绿色合成介孔碳负载(Ni)MoS<sub>2</sub>加氢脱硫催化剂

梁吉雷; 吴雯洁; 吴萌萌; 花加伟; 柳云骐; 刘晨光

doi:10.19906/j.cnki.JFCT.2023033

绿色合成介孔碳负载(Ni)MoS₂加氢脱硫催化剂

doi: 10.19906/j.cnki.JFCT.2023033

1.
泰州学院医药与化学化工学院江苏省手性医药化学品生物制造重点实验室江苏泰州 225300
2.
中国石油大学(华东)重质油国家重点实验室, 山东青岛 266580)

基金项目: 国家自然科学基金（22078227），江苏省高校“青蓝工程”，重质油国家重点实验室开放课题（SKLOP201902005），江苏省高校自然科学基金面上项目（22KJB150040）和江苏省大学生创新创业训练计划（202212917019Z）资助

详细信息

通讯作者:
E-mail: liangjilei_httplan@126.com

中图分类号: TQ426.95
计量
- 文章访问数: 245
- HTML全文浏览量: 178
- PDF下载量: 65
- 被引次数: 0
出版历程
- 收稿日期: 2023-02-15
- 修回日期: 2023-04-03
- 录用日期: 2023-04-14
- 网络出版日期: 2023-04-25
- 刊出日期: 2023-12-05

Green synthesis of mesoporous carbon supported (Ni)MoS₂ as efficient hydrodesulfurization catalyst

1.
College of Pharmacy and Chemistry & Chemical Engineering, Jiangsu Key Laboratory of Chiral Pharmaceuticals Biosynthesis, Taizhou University, Taizhou 225300, China
2.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, China)

Funds: The project was supported by the National Natural Science Foundation of China (22078227), Qing Lan Project of Jiangsu Province, State Key Laboratory of Heavy Oil Processing (SKLOP201902005), Natural Science Foundation of Jiangsu Higher Education Institutions of China (22KJB150040), and Undergraduate Training Program for Innovation and Entrepreneurship of Jiangsu Province (202212917019Z).

摘要

摘要: 以Anderson结构Ni-Mo杂多酸簇(NH₄)₄[NiMo₆O₂₄H₆]·5H₂O、硫脲、柠檬酸、氯化钠为原料，采用冻干法得到前驱体后焙烧、洗涤得到介孔碳骨架负载(Ni)MoS₂纳米颗粒的加氢脱硫催化剂，考察了其对二苯并噻吩的加氢脱硫活性，并采用X射线衍射、N₂低温吸附-脱附、拉曼光谱、X光电子能谱、扫描电子显微镜、高分辨透射电镜、程序升温还原等表征手段对催化剂进行了分析。结果表明，介孔碳骨架负载(Ni)MoS₂纳米颗粒催化剂具有较弱的载体-金属相互作用，MoS₂纳米颗粒平均长度较短（4.9 nm），层数适宜（4.8），NiMoS活性相含量较高，二苯并噻吩的转化率可达94.1%，反应速率常数及活性位转换频率分别可达1.7 × 10^–6 mol/(g·s)和2.8 × 10^–3 s^–1。该方法利用原位生成的氯化钠晶体及硫化氢气体分别作为介孔模板剂和硫化剂，实现了介孔碳载体与(Ni)MoS₂纳米颗粒的同步合成及锚定，并为加氢脱硫催化剂的绿色制备提供了新的思路。
- 加氢脱硫 /
- 冷冻干燥 /
- 盐模板 /
- 杂多酸 /
- 介孔碳
Abstract: Mesoporous carbon supported Ni-Mo hydrodesulfurization (HDS) catalysts have been successfully prepared with Anderson polyoxometalate (NH₄)₄[NiMo₆O₂₄ H₆]·5H₂O, thiourea, citric acid, and sodium chloride to evaluate the HDS performance with dibenzothiophene. The catalysts were prepared by one-step vacuum freeze-drying, followed by calcination under nitrogen and washing off the template, and then structurally characterized via many devices, including XRD, Raman, low temperature N₂ adsorption-desorption isotherm, SEM, HRTEM, XPS, and TPR. The results show these catalysts possess weaker metal-support interaction, shorter MoS₂ particles (4.9 nm) and appropriate stacking number (4.8), and higher percent of NiMoS active phase. The dibenzothiophene conversion, overall pseudo-first order rate constant and the turnover frequency can reach 94.1%, 1.7 × 10^–6 mol/(g·s) and 2.8 × 10^–3 s^–1, respectively. By using in-situ formed NaCl and H₂S as hard template and sulfidizing agent respectively, this methodology opens a new avenue for the simple and environmental friendly fabrication of HDS catalysts via the synchronization and riveting of mesoporous carbon support and MoS₂ particles.
- hydrodesulfurization /
- freeze-drying /
- salt template /
- polyoxometalate /
- mesoporous carbon

HTML全文

FIG. 2803. FIG. 2803.

下载: 全尺寸图片幻灯片

图 1 催化剂的制备流程示意图

Figure 1 Schematic illustration of the catalyst preparation

下载: 全尺寸图片幻灯片

图 2 Ni3Mo6S/C、NiMo6S/C催化剂及其未洗涤中间产物的XRD谱图

Figure 2 XRD patterns of Ni3Mo6S/C, NiMo6S/C and intermediate products

下载: 全尺寸图片幻灯片

图 3 Ni3Mo6S/C（（a）、（b））和NiMo6S/C（（c）、（d））催化剂洗涤前后的SEM照片

Figure 3 SEM images of Ni3Mo6S/C ((a), (b)) and NiMo6S/C ((c), (d))

下载: 全尺寸图片幻灯片

图 4 Ni3Mo6S/C（a）和NiMo6S/C（b）催化剂的元素分布

Figure 4 Element mapping images of Ni3Mo6S/C (a) and NiMo6S/C (b)

下载: 全尺寸图片幻灯片

图 5 样品的N₂吸附-脱附等温线（a）和孔径分布（b）

Figure 5 N₂ adsorption-desorption isotherms (a) and pore diameter distributions (b) of samples

下载: 全尺寸图片幻灯片

图 6 Ni3Mo6S/C和NiMo6S/C催化剂的拉曼光谱谱图

Figure 6 Raman spectra of Ni3Mo6S/C and NiMo6S/C

下载: 全尺寸图片幻灯片

图 7 Ni3Mo6S/C（a）和NiMo6S/C（b）催化剂的HRTEM照片

Figure 7 HRTEM images of Ni3Mo6S/C (a) and NiMo6S/C (b)

下载: 全尺寸图片幻灯片

图 8 两种催化剂表面MoS₂纳米颗粒长度（a）和堆垛层数（b）统计

Figure 8 Distributions of slab length (a) and stacking number (b) of MoS₂ slabs over the catalysts

下载: 全尺寸图片幻灯片

图 9 Ni3Mo6S/C和NiMo6S/C催化剂的XPS谱图

Figure 9 XPS spectra of Ni3Mo6S/C and NiMo6S/C

下载: 全尺寸图片幻灯片

图 10 Ni3Mo6S/C和NiMo6S/C催化剂的TPR谱图

Figure 10 TPR profiles of Ni3Mo6S/C and NiMo6S/C

下载: 全尺寸图片幻灯片

表 1 Ni3Mo6S/C和NiMo6S/C催化剂的HRTEM及XPS分析

Table 1 Characteristics of Ni3Mo6S/C and NiMo6S/C calculated by HRTEM and XPS

Catalyst	L /nm	N	Mo_Sulf/%	NiMoS /%	S^2–/%
NiMo6S/C	5.4	4.2	80.4	47.1	87.7
Ni3Mo6S/C	4.9	4.8	86.2	52.8	91.2

下载: 导出CSV

表 2 不同催化剂的DBT加氢脱硫反应

Table 2 HDS activity of DBT over different catalysts

Catalyst	x_DBT /%	k_HDS /(10^–6 mol·g^–1·s^–1)	TOF* /(10^–3·s^–1)	Product selectivity* /%
Catalyst	x_DBT /%	k_HDS /(10^–6 mol·g^–1·s^–1)	TOF* /(10^–3·s^–1)	HHBDT + THDBT	BP	CHB	BP/CHB
NiMo6S/C	82.3	1.0	2.4	20.2	71.4	8.4	8.5
NiMo6/Al₂O₃	63.2	0.6	1.2	19.2	66.4	14.4	4.6
Ni3Mo6S/C	94.1	1.7	2.8	10.2	82.6	7.2	11.5
Ni3Mo6/Al₂O₃	71.6	0.8	1.8	17.8	72.4	9.8	7.4
* Determined by controlling the LHSV to reach the x_DBT of 50%

下载: 导出CSV

参考文献(45)

[1]	聂红, 张乐, 丁石, 韩伟, 李大东. 柴油高效清洁化关键技术与应用[J]. 石油炼制与化工,2021,52(10):103−109. doi: 10.3969/j.issn.1005-2399.2021.10.018 NIE Hong, ZHANG Le, DING Shi, HAN Wei, LI Dadong. Key technologies for efficient clean diesel production and commercial applications[J]. Chin Pet Process Petrochem Technol,2021,52(10):103−109. doi: 10.3969/j.issn.1005-2399.2021.10.018
[2]	刘宾, 刘蕾, 柴永明, 赵晋翀, 刘晨光. Co调变MoS₂催化剂的作用本质及其FCC汽油选择性加氢脱硫机理[J]. 燃料化学学报,2018,46(4):441−450. doi: 10.1016/S1872-5813(18)30019-7 LIU Bin, LIU Lei, CHAI Yong-ming, ZHAO Jin-chong, LIU Chen-guang. Essential role of promoter Co on the MoS₂ catalyst in selective hydrodesulfurization of FCC gasoline[J]. J Fuel Chem Technol,2018,46(4):441−450. doi: 10.1016/S1872-5813(18)30019-7
[3]	CHU S, LI X, ZHOU X, PRINS R, WAQAS Q, WANG A, SHENG Q, HAO Q. Preparation of Ni₂P supported on Al₂O₃ and B₂O₃ mixed oxides by temperature–programmed reduction of phosphate precursors with low P/Ni ratios[J]. Top Catal,2020,63:1379−1387. doi: 10.1007/s11244-020-01344-6
[4]	SUN K, GUO H, JIAO F, CHAI Y, LI Y, LIU B, MINTOVA S, LIU C. Design of an intercalated nano-MoS₂ hydrophobic catalyst with high rim sites to improve the hydrogenation selectivity in hydrodesulfurization reaction[J]. Appl Catal B: Environ,2021,286:119907. doi: 10.1016/j.apcatb.2021.119907
[5]	CHEN Z, LIU Y, CHEN J, ZHAO Y, JIANG T, ZHAO F, YU J, YANG H, YANG F, XU C. Synthesis of alumina-nitrogen-doped carbon support for CoMo catalysts in hydrodesulfurization process[J]. Chin J Chem Eng,2022,41:392−402. doi: 10.1016/j.cjche.2021.09.015
[6]	马宝利, 徐铁钢, 韩志波, 张文成, 郭金涛. 植物固体纤维丝在NiMo柴油加氢脱硫催化剂中的应用[J]. 燃料化学学报,2019,47(7):863−869. MA Bao-li, XU Tie-gang, HAN Zhi-bo, ZHANG Wen-cheng, GUO Jin-tao. Application of plant fiber filament in NiMo diesel hydrodesulfurization catalyst[J]. J Fuel Chem Technol,2019,47(7):863−869.
[7]	尹海亮, 刘新亮, 周同娜, 赵健, 蔺爱国. 乙二醇对磷掺杂NiMo/Al₂O₃加氢催化剂性能的影响[J]. 燃料化学学报,2019,47(12):1458−1467. YIN Hai-liang, LIU Xin-liang, ZHOU Tong-na, ZHAO Jian, LIN Ai-guo. Effect of ethylene glycol on the hydrogenation performance of P-doped NiMo/Al₂O₃ catalysts[J]. J Fuel Chem Technol,2019,47(12):1458−1467.
[8]	TOPSØE H, CLAUSEN B, CANDIA R, WIVEL C, MØRUP S. In situ Mössbauer emission spectroscopy studies of unsupported and supported sulfided Co–Mo hydrodesulfurization catalysts: Evidence for and nature of a Co-Mo-S phase[J]. J Catal,1981,68:433−452. doi: 10.1016/0021-9517(81)90114-7
[9]	胡乃方, 崔海涛, 邱泽刚, 赵亮富, 孟欣欣, 赵正权, 敖广宇. 不同P负载量对Co-Mo/γ-Al₂O₃煤焦油加氢脱硫性能影响的研究[J]. 燃料化学学报,2016,44(6):745−753. HU Nai-fang, CUI Hai-tao, QIU Ze-gang, ZHAO Liang-fu, MENG Xin-xin, ZHAO Zheng-quan, AO Guang-yu. Effect of phosphorus loadings on the performance of Co-Mo/γ-Al₂O₃ in hydrodesulfurization of coal tar[J]. J Fuel Chem Technol,2016,44(6):745−753.
[10]	LAURITSEN J, NYBERG M, NORSKOV J, CLAUSEN B, TOPSØE H, LGSGAAD E, BESENBACHER F. Hydrodesulfurization reaction pathways on MoS₂ nanoclusters revealed by scanning tunneling microscopy[J]. J Catal,2004,224:94−106. doi: 10.1016/j.jcat.2004.02.009
[11]	SALEH T, ALHAMMAD S, ABDULLAHI I, MUSTAQEEM M. Synthesis of molybdenum cobalt nanocatalysts supported on carbon for hydrodesulfurization of liquid fuels[J]. J Mol Liq,2018,272:715−721. doi: 10.1016/j.molliq.2018.09.118
[12]	张革, 李国华, 杨帆, 李永峰. 碳基复合材料在深度脱硫领域的研究进展[J]. 太原理工大学学报,2022,53(3):559−570. ZHANG Ge, LI Guo-hua, YANG Fan, LI Yong-feng. Study of carbon composites in deep desulfurization[J]. J Taiyuan Univ Technol,2022,53(3):559−570.
[13]	HAJJAR Z, KAZEMEINI M, RASHIDI A, SOLTANALI S. Hydrodesulfurization catalysts based on carbon nanostructures: A review[J]. Fuller Nanotub Car N,2018,26(9):557−569. doi: 10.1080/1536383X.2018.1470509
[14]	RYABOHAPKA D, PICCOLO L, AOUINE M, BARGIELA P, BRIOIV S, AFANASIE P. Ultradispersed (Co)Mo catalysts with high hydrodesulfurization activity[J]. Appl Catal B: Environ,2022,302:120831. doi: 10.1016/j.apcatb.2021.120831
[15]	ESNEYDER P, AYALA G, BRITO J. Sulfidability and thiophene hydrodesulfurization activity of supported NiMo carbides[J]. Catal Commun,2014,53:9−14. doi: 10.1016/j.catcom.2014.04.018
[16]	XU H, JIANG W, WANG D, KANG X, SHAO L, LIU J, TIAN C, FU H. Controlling the growth of ZnNiMoSx on biomass-derived porous carbon materials for deep hydrodesulfurization[J]. Appl Catal A: Gen,2023,660:119188.
[17]	NATH P, YOGENDRA, VERMA N. Hydrodesulfurization of thiophene on activated carbon fiber supported NiMo catalysts[J]. Energy Fuels,2018,32(2):2183−2196. doi: 10.1021/acs.energyfuels.7b03407
[18]	HYNAUX A, SAYAG C, SUPPAN S, TRAWCZYNSKI J, LEWANDOWSKI M, SZYMANSKA A, DJEGA G. Kinetic study of the hydrodesulfurization of dibenzothiophene over molybdenum carbides supported on functionalized carbon black composite: Influence of indole[J]. Appl Catal B: Environ,2007,72(1):62−70.
[19]	XU J, SHI C, XIAO Z, GAO R, LI Y, ZHANG X, PAN L, ZOU J. Ni-modified MoS₂ nanoflake arrays with stepped sites on carbon nanotubes for efficient hydrodesulfurization of coal-to-liquid fuel[J]. Chem Commun,2020,56(41):5540−5543. doi: 10.1039/D0CC00960A
[20]	GUO K, GU M, YU Z. Carbon nanocatalysts for aquathermolysis of heavy crude oil: Insights into thiophene hydrodesulfurization[J]. Energy Technol,2017,5(8):1228−1234. doi: 10.1002/ente.201600522
[21]	KAZAKOV M, KAZAKOVA M, VATUTINA Y, LARINA T, CHESALOV Y, GERASIMOV E, PROSVIRIN I, KLIMOV O, NOSKOV A. Comparative study of MWCNT and alumina supported CоMо hydrotreating catalysts prepared with citric acid as chelating agent[J]. Catal Today,2020,357:221−230. doi: 10.1016/j.cattod.2019.03.051
[22]	YANG L, WANG X, LIU Y, YU Z, LI R, QIU J. Layer-dependent catalysis of MoS₂/graphene nanoribbon composites for efficient hydrodesulfurization[J]. Catal Sci Technol,2017,7(3):693−702. doi: 10.1039/C6CY02074G
[23]	SALEH T, HAMMADI A, SADDAMA A. A novel catalyst of nickel-loaded graphene decorated on molybdenum-alumina for the HDS of liquid fuels[J]. Chem Eng J,2021,406:125167. doi: 10.1016/j.cej.2020.125167
[24]	YANG L, WANG X, LIU Y, YU Z, LIANG J, CHEN B, SHI C, TIAN S, LI X, QIU J. Monolayer MoS₂ anchored on reduced graphene oxide nanosheets for efficient hydrodesulfurization[J]. Appl Catal B: Environ,2017,200:211−221. doi: 10.1016/j.apcatb.2016.07.006
[25]	XU J, GUO Y, HUANG T, FAN Y. Hexamethonium bromide-assisted synthesis of CoMo/graphene catalysts for selective hydrodesulfurization[J]. Appl Catal B: Environ,2019,244:385−395. doi: 10.1016/j.apcatb.2018.11.065
[26]	LIANG J, WU M, WEI P, ZHAO J, HUANG H, LI C, LU Y, LIU Y, LIU C. Efficient hydrodesulfurization catalysts derived from Strandberg PMoNi polyoxometalates[J]. J Catal,2018,358:155−167. doi: 10.1016/j.jcat.2017.11.026
[27]	LIANG J, WU M, WANG J, WEI P, SUN B, LU Y, SUN D, LIU Y, LIU C. A new approach to construct a hydrodesulfurization catalyst from a crystalline precursor: Ligand-induced self-assembly, sulfidation and hydrodesulfurization[J]. Catal Sci Technol,2018,8:6330−6345. doi: 10.1039/C8CY02007H
[28]	LIANG J, FAN M, WU M, HUA J, CAI W, HUANG T, LIU Y, LIU C. In situ synthesis of MoS₂ nanoflakes within a 3D mesoporous carbon framework for hydrodesulfurization of DBT[J]. J Catal,2022,415:153−164. doi: 10.1016/j.jcat.2022.10.006
[29]	LIANG J, WU M, ZHANG Z, WANG H, HUANG T, ZHAO L, LIU Y, LIU C. Constructing a superior Co-Mo HDS catalyst from a crystalline precursor separated from the impregnating solution[J]. Catal Sci Technol,2022,12:2278−2288. doi: 10.1039/D2CY00083K
[30]	LIANG J, WU M, ZHU N, GAO X, ZHU G, HUANG T, LIU Y, LIU C. A Ni-Mo polyoxometalate based on octamolybdate: Self-assemble and application in hydrotreating catalyst[J]. Catal Lett,2023,153:584−594.
[31]	NOMIYA K, TAKAHASHI T, SHIRAI T, MIWA M. Anderson-type heteropolyanions of molybdenum(VI) and tungsten(VI)[J]. Polyhedron,1987,6(3):213−218.
[32]	李彦鹏, 张婷婷, 刘大鹏, 刘宾, 柴永明, 刘晨光. 环己二胺四乙酸对NiMo/Al₂O₃催化剂加氢脱硫活性的促进作用[J]. 中国石油大学学报(自然科学版),2019,43(6):151−158. LI Yan-peng, ZHANG Ting-ting, LIU Da-peng, LIU Bin, CHAI Yong-ming, LIU Chen-guang. Effect of cyclohexanediamine tetraacetic acid on hydrodesulfurization performance of NiMo/Al₂O₃ catalyst[J]. J China Univ Pet,2019,43(6):151−158.
[33]	WEI J, HUANG H, LUO Q, LIU N, WANG X, WANG X, ZHONG M, HUANG X. Synthesis of few layer amorphous 1T/2H MoS₂ by a one-step ethanol/water solvothermal method and its hydrodesulfurization performance[J]. Catal Lett,2022,152(1):263−275. doi: 10.1007/s10562-021-03621-9
[34]	NAVA R, MOLINA I, CASTANO P, GUIL-LOPEZ R, PAWELEC B. Inhibition of CoMo/HMS catalyst deactivation in the HDS of 4, 6-DMDBT by support modification with phosphate[J]. Fuel,2011,90(8):2726−2737. doi: 10.1016/j.fuel.2011.03.049
[35]	王小平, 马怀军, 王冬娥, 田志坚. 水热法制备分散型Co促进的MoS₂悬浮床加氢脱硫催化剂[J]. 石油学报(石油加工),2021,37(6):1287−1297. WANG Xiao-ping, MA Huai-jun, WANG Dong-e, TIAN Zhi-jian. Preparation of the slurry bed hydrodesulfurization catalyst MoS₂ promoted by dispersed colbalt by means of hydrothermal synthesis[J]. Acta Pet Sin (Pet Process Sect),2021,37(6):1287−1297.
[36]	SALEH T. Carbon nanotube–incorporated alumina as a support for MoNi catalysts for the efficient hydrodesulfurization of thiophenes[J]. Chem Eng J,2021,404:126987. doi: 10.1016/j.cej.2020.126987
[37]	HU Y, BAI Y, WU X, WEI X, CHEN J. MoS₂ nanoflakes integrated in a 3D carbon framework for high-performance sodium-ion batteries[J]. J Alloy Compd,2019,797:1126−1132. doi: 10.1016/j.jallcom.2019.05.142
[38]	JORGE R, PERLA C, AIDA G, AYALA A, OSCAR C, AYALA PATRICIA M, ADOLFO R. Interaction of different molecules with the hydrogenation and desulfurization sites of NiMoS supported particles with different morphology[J]. Catal Today,2020,353:99−111. doi: 10.1016/j.cattod.2019.08.032
[39]	MENG Q, DUAN A, XU C, ZHAO Z, LI J, WANG B, LIU C, HU D, LI H, LI Y. Synthesis of novel hierarchically porous NiMo/ZSM-5–KIT-5 catalysts and their superior performance in hydrodenitrogenation of quinoline[J]. Catal Sci Technol,2018,8(19):5062−5072. doi: 10.1039/C8CY01060A
[40]	刘娟, 李文英, 冯杰, 高翔. Ni对MoS₂基催化剂活性相及加氢脱氮脱硫性能的影响[J]. 燃料化学学报,2021,49(10):1513−1521. doi: 10.1016/S1872-5813(21)60105-6 LIU Juan, LI Wen-ying, FENG Jie, GAO Xiang. Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS₂ catalysts[J]. J Fuel Chem Technol,2021,49(10):1513−1521. doi: 10.1016/S1872-5813(21)60105-6
[41]	ZHOU W, WEI Q, ZHOU Y, LIU M, DING S, YANG Q. Hydrodesulfurization of 4, 6-dimethyldibenzothiophene over NiMo sulfide catalysts supported on meso-microporous Y zeolite with different mesopore sizes[J]. Appl Catal B: Environ,2018,238:212−224.
[42]	户安鹏, 陈文斌, 龙湘云, 韩伟, 张乐, 聂红. 柠檬酸对NiMo/γ-Al₂O₃催化剂中助剂Ni作用的影响[J]. 石油炼制与化工,2018,49(10):52−57. doi: 10.3969/j.issn.1005-2399.2018.10.011 HU An-peng, CHEN Wen-bin, LONG Xiang-yun, HAN Wei, ZHANG Le, NIE Hong. Effect of citric acid on role of promotor Ni in NiMo/γ-Al₂O₃ catalyst[J]. Chin Pet Process Petrochem Technol,2018,49(10):52−57. doi: 10.3969/j.issn.1005-2399.2018.10.011
[43]	NINH T, MASSIN L, LAURENTI D, VRINAT M. A new approach in the evaluation of the support effect for NiMo hydrodesulfurization catalysts[J]. Appl Catal A: Gen,2011,407:29−39. doi: 10.1016/j.apcata.2011.08.019
[44]	CAO J, LI A, ZHANG Y, MU L, HUANG X, LI Y, YANG T, ZHANG C, ZHOU C. Highly efficient unsupported Co-doped nano-MoS₂ catalysts for p-cresol hydrodeoxygenation[J]. Mol Catal,2021,505:111507. doi: 10.1016/j.mcat.2021.111507
[45]	LIU B, LIU L, CHAI Y, ZHAO J, LI Y, LIU D, LIU Y, LIU C. Effect of sulfiding conditions on the hydrodesulfurization performance of the ex-situ presulfided CoMoS/γ-Al₂O₃ catalysts[J]. Fuel,2018,234:1144−1153. doi: 10.1016/j.fuel.2018.08.001