. SiO₂气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性[J]. 物理化学学报, 2013, 29(10): 2245 -2254 .
[14]	朱秋锋, 张荣俊, 贺德华. CaO改性对CuZnAlZr催化剂在合成气制低碳醇中性能的影响[J]. 物理化学学报, 2012, 28(06): 1461 -1466 .
[15]	毛东森, 郭强胜, 俞俊, 韩璐蓬, 卢冠忠. Ce添加对Cu-Fe/SiO₂催化合成气制低碳醇性能的影响[J]. 物理化学学报, 2011, 27(11): 2639 -2645 .

抗烧结Rh-Sm₂O₃/SiO₂催化剂的制备和表征及其甲烷部分氧化制合成气性能

Preparation and Characterization of Sinter-Resistant Rh-Sm₂O₃/SiO₂ Catalyst and Its Performance for Partial Oxidation of Methane to Syngas

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0