Mechanisms of Oxidase and Superoxide Dismutation-like Activities of Gold, Silver, Platinum, and Palladium, and Their Alloys: A General Way to the Activation of Molecular Oxygen

	Mechanisms of Oxidase and Superoxide Dismutation-like Activities of Gold, Silver, Platinum, and Palladium, and Their Alloys: A General Way to the Activation of Molecular Oxygen
	Shen XM(沈小美); Shen; XM; Liu; WQ; Gao; XJ; Lu; ZH; Wu
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2015
卷号	137 期号:50 页码:15882-15891
通讯作者	高兴发
英文摘要	Metal and alloy nahomaterials have intriguing oxidase- and superoxide dismutation-like (SOD-like) activities. However, origins of these activities remain to be studied. Using density functional theory (DFT) calculations, we investigate mechanisms of oxidase- and SOD-like properties for metals Au, Ag, Pd and Pt and alloys Au4-xMx (x = 1, 2, 3; M = Ag, Pd, Pt). We find that the simple reaction-dissociation of O-2-supported on metal surfaces can profoundly account for the oxidase-like activities of the metals. The activation (E-act) and reaction energies (E-r) calculated by DET can be used to effectively predict the activity. As verification, the calculated activity orders for series of metal and alloy nanomaterials are in excellent agreement with those obtained by experiments. Briefly, the activity is critically dependent on two factors, metal compositions and exposed facets. On the basis of these results, an energy-based model is proposed to account for the activation of molecular oxygen. AS for SOD-like activities, the mechanisms mainly consist of protonation of O-2(center dot-) and adsorption and rearrangement of HO2 center dot on Metal surfaces. Our results provide atomistic-level insights into the oxidase- and SOD-like activities of metals and pave a way to the rational design of mimetic enzymes based on metal nanomaterials. Especially, the O-2 dissociative adsorption mechanism will serve as a general way to the activation of molecular oxygen by nanosurfaces and help understand the catalytic role of nanomaterials as pro-oxidants and antioxidants.
学科主题	Chemistry
类目[WOS]	Chemistry, Multidisciplinary
收录类别	SCI ; EI
WOS记录号	WOS:000367562800047
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/229044]
专题	高能物理研究所_多学科研究中心
推荐引用方式 GB/T 7714	Shen XM,Shen,XM,et al. Mechanisms of Oxidase and Superoxide Dismutation-like Activities of Gold, Silver, Platinum, and Palladium, and Their Alloys: A General Way to the Activation of Molecular Oxygen[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015,137(50):15882-15891.
APA	沈小美.,Shen.,XM.,Liu.,WQ.,...&高兴发.(2015).Mechanisms of Oxidase and Superoxide Dismutation-like Activities of Gold, Silver, Platinum, and Palladium, and Their Alloys: A General Way to the Activation of Molecular Oxygen.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,137(50),15882-15891.
MLA	沈小美,et al."Mechanisms of Oxidase and Superoxide Dismutation-like Activities of Gold, Silver, Platinum, and Palladium, and Their Alloys: A General Way to the Activation of Molecular Oxygen".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137.50(2015):15882-15891.