可控构建Co_(3)S_(4)@CoMoS核@壳材料用于氢溢流促进的高效加氢脱硫  

Controlled construction of Co_(3)S_(4)@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect

作　　者：鲍文静 冯超[1,3] 马书妍[1] 闫登伟 张聪 岳长乐 王崇泽 郭海玲 王继乾[1] 孙道峰[2] 柳云骐 卢玉坤[1] Wenjing Bao;Chao Feng;Shuyan Ma;Dengwei Yan;Cong Zhang;Changle Yue;Chongze Wang;Hailing Guo;Jiqian Wang;Daofeng Sun;Yunqi Liu;Yukun Lu(State Key Laboratory of Heavy Oil Processing,College of Chemistry and Chemical Engineering,China University of Petroleum(East China),Qingdao 266580,Shandong,China;State Key Laboratory of Heavy Oil Processing,School of Material Science and Engineering of UPC,China University of Petroleum(East China),Qingdao 266580,Shandong,China;Key Laboratory of Biofuels,Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266101,Shandong,China)

机构地区：[1]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 [2]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 [3]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

出　　处：《Chinese Journal of Catalysis》2024年第2期154-170,共17页催化学报（英文）

基　　金：国家自然科学基金(21878336,U22B20144);山东省自然科学基金(ZR2023MB004);中央高校基础研究经费(23CX03001A).

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Co_(3)S_(4)内核构成的Co_(3)S_(4)@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Co_(3)S_(4)@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Co_(3)S_(4)@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Co_(3)S_(4)@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MoS_(2)外壳和Co_(3)S_(4)内核组成的Co_(3)S_(4)@CoMoS核@壳材料.电镜图像和氮气吸脱附等结果表明,Co_(3)S_(4)@CoMoS纳米球的外壳由(Co)MoS_(2)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MoS_(2)晶体的无序度,使得MoS_(2)纳米片上形成了大量的不饱和硫空位.钴原子锚定A yolk-shell structured Co_(3)S_(4)@CoMoS catalyst was prepared through Oswald ripening method and subsequently used for hydrodesulfurization(HDS)reaction.The shells,constructed from Co-promoted MoS_(2)nanosheets,possess abundant active sites and facilitate the adsorption of reactants through the development of pore channels.The MoS_(2)sheets are arranged in a staggered and convoluted manner,creating numerous defect sites.The shorter MoS_(2)slabs provide a wide distribution of reactive sites,ensuring efficient reactions.The Co_(3)S_(4)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 Co_(3)S_(4)phases synergistically enhance the HDS reaction.The Co_(3)S_(4)@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.

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 

分 类 号：O643.3[理学—物理化学]