Catalytic reduction of N_2O by CO over Pt_lAu-m~- clusters:A first-principles study
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摘要
Based on the density functional theory, we investigate negatively charged clusters PtlAu-m(l + m = 4), which show significant catalytic properties in the simultaneous removal of N2O and CO. We find that in these clusters, the platinum atom acts as the adsorption center for N2O, the gold and Pt atoms act as electron donors during the reaction, and the charge transfers from the bimetallic cluster to the N2O molecule. As the proportion of Au in the cluster increases, the d band center shifts down further away from the Fermi level, meanwhile more charge is transferred to the N2O molecule, resulting in weaker N–O bond strength. Therefore bimetallic cluster PtAu-3 shows better catalytic properties than the other clusters,especially pure Pt4- and Au4-clusters. This means that there is a synergetic effect between the Pt and Au atoms in the negatively charged bimetallic clusters. Our results help to reveal the mechanism of Pt l Au-m bimetallic clusters as excellent catalysts.
Based on the density functional theory, we investigate negatively charged clusters PtlAu-m(l + m = 4), which show significant catalytic properties in the simultaneous removal of N2O and CO. We find that in these clusters, the platinum atom acts as the adsorption center for N2O, the gold and Pt atoms act as electron donors during the reaction, and the charge transfers from the bimetallic cluster to the N2O molecule. As the proportion of Au in the cluster increases, the d band center shifts down further away from the Fermi level, meanwhile more charge is transferred to the N2O molecule, resulting in weaker N–O bond strength. Therefore bimetallic cluster PtAu-3 shows better catalytic properties than the other clusters,especially pure Pt4- and Au4-clusters. This means that there is a synergetic effect between the Pt and Au atoms in the negatively charged bimetallic clusters. Our results help to reveal the mechanism of Pt l Au-m bimetallic clusters as excellent catalysts.
Based on the density functional theory, we investigate negatively charged clusters PtlAu-m(l + m = 4), which show significant catalytic properties in the simultaneous removal of N2O and CO. We find that in these clusters, the platinum atom acts as the adsorption center for N2O, the gold and Pt atoms act as electron donors during the reaction, and the charge transfers from the bimetallic cluster to the N2O molecule. As the proportion of Au in the cluster increases, the d band center shifts down further away from the Fermi level, meanwhile more charge is transferred to the N2O molecule, resulting in weaker N–O bond strength. Therefore bimetallic cluster PtAu-3 shows better catalytic properties than the other clusters,especially pure Pt4- and Au4-clusters. This means that there is a synergetic effect between the Pt and Au atoms in the negatively charged bimetallic clusters. Our results help to reveal the mechanism of Pt l Au-m bimetallic clusters as excellent catalysts.
引文
[1]Ravishankara A R,Daniel J S and Portmann R W 2009 Science 326123
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[13]Zhou M,Zhang A,Dai Z,Zhang C and Feng Y P 2010 J.Chem.Phys.132 194704
[14]Wang Y C,Wang Q Y,Geng Z Y,Si Y B,Zhang J H,Li H Z and Zhang Q L 2008 Chem.Phys.Lett.460 13
[15]Yamamoto H,Miyajima K and Yasuike T 2013 J.Phys.Chem.A 11712175
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[17]Balteanu I,Petru Balaj O,Beyer M K and Bondybey V E 2004 Phys.Chem.Chem.Phys.6 2910
[18]Siu C K,Reitmeier S J,Balteanu I,Bondybey V E and Beyer M K 2007Eur.Phys.J.D 43 189
[19]Wang F,Zhang D and Ding Y 2010 J.Phys.Chem.C 114 14076
[20]Gao G P,Wei S H and Duan X M 2012 J.Phys.Chem.C 116 24930
[21]Wang Y H,Zhu J L,Zhang J C,Song L F,Hu J Y,Ong S L and Ng W J 2006 J.Power Sources 155 440
[22]Hammer B,Hansen L B and N?rskov J K 1999 Phys.Rev.B 59 7413
[23]Delley B 1990 J.Chem.Phys.92 508
[24]Delley B 2000 J.Chem.Phys.113 7756
[25]Chretien S,Gordon M S and Metiu H 2004 J.Chem.Phys.121 3756
[2]Hamilton S M,Hopkins W S,Harding D J,Walsh T R,Haertelt M,Kerpal C,Gruene P,Meijer G,Fielicke A and Mackenzie S R 2011 J.Phys.Chem.A 115 2489
[3]Chiodo S,Rondinelli F,Russo N and Toscano M 2008 J.Chem.Theory Comput.4 316
[4]Delabie A and Pierloot K 2002 J.Phys.Chem.A 106 5679
[5]Wannakao S,Nongnual T,Khongpracha P,Maihom T and Limtrakul J2012 J.Phys.Chem.C 116 16992
[6]Blagojevic V,Orlova G and Bohme D K 2005 J.Am.Chem.Soc 1273545
[7]Ryan M F,Stoeckigt D and Schwarz H 1994 J.Am.Chem.Soc 1169565
[8]Michalak A,Witko M and Hermann K 1997 J.Mol.Catal.A:Chemical119 213
[9]Kappes M M and Staley R H 1981 J.Am.Chem.Soc 103 1286
[10]Chen L L,Lu Q L and Luo Q Q 2010 Acta Phys.Sin.59 234(in Chinese)
[11]Mao H P,Sheng Y and Wang H Y 2008 Chin.Phys.B 17 2110
[12]Achatz U,Berg C,Joos S,Fox B S,Beyer M K,Niedner-Schatteburg G and Bondybey V E 2000 Chem.Phys.Lett.320 53
[13]Zhou M,Zhang A,Dai Z,Zhang C and Feng Y P 2010 J.Chem.Phys.132 194704
[14]Wang Y C,Wang Q Y,Geng Z Y,Si Y B,Zhang J H,Li H Z and Zhang Q L 2008 Chem.Phys.Lett.460 13
[15]Yamamoto H,Miyajima K and Yasuike T 2013 J.Phys.Chem.A 11712175
[16]Brnstrup M,Schrder D,Kretzschmar I,Schwarz H and Harvey J N2001 J.Am.Chem.Soc 123 142
[17]Balteanu I,Petru Balaj O,Beyer M K and Bondybey V E 2004 Phys.Chem.Chem.Phys.6 2910
[18]Siu C K,Reitmeier S J,Balteanu I,Bondybey V E and Beyer M K 2007Eur.Phys.J.D 43 189
[19]Wang F,Zhang D and Ding Y 2010 J.Phys.Chem.C 114 14076
[20]Gao G P,Wei S H and Duan X M 2012 J.Phys.Chem.C 116 24930
[21]Wang Y H,Zhu J L,Zhang J C,Song L F,Hu J Y,Ong S L and Ng W J 2006 J.Power Sources 155 440
[22]Hammer B,Hansen L B and N?rskov J K 1999 Phys.Rev.B 59 7413
[23]Delley B 1990 J.Chem.Phys.92 508
[24]Delley B 2000 J.Chem.Phys.113 7756
[25]Chretien S,Gordon M S and Metiu H 2004 J.Chem.Phys.121 3756