Synthesis of Mixed Alumina Silica Pillared Zirconium Phosphate and Its Catalytic Performance in Epoxidation of Soyate†

doi:10.7503/cjcu20150155

Abstract

Abstract:

The mixed alumina-silica pillared zirconium phosphate material was synthesized by template-directing self-assembly method. The textural properties of the material was systematically characterized by X-ray diffraction(XRD), Brunauer-Emmett-Teller(BET), Field emission scanning electron microscope(FESEM) and ²⁷Al Nuclear magnetic resonance(²⁷Al NMR). The formation mechanism of the mixed alumina-silica pillared zirconium phosphate was further studied. The results show that the aluminum source is presented as etrahedral aluminum grafted onto the gallery and the octahedral aluminum on the layer, repectively. In the evaluation of catalytic performance, the epoxidation reaction of soyate is used to study the mixed alumina-silica pillared material. It exhibits 91.7% epoxy selectivity. The analysis of the catalytic behavior indicate that the ordered interlayer structure given by the template-directing self-assembly method provokes an adequately contact between the relatively large reactants of methyl soyate and the active sites. With the FTIR spectra of adsorbed pyridine and the analysis of the reaction kinetics, it can be found that the excellent catalytic performance compared with the pure silica pillared zirconium phosphate material and other solid acids is due to the abundant Lewis sites arising from the introducing of the alumina source.

Key words: Alumina-silica pillared zirconium phosphate, Layered nanostructures, Epoxidation, Catalytic performance

CLC Number:

O643

TrendMD:

LIU Wenjin, WANG Hongning, CHEN Ruoyu. Synthesis of Mixed Alumina Silica Pillared Zirconium Phosphate and Its Catalytic Performance in Epoxidation of Soyate^†[J]. Chem. J. Chinese Universities, 2015, 36(12): 2550.

Figures/Tables 10

Fig.1 Epoxidation of the methyl soyate and epoxy product

Fig.2 XRD patterns(A) of SPZHD(a) and SAPZH(b) and TEM image(B) of SAPZH Inset: 2θ=10°—40°.

Fig.3 27Al MAS-NMR spectra for SPZHD(a) and SAPZH(b)

Fig.4 N2 adsorption-desorption isotherms for SAPZH(A) and SPZHD(B)

Table 1 Textural properties of SPZHD and SAPZH

Material	Interlayer spacing/nm	Pore diameter/nm	Pore volume/(cm³·g^-1)	S_BET/(m²·g^-1)
SPZHD	2.36	2.30	0.31	487
SAPZH	2.62	2.19	0.28	523

Fig.5 Formation model for SPZHD and SAPZH materials

Table 2 Acid properties and catalytic performance for SAPZH, SPZHD and non-catalysis situation

Catalyst	$C L a$ / (μmol·g^-1)	Double bond conversion(%)	Epoxy selectivity(%)	Yield(%)	TOF^b/h^-1	Activation energy/(kJ·mol^-1)	10^-4 Frequency factor/(L·mol^-1·s^-1)
Non-catalyst	—	69.8	61.7	43.1	—	68.3	0.13
SPZHD	552	93.0	81.2	75.5	52.4	30.1	8.67
SAPZH	708	96.2	91.7	88.2	58.6	28.3	18.01

Table 2 Acid properties and catalytic performance for SAPZH, SPZHD and non-catalysis situation

Catalyst	$C L a$ / (μmol·g^-1)	Double bond conversion(%)	Epoxy selectivity(%)	Yield(%)	TOF^b/h^-1	Activation energy/(kJ·mol^-1)	10^-4 Frequency factor/(L·mol^-1·s^-1)
Non-catalyst	—	69.8	61.7	43.1	—	68.3	0.13
SPZHD	552	93.0	81.2	75.5	52.4	30.1	8.67
SAPZH	708	96.2	91.7	88.2	58.6	28.3	18.01

Table 3 Reusability of SAPZH in the epoxidation reaction of soyate

Catalysis	Double bond conversion(%)	Selective(%)	Yield(%)	Recycle utility rate(%)
Fresh	96.2	91.7	88.2	100
1st resue	93.6	86.60	81.1	92.0
2nd reuse	91.2	83.4	76.1	86.3
3rd reuse	89.4	78.3	70.0	79.4
After regeneration^*	94.8	88.6	84.0	95.2

Fig.6 Relationships between reaction time and the epoxy selectivity over SPZHD(a) and SAPZH(b)

Fig.7 FTIR spectra of adsorbed pyridine on SPZHD(A) and SAPZH(B) at 200(a) and 450 ℃(b), respectively

References 49

[1]	Galarneau A., Barodawalla A., Chem. Commun., 1997, 17, 1661—1662
[2]	Pichowicz M., Mokaya R., Chem. Commun., 2001, 20, 2100—2101
[3]	Kuz'niarska-Biernacka I., Silva A. R., Carvalho A. P., Pires J., Freire C., Catal. Lett., 2010, 134, 63—71
[4]	Yao W., Wang H. N., Wang J. W., Zhong J., Chen R. Y., Acta Physico-Chim. Sinica,2011, 27(7), 1763—1771
	(姚微, 王红宁, 王建伍, 钟璟, 陈若愚. 物理化学学报,2011, 27(7), 1763—1771)
[5]	Jiménez-Jiménez J., Rubio-Alonso M., Quesada D. E., Rodríguez-Castellón E., Jiménez-López A., J. Mater. Chem., 2005, 15, 3466—3472
[6]	Li Y., Wang C., Chen H., Hua W., Yue Y. H., Gao Z., Catal. Lett., 2009, 131, 560—565
[7]	Jiménez-Jiménez J., Rubio-Alonso M., Eliche-Quesada D., Castellón E. R., Jiménez-López A., J. Phys. Chem. Solids,2006, 67, 1007—1010
[8]	Soriano M. D., Jiménez-Jiménez J., Concepcion P., Jiménez-López A., Rodríguez-Castellón E., Nieto J. M., Appl. Catal. B,2009, 92, 271—279
[9]	Liu W. J., Wang H. N., He M. Y., Zhong J., Chen R. Y., Catal. Lett., 2014, 144, 663—673
[10]	Biermann U., Metzger J. O., Top. Catal., 2004, 27, 119—130
[11]	Piazza G. J., Foglia T. A., J. Am. Oil Chem. Soc., 2005, 82, 481—485
[12]	Gan L. H., Goh S. H., Ooi K. S., J. Am. Oil Chem., 1992, 69, 347—351
[13]	Satyarthi J. K., Srinivas D., Appl. Catal., A, 2011, 401, 189—198
[14]	Kumar D., Ali A., Energy Fuels,2012, 26, 2953—2961
[15]	Guidotti M., Ravasio N., Psaro R., Gianotti E., Coluccia S., Marchese L., J. Mol. Catal. A: Chem., 2006, 250, 218—225
[16]	Yamaguchi K., Ebitani K., Kaneda K., J. Org. Chem., 1999, 64, 2966—2968
[17]	Maksimchuk N. V., Kovalenko K. A., Arzumanov S. S., Chesalov Y. A., Melgunov M. S., Stepanov A. G., Kholdeeva O. A., Inorg. Chem., 2010, 49, 2920—2930
[18]	Li X. L., Jiang P. P., Lu Y., Zhang W. J., Dong Y. M., Acta Chim. Sinica,2012, 70(5), 544—550
	(李小磊, 蒋平平, 卢云, 张伟杰, 董玉明. 化学学报,2012, 70(5), 544—550)
[19]	Romero M. D., Calles J. A., Ocana M. A., Gomez J. M., Microporous Mesoporous Mater., 2008, 111, 243—253
[20]	Yamaguchi K., Mori K., Mizugaki T., Ebitani K., Kaneda K., J. Org. Chem., 2000, 65, 6897—6903
[21]	Serio M. D., Turco R., Pernice P., Aronne A., Sannino F., Santacesaria E., Catal. Today,2012, 192, 112—116
[22]	Piazza G. J., Alberto N., Foglia T. A., J. Mol. Catal. B: Enzym., 2003, 21, 143—151
[23]	Piazza G. J., Foglia T. A., Alberto N., Biotechnol. Lett., 2000, 22, 217—221
[24]	Wang H. N., Liu W. J., Yao W., Zhang K., Zhong J., Chen R. Y., Appl. Surf. Sci., 2013, 268, 179—187
[25]	Ha B., Char K., Jeon H. S., J. Phys. Chem. B,2005, 109, 24434—24440
[26]	Meher L. C., Naik S. N., Das L. M., J. Sci. Ind. Res., 2004, 63, 913—918
[27]	Paquot C., Hautfenne A., Standard Methods for the Analysis of Oils, Fats and Derivatives, Applied Chemistry Division, Wiley-Blackwell, London, 1987
[28]	Sun L., Boo W. J., Browning R. L., Sue H. J., Clearfield A., Chem. Mater., 2005, 17, 5606—5609
[29]	Alberti G., Marmottini F., Cavalaglio S., Severi D., Langmuir, 2000, 16, 4165—4170
[30]	Bizeto M. A., Faria D. L. A. D., Constantino V. R. L., J. Mater. Sci., 2002, 37, 265—270
[31]	Mao H., Li B., Yue L., Wang L., Yang J., Gao X., Appl. Clay Sci., 2011, 53, 676—683
[32]	Polverejan M., Liu Y., Pinnavaia T. J., Chem. Mater., 2002, 14, 2283—2288
[33]	Mérida-Robles J. M., Olivera-Pastor P., Jiménez-López A., Rodriguez-Castellon E., J. Phys. Chem., 1996, 100, 14726—14735
[34]	Vansant E. F. Cool P., Colloids Surf., A, 2001, 179, 145—150
[35]	Wang J. G., Li F., Zhou H. J., Sun P. C., Ding D. T., Chen T. H., Chem. Mater., 2009, 21, 612—620
[36]	Mao H., Li B., Li X., Yue L., Liu Z., Ma W., Ind. Eng. Chem. Res., 2009, 49, 583—591
[37]	Mao H., Li B., Li X., Yue L., Xu J., Ding B., Gao X., Zhou Z., Microporous Mesoporous Mater., 2010, 130, 314—321
[38]	Zhou C., Li X., Ge Z., Li Q., Tong D., Catal. Today,2004, 93, 607—613
[39]	Campanella A., Baltanas M. A., Capel-Sanchez M. C., Campos-Martin J. M., Fierro J. L. G., Green Chem., 2004, 6, 330—334
[40]	Rios L. A., Weckes P., Schuster H., Hoelderich W. F., J. Catal., 2005, 232, 19—26
[41]	Sepulveda J., Teixeira S., Schuchardt U., Appl. Catal. A,2007, 318, 213—217
[42]	Amarante T. R., Neves P., Valente A. A., Almeida Paz, Fitch A. N., Pillinger M., Gonçalves I. S., Inorg. Chem., 2013, 52, 4618—4628
[43]	Wang X., Wang T., Hua W., Yue Y., Gao Z., Catal. Commun., 2014, 43, 97—101
[44]	Zhang Y. H., Chen S. P., Yuan C. L., Fang W. P., Yang Y. Q., Chinese J. Catal., 2012, 33(2), 317—322
	(张元华, 陈世萍, 袁成龙, 方维平, 杨意泉. 催化学报, 2012, 33(2), 317—322)
[45]	Lundie D. T., Mcinroy A. R., Marshall R., Winfield J. M., Jones P., Dudman C. C., Parker S. F., Mitchell C., Lennon D., J. Phys. Chem. B,2005, 109, 11592—11601
[46]	Emeis C. A., J. Catal., 1993, 141(2), 347—354
[47]	Xie X., Shen W., Nanoscale, 2009, 1, 50—60
[48]	Xie X., Li Y., Liu Z. Q., Haruta M., Shen W., Nature, 2009, 458, 746—749
[49]	Kaur N., Ali A., Fuel Process. Technol., 2014, 119, 173—184

Related Articles 15

[1]	DONG Yanhong, LU Xinhuan, YANG Lu, SUN Fanqi, DUAN Jingui, GUO Haotian, ZHANG Qinjun, ZHOU Dan, XIA Qinghua. Preparation of Bifunctional Metal-organic Framework Materials and Application in Catalytic Olefins Epoxidation [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220458.
[2]	ZHANG Taiwen, GUO Jun, ZHANG Dan, YUAN Changmei, QIU Shuangyan. Synthesis， Characterization and Catalytic Oxidation Iodine Ion Performance of trz-Cl-Cu-PMo₁₂ [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220215.
[3]	LUO Qiangqiang, JIN Shaoqing, SUN Hongmin, YANG Weimin. Post-synthesis of Ti-MWW Zeolite via Titanium Incorporation in Liquid Acid Solution [J]. Chem. J. Chinese Universities, 2021, 42(9): 2742.
[4]	ZHANG Xu, QUE Jiaqian, HOU Yuexin, LYU Jiamin, LIU Zhan, LEI Kunhao, YU Shen, LI Xiaoyun, CHEN Lihua, SU Baolian. Hierarchical Mesoporous-microporous TS-1 Single Crystal Catalysts for Epoxidation of Allyl Chloride [J]. Chem. J. Chinese Universities, 2021, 42(8): 2529.
[5]	HU Zhiyuan, WAN Qiuxiang, ZHOU Hang, SONG Chuanjun, CHANG Junbiao. Synthesis of 6β-Hydroxy-5,5,8aβ-trimethyloctahydronaphthalen-1(2H)-one Toward the Establishment of the Scaffold of Phenylspirodrimane Meroterpenoid Natural Products ^† [J]. Chem. J. Chinese Universities, 2020, 41(5): 955.
[6]	ZHANG Ronghui, MIN Deng, WANG Lailai, XIE Wenjian. Research Progress of Catalysts for Gas-phase Fluorination to Synthesize Hydorfluoroolefins^† [J]. Chem. J. Chinese Universities, 2020, 41(10): 2199.
[7]	LIU Feng, LI Qinfang, OUYANG Kunbing, YANG Nianfa. Application of Two Chiral BINOL Polymers in Asymmetric Epoxidation Reaction ^† [J]. Chem. J. Chinese Universities, 2019, 40(8): 1628.
[8]	ZOU Xiaochuan,WANG Yue,WANG Cun,HU Shiwen,SHI Kaiyun. Synthesis of Amine Functionalized ZPS-PVPA Supported Chiral Mn^Ⅲ(salen) and Asymmetric Catalytic Olefin Epoxidation^† [J]. Chem. J. Chinese Universities, 2019, 40(7): 1488.
[9]	LIU Xinchao,ZHAO Yarong,YUAN Zhenyan,ZHOU Dan,LU Xinhuan,XIA Qinghua. Controllable Synthesis of Ti-Beta Zeolite and Efficiently Catalytic Epoxidation of Cyclohexene^† [J]. Chem. J. Chinese Universities, 2019, 40(6): 1222.
[10]	LU Xinhuan,TAO Peipei,HUANG Fengfeng,ZHANG Xianggui,LIN Zhicheng,PAN Haijun,ZHANG Haifu,ZHOU Dan,XIA Qinghua. Nano-SnO₂ as Highly Efficient Catalyst for Epoxidation of Cyclic Olefins with Aqueous H₂ $O 2 †$ [J]. Chem. J. Chinese Universities, 2019, 40(3): 528.
[11]	MA Qinghai,CUI Fang,LIU Mufei,XU linxu,ZHANG Jiajia,CUI Tieyu. Synthesis and Catalytic Performance of Pd/PdO Nanocomposite Microspheres ^† [J]. Chem. J. Chinese Universities, 2019, 40(10): 2041.
[12]	MA Junfeng,ZENG Yi. Significant Improvement of CO Sensing Performance Based on Au-sensitized Double-shelled SnO₂ Hollow Nanocubes^† [J]. Chem. J. Chinese Universities, 2018, 39(9): 1867.
[13]	XIAO Shanshan, OUYANG Yiting, LI Xiaoyun, WANG Zhao, WU Pan, DENG Zhao, CHEN Lihua, SU Baolian. Synthesis of a Core-shell Structured Ag/ZIF-8 Catalyst with Mesoporous Silica Shell^† [J]. Chem. J. Chinese Universities, 2018, 39(6): 1235.
[14]	XIA Kun,WANG Yi,ZHOU Dan,HUANG Zhe,WU Zhonghan,XIA Qinghua. Rapid Synthesis of CoSAPO-5 Zeolite and Efficiently Catalytic Epoxidation of α-Pinene with Air^† [J]. Chem. J. Chinese Universities, 2018, 39(5): 941.
[15]	GAO Hongcheng, WANG Zhenlu, NIU Guiling, WEN Shoudong, WU Xiaonan, ZHANG Xiaofei, SU Pengchen, YAN Xin, QI Qiang, GAO Binbin. Preparation and Catalytic Olefin Epoxidation Properties of Carbon Nanotube/Polyoxometalates/Polypyrrole Composite Catalyst^† [J]. Chem. J. Chinese Universities, 2017, 38(7): 1223.