Citation: JIANG Jun-hui, CAO Yong-yong, NI Zhe-ming, ZHANG Lian-yang. Comparison of reaction mechanism of thiophene hydrodesulfurization on Au₁₃ and Pt₁₃ clusters[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(8): 961-969. shu

Comparison of reaction mechanism of thiophene hydrodesulfurization on Au₁₃ and Pt₁₃ clusters

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Corresponding author: NI Zhe-ming, jchx@zjut.edu.cn
Received Date: 15 March 2016
Revised Date: 25 April 2016

Figures(9)

The behaviors of thiophene adsorption and hydrodesulfurization on cubic octahedral M₁₃ (M=Au, Pt) clusters were investigated by density functional theory. The results show that the adsorption energy of thiophene on Pt₁₃ is higher than that on Au₁₃; on the Au₁₃ cluster, the Hol-tri site is most stable for the thiophene adsorption with ring, whereas on the Pt₁₃ cluster, the Hol-quadr site is most stable. By the indirect desulfurization mechanism, the desulfurization is achieved probably via the cis-hydrogenation; the removal of C-S is the rate-determining step. By the direct desulfurization mechanism, the HS hydrogenation turns to be the rate-determining step. The desulfurization is most likely via the direct desulfurization mechanism, which exhibits much lower activation energy than the indirect desulfurization mechanism. The energy change for thiophene desulfurization on the Au₁₃ cluster is exothermic, whereas on the Pt₁₃ cluster it is endothermic; as a result, the hydrodesulfurization on Au₁₃ is much easier than that on Pt₁₃.
- thiophene,
- hydrodesulfurization,
- adsorption,
- Au₁₃ cluster,
- Pt₁₃ cluster,
- density functional theory
1. [1]
  BASTON E P, FRANCA A B, NETO A V D, URQUIETA-GONZALEZ E A. Incorporation of the precursors of Mo and Ni oxides directly into the reaction mixture of sol-gel prepared gamma-Al₂O₃-ZrO₂ supports-Evaluation of the sulfided catalysts in the thiophene hydrodesulfurization[J]. Catal Today, 2015,246:184-190. doi: 10.1016/j.cattod.2014.10.035
2. [2]
  LIAO C N, WANG J Y, LI B. Mechanism of Mo-catalyzed C-S cleavage of thiophene[J]. J Organomet Chem, 2014,749:275-286. doi: 10.1016/j.jorganchem.2013.10.013
3. [3]
  ZU Yun, QIN Yu-cai, GAO Xiong-hou, MO Zhou-sheng, ZHANG Lei, ZHANG Xiao-tong, SONG Li-juan. Mechanisms of thiophene conversion over the modified Y zeolites under catalytic cracking conditions[J]. J Fuel Chem Technol, 2015,43(7):862-869.
4. [4]
  LIU Li-hua, LIU Shu-qun, YIN Hai-liang, LIU Yun-qi, LIU Chen-guang. Hydrogen spillover effect between Ni₂P and MoS₂ catalysts in hydrodesulfurization of dibenzothiophene[J]. J Fuel Chem Technol, 2015,43(6):708-713. doi: 10.1016/S1872-5813(15)30022-0
5. [5]
  SHAN J, TENHU H. Recent advances in polymer protected gold nanoparticles:Synthesis, properties and applications[J]. Chem Commun, 2007,44:4580-4598.
6. [6]
  CORMA A, SERNA P. Chemoselective hydrogenation of nitro compounds with supported gold catalysts[J]. Science, 2006,313(5785):332-334. doi: 10.1126/science.1128383
7. [7]
  LI X H, ZHENG W L, PAN H Y, YU Y, CHEN L, WU P. Pt nanoparticles supported on highly dispersed TiO₂ coated on SBA-15 as an efficient and recyclable catalyst for liquid-phase hydrogenation[J]. J Catal, 2013,300:9-19. doi: 10.1016/j.jcat.2012.12.007
8. [8]
  RAMOS-FERNANDEZ E V, PIETERS C, VAN DER LINDEN B, JNAN-ALCANIZ J, SERRA-CRESPO P, VERHOEVEN M W G M, NIEMANTSVERDRIET H, GASCON J, KAPTEIJN F. Highly dispersed platinum in metal organic framework NH₂-MIL-101(Al) containing phosphotungstic acid-Characterization and catalytic performance[J]. J Catal, 2012,289:42-52. doi: 10.1016/j.jcat.2012.01.013
9. [9]
  LUO S R, CHEN S Z, HSU Y H, YAU S L, LIN Y J, HUANG P Y, CHEN M C. In situ scanning tunneling microscopy characterization of thienothiophene-based semiconducting organic molecules adsorbed on a Au (111) electrode[J]. Surf Sci, 2013,616:155-160. doi: 10.1016/j.susc.2013.05.013
10. [10]
  WANG H M, LGLESIA E. Mechanism and site requirements of thiophene hydrodesulfurization catalyzed by supported Pt clusters[J]. Chemcatchem, 2011,3(7):1166-1175. doi: 10.1002/cctc.v3.7
11. [11]
  ZHU H Y, GUO W Y, JIANG R B, ZHAO L M, LU X Q, LI M, FU D L, SHAN H H. Decomposition of methanthiol on Pt (111):A density functional investigation[J]. Langmuir, 2010,26(14):12017-12025. doi: 10.1021/la101678d
12. [12]
  NI Zhe-ming, SHI Wei, XIA Ming-yu, XUE Ji-long. Theoretical studies on reaction mechanism of hydrodesulfurization of thiophene catalyzed by Au (111) plane[J]. Chem J Chin Univ, 2013,34(10):2353-2362.
13. [13]
  LI Z, CHEN Z X, HE X, KANG G J. Theoretical studies of acrolein hydrogenation on Au-20 nanoparticle[J]. J Chem Phys, 2010,132(18)184702. doi: 10.1063/1.3407439
14. [14]
  IMADA Y, OSAKI M, NOGUCHI M, MAEDA T, FUJIKI M, KAWAMORITA S, KOMIYA N, NAOTA T. Flavin-functionalized gold nanoparticles as an efficient catalyst for aerobic organic transformations[J]. ChemCatChem, 2015,7(1):99-106. doi: 10.1002/cctc.v7.1
15. [15]
  BUCHWALTER P, ROSE J, BRAUNSTEIN P. Multimetallic catalysis based on heterometallic complexes and clusters[J]. Chem Rev, 2015,115(1):28-126. doi: 10.1021/cr500208k
16. [16]
  LARSSON J A, NOLAN M, GREER J C. Interactions between thiol molecular linkers and the Au-13 nanoparticle[J]. J Phys Chem B, 2002,106(23):5931-5937. doi: 10.1021/jp014483k
17. [17]
  XU Kun, FENG Jie, CHU Qi, ZHANG Li-li, LI Wen-ying. Density function theory study of thiophene hydrodesulfurization onγ-Mo₂N (100) surface[J]. Acta Phys Chim Sin, 2014,30(11):2063-2070.
18. [18]
  HAMMER B, HANSEN L B, NORSKOV J K. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals[J]. Phys Rev B, 1999,59(11):7413-7421. doi: 10.1103/PhysRevB.59.7413
19. [19]
  JIANG Jun-hui, XIA Sheng-jie, NI Zhe-ming, ZHANG Lian-yang. Adsorption and selective hydrogenation mechanism of crotonaldehyde on Au (111) surface[J]. Chem J Chin Univ, 2016,37(4):693-700.
20. [20]
  DAI Guang-zhen, JIANG Xian-wei, XU Tai-long, LIU Qi, CHEN Jun-ning, DAI Yue-hua. Effect of oxygen vacancy on lattice and electronic properties of HFO₂ by means of density function theory study[J]. Acta Phys Sin, 2015,64(3)033101.
21. [21]
  GE Q, JENKINS S J, KING D A. Localisation of adsorbate-induced demagnetisation:CO chemisorbed on Ni{110}[J]. Chem Phys Lett, 2000,327(3/4):125-130.
22. [22]
  DELLEY B. Fast calculation of electrostatics in crystals and large molecules[J]. J Phys Chem, 1996,100(15):6107-6110. doi: 10.1021/jp952713n
23. [23]
  GULIAMOV O, FRENKEL A I, MENARD L D, NUZZO R G, KRONIK L. Tangential ligand-induced strain in Icosahedral Au-13[J]. J Am Chem Soc, 2007,129(36)10978. doi: 10.1021/ja0725706
24. [24]
  APRA E, FORTUNELLI A. Density-functional calculations on platinum nanoclusters:Pt-13, Pt-38, and Pt-55[J]. J Phys Chem A, 2003,107(16):2934-2942. doi: 10.1021/jp0275793
25. [25]
  MAGER-MAURY C, BONNARD G, CHIZALLET C, SAUTET P, RAYBAUD P. H-2-induced reconstruction of supported Pt clusters:Metal-support interaction versus surface hydride[J]. ChemCatChem, 2011,3(1):200-207. doi: 10.1002/cctc.201000324
26. [26]
  SHAFAI G, HONG S Y, BERTINO M, RAHMAN T S. Effect of ligands on the geometric and electronic structure of Au-13 clusters[J]. J Phys Chem C, 2009,113(28):12072-12078. doi: 10.1021/jp811200e
27. [27]
  CHENG P, ZHANG S L, WANG P, HUANG S P, TIAN H P. First-principles investigation of thiophene adsorption on Ni-13 and Zn@Ni-12 nanoclusters[J]. Comput Theor Chem, 2013,1020:136-142. doi: 10.1016/j.comptc.2013.07.044
28. [28]
  SHI W, ZHANG L Y, XIA S J, NI Z M. Adsorption of thiophene on M (111)(M=Pd, Pt, Au) surfaces[J]. Acta Phys Chim Sin, 2014,30(12):2249-2255.
29. [29]
  WANG H M, LGLESIA E. Thiophene hydrodesulfurization catalysis on supported Ru clusters:Mechanism and site requirements for hydrogenation and desulfurization pathways[J]. J Catal, 2010,273(2):245-256. doi: 10.1016/j.jcat.2010.05.019
1. [1]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
2. [2]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
3. [3]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
4. [4]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
5. [5]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . 微观结构调控的g-C₃N₄在光催化NO转化中的最新进展：吸附/活化位点的关键作用. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-. doi: 10.1016/j.actphy.2024.100039
6. [6]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
7. [7]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
8. [8]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
9. [9]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
10. [10]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
11. [11]
  Jing Wang , Pingping Li , Yuehui Wang , Yifan Xiu , Bingqian Zhang , Shuwen Wang , Hongtao Gao . Treatment and Discharge Evaluation of Phosphorus-Containing Wastewater. University Chemistry, 2024, 39(5): 52-62. doi: 10.3866/PKU.DXHX202309097
12. [12]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
13. [13]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
14. [14]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
15. [15]
  Huan LI , Shengyan WANG , Long Zhang , Yue CAO , Xiaohan YANG , Ziliang WANG , Wenjuan ZHU , Wenlei ZHU , Yang ZHOU . Growth mechanisms and application potentials of magic-size clusters of groups Ⅱ-Ⅵ semiconductors. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1425-1441. doi: 10.11862/CJIC.20240088
16. [16]
  Lubing Qin , Fang Sun , Meiyin Li , Hao Fan , Likai Wang , Qing Tang , Chundong Wang , Zhenghua Tang . 原子精确的(AgPd)₂₇团簇用于硝酸盐电还原制氨：一种配体诱导策略来调控金属核. Acta Physico-Chimica Sinica, 2025, 41(1): 2403008-. doi: 10.3866/PKU.WHXB202403008
17. [17]
  Shuanglin TIAN , Tinghong GAO , Yutao LIU , Qian CHEN , Quan XIE , Qingquan XIAO , Yongchao LIANG . First-principles study of adsorption of Cl₂ and CO gas molecules by transition metal-doped g-GaN. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1189-1200. doi: 10.11862/CJIC.20230482
18. [18]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
19. [19]
  Zhengkun QIN , Zicong PAN , Hui TIAN , Wanyi ZHANG , Mingxing SONG . A series of iridium(Ⅲ) complexes with fluorophenyl isoquinoline ligand and low-efficiency roll-off properties: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1235-1244. doi: 10.11862/CJIC.20240429
20. [20]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1600)
HTML views(108)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Comparison of reaction mechanism of thiophene hydrodesulfurization on Au13 and Pt13 clusters

Metrics

通讯作者: 陈斌, bchen63@163.com

Comparison of reaction mechanism of thiophene hydrodesulfurization on Au₁₃ and Pt₁₃ clusters