Small-sized cuprous oxide species on silica boost acrolein formation via selective oxidation of propylene

doi:10.1016/S1872-2067(20)63636-1

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (2): 320-333.DOI: 10.1016/S1872-2067(20)63636-1

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Small-sized cuprous oxide species on silica boost acrolein formation via selective oxidation of propylene

Ling-Ling Guo^a^,^h, Jing Yu^c, Wei-Wei Wang^d, Jia-Xu Liu^e^,^$(), Hong-Chen Guo^e, Chao Ma^f^,^¥(), Chun-Jiang Jia^d^,^#(), Jun-Xiang Chen^g, Rui Si^a^,^b^,^*()

^aShanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
^bShanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai 201204, China
^cShanghai Institute of Measurement and Testing Technology, Shanghai 200233, China
^dKey Laboratory for Colloid and Interface Chemistry, Ministry of Education, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, Shandong, China
^eState Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116023, Liaoning, China
^fCollege of Materials Science and Engineering, Hunan University, Changsha 410082, Hunan, China
^gDivision of China, TILON Group Technology Limited, Shanghai 200090, China
^hUniversity of Chinese Academy of Science, Beijing 100049, China

Received:2020-03-29 Accepted:2020-05-11 Online:2021-02-18 Published:2021-01-21
Contact: Jia-Xu Liu,Chao Ma,Chun-Jiang Jia,Rui Si
About author:^¥Tel: +86-731-88821727; E-mail: cma@hnu.edu.cn
^$Tel: +86-411-84986162; E-mail: liujiaxu@dlut.edu.cn;
^#Tel: +86-531-88363683; E-mail: jiacj@sdu.edu.cn;
^*Tel: +86-21-33932079; E-mail: sirui@sinap.ac.cn;
Supported by:
National Natural Science Foundation of China(21773288);National Natural Science Foundation of China(21805167);National Natural Science Foundation of China(21771117);National Key Basic Research Program of China(2017YFA0403402);Excellent Young Scientists Fund from NSFC(21622106);Outstanding Scholar Fund(JQ201703);Doctoral Fund from the Science Foundation of Shandong Province(China)(ZR2018BB010);Taishan Scholar Project of Shandong Province(China);Fundamental Research Funds for the Central Universities(China)

Abstract

Abstract:

Oxide-supported copper-containing materials have attracted considerable research attention as promising candidates for acrolein formation. Nevertheless, the elucidation of the structure-performance relationships for these systems remains a scientific challenge. In this work, copper oxide clusters deposited on a high-surface-area silica support were synthesized via a deposition-precipitation approach and exhibited remarkable catalytic reactivity (up to 25.5% conversion and 66.8% selectivity) in the propylene-selective oxidation of acrolein at 300 °C. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy combined with X-ray absorption fine structure measurements of the catalyst before and after the reaction confirmed the transformation of the small-sized copper oxide (CuO) clusters into cuprous oxide (Cu₂O) clusters. With the aid of in situ X-ray diffraction and in situ dual beam Fourier transform infrared spectroscopy (DB-FTIR), the allyl intermediate (CH₂=CHCH₂*) was clearly observed, along with the as-formed Cu₂O species. The intermediate can react with oxygen atoms from neighboring Cu₂O species to form acrolein during the catalytic process, and the small-sized Cu₂O clusters play a crucial role in the generation of acrolein via the selective oxidation of propylene.

Key words: Propylene selective oxidation, Cuprous oxide cluster, Acrolein formation, Active species, In situ characterization

Ling-Ling Guo, Jing Yu, Wei-Wei Wang, Jia-Xu Liu, Hong-Chen Guo, Chao Ma, Chun-Jiang Jia, Jun-Xiang Chen, Rui Si. Small-sized cuprous oxide species on silica boost acrolein formation via selective oxidation of propylene[J]. Chinese Journal of Catalysis, 2021, 42(2): 320-333.

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Figures/Tables 11

Table 1 Catalytic performance of catalysts with different Cu weight percentages and particle sizes in propylene oxidation.

Sample	T (°C)	Conversion (%)	Selectivity (%)						r_acrolein (mmol·h^-1·g_Cu)	r_acrolein (mmol·h^-1·g_cat)	D_Cu2O^a (nm)
Sample	T (°C)	Conversion (%)	Acrolein	CO₂	PO	Acetone	Propanal	Aldehyde	r_acrolein (mmol·h^-1·g_Cu)	r_acrolein (mmol·h^-1·g_cat)	D_Cu2O^a (nm)
5Cu-DP	300	13.6	72.8	24.5	0.9	0.4	0.2	1.2	127.1	6.1	2.6
10Cu-DP	225	0.7	41.6	43.1	11.8	1.3	0.5	1.7	1.9	0.2	2.5
10Cu-DP	250	3.4	49.6	40.9	6.7	1.0	0.3	1.5	11.1	1.0	2.5
10Cu-DP	275	12.7	57.9	38.8	1.6	0.2	0.2	1.3	47.9	4.5	2.7
10Cu-DP	300	25.5	66.8	30.7	0.4	0.1	0.1	1.9	111.2	10.5	2.8
10Cu-DP	325	29.5	61.0	36.5	0.2	0.1	0.1	2.1	117.4	12.7	3.1
15Cu-DP	300	32.7	63.3	34.2	0.2	0.1	0.1	2.1	85.3	12.7	3.5
5Cu-IM	300	2.5	75.5	20.8	0.7	0.3	0.5	2.2	23.2	1.2	12.8
10Cu-IM	300	3.8	74.7	22.0	0.4	0.6	0.4	1.9	17.2	1.7	20.3
15Cu-IM	300	4.3	72.5	23.9	0.8	0.5	0.4	1.9	12.8	1.9	28.3

Fig. 1. Catalytic performance of the Cu/SiO2 catalysts. (a) Temperature dependence of the catalytic activity of 10Cu-DP in the range 225-325 °C; (b) Cu-loading dependence of the catalytic activity of the copper-silica catalysts at 300 °C; Comparisons of (c) the propylene conversion and acrolein selectivity with time on stream and (d) the acrolein formation rates of 10Cu-DP and 10Cu-IM in the selective oxidation of propylene at 300 °C. Reaction conditions: 0.1 g catalyst, C3H6:O2:N2/Ar = 2.5:2.5:45, 30000 cm3·h-1·gcat-1.

Fig. 2. XRD patterns of the copper-silica catalysts prepared by deposition-precipitation method. (a) Fresh; (b) used.

Fig. 3. Cu K-edge XANES profiles (a, c) and EXAFS fitting results (b, d) in R space for fresh (a, b) and used (c, d) copper-silica samples prepared by the deposition-precipitation method.

Table 2 EXAFS fitting results for fresh copper-silica samples with different Cu loadings.

Sample	Cu-O		Cu-Cu
Sample	R (Å)	CN	R (Å)	CN
CuO 5Cu-DP	1.948 1.89 ± 0.01	4 2.9 ± 0.2	2.935 2.99 ±0.02	10 2.3 ± 0.6
10Cu-DP	1.93 ± 0.01	4.7 ± 0.2	2.96 ± 0.01	3.1 ± 0.6
15Cu-DP	1.93 ± 0.01	4.7 ± 0.2	2.96 ± 0.01	3.0 ± 0.6

Table 3 EXAFS fitting results of used 10Cu-DP samples.

Sample	Cu-O		Cu-Cu
Sample	R (Å)	CN	R (Å)	CN
Cu₂O	1.849	2	3.019	12
Cu₂O	3.540	6	3.019	12
10Cu-DP-275-used	1.87 ± 0.01	1.9 ± 0.1	2.56 ± 0.01	3.1 ± 1.2
10Cu-DP-275-used	3.51 ± 0.02	2.9 ± 0.6	2.94 ± 0.02	3.3 ± 1.6
10Cu-DP-300-used	1.87 ± 0.01	2.3 ± 0.1	3.00 ± 0.01	4.4 ± 1.4
10Cu-DP-300-used	3.55 ± 0.03	2.0 ± 0.7	3.00 ± 0.01	4.4 ± 1.4
10Cu-DP-325-used	1.87 ± 0.01	2.3 ± 0.1	3.00 ± 0.01	4.8 ± 1.5
10Cu-DP-325-used	3.55 ± 0.02	2.3 ± 0.7	3.00 ± 0.01	4.8 ± 1.5

Fig. 4. Aberration-corrected HAADF-STEM images of (a) fresh and (b) used 10Cu-DP. (c) Schematic of the synthesis and structural transformation of 10Cu-DP.

Fig. 5. Structural evolution of the Cu/SiO2 catalysts. In situ XRD patterns of 10Cu-DP (a, b) and 10Cu-IM (c, d) during hydrogen reduction at different temperatures (a, c) and the propylene oxidation reaction (b, d).

Fig. 6. Dissociation adsorption ability of 10Cu-DP. In situ DB-FTIR results for 10Cu-DP during (a) propylene adsorption at 300 °C under a flowing mixture of propylene and nitrogen gases at a time on stream of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30 min (0.01 g catalyst, C3H6:N2 = 2.5: 90, 92.5 mL·min-1, 1 atm), and (b) propylene and oxygen coadsorption at 300 °C under a flowing mixture of propylene, oxygen, and nitrogen gases at a time on stream of 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90 min (0.01 g catalyst, C3H6:O2:N2 = 2.5:2.5:90, 95 mL·min-1, 1 atm).

Fig. 7. Dissociation adsorption ability of 10Cu/SiO2-IM. In situ DB-FTIR results for 10Cu/SiO2-IM during (a) propylene adsorption at 300 °C under a flowing mixture of propylene and nitrogen gases at a time on stream of 2, 5, 10, 15, 20, 25, and 30 min (0.01 g catalyst, C3H6:N2 = 2.5:90, 92.5 mL·min-1, 1 atm), and (b) propylene and oxygen coadsorption at 300 °C under a flowing mixture of propylene, oxygen, and nitrogen gases with a time on stream of 1, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, and 90 min (0.01 g catalyst, C3H6:O2:N2 = 2.5:2.5:90, 95 mL·min-1, 1 atm).

Fig. 8. H2-TPR profiles of 10Cu-DP and 10Cu-IM. Dashed and solid lines are the hydrogen consumption profiles measured for the first (after O2 pretreatment) and second (after N2O oxidation) runs, respectively.

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Small-sized cuprous oxide species on silica boost acrolein formation via selective oxidation of propylene

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