Direct Syntheses of Cu-Zn-Zr/SBA-15 Mesoporous Catalysts for CO2 Hydrogenation to Methanol†

doi:10.7503/cjcu20140684

Abstract

Abstract:

A series of high surface areas and different mental oxide contents of Cu-Zn-Zr/SBA-15 mesoporous catalysts CZZ_x/SBA-15(x=0.3, 0.4, 0.5, 0.6) was directly synthesized by impregnation method. The catalysts were characterized by N₂ adsorption-desorption(BET), X-ray diffraction(XRD), transmission electron microscopy(TEM), H₂ temperature-programmed reduction(H₂-TPR), CO₂ temperature-programmed desorption(CO₂-TPD) and N₂O titration technique(N₂O-RFC). The catalytic activities of these catalysts were determined on the hydrogenation of CO₂ to methanol in a fixed-bed reactor. The results showed that CZZ_x/SBA-15 catalysts possessed a highly ordered mesoporous structure, in which different grain size CuO, ZnO, ZrO₂ species dispersed on the surface of SBA-15. A approximate linear relationship between the methanol synthesis activity and the total Cu⁰ surface area S_Cu was observed. CZZ_0.4/SBA-15 catalyst showed the largest methanol selectivity $S C H 3 OH$ =54.32%, which increased by 24.85% as compared with CZZ catalyst. However, the methanol synthesis selectivity and yield decreased with the increasing of metal oxide content, which strongly suggested that the surface structure of the CZZ_x/SBA-15 catalysts played an important role in CO₂ hydrogenation to methanol.

Key words: Impregnation method, Cu-Zn-Zr catalyst, SBA-15 molecular seive, CO₂ hydrogenation, Methanol selectivity

CLC Number:

O643

TrendMD:

LI Zhixiong, NA Wei, WANG Hua, GAO Wengui. Direct Syntheses of Cu-Zn-Zr/SBA-15 Mesoporous Catalysts for CO₂ Hydrogenation to Methanol^†[J]. Chem. J. Chinese Universities, 2014, 35(12): 2616.

Figures/Tables 10

Fig.1 N2 adsorption-desorption isotherms of catalysts a. CZZ; b. CZZ0.6/SBA-15; c. CZZ0.5/SBA-15;d. CZZ0.4/SBA-15; e. CZZ0.3/SBA-15; f. SBA-15.

Table 1 Textural properties of catalysts

Catalyst	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	D_BJH/nm
SBA-15	872.28	1.23	7.57
CZZ	70.51	0.09	3.04
CZZ_0.3/SBA-15	419.40	0.65	5.69
CZZ_0.4/SBA-15	417.90	0.46	4.94
CZZ_0.5/SBA-15	336.73	0.39	4.35
CZZ_0.6/SBA-15	273.15	0.41	4.95

Fig.2 Small-angle XRD patterns of catalysts a. SBA-15; b. CZZ0.3/SBA-15; c. CZZ0.4/SBA-15;d. CZZ0.5/SBA-15; e. CZZ0.6/SBA-15; f. CZZ.

Fig.3 XRD patterns of catalysts a. CZZ0.3/SBA-15; b. CZZ0.4/SBA-15; c. CZZ0.5/SBA-15;d. CZZ0.6/SBA-15; e. CZZ.

Table 2 Chemical composition and textural properties of catalysts*

Catalyst	Content(%, mass fraction)			d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
Catalyst	CuO	ZnO	ZrO₂	d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
CZZ	42.2	43.2	14.5	17.6	24.3	15.6	7.1
CZZ_0.3/SBA-15	16.0	16.4	5.6	16.3	18.6	21.4	16.5
CZZ_0.4/SBA-15	20.0	20.5	7.0	17.5	24.9	25.9	19.2
CZZ_0.5/SBA-15	22.8	23.3	7.8	19.9	25.8	16.3	11.5
CZZ_0.6/SBA-15	25.0	25.5	8.6	22.4	27.8	13.6	9.8

Table 2 Chemical composition and textural properties of catalysts*

Catalyst	Content(%, mass fraction)			d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
Catalyst	CuO	ZnO	ZrO₂	d(CuO)/nm	d(ZnO)/nm	$S Cu a$ /(m²·g^-1)	$D Cu b$ (%)
CZZ	42.2	43.2	14.5	17.6	24.3	15.6	7.1
CZZ_0.3/SBA-15	16.0	16.4	5.6	16.3	18.6	21.4	16.5
CZZ_0.4/SBA-15	20.0	20.5	7.0	17.5	24.9	25.9	19.2
CZZ_0.5/SBA-15	22.8	23.3	7.8	19.9	25.8	16.3	11.5
CZZ_0.6/SBA-15	25.0	25.5	8.6	22.4	27.8	13.6	9.8

Fig.4 TEM image(A) and EDX pattern(B) of the representative CZZ0.4/SBA-15 catalyst

Fig.5 H2-TPR profiles of catalysts a. CZZ; b. CZZ0.3/SBA-15; c. CZZ0.4/SBA-15;d. CZZ0.5/SBA-15; e. CZZ0.6/SBA-15.

Fig.6 CO2-TPD profiles of catalysts a. CZZ; b. CZZ0.3/SBA-15; c. CZZ0.4/SBA-15;d. CZZ0.5/SBA-15; e. CZZ0.6/SBA-15.

Table 3 Catalytic performance for methanol synthesis

Catalyst	CO₂ conversion(%)	Selectivity(%)			Yield(CH₃OH)/ (g·mL^-1·h^-1)
Catalyst	CO₂ conversion(%)	$S C H 4$	S_CO	$S C H 3 OH$	Yield(CH₃OH)/ (g·mL^-1·h^-1)
CZZ	15.01	5.10	65.43	29.47	0.04
CZZ_0.3/SBA-15	14.81	4.16	53.01	42.83	0.07
CZZ_0.4/SBA-15	16.45	1.92	43.76	54.32	0.08
CZZ_0.5/SBA-15	13.19	2.25	58.88	38.86	0.05
CZZ_0.6/SBA-15	10.36	2.84	65.96	31.19	0.03

Table 3 Catalytic performance for methanol synthesis

Catalyst	CO₂ conversion(%)	Selectivity(%)			Yield(CH₃OH)/ (g·mL^-1·h^-1)
Catalyst	CO₂ conversion(%)	$S C H 4$	S_CO	$S C H 3 OH$	Yield(CH₃OH)/ (g·mL^-1·h^-1)
CZZ	15.01	5.10	65.43	29.47	0.04
CZZ_0.3/SBA-15	14.81	4.16	53.01	42.83	0.07
CZZ_0.4/SBA-15	16.45	1.92	43.76	54.32	0.08
CZZ_0.5/SBA-15	13.19	2.25	58.88	38.86	0.05
CZZ_0.6/SBA-15	10.36	2.84	65.96	31.19	0.03

Fig.7 Turnover frequency(TOF) and CH3OH selectivity as a function of the metallic copper surface areas

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Direct Syntheses of Cu-Zn-Zr/SBA-15 Mesoporous Catalysts for CO₂ Hydrogenation to Methanol^†

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