团簇Fe_3Cr_3催化性质与反应活性
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摘要
基于密度泛函理论,获得团簇Fe_3Cr_3的优化构型。从前线轨道角度对其催化性质展开研究,结果如下:团簇Fe_3Cr_3可能具有以Fe原子为主、Cr原子为辅的双催化中心;构型8~((3))催化活性最强,构型5(1)最弱;团簇Fe_3Cr_3在作催化剂时具有较强提供电子的能力和相对较弱的接受电子的能力。另分析了三重态不同构型的反应活性,发现团簇Fe_3Cr_3提供电子的能力普遍比接受电子的能力强;构型3~((3))反应活性最弱而6~((3))较弱;构型7~((3))与8~((3))均具较强反应活性,且构型8~((3))提供电子的能力远大于接受电子的能力。此外,构型2~((3))在化学反应中活性一般。
Based on the density functional theory,optimized configurations of cluster Fe_3Cr_3 were obtained.From the perspective of frontier orbital,the catalytic properties of the cluster Fe_3Cr_3 were studied. The results show that the cluster Fe_3Cr_3 may have double catalytic centers with Fe atoms as the main sites and Cr atoms as the auxiliary sites. Configuration 8~((3))has the strongest reactivity while configuration 5(1)has the weakest reactivity. When used as catalysts,the cluster Fe_3Cr_3 has stronger ability to provide electrons and relatively weaker ability to accept electrons. In addition,the reactivity of different triplet configurations was also analyzed,and it was found that the ability of the cluster Fe_3Cr_3 to provide electrons is generally stronger than that of accepting electrons. While configuration 6~((3))has weaker reactivity,configuration 3~((3))has the weakest reactivity. Configurations 7~((3))and 8~((3))both possess stronger reactivity,and the ability of configuration 8~((3))to provide electrons is far greater than that of accepting electrons. Besides,configuration 2~((3))has general reactivity in chemical reactions.
Based on the density functional theory,optimized configurations of cluster Fe_3Cr_3 were obtained.From the perspective of frontier orbital,the catalytic properties of the cluster Fe_3Cr_3 were studied. The results show that the cluster Fe_3Cr_3 may have double catalytic centers with Fe atoms as the main sites and Cr atoms as the auxiliary sites. Configuration 8~((3))has the strongest reactivity while configuration 5(1)has the weakest reactivity. When used as catalysts,the cluster Fe_3Cr_3 has stronger ability to provide electrons and relatively weaker ability to accept electrons. In addition,the reactivity of different triplet configurations was also analyzed,and it was found that the ability of the cluster Fe_3Cr_3 to provide electrons is generally stronger than that of accepting electrons. While configuration 6~((3))has weaker reactivity,configuration 3~((3))has the weakest reactivity. Configurations 7~((3))and 8~((3))both possess stronger reactivity,and the ability of configuration 8~((3))to provide electrons is far greater than that of accepting electrons. Besides,configuration 2~((3))has general reactivity in chemical reactions.
引文
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[3]CHAUHAN S,VERMA V,PRAKASH U,et al.Influence of sintering temperature and cooling rate on microstructure and mechanical properties of pre-alloyed Fe-CrMo powder metallurgy steel[J].Transactions of the Indian Institute of Metals,2018,71(1):219-224.
[4]KOMAKI M,MIMURA T,KURAHASI R,et al.High chromium Fe-Cr-Mo-PC amorphous coating films produced by thermal spraying technique[J].Materials Transactions,2011,52(3):474-480.
[5]YUAN L,PONGE D,WITTIG J,et al.Nanoscale austenite reversion through partitioning,segregation and kinetic freezing:Example of a ductile 2 GPa Fe-Cr-C steel[J].Acta Materialia,2012,60(6-7):2790-2804.
[6]CHOTěBORSKYR,HRABěP,MüLLER M,et al.Abrasive wear of high chromium Fe-Cr-C hardfacing alloys[J].Research in Agricultural Engineering,2008,54(4):192-198.
[7]QUADAKKERS W J,?UREK J,H?NSEL M.Effect of water vapor on high-temperature oxidation of Fe-Cr alloys[J].Jom,2009,61(7):44-50.
[8]RIFAI M,YUASA M,MIYAMOTO H.Enhanced corrosion resistance of ultrafine-grained Fe-Cr alloys with subcritical Cr contents for passivity[J].Metals-Open Access Metallurgy Journal,2018,8(3):149-158.
[9]WEN W,CAPOLUNGO L,PATRA A,et al.A physicsbased crystallographic modeling framework for describing the thermal creep behavior of Fe-Cr alloys[J].Metallurgical and Materials Transactions A,2017,48(5):2603-2617.
[10]SHISHIDO R,UCHIKOSHI M,SATO S,et al.Microportion image analysis of light elements in Fe-Cr based alloys by time-of-flight secondary ion mass spectrometry[J].ISIJ International,2017,57(8):1425-1432.
[11]MANI P,SRIVASTAVA R,STRASSER P.Dealloyed binary PtM3(M=Cu,Co,Ni)and ternary PtNi3M(M=Cu,Co,Fe,Cr)electrocatalysts for the oxygen reduction reaction:Performance in polymer electrolyte membrane fuel cells[J].Journal of Power Sources,2011,196(2):666-673.
[12]KAUR M,DAI Q,BOWDEN M,et al.Watermelonlike iron nanoparticles:Cr doping effect on magnetism and magnetization interaction reversal[J].Nanoscale,2013,5(17):7872-7881.
[13]YU X G.Hyperbolic multi-topology and the basic principle in quantum mechanics[J].Advances in Applied Clifford Algebras,1999,9(1):109-118.
[14]BECK A.Density-functional thermochemistry.III.The role of exact exchange[J].The Journal of Chemical Physics,1993,98(7):5648-5652.
[15]SASTRI V S,PERUMAREDDI J R.Molecular orbital theoretical studies of some organic corrosion inhibitors[J].Corrosion-Houston Tx-,1997,53(8):617-622.