Preparation of Ce Modified Mg-Al Mixed Metal Oxides by Aqueous Reconstruction for Vapor Self-condensation of Acetone†

doi:10.7503/cjcu20150653

Abstract

Abstract:

Ce modified Mg-Al mixed metal oxides(HTc-Ce) were prepared by aqueous reconstruction method. The construct and surface properties of catalysts were characterized by X-ray diffraction(XRD), X-ray photoelectron spectrometry(XPS), transmission electron microscopy(TEM) and N₂ adsorption and desorption isotherms. Aqueous reconstruction process promotes forming more defects on the Mg-Al mixed oxides, Ce is successfully embedded into the interlayer of hydrotalcite framework and enlarges its spaces, which improves the accessibility of active sites. The oxygen mobility of ceria increases the amount of basic sites on the surface. XPS results indicate that there is about 30% of Ce(Ⅲ) in cerium oxides. Oxygen vacancies are beneficial to enhancing the ability of oxygen mobility. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) verifies the augment of low-coordinated oxygen, CO₂-temperature programmed desorption(CO₂-TPD) experiment reveals that modification of Ce increases the density of basic sites on surface. Aqueous reconstructed HTc-Ce-3.2 catalyst exhibits high activity for acetone self-condensation. The conversion of acetone is 56.8%. It is 2.5 times higher than that of HTc catalyst, the selectivity of pentamers enhance significantly.

Key words: Aqueous reconstruction, Oxygen vacancy, Mixed metal oxide, Vapor self condensation of acetone, Ce modification

CLC Number:

O643.3

TrendMD:

WU Binquan, WANG Sheng, HUANG Liang, QIN Feng, HUANG Zhen, XU Hualong, SHEN Wei. Preparation of Ce Modified Mg-Al Mixed Metal Oxides by Aqueous Reconstruction for Vapor Self-condensation of Acetone^†[J]. Chem. J. Chinese Universities, 2016, 37(4): 745.

Figures/Tables 9

References 26

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Sample	Cell parameter		Particle size/nm	Sample	Cell parameter		Particle size/nm
Sample	a/nm		Particle size/nm	c/nm		a/nm	c/nm
HT	0.304	22.71	50	HT-Ce-1.6	0.304	22.84	11
HT-rh	0.304	22.72	15	HT-Ce-3.2	0.304	23.31	11
HT-Ce-0.8	0.304	22.81	12	HT-Ce-6.3	0.304	26.26	18

Sample	Cell parameter		Particle size/nm	Sample	Cell parameter		Particle size/nm
Sample	a/nm		Particle size/nm	c/nm		a/nm	c/nm
HT	0.304	22.71	50	HT-Ce-1.6	0.304	22.84	11
HT-rh	0.304	22.72	15	HT-Ce-3.2	0.304	23.31	11
HT-Ce-0.8	0.304	22.81	12	HT-Ce-6.3	0.304	26.26	18

Sample	Atomic mass fraction^a(%)		Bulk atomic ratio^a		Surface atomic ratio^b
Sample	Mg	Ce	Al	Mg/Al	Mg/Ce	Mg/Al	Mg/Ce
HTc	7.90		13.37	1.90		1.23
HTc-rh	8.76		14.33	1.84		1.00
HTc-Ce-0.8	7.69	1.18	12.88	1.88	63.67	1.09	34.82
HTc-Ce-1.6	7.96	2.20	13.14	1.86	34.84	1.34	18.61
HTc-Ce-3.2	7.67	4.15	13.18	1.93	18.53	1.36	5.27
HTc-Ce-6.3	6.43	6.41	11.21	1.96	10.20	1.49	3.49

Sample	Atomic mass fraction^a(%)		Bulk atomic ratio^a		Surface atomic ratio^b
Sample	Mg	Ce	Al	Mg/Al	Mg/Ce	Mg/Al	Mg/Ce
HTc	7.90		13.37	1.90		1.23
HTc-rh	8.76		14.33	1.84		1.00
HTc-Ce-0.8	7.69	1.18	12.88	1.88	63.67	1.09	34.82
HTc-Ce-1.6	7.96	2.20	13.14	1.86	34.84	1.34	18.61
HTc-Ce-3.2	7.67	4.15	13.18	1.93	18.53	1.36	5.27
HTc-Ce-6.3	6.43	6.41	11.21	1.96	10.20	1.49	3.49

Sample	Temperature/℃		Weak basicity/ (mmol·g^-1)	Strong basicity/ (mmol·g^-1)	Surface area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	WBPC^a/ (mmol·g^-1)	SBPC^b/ (mmol·g^-1)
Sample	First peak	Second peak	Weak basicity/ (mmol·g^-1)	Strong basicity/ (mmol·g^-1)	Surface area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	WBPC^a/ (mmol·g^-1)	SBPC^b/ (mmol·g^-1)
HTc	109	234	0.082	0.096	127	0.19	0.082	0.096
HTc-rh	105	257	0.093	0.103	188	0.41	0.093	0.103
HTc-Ce-0.8	99	244	0.105	0.116	220	0.57	0.108	0.120
HTc-Ce-1.6	102	250	0.103	0.125	178	0.48	0.110	0.133
HTc-Ce-3.2	105	253	0.105	0.144	137	0.47	0.119	0.163
HTc-Ce-6.3	101	271	0.104	0.134	146	0.42	0.131	0.169