Controlled construction of Co3S4@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect

doi:10.1016/S1872-2067(23)64573-5

Abstract

Abstract:

A yolk-shell structured Co₃S₄@CoMoS catalyst was prepared through Oswald ripening method and subsequently used for hydrodesulfurization (HDS) reaction. The shells, constructed from Co-promoted MoS₂ nanosheets, possess abundant active sites and facilitate the adsorption of reactants through the development of pore channels. The MoS₂ sheets are arranged in a staggered and convoluted manner, creating numerous defect sites. The shorter MoS₂ slabs provide a wide distribution of reactive sites, ensuring efficient reactions. The Co₃S₄ species within the inner core acts as an auxiliary active phase, inducing the hydrogen spillover effect in the HDS system. This facilitates the transfer of active hydrogen species to the CoMoS shell, where both CoMoS and Co₃S₄ phases synergistically enhance the HDS reaction. The Co₃S₄@CoMoS catalyst achieved up to 99.2% dibenzothiophene (DBT) conversion and 94.9% 4,6-dimethyldibenzothiophene conversion at the lower dosage (30 mg). The structure-activity relationships between active phase and HDS activity were investigated via in-situ infrared spectroscopy and other characterizations as well as density functional theory calculations.

Key words: Hydrodesulfurization, Hydrogen spillover effect, Yolk-shell structure, CoMoS active phase, Dual active phase synergy

Wenjing Bao, Chao Feng, Shuyan Ma, Dengwei Yan, Cong Zhang, Changle Yue, Chongze Wang, Hailing Guo, Jiqian Wang, Daofeng Sun, Yunqi Liu, Yukun Lu. Controlled construction of Co₃S₄@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect[J]. Chinese Journal of Catalysis, 2024, 57: 154-170.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64573-5

https://www.cjcatal.com/EN/Y2024/V57/I2/154

Figures/Tables 18

Fig. 1. Schematic diagram of the synthesis process of Co3S4@CoMoS catalyst.

Fig. 2. Schematic illustration of the formation process of Co3S4@CoMoS yolk shell spheres. SEM (a), TEM (b,c) images, and corresponding EDX elemental mappings of Co3S4@CoMoS sample.

Fig. 3. The XRD patterns of different catalysts.

Fig. 4. Nitrogen physisorption analysis of catalysts. Adsorption/desorption isotherms (a) and pore size distribution (b).

Table 1 Textual properties of the catalysts.

Catalyst	BET surface area (m² g^-1)	Average pore diameter (nm)	Total pore volume (cm³ g^-1)
Co₃S₄@CoMoS	72	9.60	0.17
H-CoMoS	40	10.4	0.13
MM-Co₃S₄/MoS₂	38	10.6	0.13
O-MoS₂	36	9.90	0.10

Fig. 5. H2-TPR (a) and H2-TPD (b) curves of catalysts and photographs of samples made of WO3 mixed with the Co3S4@CoMoS (c), MM-Co3S4/MoS2 (d), H-CoMoS (e), and O-MoS2 (f) catalysts after H2 treatment.

Fig. 6. HRTEM images of the catalysts Co3S4@CoMoS (a), H-CoMoS (b), MM-Co3S4/MoS2 (c), and O-MoS2 (d). (e,f) Distribution of the length and number of layers of the MoS2 slabs. (g,h) Schematic diagram of (Co)MoS2 slabs curvature and defect sites.

Table 2 Average length (L?), Average stacking (N?) and the average fraction of Mo atoms (fMo) on the edge surface of the MoS2 crystals.

Catalyst	Average length (nm)	Average stacking	f_Mo
Co₃S₄@CoMoS	6.1	3.2	0.22
H-CoMoS	6.7	3.1	0.20
MM-Co₃S₄/MoS₂	9.2	3.6	0.14
O-MoS₂	9.4	3.7	0.14

Fig. 7. Mo 3d and Co 2p3/2 patterns of Co3S4@CoMoS (a), H-CoMoS (b), MM-Co3S4/MoS2 (c), and O-MoS2 (d) catalysts.

Table 3 XPS parameters of Mo 3d and Co 2p contributions of Co3S4@CoMoS, H-CoMoS, MM-Co3S4/MoS2 and O-MoS2 catalysts.

Catalyst	Mo⁵⁺ area (%)	Mo⁶⁺ area (%)	Mo_sulfidation ^a (%)	CoS_x area (%)	Co²⁺ area (%)	[CoMoS]^b (%)
Co₃S₄@CoMoS	22	8.0	70	7.5	9.5	83
H-CoMoS	19	14	67	11	19	70
MM-Co₃S₄/MoS₂	15	24	61	77	23	—
O-MoS₂	13	29	58	—	—	—

Fig. 8. FTIR spectra of CO adsorbed over Co3S4@CoMoS (a), H-CoMoS (b), MM-Co3S4/MoS2 (c) and O-MoS2 (d) catalysts.

Table 4 HDS activity and product distribution over Co3S4@CoMoS, H-CoMoS, MM-Co3S4/MoS2 and O-MoS2 catalysts.

Catalyst	HDS conversion (%)	E_a (kJ mol^-1)	k_HDS (10^-6 mol_DBT g_cat^-1 s^-1)	TOF values ^a (10^-3 s^-1)	Product selectivity ^a
Catalyst	HDS conversion (%)	E_a (kJ mol^-1)	k_HDS (10^-6 mol_DBT g_cat^-1 s^-1)	TOF values ^a (10^-3 s^-1)	BP (%)	CHB (%)	THDBT+HHDBT (%)	S_DDS/HYD
Co₃S₄@CoMoS	99.2	76	5.0	4.4	79	20	1	3.8
H-CoMoS	60.3	102	1.1	2.2	68	28	4	2.1
MM-Co₃S₄/MoS₂	59.0	117	0.9	1.2	66	30	4	1.9
O-MoS₂	40.9	139	0.5	0.93	60	35	5	1.5

Fig. 9. Variation in ln(c0/c) vs. reaction time (a) and Arrhenius plots of the reaction rate (ln kHDS) vs. 1/T (b) for the DBT HDS of Co3S4@CoMoS, H-CoMoS, MM-Co3S4/MoS2, O-MoS2 catalysts. (c) Cycle stability experiment of DBT of Co3S4@CoMoS catalyst. (d) Product yield, DBT conversion and pathway selectivity of Co3S4@CoMoS-1, Co3S4@CoMoS-3, Co3S4@CoMoS-6, Co3S4@CoMoS-8 and Co3S4@CoMoS catalysts.

Fig. 10. XRD patterns (a) and SEM image (b) of spent Co3S4@CoMoS catalyst.

Table 5 4,6-DMDBT HDS activity and product distribution over Co3S4@CoMoS, H-CoMoS, MM-Co3S4/MoS2 and O-MoS2 catalysts.

Catalyst	HDS conversion (%)	Product selectivity ^a
Catalyst	HDS conversion (%)	3,3'-DMCHB (%)	4,6-THDMDBT+4,6-HHDMDBT (%)	3,3'-DMBCH (%)	3,3'-DMBP (%)	S_DDS/HYD
Co₃S₄@CoMoS	94.9	59	2.0	17	22	0.3
H-CoMoS	44.3	38	18	16	28	0.4
MM-Co₃S₄/MoS₂	38.0	31	19	15	35	0.5
O-MoS₂	15.1	6.6	52	5.4	36	0.6

Fig. 11. (a) Difference charge density of CoMoS-Co3S4 model. The interface energy is 0.004 eV. Red region represents charge accumulation, blue region represents charge reduction. Color scheme: Yellow spheres represent S atoms; Reddish brown spheres represent Mo atoms; Dark blue spheres represent Co atoms. (b) Electron localization function of CoMoS-Co3S4 and CoMoS model. Density of states of CoMoS-Co3S4 (c) and CoMoS (d) model.

Fig. 12. Gibbs energy changes of hydrogen dissociation (a) and DBT decomposition (b) on CoMoS-Co3S4 model and CoMoS model.

Fig. 13. Schematic illustration of the dual active sites of hydrogen spillover and CoMoS for the synergistic catalytic HDS reaction. (process I represent the diffusion of H2; process II represents the activation of H2 to Hso; process III represents the diffusion of Hso; process IV represents the HDS reaction of 4,6-DMDBT on CoMoS phase.)

References

[1]	J. J. Xu, Z. G. Zhu, T. Su, W. P. Liao, C. L. Deng, D. M. Hao, Y. C. Zhao, W. Z. Ren, H. Y. Lü, Chin. J. Catal., 2020, 41, 868-876.
[2]	S. S. He, T. T. Huang, Y. Fan, Appl. Catal. B, 2022, 317, 121801.
[3]	W. J. Bao, T. T. Huang, C. Z. Wang, S. Y. Ma, H. L .Guo, Y. Pan, Y. Q. Liu, C. G. Liu, D. F. Sun, Y. K. Lu, J. Catal., 2022, 413, 374-387.
[4]	T. Roy, J. Rousseau, A. Daudin, G. Pirngruber, B. Lebeau, J.-L. Blin, S. Brunet, Catal. Today, 2021, 377, 17-25.
[5]	E. L. Wang, F. H. Yang, M. Y. Song, G. L. Chen, Q. Q. Zhang, F. Wang, L. C. Bing, G. J. Wang, D. Z. Han, Fuel Process. Technol., 2022, 235, 107386.
[6]	K. Sun, G. Yang, J. X. Han, Y. M. Chai, Y. P. Li, C. Z. Wang, S. Mintova, C. G. Liu, H. L. Guo, Inorg. Chem. Front., 2022, 9, 3384-3391.
[7]	B. Liu, L. Liu, Z. Wang, Y. M. Chai, H. Liu, C. L. Yin, C. G. Liu, Catal. Today, 2017, 282, 214-221.
[8]	F. Jiao, H. L. Guo, Y. M. Chai, H. Awala, S. Mintova, C. G. Liu, J. Catal., 2018, 368, 89-97.
[9]	N. Escalona, R. Garcia, G. Lagos, C. Navarrete, P. Baeza, F. J. Gil-Llambias, Catal. Commun., 2006, 7, 1053-1056.
[10]	M. Z. Hou, Y. T. Qiu, G. S. Yan, J. M. Wang, D. Zhan, X. Liu, J. C. Gao, L. F. Lai, Nano Energy, 2019, 62, 299-309.
[11]	Q. Sun, X.-Q. Zhang, Y. Wang, A.-H. Lu, Chin. J. Catal., 2015, 36, 683-691.
[12]	M. Zhao, J. Xu, S. Y. Song, H. J. Zhang, Chin. J. Catal., 2023, 50, 83-108.
[13]	K. Yu, W.-M. Kong, Z. Zhao, A.-J. Duan, L. Kong, X.-L. Wang, Pet. Sci., 2023, doi.org/10.1016/j.petsci.2023.08.007.
[14]	Y. Ma, M. Zhang, M. Sun, D. Xie, N. Mominou, C. Jing, L. Wang, Fuel, 2022, 324, 124577.
[15]	W. Lai, Z. Chen, J. Zhu, L. Yang, J. Zheng, X. Yi, W. Fang, Nanoscale, 2016, 8, 3823-3833.
[16]	X. Kang, D. Wang, J. Liu, C. Tian, H. Xu, J. Xu, H. Fu, J. Mater. Chem. A, 2022, 10, 7263-7270.
[17]	L. Shen, L. Yu, H. B. Wu, X. Y. Yu, X. Zhang, X. W. Lou, Nat. Commun., 2015, 6, 6694.
[18]	L. Qi, P. Zheng, Z. Zhao, A. Duan, C. Xu, X. Wang, J. Catal., 2022, 408, 279-293.
[19]	C. Sattayanon, S. Namuangruk, N. Kungwan, M. Kunaseth, Fuel Process. Technol., 2017, 166, 217-227.
[20]	Y. F. Chen, Y. Lu, Z. Guan, S. Liu, C. Feng, G. Sun, J. Liang, Y. Pan, C. Liu, Y. Liu, Fuel, 2022, 315, 123134.
[21]	S. Rangarajan, M. Mavrikakis, ACS Catal., 2016, 7, 501-509.
[22]	X. Tan, X. Wang, X. Wang, Y. Wang, C. Li, D. Xia, Ionics, 2019, 25, 4047-4056.
[23]	Y. Wang, L. Yu, X. W. Lou, Angew. Chem. Int. Ed., 2016, 55, 7423-7426.
[24]	J. Wang, L. Zhu, F. Li, T. Yao, T. Liu, Y. Cheng, Z. Yin, H. Wang, Small, 2020, 16, e2002487.
[25]	S. Palencia-Ruiz, D. Uzio, C. Legens, D. Laurenti, P. Afanasiev, Appl. Catal. A, 2021, 626, 118355.
[26]	M. Li, D. G. Wang, J. H. Li, Z. D. Pan, H. J. Ma, Y. X. Jiang, Z. J. Tian, A. H. Lu, Chin. J. Catal., 2017, 38, 597-606.
[27]	R. K. Chowdari, J. N. Diaz de Leon, S. Fuentes-Moyado, Catal. Today, 2022, 394- 396, 13-24.
[28]	K. Yu, W. Kong, Z. Zhao, A. Duan, L. Kong, X. Wang, J. Catal., 2022, 410, 128-143.
[29]	W. Zhou, M. Liu, Q. Zhang, Q. Wei, S. Ding, Y. Zhou, ACS Catal., 2017, 7, 7665-7679.
[30]	X. Niu, W. Zhou, Y. Han, Y. Liu, Langmuir, 2021, 37, 14254-14264.
[31]	A. N. Varakin, A. V. Mozhaev, A. A. Pimerzin, P. A. Nikulshin, Appl. Catal. B, 2018, 238, 498-508.
[32]	L. H. Liu, S. Q. Liu, H. L. Yin, Y. Q. Liu, C. G. Liu, J. Fuel Chem. Technol., 2015, 43, 708-713.
[33]	S. Kasztelan, G. B. McGarvey, J. Catal., 1994, 147, 476-483.
[34]	X. S. Li, Q. Xin, X. X. GuO, P. Grange, B. Delmon, J. Catal., 1992, 137, 385-393.
[35]	S. Zhang, Z. Xia, M. Zhang, Y. Zou, H. Shen, J. Li, X. Chen, Y. Qu, Appl. Catal. B, 2021, 297, 120418.
[36]	C. Wang, E. Guan, L. Wang, X. Chu, Z. Wu, J. Zhang, Z. Yang, Y. Jiang, L. Zhang, X. Meng, B. C. Gates, F.-S. Xiao, J. Am. Chem. Soc., 2019, 141, 8482-8488.
[37]	S. Xing, M. Xiong, S. Zhao, B. Zhang, Y. Qin, Z. Gao, ACS Catal., 2023, 13, 4003-4011.
[38]	C. Yang, D. Wang, R. Huang, J. Han, N. Ta, H. Ma, W. Qu, Z. Pan, C. Wang, Z. Tian, Chin. J. Catal., 2023, 46, 125-136.
[39]	H. Cao, Z. Bai, Y. Li, Z. Xiao, X. Zhang, G. Li, ACS Sustainable Chem. Eng., 2020, 8, 7343-7352.
[40]	P. Afanasiev, Appl. Catal. B, 2018, 227, 44-53.
[41]	H. Wu, A. Duan, Z. Zhao, T. Li, R. Prins, X. Zhou, J. Catal., 2014, 317, 303-317.
[42]	J. Chen, E. Dominguez Garcia, E. Oliviero, L. Oliviero, F. Maugé, J. Catal., 2016, 339, 153-162.
[43]	A. Romero-Galarza, A. Gutiérrez-Alejandre, J. Ramirez, J. Catal., 2011, 280, 230-238.
[44]	E. Dominguez Garcia, J. Chen, E. Oliviero, L. Oliviero, F. Maugé, Appl. Catal. B, 2020, 260, 117975.
[45]	L. Oliviero, A. Travert, E. Dominguez Garcia, J. Chen, F. Maugé, J. Catal., 2021, 403, 87-97.
[46]	K. Sun, H. Guo, F. Jiao, Y. Chai, Y. Li, B. Liu, S. Mintova, C. Liu, Appl. Catal. B, 2021, 286, 119907.
[47]	R. V. Mom, J. N. Louwen, J. W. M. Frenken, I. M. N. Groot, Nat. Commun., 2019, 10, 2546.
[48]	M. F. Wagenhofer, H. Shi, O. Y. Gutiérrez, A. Jentys, J. A. Lercher, Sci. Adv., 2020, 6, eaax5331.
[49]	J. Liang, M. Fan, M. Wu, J. Hua, W. Cai, T. Huang, Y. Liu, C. Liu, J. Catal., 2022, 415, 153-164.
[50]	C. Arrouvel, M. Breysse, H. Toulhoat, P. Raybaud, J. Catal., 2005, 232, 161-178.
[51]	J. Espino, L. Alvarez, C. Ornelas, J. L. Rico, S. Fuentes, G. Berhault, G. Alonso, Catal. Lett., 2003, 90, 71-80.
[52]	L. Yang, X. Li, A. Wang, R. Prins, Y. Chen, X. Duan, J. Catal., 2015, 330, 330-343.
[53]	Y. Gao, W. Han, X. Y. Long, H. Nie, D. D. Li, Appl. Catal. B, 2018, 224, 330-340.
[54]	N. Salazar, S. Rangarajan, J. Rodriguez-Fernandez, M. Mavrikakis, J. V. Lauritsen, Nat. Commun., 2020, 11, 4369.
[55]	E. Krebs, B. Silvi, A. Daudin, P. Raybaud, J. Catal., 2008, 260, 276-287.
[56]	X. M. Zhao, M. L. Bo, Z. K. Huang, J. Q. Zhou, C. Peng, L. Li, Appl. Surf. Sci., 2018, 462, 508-516.
[57]	X. B. Hou, K. F. Xie, Z. L. Huang, C. Shi, Q. Wei, Y. Hu, Appl. Surf. Sci,. 2023, 616, 156486.
[58]	A. S. Dumon, A. Sahu, P. Raybaud, J. Catal., 2021, 403, 32-42.
[59]	M. Vrinat, R. Bacaud, D. Laurenti, M. Cattenot, N. Escalona, S. Gamez, Catal. Today, 2005, 107- 108, 570-577.
[60]	H. Topsøe, B. Hinnemann, J. K. Nørskov, J. V. Lauritsen, F. Besenbacher, P. L. Hansen, G. Hytoft, R. G. Egeberg, K. G. Knudsen, Catal. Today, 2005, 107- 108, 12-22.

Controlled construction of Co₃S₄@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect

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