Effect of Structure and Properties of CuO-WO3-ZrO2 on Hydrogenation Catalytic of Benzaldehyde†

doi:10.7503/cjcu20180757

Abstract

Abstract:

CuO-WO₃-ZrO₂ catalysts were prepared by co-precipitation method. Structures and surface properties of the catalysts were characterized by X-ray powder diffraction(XRD), scanning electron microscope(SEM), X-ray fluorescence(XRF), N₂ physisorption, temperature programmed hydrogen reduction(H₂-TPR), X-ray photoelectron spectroscopy(XPS) and temperature programmed desorption(TPD). Addition of WO₃ into CuO-ZrO₂ induced the transformation of ZrO₂ from monoclinic to tetragonal phases, improved the dispersion of CuO species, changed the acid-base properties of the catalysts as well as the catalyst textural features such as surface area and the average pore diameter. As a consequence, the catalytic performance for the hydrogenation of benzaldehyde to benzyl alcohol was greatly promoted by the introduction of WO₃. For the optimal catalyst containing 10%(mass fraction) CuO and 18%(mass fraction) WO₃, the conversion of benzaldehyde and the selectivity to benzyl alcohol reached 94.76% and 92.03%, respectively.

Key words: CuO-WO₃-ZrO₂ Catalyst, Hydrogenation, Benzyl alcohol, Benzaldehyde

CLC Number:

O643
O625

TrendMD:

HUANG Rui,YAO Zhilong,SUN Peiyong,ZHANG Shenghong. Effect of Structure and Properties of CuO-WO₃-ZrO₂ on Hydrogenation Catalytic of Benzaldehyde^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 1005.

Figures/Tables 15

Fig.1 XRD patterns of catalysts with different WO3 contents a. 18CuO-12WO3-ZrO2; b. 18CuO-10WO3-ZrO2; c. 18CuO-8WO3-ZrO2; d. 18CuO-6WO3-ZrO2; e. 18CuO-4WO3-ZrO2; f. 18CuO-0WO3-ZrO2.

Fig.2 H2-TPR profiles of catalysts with different WO3 contentsa. 18CuO-14WO3-ZrO2; b. 18CuO-12WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 18CuO-8WO3-ZrO2; e. 18CuO-6WO3-ZrO2; f. 18CuO-4WO3-ZrO2; g. 18CuO-0WO3-ZrO2.

Table 1 Textural properties of catalysts with different WO3 contents

Catalyst				Catalyst
18CuO-0WO₃-ZrO₂	0.00	10.3	16.91	18CuO-10WO₃-ZrO₂	9.83	35.5	8.95
18CuO-4WO₃-ZrO₂	3.25	19.8	15.37	18CuO-12WO₃-ZrO₂	10.86	36.3	8.50
18CuO-6WO₃-ZrO₂	5.80	25.9	10.77	18CuO-14WO₃-ZrO₂	11.42	37.0	8.37
18CuO-8WO₃-ZrO₂	8.08	31.5	9.60

Fig.3 Cu2p XPS spectra of catalysts with different WO3 contentsa. 18CuO-10WO3-ZrO2; b. 18CuO-6WO3-ZrO2; c. 18CuO-0WO3-ZrO2.

Fig.4 CO2-TPD profiles of catalysts with different WO3 contentsa. 18CuO-14WO3-ZrO2; b. 18CuO-12WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 18CuO-8WO3-ZrO2; e. 18CuO-6WO3-ZrO2.

Fig.5 XRD patterns of catalysts with different CuO contents a. 24CuO-10WO3-ZrO2; b. 21CuO-10WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 15CuO-10WO3-ZrO2; e. 12CuO-10WO3-ZrO2; f. 0CuO-10WO3-ZrO2.

Fig.6 H2-TPR profiles of catalysts with different CuO contentsa. 24CuO-10WO3-ZrO2; b. 21CuO-10WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 15CuO-10WO3-ZrO2; e. 12CuO-10WO3-ZrO2; f. 0CuO-10WO3-ZrO2.

Table 2 Textural properties of catalysts with different CuO contents

Catalyst	Surface area/(m²·g^-1)	Average pore diameter/nm	Catalyst	Surface area/(m²·g^-1)	Average pore diameter/nm
12CuO-10WO₃-ZrO₂	36.4	9.02	21CuO-10WO₃-ZrO₂	33.0	9.96
15CuO-10WO₃-ZrO₂	36.4	9.68	24CuO-10WO₃-ZrO₂	32.2	9.39
18CuO-10WO₃-ZrO₂	35.5	8.95

Fig.7 SEM images of catalysts with different CuO contents(A) 12CuO-10WO3-ZrO2; (B) 18CuO-10WO3-ZrO2; (C) 24CuO-10WO3-ZrO2.

Fig.8 NH3-TPD profiles of catalysts with different CuO contentsa. 24CuO-10WO-ZrO23; b. 21CuO-10WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 15CuO-10WO3-ZrO2; e. 12CuO-10WO3-ZrO2.

Table 3 Performance of catalysts with different WO3 contents*

w(WO₃)(%)	Conversion(%)	Selectivity(%)
w(WO₃)(%)	Conversion(%)	Benzyl alcohol	Benzyl benzoate	Diphenylmethane
0	60.38	90.85	0.28	Trace
4	79.34	89.24	0.46	1.06
6	84.07	90.28	1.25	1.01
8	88.99	90.89	1.33	0.97
10	94.76	92.03	1.59	0.97
12	94.08	92.17	0.74	0.96

Table 4 Performance of catalysts with different CuO contents*

w(CuO)(%)	Conversion(%)	Selectivity(%)
w(CuO)(%)	Conversion(%)	Benzyl alcohol	Toluene	Diphenylmethane	Benzene
0	15.56	42.38	1.45	Trace	Trace
12	47.61	92.70	1.96	0.98	0.22
15	81.80	90.96	2.68	0.98	0.23
18	94.76	92.03	4.34	0.97	0.20
21	74.42	90.52	2.58	0.89	0.22
24	66.93	96.36	2.05	0.87	0.21

Scheme 1 Plausible mechanism of 1,2 nucleophilic addition reaction

Fig.9 Effects of reaction temperature on catalytic performance of 12CuO-10WO3-ZrO2 for pincipal products

Scheme 2 Possible reaction pathways associated with the hydrogenation of benzaldehyde to the target benzyl alcohol and isolated byproducts(Ⅰ) Hydrogenation of benzaldehyde; (Ⅱ) hydrogenation of benzyl alcohol; (Ⅲ) decarburization of benzaldehyde; (Ⅳ) dehydrogenation and condensation of benzaldehyde and benzyl alcohol; (Ⅴ) alkylation of benzyl alcohol and benzene.

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Effect of Structure and Properties of CuO-WO₃-ZrO₂ on Hydrogenation Catalytic of Benzaldehyde^†

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