可控构建Co3S4@CoMoS核@壳材料用于氢溢流促进的高效加氢脱硫

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

催化学报 ›› 2024, Vol. 57: 154-170.DOI: 10.1016/S1872-2067(23)64573-5

可控构建Co₃S₄@CoMoS核@壳材料用于氢溢流促进的高效加氢脱硫

鲍文静^a, 冯超^a^,^c, 马书妍^a, 闫登伟^a, 张聪^a, 岳长乐^a, 王崇泽^a, 郭海玲^a, 王继乾^a, 孙道峰^b, 柳云骐^a, 卢玉坤^a^,^*()

^a中国石油大学(华东)化学化工学院, 重质油加工国家重点实验室, 山东青岛 266580
^b中国石油大学(华东)材料科学与工程学院, 重质油加工国家重点实验室, 山东青岛 266580
^c中国科学院青岛生物能源与生物过程技术研究所, 生物燃料重点实验室, 山东青岛 266101

收稿日期:2023-11-02 接受日期:2023-11-27 出版日期:2024-02-18 发布日期:2024-02-10
通讯作者: * 电子信箱: lyk@upc.edu.cn (卢玉坤).
基金资助:
国家自然科学基金(21878336);国家自然科学基金(U22B20144);山东省自然科学基金(ZR2023MB004);中央高校基础研究经费(23CX03001A)

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

Wenjing Bao^a, Chao Feng^a^,^c, Shuyan Ma^a, Dengwei Yan^a, Cong Zhang^a, Changle Yue^a, Chongze Wang^a, Hailing Guo^a, Jiqian Wang^a, Daofeng Sun^b, Yunqi Liu^a, Yukun Lu^a^,^*()

^aState Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^bState Key Laboratory of Heavy Oil Processing, School of Material Science and Engineering of UPC, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^cKey Laboratory of Biofuels, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong, China

Received:2023-11-02 Accepted:2023-11-27 Online:2024-02-18 Published:2024-02-10
Contact: * E-mail: lyk@upc.edu.cn (Y. Lu).
Supported by:
National Natural Science Foundation of China(21878336);National Natural Science Foundation of China(U22B20144);Shandong Provincial Natural Science Foundation(ZR2023MB004);Fundamental Research Funds for the Central Universities(23CX03001A)

摘要/Abstract

摘要：

过去几十年, 通过催化加氢脱硫(HDS)实现超清洁油品的生产一直是石油炼制领域的研究重点. 然而, 常规的HDS催化剂因金属负载量较低及金属与载体之间的强相互作用, 导致其对4,6-二甲基二苯并噻吩(4,6-DMDBT)类大分子的脱除效率较低. 这类大分子反应物由于具有较大的空间位阻, 使得其在催化剂表面活性位点上的吸附和反应更为困难, 往往通过氢化反应进行脱硫反应. 因此, 为实现有效的脱硫反应, 必须发展能高效解离和活化氢物种的催化剂. 此外, 通过氢化反应高效地脱除4,6-DMDBT通常需要在高温高压等苛刻条件下进行, 这要求催化剂具备更高的活性、选择性和稳定性.

为解决上述问题, 本文通过奥斯瓦尔德熟化法制备了一种由多孔CoMoS外壳和Co₃S₄内核构成的Co₃S₄@CoMoS核@壳材料, 并用于4,6-DMDBT类大分子的脱除. 同时, 通过原位表征和理论计算研究了该催化材料在HDS反应中的构效关系. SEM结果显示, 制得的Co₃S₄@CoMoS空心球外表面粗糙, 由许多小纳米颗粒组成. TEM图像直观地显示了Co₃S₄@CoMoS催化剂的结构, 其外壳和间隙厚度分别为80和100 nm, 高度多孔的球体使核@壳材料能够提供较短的氢溢流距离, 从而构建了一种高效的HDS纳米反应器. EDX结果显示Co, Mo和S元素在Co₃S₄@CoMoS催化剂上均匀分布. 其中, Mo金属仅存在于纳米球的外壳上; 除外层的CoMoS相外, Co元素还形成了一个由Co-S物种组成的独立核心. 结合XRD结果可以确定, 该催化剂是由Co促进的MoS₂外壳和Co₃S₄内核组成的Co₃S₄@CoMoS核@壳材料. 电镜图像和氮气吸脱附等结果表明, Co₃S₄@CoMoS纳米球的外壳由(Co)MoS₂纳米片交错卷曲组装而成, 壳层含有丰富的活性位点和发达的孔道结构, 为反应物提供了充足的吸附位点. Co金属的掺杂增加了MoS₂晶体的无序度, 使得MoS₂纳米片上形成了大量的不饱和硫空位. 钴原子锚定在MoS₂边缘还可以抑制MoS₂纳米片的团聚, 使得Co₃S₄@CoMoS催化剂上的层状MoS₂长度较短且堆叠层数较低, 有利于活性位点的充分暴露. H₂-程序升温脱附和WO₃变色实验结果证实了Co₃S₄@CoMoS结构中的氢溢流效应. HDS实验结果表明, 仅使用30 mg Co₃S₄@CoMoS催化剂就能够实现99.2%的二苯并噻吩转化率和94.9%的4,6-DMDBT转化率. 推测在HDS反应中, 含硫大分子锚定在CoMoS外壳的硫空位上, 而内核Co₃S₄相能够引发氢溢流效应, 并将活性氢物种传递给CoMoS相, 用于吸附和脱除含硫反应物, 从而在HDS反应中使CoMoS和Co₃S₄两相起到协同作用, 进而实现针对4,6-DMDBT类大分子的深度加氢脱硫. 同时, 反应过程中小分子H₂则可以自由地通过壳体扩散到内核的Co₃S₄相上, 被解离成溢流氢物种后又传递给外层壳体, 使得硫空位在HDS中不断地形成和再生. 此外, 核@壳球体内部连续的介孔通道缩短了溢流氢物种的迁移距离, 提高了活性物种的利用率. 致密的壳体使催化剂在多次循环反应中保留了核@壳结构, 提高了催化剂的使用寿命. 理论计算结果表明, CoMoS相和Co₃S₄相间的强电荷转移增加了CoMoS相中硫原子的电子云密度, 有利于反应物在活性物种上的吸附. 此外, 得益于Co₃S₄相的氢溢流效应, 在CoMoS/Co₃S₄双相结构上的氢解离能远低于单相结构, 这使得H₂分子能够在核@壳催化剂上被快速活化, 以促进反应物分子的下一步脱硫进程.

综上所述, 本文制备的多组分Co₃S₄@CoMoS核@壳催化剂表现出较好的加氢脱硫性能. 文章还提出了活性相结构与催化活性及反应路径选择性之间的作用机制, 为进一步开发高效非负载加氢脱硫催化剂提供了新思路.

关键词: 加氢脱硫, 氢溢流效应, 核@壳结构, CoMoS活性相, 双活性相协同

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

鲍文静, 冯超, 马书妍, 闫登伟, 张聪, 岳长乐, 王崇泽, 郭海玲, 王继乾, 孙道峰, 柳云骐, 卢玉坤. 可控构建Co₃S₄@CoMoS核@壳材料用于氢溢流促进的高效加氢脱硫[J]. 催化学报, 2024, 57: 154-170.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64573-5

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图/表 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.)

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可控构建Co₃S₄@CoMoS核@壳材料用于氢溢流促进的高效加氢脱硫

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

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