Ag_9团簇上由H_2和O_2直接合成H_2O_2的密度泛函理论研究
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摘要
应用密度泛函理论对H_2和O_2在Ag_9团簇上直接合成H_2O_2的可能性进行研究。计算H_2和O_2在Ag_9团簇上的吸附性质以及由H_2和O_2生成H_2O_2的反应机制。结果表明:O_2可以在Ag_9团簇上稳定吸附,但H_2很难与Ag_9团簇作用,只有通过Ag—O键才能发生解离。生成H_2O_2的过程可以分为两个阶段:首先解离两个H_2分子形成第一个H_2O_2分子,其中裂解第二个H_2分子为速度控制步骤,所需活化能为108.7 kJ/mol;再吸附的O_2分子夺取Ag_9团簇上两个H原子形成第二个H_2O_2分子,其中OOH自由基夺取Ag_9团簇上的H原子为速度控制步骤,活化能为124.7 kJ/mol。与文献中Pd、Au和Pd-Au团簇上由H_2和O_2生成H_2O_2的理论研究结果相比,Ag_9团簇具有促进H_2和O_2直接合成H_2O_2的催化活性。
The theoretical possibility of direct synthesis of H_2O_2 from H_2 and O_2 on Ag_9 cluster was studied with density functional theory calculations. The adsorption of H_2 and O_2 and the mechanism for H_2O_2 formation on Ag_9 cluster was considered. Results showed that O_2 could be steadily adsorbed on Ag_9 cluster, but H_2 could not interact with Ag_9 cluster. H_2 only could react with the Ag—O bond. There were two stages through the path of H_2O_2 production from H_2 and O_2 on Ag_9 cluster: the first H_2O_2 molecule was formed by cleaving two H_2 molecules, in which the rate-limiting step was the dissociation of the second H_2 with an activation energy of 108.7 kJ/mol. The second H_2O_2 molecule was formed from the reaction of the H atoms on Ag_9 cluster with a new O_2 molecule, in which the rate-limiting step was the coupling of the hydroperoxy(OOH) raclical intermediate with an H atom with an activation energy of 124.7 kJ/mol. By comparison with the theoretical study results on Pd, Au and Pd-Au clusters in the literature, it was known that Ag_9 cluster should have catalytic activity for the direct synthesis of H_2O_2 from H_2 and O_2.
The theoretical possibility of direct synthesis of H_2O_2 from H_2 and O_2 on Ag_9 cluster was studied with density functional theory calculations. The adsorption of H_2 and O_2 and the mechanism for H_2O_2 formation on Ag_9 cluster was considered. Results showed that O_2 could be steadily adsorbed on Ag_9 cluster, but H_2 could not interact with Ag_9 cluster. H_2 only could react with the Ag—O bond. There were two stages through the path of H_2O_2 production from H_2 and O_2 on Ag_9 cluster: the first H_2O_2 molecule was formed by cleaving two H_2 molecules, in which the rate-limiting step was the dissociation of the second H_2 with an activation energy of 108.7 kJ/mol. The second H_2O_2 molecule was formed from the reaction of the H atoms on Ag_9 cluster with a new O_2 molecule, in which the rate-limiting step was the coupling of the hydroperoxy(OOH) raclical intermediate with an H atom with an activation energy of 124.7 kJ/mol. By comparison with the theoretical study results on Pd, Au and Pd-Au clusters in the literature, it was known that Ag_9 cluster should have catalytic activity for the direct synthesis of H_2O_2 from H_2 and O_2.
引文
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[2] SAMANTA C.Direct synthesis of hydrogen peroxide from hydrogen and oxygen:an overview of recent developments in the process[J].Applied Catalysis A(General),2008,350(2):133.
[3] EDWARDS J K,HUTCHINGS G J.Palladium and gold-palladium catalysts for the direct synthesis of hydrogen peroxide[J].Angewandte Chemie(International Edition),2008,47(48):9192.
[4] SUN M,ZHANG J Z,ZHANG Q H,et al.Polyoxometalate-supported Pd nanoparticles as efficient catalysts for the direct synthesis of hydrogen peroxide in the absence of acid or halide promoters[J].Chemical Communications,2009,34:5174.
[5] KIM S,LEE D W,LEE K Y,et al.Effect of Pd particle size on the direct synthesis of hydrogen peroxide from hydrogen and oxygen over Pd core-porous SiO2 shell catalysts[J].Catalysis Letters,2014,144(5):905.
[6] HU B Z,DENG W P,LI R S,et al.Carbon-supported palladium catalysts for the direct synthesis of hydrogen peroxide from hydrogen and oxygen[J].Journal of Catalysis,2014,319:15.
[7] YOOK S,SHIN H,KIM H,et al.Selective dissociation of dihydrogen over dioxygen on a hindered platinum surface for the direct synthesis of hydrogen peroxide[J].ChemCatChem,2014,6(10):2836.
[8] OUYANG L,DA G J,TIAN P F,et al.Insight into active sites of Pd-Au/TiO2 catalysts in hydrogen peroxide synthesis directly from H2 and O2[J].Journal of Catalysis,2014,311:129.
[9] OUYANG L,TIAN P F,DA G J,et al.The origin of active sites for direct synthesis of H2O2 on Pd/TiO2 catalysts:interfaces of Pd and PdO domains[J].Journal of Catalysis,2015,321:70.
[10] LANDON P,COLLIER P J,PAPWORTH A J,et al.Direct formation of hydrogenperoxide from H2/O2 using a gold catalyst[J].Chemical Communications,2002,18:2058.
[11] EDWARDS J K,SOLSONA B,NTAINJUA N E,et al.Switching off hydrogen peroxide hydrogenation in the direct synthesis process[J].Science,2009,323:1037.
[12] HAM H C,HWANG G S,HAN J,et al.On the role of Pd ensembles in selective H2O2 formation on PdAu alloys[J].Journal of Physical Chemistry C,2009,113(30):12943.
[13] TODOROVIC R,MEYER R J.A comparative density functional theory study of the direct synthesis of H2O2 on Pd,Pt and Au surfaces[J].Catalysis Today,2011,160(1):242.
[14] RANKIN R B,GREELEY J.Trends in selective hydrogen peroxide production on transition metal surfaces from first principles[J].ACS Catalysis,2012,2(12):2664.
[15] TIAN P F,OUYANG L K,XU X C,et al.Density functional theory study of direct synthesis of H2O2 from H2 and O2 on Pd(111),Pd(100),and Pd(110) surfaces[J].Chinese Journal of Catalysis,2013,34(5):1002.
[16] STAYKOV A,KAMACHI T,ISHIHARA T,et al.Theoretical study of the direct synthesis of H2O2 on Pd and Pd/Au surfaces[J].Journal of Physical Chemistry C,2008,112(49):19501.
[17] LI J,STAYKOV A,ISHIHARA T,et al.Theoretical study of the decomposition and hydrogenation of H2O2 on Pd and Au@Pd surfaces:understanding toward high selectivity of H2O2 synthesis[J].Journal of Physical Chemistry C,2011,115(15):7392.
[18] LI J,ISHIHARA T,YOSHIZAWA K.Theoretical revisit of the direct synthesis of H2O2 on Pd and Au@Pd surfaces:a comprehensive mechanistic study[J].Journal of Physical Chemistry C,2011,115(51):25359.
[19] FORD D C,NILEKAR A U,XU Y,et al.Partial and complete reduction of O2 by hydrogen on transition metal surfaces[J].Surface Science,2010,604(19/20):1565.
[20] WEN C,YIN A Y,DAI W L.Recent advances in silver-based heterogeneous catalysts for green chemistry processes[J].Applied Catalysis B( Environmental),2014,160:730.
[21] ZHANG D,ZHANG C Z,MU D B,et al.A review of Ag-based catalysts for oxygen reduction reaction[J].Acta Chimica Sinica,2013,71(8):1101.
[22] LIU X,LI Y,LEE J W,et al.Selective hydrogenation of acetylene in excess ethylene over SiO2 supported Au-Ag bimetallic catalyst[J].Applied Catalysis A(General),2012,439,8.
[23] WELLS D H,DELGASS W N,THOMSON K T.Formation of hydrogen peroxide from H2 and O2 over a neutral gold trimer:a DFT study[J].Journal of Catalysis,2004,225(1):69.
[24] JOSHI A M,DELGASS W N,THOMSON K T.Comparison of the catalytic activity of Au3,Au+4,Au5,and Au-5 in the gas-phase reaction of H2 and O2 to form hydrogen peroxide:a density functional theory investigation[J].Journal of Physical Chemistry B,2005,109(47):22392.
[25] JOSHI A M,DELGASS W N,THOMSON K T.Investigation of gold-silver,gold-copper,and gold-palladium dimers and trimers for hydrogen peroxide formation from H2 and O2[J].Journal of Physical Chemistry C,2007,111(20):7384.
[26] WANG F,ZHANG D J,SUN H,et al.Theoretical investigation of the formation of hydrogen peroxide from H2 and O2 over anionic gold clusters Au-n (n=1-4)[J].Journal of Physical Chemistry C,2007,111(31):11590.
[27] TSUKAMOTO D,SHIRO A,SHIRAISHI Y,et al.Photocatalytic H2O2 production from ethanol/O2 system using TiO2 loaded with Au-Ag bimetallic alloy nanoparticles[J].ACS Catalysis,2012,2(4):599.
[28] DEGUCHI T,IWAMOTO M.Catalytic properties of surface sites on Pd clusters for direct H2O2 synthesis from H2 and O2:a DFT study[J].Journal of Physical Chemistry C,2013,117(36):18540.
[29] BELETSKAYA A V,PICHUGINA D A,SHESTAKOV A F,et al.Formation of H2O2 on Au20 and Au19Pd clusters:understanding the structure effect on the atomic level[J].Journal of Physical Chemistry A,2013,117(31):6817.
[30] FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09,RevisionD.01[M] Seattle:Gaussian,Inc.2013.
[31] BECKE AD.Density-functional thermochemistry III the role of exact exchange[J].Journal of Chemical Physics,1993,98(7):5648.
[32] HAY P J,WADT W R.Ab initio effective core potentials for molecular calculations,potentials for the transition metal atoms Sc to Hg[J].Journal of Chemical Physics,1985,82(1):270.
[33] HAY P J,WADT W R.Ab initio effective core potentials for molecular calculations,potentials for K to Au including the outermost core orbitals[J].Journal of Chemical Physics,1985,82(1):299.