噻吩在Au<sub>13</sub>和Pt<sub>13</sub>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

噻吩在Au₁₃和Pt₁₃团簇上加氢脱硫的反应机理比较

浙江工业大学化学工程学院, 浙江杭州 310014

基金项目:

国家自然科学基金资助 21503188

详细信息

中图分类号: O641
计量
- 文章访问数: 97
- HTML全文浏览量: 81
- PDF下载量: 7
- 被引次数: 0
出版历程
- 收稿日期: 2016-03-15
- 修回日期: 2016-04-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-08-10

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

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

More Information

Corresponding author: Tel: +86-13858123256, E-mail: jchx@zjut.edu.cn

摘要

摘要: 采用密度泛函理论研究了噻吩在立方正八面体的M₁₃（M=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。
- 噻吩 /
- 加氢脱硫 /
- 吸附 /
- Au₁₃团簇 /
- Pt₁₃团簇 /
- 密度泛函理论
Abstract: 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

HTML全文

图 1 M₁₃团簇模型

Figure 1 Model of M₁₃ cluster

(a): top view; (b): side view

下载: 全尺寸图片幻灯片

图 2 噻吩在M₁₃上的稳定吸附构型

Figure 2 Most stable adsorption configurations of thiophene adsorbed on M₁₃

(a): thiophene molecule; (b): on Au₁₃; (c): on Pt₁₃

下载: 全尺寸图片幻灯片

图 3 噻吩在M₁₃上稳定吸附构型的差分电荷密度

Figure 3 Charge density difference of thiophene at preferential adsorption site on M₁₃

(a): Au₁₃; (b): Pt₁₃

下载: 全尺寸图片幻灯片

图 4 噻吩加氢脱硫的不同反应路径

Figure 4 Different reaction pathways for the hydrodesulfurization of thiophene

下载: 全尺寸图片幻灯片

图 5 机理C在Au₁₃上以及机理D在Pt₁₃上各反应的能量变化示意图

Figure 5 Energy change for reactions of mechanism C on Au₁₃ and mechanism D on Pt₁₃

(a and b represent the reaction on the Au₁₃ and Pt₁₃, respectively; the thick line represents the rate-determining step)

下载: 全尺寸图片幻灯片

图 6 机理C各反应物在Au₁₃上结构变化示意图

Figure 6 Structure change for the reactants of mechanism C on Au₁₃

下载: 全尺寸图片幻灯片

图 7 机理D各反应物在Pt₁₃上结构变化示意图

Figure 7 Structure change for the reactants of mechanism D on Pt₁₃

下载: 全尺寸图片幻灯片

图 8 机理F各反应在M₁₃上能量变化示意图

Figure 8 Energy change for the reactions of mechanism F on M₁₃

下载: 全尺寸图片幻灯片

图 9 机理F各反应物在M₁₃上结构变化示意图

Figure 9 Structure change for the reactants of mechanism F on M₁₃

下载: 全尺寸图片幻灯片

表 1 噻吩在M₁₃上的吸附能

Table 1 Adsorption energies of thiophene on M₁₃

M₁₃	E_ads/(kJ·mol^-1)
M₁₃	top	bridge	hol-tri	hol-quadr
Au₁₃	-76.5	-80.4	-89.9	-66.6
Pt₁₃	-98.5	-194.0	-287.8	-300.0

下载: 导出CSV

表 2 噻吩在M₁₃上稳定吸附构型的吸附能和结构参数

Table 2 Adsorption energies and structure parameters of thiophene on M₁₃

Model	E_ads/(kJ·mol^-1)	d₁/nm	d₂/nm	d₃/nm	d₄/nm	d₅/nm
Thiophene (simulation)	-	0.172 9	0.137 6	0.142 4	0.137 6	0.172 9
Thiophene/Au₁₃	-89.9	0.183 5	0.145 2	0.137 5	0.145 1	0.183 0
Thiophene/Pt₁₃	-300.0	0.186 8	0.148 2	0.143 8	0.148 2	0.187 0
Δd/(Au₁₃)	-	0.010 6	0.007 6	-0.004 9	0.007 5	0.010 1
Δd/(Pt₁₃)	-	0.013 9	0.010 6	0.001 4	0.010 6	0.014 1

下载: 导出CSV

表 3 噻吩在M₁₃上的稳定吸附构型的Mulliken电荷布居

Table 3 Mulliken charges of thiophene at preferential advantage adsorption site on M₁₃

Atom	Charge /e
Atom	S	C₁	C₂	C₃	C₄	H₁	H₂	H₃	H₄	tol
Thiophene/Au₁₃	0.029	-0.032	0.009	0.009	-0.039	0.170	0.115	0.115	0.170	0.537
Thiophene/Pt₁₃	0.145	0.053	0.044	0.045	0.053	0.154	0.136	0.136	0.154	0.920

下载: 导出CSV

表 4 间接脱硫各反应在M₁₃上的活化能和反应能量变化

Table 4 Activation barriers and reaction energy of indirect desulfurization reaction on M₁₃

Step	Au₁₃/(kJ·mol^-1)				Pt₁₃/(kJ·mol^-1)
Step	reactant	product	ΔE	E_a	reactant	product	ΔE	E_a
	H₂	H	-12.4	69.8	H₂	H	-99.6	5.0
(1)	C₄H₄S	α-C₄H₅S	-33.7	16.0	C₄H₄S	α-C₄H₅S	135.0	138.8
(2)	C₄H₄S	β-C₄H₅S	-75.6	129.2	C₄H₄S	β-C₄H₅S	44.2	138.1
(3)	α-C₄H₅S	α, α-C₄H₆S	-34.6	100.8	β-C₄H₅S	β, α-C₄H₆S	81.7	116.8
(4)	α-C₄H₅S	α, β-C₄H₆S	-38.8	99.7	-	-	-	-
(5)	α, β-C₄H₆S	α, β, α-C₄H₇S	-68.5	48.6	β, α-C₄H₆S	β, α, α-C₄H₇S	18.6	166.0
(6)	α, β-C₄H₆S	α, β, β-C₄H₇S	25.1	33.1	β, α-C₄H₆S	β, α, β-C₄H₇S	12.8	126.2
(7)	α, β, β-C₄H₇S	C₄H₈S	-155.6	96.1	β, α, β-C₄H₇S	C₄H₈S	68.2	123.9
(8)	C₄H₈S	C₄H₉S	-9.0	227.9	C₄H₈S	C₄H₉S	40.9	220.4
(9)	C₄H₉S	C₄H₁₀+S	-148.0	111.5	C₄H₉S	C₄H₁₀+S	-20.6	149.7
(10)	S	HS	44.2	46.6	S	HS	81.9	104.2
(11)	HS	H₂S	43.2	80.3	HS	H₂S	150.7	166.6

下载: 导出CSV

表 5 直接脱硫各反应在M₁₃上的活化能和反应能量变化

Table 5 Activation barriers and reaction energy of direct desulfurization reaction on M₁₃

Step	Reaction	Au₁₃		Pt₁₃
Step	Reaction	ΔE/(kJ·mol^-1)	E_a/(kJ·mol^-1)	ΔE/(kJ·mol^-1)	E_a/(kJ·mol^-1)
(1′)	C₄H₄S+H→C₄H₅S	-88.8	54.7	92.2	151.4
(2′)	C₄H₅S+H→C₄H₆+S	-5.3	22.2	-190.8	137.1
(3′)	C₄H₆+S+H→C₄H₆+HS	-16.6	45.9	9.0	19.8
(4′)	C₄H₆+HS+H→C₄H₆+H₂S	-18.5	82.9	150.5	154.8

下载: 导出CSV

参考文献(29)

[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]	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]	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. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18664.shtml 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. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18664.shtml
[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. doi: 10.1016/S1872-5813(15)30022-0 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]	SHAN J, TENHU H.Recent advances in polymer protected gold nanoparticles:Synthesis, properties and applications[J].Chem Commun, 2007, 44:4580-4598.
[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]	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]	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]	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]	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]	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]	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. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201310020.htm 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. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201310020.htm
[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]	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]	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]	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]	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]	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]	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. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201604016.htm 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. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201604016.htm
[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]	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]	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]	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]	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]	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]	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]	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]	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]	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