title: The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.
abstract: Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.
authors.affiliation: School of Engineering and Applied Sciences, Harvard University, Cambridge MA 02138, USA.
authors.forename: Thomas A
authors.initials: TA
authors.lastname: Baker
authors.forename: Xiaoying
authors.initials: X
authors.lastname: Liu
authors.forename: Cynthia M
authors.initials: CM
authors.lastname: Friend
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D002384:Catalysis; D006046:Gold / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000438:Alcohols; D000475:Alkenes; D000588:Amines; D006046:Gold; D002248:Carbon Monoxide; D010100:Oxygen