原子尺度钼系加氢脱硫催化剂的研究进展与展望

doi:10.11949/0438-1157.20231191

摘要/Abstract

摘要：

深入探讨了原子尺度钼系加氢脱硫催化剂在加氢脱硫反应中的研究进展。重点关注了MoS₂和Co（Ni）MoS微观结构对催化性能的影响，以及活性氢原子生成、硫化条件对催化剂结构和活性的影响。探讨了不同类型MoS₂和Co（Ni）MoS边缘结构与加氢脱硫性能的构效关系，强调了MoS₂边缘的硫-氢基团在反应中的关键作用。此外，详细讨论了噻吩分子在催化剂表面的吸附方式，加深了对噻吩的加氢脱硫机理的了解。最后，强调了载体Al₂O₃表面氢溢流效应的重要性，通过调控氧化铝载体表面的羟基基团与钼酸根的相互作用，提高了催化活性。总体而言，这些研究结果突显了微观结构在催化活性调控中的关键作用，为提高工业加氢脱硫反应速率提供了有力的支持。

关键词: 加氢脱硫, 催化剂, 催化剂载体, 密度泛函理论, 二硫化钼

Abstract:

The research progress of atomic-scale molybdenum-based hydrodesulfurization catalysts in hydrodesulfurization reactions was discussed in depth. Emphasis is placed on the influence of the microstructures of MoS₂ and Co(Ni)MoS on catalytic performance, as well as the effects of active hydrogen atom generation and sulfurization conditions on catalyst morphology and activity. The correlation between different types of MoS₂ and Co(Ni)MoS edge morphology and hydrodesulfurization performance was discussed, with particular emphasis on the crucial role of S—H groups at the edges of MoS₂ during the reaction. Furthermore, a detailed examination of the adsorption mode of thiophene molecules on the catalyst sites provided valuable clues to the hydrodesulfurization mechanism of thiophene. Finally, the significance of the surface hydrogen spillover effect on the Al₂O₃ support was underscored. By controlling the interaction between hydroxyl groups on the alumina support's surface and molybdate ions, the catalytic activity is enhanced. In conclusion, the research findings highlight the pivotal role of microstructures in catalytic activity, offering promising support for enhancing the industrial hydrodesulfurization reaction rate while contributing significantly to environmental protection.

Key words: hydrodesulfurization, catalyst, catalyst support, density functional theory, molybdenum disulfide

中图分类号:

O 643.38

丁禹, 杨昌泽, 李军, 孙会东, 商辉. 原子尺度钼系加氢脱硫催化剂的研究进展与展望[J]. 化工学报, 2024, 75(5): 1735-1749.

Yu DING, Changze YANG, Jun LI, Huidong SUN, Hui SHANG. Research progress and prospects of atomic-scale molybdenum-based hydrodesulfurization catalysts[J]. CIESC Journal, 2024, 75(5): 1735-1749.

图/表 11

图1 Pecoraro等[9]观察到的二苯并噻吩在400℃时的HDS周期性变化趋势（由Toulhoat等[10]改编）

Fig.1 The periodic variations in the hydrodesulfurization (HDS) of dibenzothiophene at 400℃ observed by Pecoraro et al.[9]

图2 Toulhoat等[10]整理的过渡金属硫化物加氢脱硫的“火山曲线”(1 cal=4.184 J)

Fig.2 “Volcano curve” for HDS over transition metal sulfides, as compiled by Toulhoat et al.[10]

图3 MoS2颗粒的原子分辨率STM图像[21]

Fig.3 Atomic-resolution STM images of MoS2 particles[21]

图4 在H2/H2S混合气氛中Au负载的MoS2边缘结构的Ab initio热力学相图[24]（1 bar=0.1 MPa)

Fig.4 Ab initio thermodynamics phase diagram of the MoS2 edge structures in H2/H2S mixtures for Au-supported MoS2[24]

图5 MoS2/Au(111)上CH3SH脱硫的反应网络[24]

Fig.5 Reaction network for CH3SH desulfurization on MoS2/Au(111)[24]

图6 Co-Mo-S团簇的原子分辨STM图像和球体模型[30]

Fig.6 STM image and spherical model of Co-Mo-S cluster[30]

图7 Ni-Mo-S团簇的原子分辨STM图像和球体模型[30](1 Å=0.1 nm)

Fig.7 Ni-Mo-S clusters: STM image & spherical model[30]

图8 Co-Mo-S结构S边的相图[32]

Fig.8 Phase diagram for the S edge of Co-Mo-S [32]

图9 边缘形成硫空位的MoS2纳米颗粒的原子级结构[44]

Fig.9 Atomic-scale structure of MoS2 nanoparticle with sulfur vacancies formed on the edges[44]

图10 理论计算噻吩吸附构型[44]

Fig.10 Thiophene adsorption modes from theory [44]

表1 活性位点的加氢和碳硫键断裂能垒

Table 1 Hydrogenation and carbon-sulfur bond-breaking energy barriers at the active sites

位点	第一次加氢/（kJ/mol）	第二次加氢/（kJ/mol）	第一次碳硫键断裂/（kJ/mol）	路径	文献
MoS₂角位	68.76	39.52	125.96	HYD（PH）	[57]
MoS₂角位	68.76	39.52	200.18	HYD（FH）	[57]
MoS₂角位	68.76	49.50	72.76	DDS	[57]
CoMoS硫边	42.45	0	161.13	HYD	[55]
CoMoS硫边	42.45	92.63	60.79	DDS	[55]
MoS₂硫边	77.19	0.00	79.12	HYD	[55]
MoS₂钼边	55.00	0.00	109.03	HYD	[55]
MoS₂硫边	77.19	—	20.26	DDS	[55]
MoS₂钼边	55.00	—	106.13	DDS	[55]
NiMoS硫边	94.56	98.41	50.17	DDS	[58]

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