噻吩在Au13和Pt13团簇上加氢脱硫的反应机理比较

蒋军辉 曹勇勇 倪哲明 张连阳

引用本文: 蒋军辉, 曹勇勇, 倪哲明, 张连阳. 噻吩在Au13和Pt13团簇上加氢脱硫的反应机理比较[J]. 燃料化学学报, 2016, 44(08): 961-969. shu
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(08): 961-969. shu

噻吩在Au13和Pt13团簇上加氢脱硫的反应机理比较

    通讯作者: 倪哲明
  • 基金项目:

    国家自然科学基金(21503188)资助 

摘要: 采用密度泛函理论研究了噻吩在立方正八面体的M13M=Au、Pt)团簇上的吸附和加氢脱硫行为。结果表明,噻吩以环吸附于Au13上的Hol-tri位或Pt13上的Hol-quadr位时最稳定,且Pt13上的吸附稳定性更高。在M13催化体系中,按间接加氢脱硫机理,反应可能依顺式加氢的方式进行;其中,C-S键断裂开环所需的活化能最高,是反应的限速步骤;按直接加氢脱硫机理,HS加氢所需活化能最高,是反应的限速步骤。同时该机理总体所需活化能较间接加氢脱硫机理更低,是更为合理的脱硫机理。噻吩加氢脱硫过程中,Au13体系为放热反应,而Pt13体系为吸热反应,并且Au13体系加氢所需活化能更低;因此,Au13更有利于噻吩加氢脱硫反应的进行。

English

  • 
    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.[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.

    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.[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.

    3. [3] 祖运,秦玉才,高雄厚,莫周胜,张磊,张晓彤,宋丽娟.催化裂化条件下噻吩与改性Y分子筛的作用机制[J].燃料化学学报,2015,43(7):862-869.(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.)[3] 祖运,秦玉才,高雄厚,莫周胜,张磊,张晓彤,宋丽娟.催化裂化条件下噻吩与改性Y分子筛的作用机制[J].燃料化学学报,2015,43(7):862-869.(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] 刘理华,刘书群,尹海亮,柳云骐,刘晨光.Ni2P和MoS2催化剂在二苯并噻吩加氢脱硫反应中的氢溢流效应[J].燃料化学学报,2015,43(6):708-713.(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.)[4] 刘理华,刘书群,尹海亮,柳云骐,刘晨光.Ni2P和MoS2催化剂在二苯并噻吩加氢脱硫反应中的氢溢流效应[J].燃料化学学报,2015,43(6):708-713.(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.)

    5. [5] SHAN J,TENHU H.Recent advances in polymer protected gold nanoparticles:Synthesis,properties and applications[J].Chem Commun,2007,44:4580-4598.[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.[6] CORMA A,SERNA P.Chemoselective hydrogenation of nitro compounds with supported gold catalysts[J].Science,2006,313(5785):332-334.

    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.[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.

    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.[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.

    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.[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.

    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.[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.

    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.[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.

    12. [12] 倪哲明,施炜,夏明玉,薛继龙.Au (111)面上噻吩加氢脱硫反应机理的理论研究[J].高等学校化学学报,2013,34(10):2353-2362.(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.)[12] 倪哲明,施炜,夏明玉,薛继龙.Au (111)面上噻吩加氢脱硫反应机理的理论研究[J].高等学校化学学报,2013,34(10):2353-2362.(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.[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.

    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.[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.

    15. [15] BUCHWALTER P,ROSE J,BRAUNSTEIN P.Multimetallic catalysis based on heterometallic complexes and clusters[J].Chem Rev,2015,115(1):28-126.[15] BUCHWALTER P,ROSE J,BRAUNSTEIN P.Multimetallic catalysis based on heterometallic complexes and clusters[J].Chem Rev,2015,115(1):28-126.

    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.[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.

    17. [17] 徐坤,冯杰,褚绮,张丽丽,李文英.噻吩在γ-Mo2N (100)表面上加氢脱硫反应的密度泛函理论研究[J].物理化学学报,2014,30(11):2063-2070.(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.)[17] 徐坤,冯杰,褚绮,张丽丽,李文英.噻吩在γ-Mo2N (100)表面上加氢脱硫反应的密度泛函理论研究[J].物理化学学报,2014,30(11):2063-2070.(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.[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.

    19. [19] 蒋军辉,夏盛杰,倪哲明,张连阳.巴豆醛在Au (111)面上的吸附及选择性加氢机理研究[J].高等学校化学学报,2016,37(4):693-700.(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.)[19] 蒋军辉,夏盛杰,倪哲明,张连阳.巴豆醛在Au (111)面上的吸附及选择性加氢机理研究[J].高等学校化学学报,2016,37(4):693-700.(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] 代广珍,蒋先伟,徐太龙,刘琦,陈军宁,代月花.密度泛函理论研究氧空位对HFO2晶格结构和电学特性影响[J].物理学报,2015,64(3):033101.(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.)[20] 代广珍,蒋先伟,徐太龙,刘琦,陈军宁,代月花.密度泛函理论研究氧空位对HFO2晶格结构和电学特性影响[J].物理学报,2015,64(3):033101.(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.[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.[22] DELLEY B.Fast calculation of electrostatics in crystals and large molecules[J].J Phys Chem,1996,100(15):6107-6110.

    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.[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.

    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.[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.

    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.[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.

    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.[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.

    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.[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.

    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.[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.[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.

  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  0
  • HTML全文浏览量:  0
文章相关
  • 收稿日期:  2016-03-15
  • 网络出版日期:  2016-04-25
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

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章