表面活性剂辅助水热制备形貌结构可控的MoS2及其蒽加氢性能

doi:10.1016/S1872-2067(17)62779-7

催化学报 ›› 2017, Vol. 38 ›› Issue (3): 597-606.DOI: 10.1016/S1872-2067(17)62779-7

表面活性剂辅助水热制备形貌结构可控的MoS₂及其蒽加氢性能

李敏^a,b,c, 王冬娥^b, 李佳鹤^b,c, 潘振栋^b, 马怀军^b, 姜玉霞^b,c, 田志坚^b,d, 陆安慧^a

a 大连理工大学化工学院精细化工国家重点实验室, 辽宁大连 116024;
b 中国科学院大连化学物理研究所洁净能源国家实验室(筹), 辽宁大连 116023;
c 中国科学院大学, 北京 100049;
d 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023

收稿日期:2016-11-30 修回日期:2016-12-30 出版日期:2017-03-18 发布日期:2017-03-22
通讯作者: Zhijian Tian
基金资助:
国家自然科学基金（21303186）；中国科学院重点战略研究项目（XDA07020300）.

Surfactant-assisted hydrothermally synthesized MoS₂ samples with controllable morphologies and structures for anthracene hydrogenation

Min Li^a,b,c, Donge Wang^b, Jiahe Li^b,c, Zhendong Pan^b, Huaijun Ma^b, Yuxia Jiang^b,c, Zhijian Tian^b,d, Anhui Lu^a

a State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
b Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c University of Chinese Academy of Sciences, Beijing 100049, China;
d State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, ChiZhendong nese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2016-11-30 Revised:2016-12-30 Online:2017-03-18 Published:2017-03-22
Supported by:
This work was supported by the National Natural Science Foundation of China (21303186) and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA07020300).

摘要/Abstract

摘要：

随着原油资源重质化和劣质化的加剧以及对清洁燃料油品需求的不断增加，将重质油加工成清洁燃料成为现代炼厂面临的挑战.悬浮床加氢是重质油转化为清洁液体燃料的先进技术，其核心难题是高效加氢催化剂的开发.MoS₂在石油化工领域油品加氢提质研究中表现出非常好的催化加氢性能.MoS₂晶体结构中有两种面：沿S-Mo-S层间的剥离面，又称基面，化学性质稳定；沿Mo-S的断裂面，又称棱面，具有大量的不饱和键，化学性质不稳定，可做催化活性中心.由于MoS₂结构和形貌对其物理化学性能有重要影响，所以通过合理设计和调控MoS₂的结构和形貌可增加暴露的催化活性位，进而改善其催化性能.
本文以七钼酸铵和硫代乙酰胺为原料，水合肼做还原剂，采用不同表面活性剂（包括PEG，PVP，P123，SDS，AOT和CTAB）辅助的水热合成法制备了结构及形貌可控的MoS₂，并提出不同表面活性剂条件下MoS₂催化剂的生长机理，进一步研究了重油模型化合物稠环芳烃蒽的催化加氢性能.结果表明，在不同表面活性剂辅助的条件下分别制得了由MoS₂纳米片组装而成的球形、块状和花状的MoS₂产物；通过改变表面活性剂种类可调变MoS₂纳米片的长度、堆积层数、层间距以及最终产物的形貌.在PEG或PVP辅助下得到了球形MoS₂产物，其中MoS₂纳米片长<15 nm，堆积层数<6.在PEG辅助下制备的球形MoS₂粒径约为250 nm，尺寸均一且分散性好.在PVP辅助下MoS₂粒径在200-450 nm，粒径分布范围宽且有明显团聚.在P123或SDS辅助下得到了团聚较明显的块状微米级MoS₂产物.在P123辅助下得到的MoS₂纳米片长<15 nm，层数<6.在SDS辅助下制备的MoS₂纳米片长>20 nm，堆积层数>8.在AOT或CTAB辅助下得到团聚比较严重的花状微米级MoS₂产物，其中MoS₂纳米片长>20 nm，堆积层数>8.另外，水热反应过程中，高温高压的环境促进了反应体系中游离的NH₄⁺插入到MoS₂层状结构中，导致MoS₂纳米片层间距增大.基于此，本文提出了不同表面活性剂辅助的水热过程中不同结构和形貌MoS₂产物的形成机理.
对不同结构和形貌的MoS₂样品进行了悬浮床蒽加氢催化性能评价.结果表明，PEG辅助制备的MoS₂催化剂具有最高催化加氢活性.该MoS₂催化剂中纳米片层短，堆积层数少，暴露了更多的加氢活性位.单分散的球形MoS₂颗粒粒径小，分散性好，有利于加氢活性位的充分暴露，进而表现出较好的催化性能.本文所采用的表面活性剂辅助的水热法为可控合成不同结构和形貌的过渡金属硫化物提供了有效指导和借鉴.

关键词: 二硫化钼, 表面活性剂辅助, 形貌可控, 单分散, 活性位, 蒽加氢

Abstract:

MoS₂ samples with controllable morphologies and structures were synthesized using surfactant-assisted hydrothermal processes. The effects of surfactants (PEG, PVP, P123, SDS, AOT, and CTAB) on the morphologies and structures of MoS₂ samples were investigated. The results revealed that spherical, bulk-like, and flower-like MoS₂ particles assembled by NH₄⁺-intercalated MoS₂ nano-sheets were synthesized. The morphologies of the MoS₂ samples and their structures (including the slab length and the number of stacked layers) of MoS₂ nano-sheets in these samples could be controlled by adjusting the surfactants. Mono-dispersed spherical MoS₂ particles could be synthesized with PEG via the creation of MoS₂ nano-sheets with slab lengths shorter than 15 nm and fewer than six stacked layers. Possible formation mechanisms of these MoS₂ samples created via surfactant-assisted hydrothermal processes are proposed. Further, the catalytic activities of MoS₂ samples for anthracene hydrogenation were evaluated in a slurry-bed reactor. The catalyst synthesized with the surfactant PEG exhibited the highest catalytic hydrogenation activity. Compared with the other catalysts, it had a smaller particle size, mono-dispersed spherical morphology, shorter slab length, and fewer stacked layers; these were all beneficial to exposing its active edges. This work provides an efficient approach to synthesize transition metal sulfides with controllable morphologies and structures.

Key words: Molybdenum sulfide, Surfactant-assisted, Controllable morphology, Mono-dispersed, Active edges, Anthracene hydrogenation

李敏, 王冬娥, 李佳鹤, 潘振栋, 马怀军, 姜玉霞, 田志坚, 陆安慧. 表面活性剂辅助水热制备形貌结构可控的MoS₂及其蒽加氢性能[J]. 催化学报, 2017, 38(3): 597-606.

Min Li, Donge Wang, Jiahe Li, Zhendong Pan, Huaijun Ma, Yuxia Jiang, Zhijian Tian, Anhui Lu. Surfactant-assisted hydrothermally synthesized MoS₂ samples with controllable morphologies and structures for anthracene hydrogenation[J]. Chinese Journal of Catalysis, 2017, 38(3): 597-606.

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表面活性剂辅助水热制备形貌结构可控的MoS₂及其蒽加氢性能

Surfactant-assisted hydrothermally synthesized MoS₂ samples with controllable morphologies and structures for anthracene hydrogenation

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