Adsorption Mechanisms of TMPDO and 4-NOH-TMPD in HTS/H2O2 System and Effects on the Stabilization of Ti—OOH†

doi:10.7503/cjcu20150779

Abstract

Abstract:

The adsorption mechanisms of 2,2,6,6-tetramethyl-piperdin-4-one(TMPDO) and 2,2,6,6-tetramethyl-piperdin-4-one-oxime(4-NOH-TMPD) in HTS/H₂O₂ system were investigated by thermogravimetry analysis(TG), NH₃ temperature programmed desorption(NH₃-TPD), Fourier transform infrared spectrum(FTIR) and in situ IR. The results showed that there were Si—OH and Ti—OOH active sites on the surface of the catalyst in HTS/H₂O₂ system. Two-site adsorption was formed by the interaction of alkali group ═N—H of TMPDO or 4-NOH-TMPD with strong acid center Si—OH, and para group —C═O in TMPDO or —N═OH in 4-NOH-TMPD with Ti—OOH center. Such two-center adsorption of TMPDO or 4-NOH-TMPD on surface of HTS significantly increased the stability and concentration of active site Ti—OOH in HTS/H₂O₂ system, and thus caused an evident decrease of strong acid sites and an increase of weak acid sites on surface of the catalyst. Therefore, it is expected to improve the catalytic activity and selectivity of HTS/H₂O₂ system by modifying the surface properties of catalyst with adsorption of appropriate organic bases.

Key words: HTS/H2O2, 2,2,6,6-Tetramethyl-piperdin-4-one(TMPDO), 2,2,6,6-Tetramethyl-piperdin-4-one-oxime(4-NOH-TMPD), Adsorption mechanism

CLC Number:

O643.31

TrendMD:

YAN Shan, ZHANG Shengjian, ZHAO Yingxian, LI Xianming, ZHANG Yongming, ZHANG Hong, WANG Jian, FU Jianqiong. Adsorption Mechanisms of TMPDO and 4-NOH-TMPD in HTS/H₂O₂System and Effects on the Stabilization of Ti—OOH^†[J]. Chem. J. Chinese Universities, 2016, 37(5): 946.

Figures/Tables 16

Scheme 1 Structures of surface active sites in TS-1/H2O2 system

Scheme 2 Cyclic structure formed by methanol and Ti—OOH interaction in TS-1/H2O2 system

Scheme 3 Stable structure formed by interaction of KH2PO4 and Ti-OOH in TS-1/H2O2 system

Fig.1 TG curves of different systemsa. HTS/H2O2, 0.1 g HTS and 10 g H2O2; b. HTS/H2O/TMPDO, 0.1 g HTS, 10 g H2O and 0.1 g TMPDO; c. HTS/H2O/4-NOH-TMPD, 0.1 g HTS, 10 g H2O and 0.1 g 4-NOH-TMPD; d. HTS/H2O2/TMPDO, 0.1 g HTS, 10 g H2O2, and 0.1 g TMPDO; e. HTS/H2O2/4-NOH-TMPD, 0.1 g HTS, 10 g H2O2, and 0.1 g 4-NOH-TMPD; f. HTS/H2O, 0.1 g HTS and 10 g H2O.

Table 1 Mass loss of different systems

System	Mass loss, w(%)
System	100—200 ℃	200—400 ℃	400—700 ℃	Total
HTS/H₂O	0.1	0.1	0	0.2
HTS/H₂O₂	0.2	0.3	0	0.5
HTS/H₂O/TMPDO	1.7	1.3	0.4	3.4
HTS /H₂O/4-NOH-TMPD	2.8	2.6	0.4	5.8
HTS/H₂O₂/TMPDO	5.4	5.1	0.8	11.3
HTS /H₂O₂/4-NOH-TMPD	7.0	4.0	0.6	11.6

Scheme 4 Ti—OH(B3) and Si—OH(B1) formed by H2O adsorption on TS-1

Scheme 5 Active sites Ti—OOH(B2) and Si—OH(B1) formed by the adsorption of H2O2/H2O on HTS

Fig.2 Infrared spectra, pyridine absorbed in HTS(a) and HTS/H2O2(b) system with vacuum <1 Pa, pretreatment at 70 ℃ for 1 h

Table 2 Molar adsorption quantity of vasious sytems

System	Adsorbate	R_wl(%)	c_ad/(μmol·g^-1)	Adsorption rate^*(%)
HTS/H₂O	H₂O	0.2	111	12
HTS/H₂O₂	H₂O+H₂O₂	0.5	147	16
HTS/H₂O/TMPDO	H₂O+TMPDO	3.4	203	22
HTS/H₂O/4-NOH-TMPD	H₂O+4-NOH-TMPD	5.8	328	36
HTS/H₂O₂/TMPDO	H₂O+H₂O₂+TMPDO	11.3	674	74
HTS/H₂O₂/4-NOH-TMPD	H₂O+H₂O₂+4-NOH-TMPD	11.6	643	71

Fig.3 FTIR spectra of HTS(a), HTS/H2O2(b), HTS/H2O2/TMPDO(c) and HTS/H2O2/4-NOH-TMPD(d) with different mass ratios of HTS/4-NOH-TMPD(e, f)Sample compositions:a. 0.1 g HTS; b. 0.1 g HTS, 10 g H2O2; c. 0.1 g HTS, 10 g H2O and 0.1 g TMPDO; d. 0.1 g HTS, 10 g H2O and 0.01 g 4-NOH-TMPD; e. 0.1 g HTS, 10 g H2O2 and 0.05 g TMPDO; f. 0.1 g HTS, 10 g H2O2 and 0.1 g 4-NOH-TMPD.

Fig.4 NH3-TPD profiles of HTS(a), HTS/H2O(b), HTS/H2O2(c), HTS/H2O2/TMPDO(d) and HTS/H2O2/4-NOH-TMPD(e)Sample compositions: a. 0.1 g HTS; b. 0.1 g HTS and 10 g H2O; c. 0.1 g HTS and 10 g H2O2; d. 0.1 g HTS, 10 g H2O2 and 0.1 g TMPDO; e. 0.1 g HTS, 10 g H2O2 and 0.1 g 4-NOH-TMPD.

Table 3 Acid strength distribution of HTS in different mediums measured by NH3-TPD

Temperature/℃	Acidity/(μmol·g^-1)
Temperature/℃	HTS	HTS/H₂O	HTS/H₂O₂	HTS/H₂O₂/TMPDO	HTS/H₂O₂/4-NOH-TMPD
150—200	78	23	157	389	432
200—250	10	63	165	120	64
250—300	0	82	124	47	28
300—350	0	0	75	0	0
Total	88	168	521	556	524

Fig.5 IR spectra of HTS/H2O2 sample after TMPDO adsorption at 70 ℃ followed by desorption in vacuum(<1 Pa) at different temperatures(A) 1300—1800 cm-1. a. 80 ℃; b. 150 ℃; c. 200 ℃; d. 300 ℃; e. 350 ℃.(B) 2800—3800 cm-1. a. 80 ℃; b. 150 ℃; c. 200 ℃; d. 250 ℃; e. 300 ℃; f. 350 ℃.

Fig.6 IR spectra of HTS/H2O2 sample after 4-NOH-TMPD adsorption at 70 ℃ followed by desorption in vacuum(<1 Pa) at different temperatures(A) 1300—1800 cm-1; (B) 2800—3800 cm-1. a. 70 ℃; b. 150 ℃; c. 200 ℃; d. 250 ℃; e. 300 ℃; f. 350 ℃.

Scheme 6 Model of two-center adsorption in HTS/H2O2/TMPDO system

Scheme 7 Two different models of two-site adsorption in HTS/H2O2/4-NOH-TMPD system

References 29

[1]	Taramasso M., Perego G., Notari B., Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides, US Patent 4410501, 1983-10-18
[2]	Bhaumik A., Mukherjee P., Kumar R., J. Catal., 1998, 178(1), 101—107
[3]	Bengoa J. F., Gallegos N. G., Marchetti S. G., Alvarez A. M., Cagnoli M. V., Yeramian A. A., Microporous MesoporousMater., 1998, 24(4—6), 163—172
[4]	Le Bars J., Dakka J., Sheldon R. A., Appl. Catal. A:Gen., 1996, 136(1), 69—80
[5]	Tatsumi T., Jappar N., J. Catal., 1996, 161(2), 570—576
[6]	Shi C. F., Zhu B., Lin M., Long J., Wang R. W., Catal.Today, 2011, 175(1), 398—403
[7]	Chen R. Z., Bu Z., Li Z. H., Zhong Z. X., Jin W. Q., Xing W. H., Chem. Eng.J., 2010, 156(14), 418—422
[8]	Zheng A. G., Xia C. J., Xiang Y. J., Xin M. D., Zhu B., Lin M., Xu G. T., Shu X. T., Catal.Commun., 2014, 45, 34—38
[9]	Bordiga S., Bonino F., Damin A., Lamberti C., Phys. Chem. Chem.Phys., 2007, 9(35), 4854—4878
[10]	Spanó E., Tabacchi G., Gamba A., Fois E., J. Phys. Chem.B, 2006, 110(43), 21651—21661.
[11]	Panyaburapa W., Nanok T., Limtrakul J., J. Phys. Chem.C, 2007, 111(8), 3433—3441
[12]	Wang L. L., Xiong G., Su J., Li P., Guo H. C., J. Phys. Chem.C, 2012, 116(16), 9122—9131
[13]	Yoon C. W., Hirsekorn K. F., Neidig M. L.,Yang X. Z., Tilley T. D., ACSCatal., 2011, 1(12), 1665—1678
[14]	Cordeiro P. J., Tilley T. D., ACSCatal., 2011, 1(5), 455—467
[15]	Wang Y., Zhang S. J., Zhao Y. X., Lin M., J. Mol. Catal. A: Chem., 2014, 385, 1—6
[16]	Tozzola G., Mantegazza M. A., Ranghino G., Petrini G., Bordiga S., Ricchiardi G., Lamberti C., Zulian R., Zecchina A., J. Catal., 1998, 179(1), 64—71
[17]	Zhuang J. Q., Yan Z. M., Liu X. M., Liu X. C., Han X. W., Bao X. H., Mueller U., Catal.Lett., 2002, 83(1/2), 87—91
[18]	Zhu Y. X., Lin W., Tian H. P., Long J., PetrochemicalTechnol., 2006, 35(7), 607—614
	(朱玉霞, 林伟, 田辉平, 龙军. 石油化工, 2006, 35(7), 607—614)
[19]	Li H., Lei Q., Zhang X. M., Suo J. S., Chinese J.Catal., 2013, 34(7), 1363—1372
	(李颢,雷骞,张小明,索继栓.催化学报, 2013, 34(7), 1363—1372)
[20]	Li H., Lei Q., Zhang X. M., Suo J. S., Microporous MesoporousMater., 2012, 147(1), 110—116
[21]	Katada N., Niwa M., Catal. Surv.Asia, 2004, 8, 161—170
[22]	Prakash A. M., Sung-Suh H. M., Kevan L., J. Phys. Chem.B, 1998, 102(5), 857—864
[23]	Yang G., Zhou L. J., Han X. W., J. Mol. Catal. A: Chem., 2012, 363/364, 371—379
[24]	Liu W. H., Guo P., Su J., Hu J., Wang Y. M., Liu N., Guo H. C., Chinese J.Catal., 2009, 30(6), 482—484
	(刘文欢, 郭鹏, 苏际, 胡佳, 王艳梅, 刘娜, 郭洪臣. 催化学报, 2009, 30(6), 482—484)
[25]	Zakrzewski J., Monatsh. Chem. ChemicalMonthly, 1990, 121(10), 803—808
[26]	Bordiga S., Damin A., Bonino F., Zecchina A., Spanò G., Rivetti F., Bolis V., Prestipino C., Lamberti C., J. Phys. Chem.B, 2002, 106(38), 9892—9905
[27]	Rozantsev E. G., Chudinov A. V., Sholle V. D., Bull. Acad. Sci. USSR Div. Chem. Sci., 1980, 29(9), 1510—1513
[28]	Liu H. J., Liu P. L., You K. Y., Luo H. A., Catal.Commun., 2010, 11(10), 887—891
[29]	Krinitskaya L. A., Volodarskii L. B., Bull. Acad. Sci. USSR Div. Chem. Sci., 1983, 32(2), 352—355

Adsorption Mechanisms of TMPDO and 4-NOH-TMPD in HTS/H₂O₂System and Effects on the Stabilization of Ti—OOH^†

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