封装型Pt/SOD分子筛的合成及表征

刘红蕾; 刘帆; 薛达; 李福祥

封装型Pt/SOD分子筛的合成及表征

刘红蕾^{1, 2},
刘帆¹,
薛达¹,
李福祥^1, ,

基金项目:

国家自然科学基金 50972097

详细信息

中图分类号: O643.32
计量
- 文章访问数: 172
- HTML全文浏览量: 192
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2015-07-15
- 修回日期: 2015-10-28

Synthesis and characterization of encapsulated Pt/SOD zeolites

LIU Hong-lei^{1, 2},
LIU Fan¹,
XUE Da¹,
LI Fu-xiang^{1
, ,}

More Information

Corresponding author: LI Fu-xiang, E-mail: l63f64x@163.com

摘要

摘要: 基于封装型贵金属分子筛的合成, 充分利用其择形性和氢溢流特性构建新型加氢催化剂, 选定Pt作为活性组分, 方钠石作为载体, 通过水热合成法直接将金属前驱体Pt (NH₃)₄Cl₂引进SOD合成母液中进行晶化, 合成了不同封装量的Pt/SOD分子筛。采用苯加氢反应测试样品的催化活性, 并运用XRD、SEM、TEM和H₂-TPD对样品进行表征。结果表明, 合成的不同封装量的Pt/SOD样品均具有良好的催化活性, 与溢流氢受体HZSM-5间均具有良好的氢溢流效应。其中, 当金属前驱体Pt (NH₃)₄Cl₂的用量为 (Pt (NH₃)₄Cl₂):(Si-Al gel) 比为0.030 g/g时, 所合成的Pt/SOD样品最佳, 催化苯加氢反应的苯转化率可达54.38%。
- 封装 /
- 方钠石 /
- Pt /
- 氢溢流
Abstract: An advanced hydrogenation catalyst was designed based on the good properties of encapsulated noble metal catalysts, which could be applied in the shape selectivity and hydrogen spillover reactions.Pt, sodalite zeolites and Pt (NH₃)₄Cl₂ were selected as the active components, carriers and metal precursors, respectively.Pt/SOD zeolites encapsulated with different amounts of Pt were hydrothermal synthesized.Then benzene hydrogenation reaction was used as probe reaction to test the catalytic activity of the samples.XRD, SEM, TEM and H₂-TPD were used to characterized the catalysts.The results showed that all Pt/SOD samples had good catalytic activity and excellent hydrogen spillover effect with spillover hydrogen acceptor HZSM-5.When the dosage of Pt (NH₃)₄Cl₂ was 0.063 6 g ((Pt (NH₃)₄Cl₂):(Si-Al gel)=0.030 g/g), the Pt/SOD sample obtained showed the highest catalytic activity for benzene hydrogenation and the benzene conversion was 54.38%.
- encapsulation /
- SOD /
- Pt /
- hydrogen spillover

HTML全文

图 1 不同封装量Pt/SOD样品的XRD谱图

Figure 1. XRD patterns of Pt/SOD samples encapsulated with different amounts of Pt

下载: 全尺寸图片幻灯片

图 2 不同封装量Pt/SOD样品的SEM照片

Figure 2. SEM images of Pt/SOD samples encapsulated with different amounts of Pt

(a): Pt/SOD-1; (b): Pt/SOD-2; (c): Pt/SOD-3; (d): Pt/SOD-4; (e): Pt/SOD-5; (f): SOD

下载: 全尺寸图片幻灯片

图 3 Pt/SOD-3样品的TEM照片 (a, b) 和XRD谱图 (c)

Figure 3. TEM images (a, b) and XRD patterns (c) of Pt/SOD-3 sample

下载: 全尺寸图片幻灯片

图 4 不同封装量Pt/SOD分子筛的H₂-TPD谱图

Figure 4. H₂-TPD spectra of Pt/SOD samples encapsulated with different amounts of Pt

a: SOD; b: Pt/SOD-1; c: Pt/SOD-2; d: Pt/SOD-3; e: Pt/SOD-4; f: Pt/SOD-5

下载: 全尺寸图片幻灯片

图 5 不同封装量的Pt/SOD样品掺混HZSM-5后的H₂-TPD谱图

Figure 5. H₂-TPD spectra of Pt/SOD samples encapsulated with different amounts of Pt

after mixing with HZSM-5 a: Pt/SOD-1+HZSM-5; b: Pt/SOD-2+HZSM-5; c: Pt/SOD-3+HZSM-5; d: Pt/SOD-4+HZSM-5; e: Pt/SOD-5+HZSM-5

下载: 全尺寸图片幻灯片

图 6 不同封装量的Pt/SOD和Pt/SOD+HZSM-5的H₂-TPD谱图

Figure 6. H₂-TPD spectra of Pt/SOD samples encapsulated with different amounts of Pt before and after mixing with HZSM-5

下载: 全尺寸图片幻灯片

表 1 不同封装量的Pt/SOD样品混合HZSM-5前后催化苯加氢反应的苯转化率

Table 1. Data of benzene hydrogenation activity of Pt/SOD samples encapsulated with different amounts of Pt before and after mixing with HZSM-5

Sample	Conversion x/%^a
Sample	before mixing with HZSM-5	after mixing with HZSM-5
Pt/SOD-1	55.2	60.0
Pt/SOD-2	8.4	53.9
Pt/SOD-3	0.7	54.4
Pt/SOD-4	0.0	36.9
Pt/SOD-5	0.0	11.0
^a: determined by GC using the area normalization method

下载: 导出CSV

表 2 不同封装量的Pt/SOD样品的Pt含量

Table 2. Pt content of the Pt/SOD samples encapsulated with different amounts of Pt

Sample	Pt content w/(mg·kg^-1)
Pt/SOD-3	14981.93
Pt/SOD-4	2802.84
Pt/SOD-5	1410.44

下载: 导出CSV

参考文献(22)

[1]	REIFSNYDER S N, OTTEN M M, SAYERS D E, LAMB H H.Hydrogen chemisorption on silica-supported Pt clusters:In situ X-ray absorption spectroscopy[J].J Phys Chem B, 1997, 101(25):4972-4977. doi: 10.1021/jp970244e
[2]	YOO J W, HATHCOCK D, EL-SAYED M A.Characterization of Pt nanoparticles encapsulated in Al₂O₃ and their catalytic efficiency in propene hydrogenation[J].J Phys Chem A, 2002, 106(10):2049-2054. doi: 10.1021/jp0121318
[3]	BOSKOVIC G, MICIC R, PAVLOVIC P, PUTANOV P.n-hexane isomerization over Pt-Na (H) Y catalysts obtained by different preparation methods[J].Catal Today, 2001, 65(2/4):123-128. http://www.baidu.com/link?url=gqck77yXlb1KxOvIJhTsYNFGkyamNawG_izatZTjG-bkCoBjJfC1yQSLsqvjuUi1wMZDYHu4S84Zj4XbuZC5e4-RU4VdlsU7MAfNNhiPd1PQIutJKdAxhiOygmN1WZXz87gGk-YgMciROoIzu24OadN0fE7qFimOLE4NlmriVXhWE_RSDO3QhIeJUrYZUy1hysT0g6hzjLs7kONrkuvaSnYPv5Chuv281GtYfEnnFZRwI_MNPWfOfbUX9FQxYUWMvesrs2VqukEb2QpRLzRvD4ke9rTWDvqsbDbOhqyE61tP0HEGmfvyfu9mQyBnQ6S9WHCzOSPdXiEi3c0u1GZ_HOLMFTYFPw1FcJMY9zufJIBlKXER9Xu9t9tFtQCrM4nd&wd=&eqid=a201338d0004b7210000000558bfe2fd
[4]	ATSUSHI F, NAONORI H, YUZURU S, SHINJI I, YOSHIAKI F, MASARU I.Preparation and catalysis of Pt and Rh nanowires and particles in FSM-16[J].Microporous Mesoporous Mater, 2001, 48(1/3):171-179. http://www.baidu.com/link?url=xp3SITApY9HwxUgPTASpa2ktb4PkPMGiyWTr2bGelu4LvbMQa1bxL7hSWCS9wfReEaCXhY_M34_j7xuaXXflkdA1FprBelcv1Y2Ys18jjl3narNRJw45QkVZIq9O4VSG_SrOmegLERRg6kFeDx1wolCGcXikYxJs674Fr-3R69N62D3WRWorRfe0-HEKL33uouKj6Q6iYcCEg2SrN8U5OXe56Y2gmiXwitFtGLRg4E0E8CQ842kdMPFZGLV7qIx1Rn1M6wLqeau1KugfVDd5MUqxY--Gp1hKN8DWC7On4vg7Fsb9r7OMjf6ojk5Whq5kRgNMWdZVWyg8zXQfADZaGq&wd=&eqid=a66e0c01000496b60000000558bfe30b
[5]	ZHANG H J, MENG X C, LI Y D, LIN Y S.MCM-41 Overgrown on Y composite zeolite as support of Pd-Pt catalyst for hydrogenation of polyaromatic compounds[J].Ind Eng Chem Res, 2007, 46(12):4186-4192. doi: 10.1021/ie061138e
[6]	SONG C S, MA X L.New design approaches to ultra-clean diesel fuels by deep desulfurization and deep dearomatization[J].Appl Catal B:Environ, 2003, 41(1/2):207-238. http://www.baidu.com/link?url=gMoMUr2J5Q2RFPKlux5dZJR02wM0OdtEQP2ZIQruGipp8OD6xWVDA7hUrvtLSofF-upaa2SGChjc2MuvbMsFjK3Dzvpigu5dFifXvIVwE3T95kwNLcHSnAaa03s2NCgwP8Lqz0JFIvyTWA0hMJPuLlA40PylIdx8qmJ2FQ6R2C2dS8q43FkjjMfmVHJi0gJwq5egCA8Q1m3rgSDITpEaEngIb7ZWCfYOvaAQJ6spGaUjRa_w4QbZTJAKs9Iq6cnSEFk6JvBTStZRUtz-buO4q3APKbFoNUvbPtWB-m37zwtqFYWcAYyWjb2zg4CFnIUKKzuq0ry1sVxwMwXqcqqJExN2yPgtP746204Zhp75ZCmFxGGVS7NdAWdoGdX9NUyS&wd=&eqid=a063f8b100042ed90000000558bfe318
[7]	ZHANG H J, LI Y D.Preparation and characterization of Beta/MCM-41composite zeolite with a stepwise-distributed pore structure[J].Powder Technol, 2008, 183(1):73-78. doi: 10.1016/j.powtec.2007.11.013
[8]	ITO K, TOMINO T, OHSHIMA M A, KUROKAWA H, SUGIYAMA K, MIURA H.Sulfur tolerance of Pd/Al₂O₃ and Pd/TiO₂ in naphthalene hydrogenation in the presence of dimethyldisulfide[J].Appl Catal A:Gen, 2003, 249(1):19-26. doi: 10.1016/S0926-860X(03)00207-2
[9]	JASIK A, WOJCIESZAK R, MONTEVERDI S, ZIOLEK M, BETTAHAR M M.Study of nickel catalysts supported on Al₂O₃, SiO₂ or Nb₂O₅ oxides[J].J Mol Catal A:Chem, 2005, 242(1/2):81-90. http://www.baidu.com/link?url=C4GK-OOq1e8exUD_7Cz_tkMkTbXroacceY4YWOh_H50KneV3DnPij0pdOf9djYKH3e3fA2crole_GNYUnMmIzSJNZdi-g_QHUv3Ypa2wPLC-q2YU87XTGT4ew8aYDMnM3xbUPDN2YuUjYW2wiK0i2Esm08u54eNX6Bg69HYfCo4XLQpF9WvQu9Vvq5VRYBjWjU6_jqod9A6F3G7YzHyQDzAcZfbYQ6ZjaPRfEjhaGUcMR10ZMsB4-It5KcpQc92EtIBFYYAFWeUylvBuu9Pa2WNRNA8sq1ANMX8GHbD5GZ9v7yXUz6Dbicvlro7Hx_Y1B9M8Jdy1zJQ7c0As8ENzQc_QADg_nAzKgWTTtaufqN7&wd=&eqid=a76f412b0004c1e00000000558bfe325
[10]	LU S L, LONERGAN W, ZHU Y X, XIE Y C, CHEN J G.Support effect on the low-temperature hydrogenation of benzene over PtCo bimetallic and the corresponding monometallic catalysts[J].Appl Catal B:Environ, 2009, 91(3/4):610-618. http://www.baidu.com/link?url=EFhhi8L-CoEhRMX8aHhdrX7CrJaOc-09WNkF_ykTLJkVHSB3Xy3637uoREe0foDNkAQaQAv2I9D3a__-oRA4rtOOF2DDnvN7oSZ2vrJX5emQ3qSdqx61s9RjPsBBWD6ZI1sIr-Vp5hgqwIdNMvN0PwxxpMSBjrf372tvX74OBCuAIXcYNNnnqlnFmVTjlTl7ZQjeBdUy_s3nSKlbb6xN_rJn8_YzEiFC4it5HxvwmDTrm_YtB7VJg28V-D9XNuSnQrdFlgWjsvAhACPnDzzJrAeRlPI_S6In4lExIko66TNQfGeZncLfnQfwcORJAUyl_BFhj55UpumI_ahN7b_Zw7CfpgzPj5Dxw6BqreYXaLf1zyIqDzg0X7VvSmgW0vlBdgBBVd4Hr-TkWGvwPUT_C5iaIyhdQXn1IQQjZAb2O7a&wd=&eqid=a5a0d8bd0004a1000000000558bfe331
[11]	IM J, SHIN H, JANG H, KIM H, CHOI M.Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures[J].Nat Commun, 2014, 5(1):40-45. http://www.baidu.com/link?url=VmGLq4JIGjez0Dlo6sXUXfwM002n0o_sTVsg8bgjS0eOZMzJQY1J8Dcm23HVzRnfy2NQ46toHDS5gqAYQpWtOvecMFFfilgjKnZ_e9xM-l1hqxhuZNjFLyiGEvkrdzrVypilgWiSwWhVOcKFJsTZwcof48nigJIPv8Gqq0QwErZthHePd8U3k4RTuWD4ECFVcI0CIX9raHbT3wOFLX8TnGnFrdWcd4IL1OlcEptdoZSHC9KZQABZnXKmAXa3z7YqqewF037Go26sPLrp1SYZU3dtDvO-OqxkT-l58jQ8TX__NyXuMDhCj-G1B3WwixrEt6AqiesgG8tQ_rLazyvM-zdJNYfSe-GY6S-hsGJy-SVg2FYMYBttfkw4kVduNUeCiNn1hAxW5zgwY3BSs0Z2TskX1DnHhBz8D9Uaj_C8opO&wd=&eqid=a6a20de700046b300000000558bfe33d
[12]	MINKEE C, SUNWOO Y, HYUNGJUN K.Hydrogen spillover in encapsulated metal catalysts:New opportunities for designing advanced hydroprocessing catalysts[J].Chem Cat Chem, 2015, 7(23):1048-1057. http://www.baidu.com/link?url=ENZJECKrSZ-l1EpQaMWITZD5unMVHxug54_uPZ1e1FZNvO1cLFHmY6AEoO8n0TgZgEYqEeG1_1qoJC9u7C51CxOknBV3x-2w1QzAUrVgYQLOYLdcJt3fIeQS08N-Z6btwRf81himZjh-gOEfq3fDWkB5dYRDOnKObUJ-BqmmTLAG7w-vdCM6WFrshT4XhKI2IkPTzngSdZ2wwCIdmmJ0gi-pNnuQVxED9HJAQBdYXGkGk3_ZD4LNKMIIRV1buIOotHKVA760YvDTR90VP6UP1056bqwCqw0ZGOQmWXY5b9_k7vqxi-8LdGvE1orV9sKoV2DHKK7oyVPhgIs-YUdiGV-nIB2QERo1eSTHl38764tFyhHm8nuTQEh-f9puJ6Kbm2T29ZRNXZlVIM0zyF_VGq&wd=&eqid=a063f8b10004347d0000000558bfe35a
[13]	YANG H, CHEN H L, CHEN J W, OMOTOSO O, RING Z.Shape selective and hydrogen spillover approach in the design of sulfur-tolerant hydrogenation catalysts[J].J Catal, 2006, 243(1):36-42. doi: 10.1016/j.jcat.2006.06.026
[14]	BOSKOVIC G, MICIC R, PAVLOVIC P, PUTANOV P.n-hexane isomerization over Pt-Na (H) Y catalysts obtained by different preparation methods[J].Catal Today, 2001, 65(2/4):123-128.
[15]	ATSUSHI F, NAONORI H, YUZURU S, SHINJI I, YOSHIAKI F, MASARU I.Preparation and catalysis of Pt and Rh nanowires and particles in FSM-16[J].Microporous Mesoporous Mater, 2001, 48(1/3):171-179. http://www.baidu.com/link?url=xp3SITApY9HwxUgPTASpa2ktb4PkPMGiyWTr2bGelu4LvbMQa1bxL7hSWCS9wfReEaCXhY_M34_j7xuaXXflkdA1FprBelcv1Y2Ys18jjl3narNRJw45QkVZIq9O4VSG_SrOmegLERRg6kFeDx1wolCGcXikYxJs674Fr-3R69N62D3WRWorRfe0-HEKL33uouKj6Q6iYcCEg2SrN8U5OXe56Y2gmiXwitFtGLRg4E0E8CQ842kdMPFZGLV7qIx1Rn1M6wLqeau1KugfVDd5MUqxY--Gp1hKN8DWC7On4vg7Fsb9r7OMjf6ojk5Whq5kRgNMWdZVWyg8zXQfADZaGq&wd=&eqid=a66e0c01000496b60000000558bfe30b
[16]	SUN H J, PENG T J, LIU H F, XU H L.Synthesis and characterization of ultraviolet photochromic sodilite[J].China Powder Sci Technol, 2010, 16(6):25-28.
[17]	胡涛, 孟长功, 吴晓金, 谭震.一种储氢方钠石复合材料的制备方法, 中国, 101503196[P].2009-03-05. HU Tao, MENG Chang-gong, WU Xiao-jin, TAN Zhen.Preparation method of hydrogen storage sodalite composites, China, 101503196[P].2009-03-05.
[18]	臧丽君, 邵国林, 李昆兰, 戴洪义.微波离子热合成纳米方钠石粉体[J].大连工业大学学报, 2013, 32(3):220-223. ZANG Li-jun, SHAO Guo-lin, LI Kun-lan, DAI Hong-yi.Preparation of nano-sized sodalite using microware-assisted ionothermal synthesis[J].J Dalian Polytech Univ, 2013, 32(3):220-223.
[19]	SONG J N, YU F, HUANG Y F, HUANG Y.Preparation and investigation of NO sensor modified by sodalite zeolite[J].J Instr Anal (China), 2009, (7):769-772.
[20]	XU R R, PANG W Q, TU K G.Zeolite molecular sieves structure and synthesis[M].Changchun:Jilin University Press, 1987, 11-18.
[21]	GOEL S, WU Z JF, ZONES S, IGLESIA E.Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites[J].J Am Chem Soc, 2012, 134(42):17688-17695. doi: 10.1021/ja307370z
[22]	CHEN S, DING L H, CHEN J W, FAIRBRIDGE C, SHI Y.In-situ synthesis of zeolite with encapsulated Pt and its hydrogenation activity at high levels of Sulfur[R].San Francisco, World Congress on Engineering and Computer Science, 2010.