Citation:
JIN Ya-mei, DONG Mei, WANG Guo-fu, WANG Hao, LI Jun-fen, FAN Wei-bin, WANG Jian-guo, QIN Zhang-feng. Synthesis of Silicalite-1 hollow sphere catalyst and its application for Beckmann rearrangement reaction[J]. Journal of Fuel Chemistry and Technology,
;2016, 44(08): 1001-1009.
-
Silicalite-1 zeolite hollow sphere structured material was hydrothermally synthesized via the aid of carbon microspheres as hard-template. The morphology, structure, textural and physicochemical properties of the material were characterized with XRD, SEM, FT-IR, N2 adsorption-desorption isotherm, 29Si MAS NMR, TG, and XPS techniques. It was suggested that the obtained Silicalite-1 hollow spheres were highly crystallized with developed multiple channel structure and abundant surface hydroxyl groups, which endowed the material with excellent catalytic properties in Beckmann rearrangement reaction of cyclohexanone-oxime. Compared with the Silicalite-1 catalyst prepared from conventional method, the Silicalite-1 hollow sphere catalyst showed much higher activity to the conversion of cyclohexanone-oxime (99%) and selectivity of caprolactam (94%), with excellent stability at the same time. The abundant nest silanols and terminal silanols in Silicalite-1 hollow sphere were main active sites for Beckmann rearrangement reaction, and could be easily recovered from the deactivated catalysts by calcination.
-
-
-
[1]
[1] LI Y,SHI J.Hollow-structured mesoporous materials:Chemical synthesis,functionalization and applications[J].Adv Mater,2014,26(20):3176-3205.
-
[2]
[2] FUJI M,TAKAI C,RIVERA VIRTUDAZO R V.Development of new templating approach for hollow nanoparticles and their applications[J].Adv Powder Technol,2014,25(1):91-100.
-
[3]
[3] OKAMOTO M.Synthesis of core-shell structured porous materials and applications as catalysts and precursors for hollow porous materials[J].Bull Jpn Petro Inst,2013,56(4):198-205.
-
[4]
[4] 金炜阳,程党国,陈丰秋,詹晓力.分子筛膜包覆型催化剂的制备和应用[J].化学进展,2011,23(10):2021-2030.(JIN Wei-yang,CHENG Dang-guo,CHEN Feng-qiu,ZHAN Xiao-li.Synthesis and application of zeolite membrane encapsulated catalysts[J].Prog Chem,2011,23(10):2021-2030.)
-
[5]
[5] WANG X D,TANG Y,WANG Y J,GAO Z,YANG W L,FU S K.Fabrication of hollow zeolite spheres[J].Chem Commun,2000,21:2161-2162.
-
[6]
[6] LAI Z,BONILLA G,DIAZ I,NERY J G,SUJAOTI K,AMAT M A,KOKKOLI E,TERASAKI O,THOMPSON R W,TSAPATSIS M,VLACHOS D G.Microstructural optimization of a zeolite membrane for organic vapor separation[J].Science,2003,300(5618):456-460.
-
[7]
[7] YU G,SUN B,PEI Y,XIE S,YAN S,QIAO M,FAN K,ZHANG X,ZONG B.FexO<em>y@C spheres as an excellent catalyst for Fischer-Tropsch synthesis[J].J Am Chem Soc,2010,132(3):935-937.
-
[8]
[8] KHAN E A,HU E,LAI Z.Preparation of metal oxide/zeolite core-shell nanostructures[J].Microporous Mesoporous Mater,2009,118(1/3):210-217.
-
[9]
[9] WANG X D,ZHANG B Q,LIU X F,LIN J Y S.Synthesis of b-oriented TS-1 films on chitosan-modifiedα-Al2O3 substrates[J].Adv Mater,2006,18(24):3261-3265.
-
[10]
[10] WANG X,YAN J,HUANG W.Synthesis of b-oriented TS-1 zeolite membranes with high performance in the oxyfunctionalization of n-hexane[J].Thin Solid Films,2013,534:40-44.
-
[11]
[11] PENG H,XU L,WU H,WANG Z,LIU Y,LI X,HE M,WU P.Synthesis and formation mechanism of TS-1@mesosilica core-shell materials templated by triblock copolymer surfactant[J].Microporous Mesoporous Mater,2012,153:8-17.
-
[12]
[12] CHU N,WANG J,ZHANG Y,YANG J,LU J,YIN D.Nestlike hollow hierarchical MCM-22 microspheres:Synthesis and exceptional catalytic properties[J].Chem Mater,2010,22(9):2757-2763.
-
[13]
[13] GARCÍA-MARTÍNEZ J,CAZORLA-AMORÓ S D,LINARES-SOLANO A,LIN Y S.Synthesis and characterisation of MFI-type zeolites supported on carbon materials[J].Microporous Mesoporous Mater,2001,42(2/3):255-268.
-
[14]
[14] VALTCHEV V,MINTOVA S.Layer-by-layer preparation of zeolite coatings of nanosized crystals[J].Microporous Mesoporous Mater,2001,43(1):41-49.
-
[15]
[15] CARUSO F,CARUSO R A,MOHWALD H.Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating[J].Science,1998,282(5391):1111-1114.
-
[16]
[16] VALTCHEV V.Silicalite-1 hollow spheres and bodies with a regular system of macrocavities[J].Chem Mater,2002,14(10):4371-4377.
-
[17]
[17] VALTCHEV V.Core-shell polystyrene/zeolite a microbeads[J].Chem Mater,2002,14(3):956-958.
-
[18]
[18] JI Y J,ZHANG B,XU L,WU H,PENG H,CHEN L,LIU Y,WU P.Core/shell-structured Al-MWW@B-MWW zeolites for shape-selective toluene disproportionation to para-xylene[J].J Catal,2011,283(2):168-177.
-
[19]
[19] LV Y,QIAN X,TU B,ZHAO D.Generalized synthesis of core-shell structured nano-zeolite@ordered mesoporous silica composites[J].Catal Today,2013,204:2-7.
-
[20]
[20] CHAMNANKID B,WITOON T,KONGKACHUICHAY P,CHAREONPANICH M.One-pot synthesis of core-shell silica-aluminosilicate composites:Effect of pH and chitosan addition[J].Colloids Surf A,2011,380(1/3):319-326.
-
[21]
[21] DONG A,WANG Y,TANG Y,REN N,ZHANG Y,GAO Z.Hollow zeolite capsules:A novel approach for fabrication and guest encapsulation[J].Chem Mater,2002,14(8):3217-3219.
-
[22]
[22] KIM J,PARK W,RYOO R.Surfactant-directed zeolite nanosheets:A high-performance catalyst for gas-phase beckmann rearrangement[J].ACS Catal,2011,1(4):337-341.
-
[23]
[23] TAKAHASHI T,NISHI M,TAGAWA Y,KAI T.Catalyst deactivation of high-silica HZSM-5 in the Beckmann rearrangement reaction of cyclohexanone oxime[J].Microporous Mater,1995,3(s 4/5):467-471.
-
[24]
[24] KUMAR R,CHOWDHURY B.Comprehensive study for vapor phase beckmann rearrangement reaction over zeolite systems[J].Ind Eng Chem Res,2014,53(43):16587-16599.
-
[25]
[25] 李倩,严罗一,夏定,申永存.贝克曼重排反应研究进展[J].有机化学,2011,31(12):2034-2042.(LI Qian,YAN Luo-yi,XIA Ding,SHEN Yong-cun.Research progress of Beckmann rearrangement[J].Chin J Org Chem,2011,31(12):2034-2042.)
-
[26]
[26] LI W C,LU A H,PALKOVITS R,SCHMIDT W,SPLIETHOFF B,SCHVTH F.Hierarchically structured monolithic silicalite-1 consisting of crystallized nanoparticles and its performance in the beckmann rearrangement of cyclohexanone oxime[J].J Am Chem Soc,2005,127(36):12595-12600.
-
[27]
[27] HEITMANN G P,DAHLHOFF G,HOLDERICH W F.Catalytically active sites for the beckmann rearrangement of cyclohexanone oxime to epsilon-caprolactam[J].J Catal,1999,186(1):12-19.
-
[28]
[28] YIN C,NI R,BAO X,CHEN Y.Synthesis of hierarchical porous silicalite-1 and its catalytic performance in Beckmann rearrangement[J].Microporous Mesoporous Mater,2015,202:133-137.
-
[29]
[29] SONG H,XING C,LI B,SHEN W.Spherical carbon with SO3H groups as an efficient solid acid catalyst for 2,4,5-triphenyl-imidazole synthesis[J].Chem Select,2016,1(2):301-308.
-
[30]
[30] BERENGUER-MURCIAÁ,GARCÍA-MARTÍNEZ J,CAZORLA-AMORÓ S D,LINARES-SOLANO Á,FUERTES A B.Silicalite-1 membranes supported on porous carbon discs[J].Microporous Mesoporous Mater,2003,59(2/3):147-159.
-
[31]
[31] LI Q,HEDLUND J,STERTE J,CREASER D,BONS A J.Synthesis and characterization of zoned MFI films by seeded growth[J].Microporous Mesoporous Mater,2002,56(3):291-302.
-
[32]
[32] KULKARNI S B S V P,KOTASTHANE A N BORADE R B,RATNASAMY P.Studies in the synthesis of ZSM-5 zeolites[J].Zeolites,1982,2(4):313-318.
-
[33]
[33] SUGIMOTO M K H,TAKATSU K,KAWATA N.Correlation between the crystal size and catalytic properties of ZSM-5 zeolite[J].Zeolites,1987,7(6):503-507.
-
[34]
[34] OUTIRITE M,LAGRENÉE M,LEBRINI M,TRAISNEL M,JAMA C,VEZIN H,BENTISS F.Ac impedance,X-ray photoelectron spectroscopy and density functional theory studies of 3,5-bis (n-pyridyl)-1,2,4-oxadiazoles as efficient corrosion inhibitors for carbon steel surface in hydrochloric acid solution[J].Electrochim Acta,2010,55(5):1670-1681.
-
[35]
[35] BOUMHARA K,TABYAOUI M,JAMA C,BENTISS F.Artemisia Mesatlantica essential oil as green inhibitor for carbon steel corrosion in 1M HCl solution:Electrochemical and XPS investigations[J].J Ind Eng Chem,2015,29:146-155.
-
[36]
[36] HUNGER M,KÄRGER J,PFEIFER H,CARO J,ZIBROWIUS B,BVLOW M,MOSTOWICZ R.Investigation of internal silanol groups as structural defects in ZSM-5-type zeolites[J].J Chem Soc Faraday Trans,1987,83(1):3459-3468.
-
[37]
[37] KUHN J,MOTEGH M,GROSS J,KAPTEIJN F.Detemplation of[B]MFI zeolite crystals by ozonication[J].Microporous Mesoporous Mater,2009,120(1/2):35-38.
-
[38]
[38] YAMAGISHI K,NAMBA S,YASHIMA T.Defect sites in highly siliceous HZSM-5 zeolites:A study performed by alumination and IR spectroscopy[J].J Phy Chem,1991,95(2):872-877.
-
[39]
[39] BARBERA K,BONINO F,BORDIGA S,JANSSENS T V W,BEATO P.Structure-deactivation relationship for ZSM-5 catalysts governed by framework defects[J].J Catal,2011,280(2):196-205.
-
[40]
[40] VASCHETTO E G,CASUSCELLI S G,EIMER G A.Improvements in the Beckmann rearrangement process by using highly selective mesoporous catalysts[J].Microporous Mesoporous Mater,2016,221:175-181.
-
[41]
[41] IZUMI Y,ICHIHASHI H,SHIMAZU Y,KITAMURA M,SATO H.Development and industrialization of the vapor-phase beckmann rearrangement process[J].Bull Chem Soc Jpn,2007,80(7):1280-1287.
-
[42]
[42] ICHIHASHI H,SATO H.The development of new heterogeneous catalytic processes for the production of ε-caprolactam[J].Appl Catal A:Gen,2001,221(1/2):359-366.
-
[43]
[43] SINGH P S,BANDYOPADHYAY R,HEGDE S G,RAO B S.Vapor phase Beckmann rearrangement of cyclohexanone oxime over SAPO-11 molecular sieve[J].Appl Catal A:Gen,1996,136:249-263.
-
[44]
[44] RÖSELER J,HEITMANN G,HÖLDERICH W F.Vapor-phase Beckmann using B-MFI zeolites[J].Appl Catal A:Gen,1996,144:319-333.
-
[45]
[45] KO A N,HUNG C C,CHEN C W,OUYANG K H.Mesoporous molecular sieve Al-MCM-41 as a novel catalyst for vapor-phase Beckmann rearrangement of cyclohexanone oxime[J].Catal Lett,2001,71(3/4):219-224.
-
[46]
[46] KELEMEN S R,M.AFEWORKI A,GORBATY M L,COHEN A D.Characterization of organically bound oxygen forms in lignites,peats,and pyrolyzed peats by X-ray photoelectron spectroscopy (XPS) and solid-state 13C NMR methods[J].Energy Fuels,2002,16(6):1450-1462.
-
[1]
-
-
-
[1]
Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
-
[2]
Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, 2024, 39(8): 331-337. doi: 10.12461/PKU.DXHX202403012
-
[3]
Zhuo Wang , Xue Bai , Kexin Zhang , Hongzhi Wang , Jiabao Dong , Yuan Gao , Bin Zhao . MOF模板法合成氮掺杂碳材料用于增强电化学钠离子储存和去除. Acta Physico-Chimica Sinica, 2025, 41(3): 2405002-. doi: 10.3866/PKU.WHXB202405002
-
[4]
Zhicheng JU , Wenxuan FU , Baoyan WANG , Ao LUO , Jiangmin JIANG , Yueli SHI , Yongli CUI . MOF-derived nickel-cobalt bimetallic sulfide microspheres coated by carbon: Preparation and long cycling performance for sodium storage. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 661-674. doi: 10.11862/CJIC.20240363
-
[5]
Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
-
[6]
Xiutao Xu , Chunfeng Shao , Jinfeng Zhang , Zhongliao Wang , Kai Dai . Rational Design of S-Scheme CeO2/Bi2MoO6 Microsphere Heterojunction for Efficient Photocatalytic CO2 Reduction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309031-. doi: 10.3866/PKU.WHXB202309031
-
[7]
Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al2O3 for promoting plasma-catalyzed CO2 hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054
-
[8]
Jiaxing Cai , Wendi Xu , Haoqiang Chi , Qian Liu , Wa Gao , Li Shi , Jingxiang Low , Zhigang Zou , Yong Zhou . 具有0D/2D界面的InOOH/ZnIn2S4空心球S型异质结用于增强光催化CO2转化性能. Acta Physico-Chimica Sinica, 2024, 40(11): 2407002-. doi: 10.3866/PKU.WHXB202407002
-
[9]
Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
-
[10]
Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270
-
[11]
Zhaomei LIU , Wenshi ZHONG , Jiaxin LI , Gengshen HU . Preparation of nitrogen-doped porous carbons with ultra-high surface areas for high-performance supercapacitors. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 677-685. doi: 10.11862/CJIC.20230404
-
[12]
Yueguang Chen , Wenqiang Sun . “Carbon” Adventures. University Chemistry, 2024, 39(9): 248-253. doi: 10.3866/PKU.DXHX202308074
-
[13]
Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
-
[14]
Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
-
[15]
Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
-
[16]
Pengyang FAN , Shan FAN , Qinjin DAI , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Xiaoxiao HUANG , Yong ZHANG . Preparation and performance of rich 1T-MoS2 nanosheets for high-performance aqueous zinc ion battery cathode materials. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 675-682. doi: 10.11862/CJIC.20240339
-
[17]
Lei Shu , Zimin Duan , Yushen Kang , Zijian Zhao , Hong Wang , Lihua Zhu , Hui Xiong , Nan Wang . An Exploration of the CO2-Involved Carbon Cycle World. University Chemistry, 2024, 39(5): 144-153. doi: 10.3866/PKU.DXHX202309084
-
[18]
Zhou Fang , Zhihao Zhang , Weihan Jiang , Kin Shing Chan . Warfarin: From Poison to Cure, the Remarkable Journey of a Molecule. University Chemistry, 2025, 40(4): 326-330. doi: 10.12461/PKU.DXHX202406038
-
[19]
Gaofeng Zeng , Shuyu Liu , Manle Jiang , Yu Wang , Ping Xu , Lei Wang . Micro/Nanorobots for Pollution Detection and Toxic Removal. University Chemistry, 2024, 39(9): 229-234. doi: 10.12461/PKU.DXHX202311055
-
[20]
Peng GENG , Guangcan XIANG , Wen ZHANG , Haichuang LAN , Shuzhang XIAO . Hollow copper sulfide loaded protoporphyrin for photothermal-sonodynamic therapy of cancer cells. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1903-1910. doi: 10.11862/CJIC.20240155
-
[1]
Metrics
- PDF Downloads(0)
- Abstract views(478)
- HTML views(38)