Effect of Metal Particle Size on the Performance of Tethered-phosphine Modified Rh/SiO2 in Hydroformylation†

doi:10.7503/cjcu20150450

Abstract

Abstract:

A series of tethered-phosphine modified Rh/SiO₂ catalysts with different Rh particle size was prepared by preparation technology of shell-type catalyst, which shared the same Rh loading and P/Rh ratio. Ethylene hydroformylation was used as a probe reaction to test the performance of those catalysts. The results show that Rh particle size has a great effect on the performances of phosphine modified Rh/SiO₂ catalysts. The catalytic activity increased as Rh particle size decreased, but meanwhile the induction period prolonged. The catalysts were characterized by H₂ chemical adsorption, transmission electron microscope, N₂ adsorption-desorption isotherms, in situ Fourier-transform spectra and solid ³¹P nuclear magnetic resonance technology. The active species were Rh-phosphine complex, and more amount of active species were produced over catalyst with smaller Rh particle size. With the decreasing of Rh particle size, the density of Rh particle on the surface decreased and it took more time for DPPPTS to reach Rh and form Rh-phosphine complex.

Key words: Tethered phosphine, Rh/SiO2, Shell-type catalyst, Ethylene, Hydroformylation

CLC Number:

O643.3

TrendMD:

LIU Jia, YAN Li, JIANG Miao, DING Yunjie. Effect of Metal Particle Size on the Performance of Tethered-phosphine Modified Rh/SiO₂ in Hydroformylation^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 114.

Figures/Tables 7

Fig.1 Images of Rh/SiO2-n^(A) Rh/SiO2-0.2; (B) Rh/SiO2-0.4; (C) Rh/SiO2-0.6; (D) Rh/SiO2-0.8.

Table 1 H2 chemical adsorption of samples

Catalyst	H₂ uptake /(μmol·g^-1)	Dispersion(%)	Diameter/nm
Rh/SiO₂-0.2	10.71	44.07	2.45
Rh/SiO₂-0.4	12.44	51.22	2.11
Rh/SiO₂-0.6	14.12	58.11	1.85
Rh/SiO₂-0.8	14.37	59.16	1.82

Fig.2 TEM images(A—D) and corresponding Rh particle size distributions(A'—D') of Rh/SiO2-n^ (A, A') Rh/SiO2-0.2; (B, B') Rh/SiO2-0.4; (C, C') Rh/SiO2-0.6; (D, D') Rh/SiO2-0.8.

Fig.3 Catalytic performance of catalysts in ethylene hydroformylation

Table 2 Texture properties of samples

Sample	S_BET/(m²·g^-1)	Total pore volume, V_p/(cm³·g^-1)	Average pore radius, D_p/nm
SiO₂	256.3	0.95	7.4
Rh/SiO₂-0.2	229.7	0.79	6.9
Rh/SiO₂-0.4	235.2	0.79	6.7
Rh/SiO₂-0.6	229.3	0.73	6.4
Rh/SiO₂-0.8	230.4	0.81	7.0
D-Rh/SiO₂-0.2	221.0	0.77	7.0
D-Rh/SiO₂-0.4	224.1	0.75	6.7
D-Rh/SiO₂-0.6	221.5	0.75	6.7
D-Rh/SiO₂-0.8	220.2	0.71	6.4

Fig.4 In situ FTIR spectra of catalysts treated with syngas^a. D-Rh/SiO2-0.8; b. D-Rh/SiO2-0.6; c. D-Rh/SiO2-0.4; d. D-Rh/SiO2-0.2.

Fig.5 31P NMR spectra of fresh(A) and used(B) catalysts^a. D-Rh/SiO2-0.8; b. D-Rh/SiO2-0.6; c. D-Rh/SiO2-0.4; d. D-Rh/SiO2-0.2.

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Effect of Metal Particle Size on the Performance of Tethered-phosphine Modified Rh/SiO₂ in Hydroformylation^†

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