Effect of Surface Oxygen Groups on the Two-component Non-mercury AuCl3-CuCl2/C Catalyst†

doi:10.7503/cjcu20131000

Abstract

Abstract:

The coconut shell activated carbon was oxidized by HNO₃ and calcined at different temperature in the atmosphere of He. It demonstrated that the physical properties of the activated carbons were basically identical before and after different treatments. However, the content of surface oxygen groups, such as phenol and carboxylic, were increased after oxidizing by HNO₃ and decreased in the order of carboxyl, phenol and carbonyl after calcing in different temperatures. Taking the above activated carbons as the carrier, two-component catalysts of AuCl₃-CuCl₂ were prepared by impregnation method. And the catalysts were evaluated by the acetylene hydrochlorination. The results showed that the acetylene conversion rates of the catalysts, which were prepared with the carrier of original activated carbon, pre-treated by HNO₃ oxidation and calcined in 400 ℃ for 1 h, could reach above 96%, 98%and 90%, respectively. And they had good reaction stability in 10 h. The acetylene conversion rates dropped sharply to around 30% after 4 h for the AuCl₃-CuCl₂/He700-C and AuCl₃-CuCl₂/He1000-C catalysts, whose carriers were calcined in 700 and 1000 ℃. The analysis results by BET, H₂-TPR and SEM show that the BET specific surface area decreases mostly, carbon deposition is more serious and active component dispersion is poorer. It prove that the surface oxygen groups, especially for the hydroxyl group, plays an important role in promoting the dispersion of Au, enhancing the stability and reducing the carbon deposition.

Key words: Acetylene hydrochlorination, Oxygen-containing group, Dispersion, Stability, Active carbon

CLC Number:

O643

TrendMD:

CHENG Xiaoguang, ZHAO Jigang, WANG Lei, REN Ruofan, YANG Henghua, SHEN Benxian. Effect of Surface Oxygen Groups on the Two-component Non-mercury AuCl₃-CuCl₂/C Catalyst^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 582.

Figures/Tables 9

Table 1 Textural data of the active carbons before and after different pre-treatments

Sample	$S BET a$ /(m²·g^-1)	$V p b$ /(cm³·g^-1)	$D p c$ /nm
C	713.8	0.0673	8.32
HNO₃-C	699.4	0.0705	8.68
He500-C	700.6	0.0683	8.58
He700-C	695.4	0.0679	8.95
He1000-C	694.9	0.0676	9.58

Table 1 Textural data of the active carbons before and after different pre-treatments

Sample	$S BET a$ /(m²·g^-1)	$V p b$ /(cm³·g^-1)	$D p c$ /nm
C	713.8	0.0673	8.32
HNO₃-C	699.4	0.0705	8.68
He500-C	700.6	0.0683	8.58
He700-C	695.4	0.0679	8.95
He1000-C	694.9	0.0676	9.58

Fig.1 FTIR spectra of the active carbons before and after different pre-treatments

Fig.2 Curve fitted C1s core level spectra for the original active carbon

Table 2 Results of the fits of the C1s region and C, O contents from XPS for the samples

Sample	Surface functional group(mass fraction, %)					Surface element(mass fraction, %)
Sample	Phenol	Carbonyl	Carboxyl	Lactone	C—C	O	C
C	10.75	5.40	1.66	11.91	70.28	18.7	77.4
HNO₃-C	23.61	6.33	6.86	3.11	60.09	25.2	69.5
He500-C	9.83	6.54	0.68	10.83	71.68	15.6	80.9
He700-C	5.03	5.99	0.45	6.43	81.90	14.8	81.8
He1000-C	3.21	3.32	0.08	3.28	90.11	10.6	86.8

Fig.3 Variation curves of the C2H2 conversion with the reaction time for different catalysts —■— AuCl3-CuCl2/C; —○— AuCl3-CuCl2/HNO3-C; —▲— AuCl3-CuCl2/He500-C; —□— AuCl3-CuCl2/He700-C; —●— AuCl3-CuCl2/He1000-C.

Table 3 Textural data of the as-prepared AuCl3-CuCl2/C catalysts

Sample	Fresh			Used
Sample	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D_p/nm	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	D_p/nm
AuCl₃-CuCl₂/C	711.5	0.0662	8.32	650.6	0.0641	8.21
AuCl₃-CuCl₂/HNO₃-C	698.1	0.0683	8.68	661.8	0.0647	8.49
AuCl₃-CuCl₂/He500-C	701.3	0.0683	8.58	647.7	0.0678	8.65
AuCl₃-CuCl₂/He700-C	690.9	0.0679	8.95	620.5	0.0620	8.75
AuCl₃-CuCl₂/He1000-C	692.0	0.0659	9.37	613.7	0.0608	8.92

Fig.4 FTIR substract spectrum between used and fresh catalyst of AuCl3-CuCl2/He1000-C

Fig.5 H2-TPR spectra for five fresh catalystsa. AuCl3-CuCl2/C; b. AuCl3-CuCl2/HNO3-C; c. AuCl3-CuCl2/He500-C; d. AuCl3-CuCl2/He700-C; e. AuCl3-CuCl2/He1000-C.

Fig.6 SEM images of the AuCl3-CuCl2/HNO3-C(A—C) and AuCl3-CuCl2/He1000-C(D—F) both fresh(A, D) and used(B, C, E, F)

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Effect of Surface Oxygen Groups on the Two-component Non-mercury AuCl₃-CuCl₂/C Catalyst^†

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