Surface-Mediated NH and N Addition to Styrene on Ag(110)

Li, Xiaoying; Madix, Robert J.; Friend, Cynthia M.

doi:10.1021/ja065344p

Cited by 4 publications

(3 citation statements)

References 17 publications

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“…Atomic oxygen bound to single-crystal gold is highly active for CO oxidation [30][31][32][33][34] and for activation of O-H, C-H, and N-H bonds in a variety of organic molecules. [35][36][37][38][39][40][41][42][43][44] Many of the reactions on single-crystal gold parallel those observed on supported and unsupported Au at higher pressures and in solution when O 2 is used as an oxidant as discussed above; thus, establishing the relevance of these studies.…”

Section: High Activity Of Atomic Oxygen On Metallic Goldmentioning

confidence: 58%

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen

Baker

Friend

2011

Phys. Chem. Chem. Phys.

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107

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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.

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Section: High Activity Of Atomic Oxygen On Metallic Goldmentioning

confidence: 58%

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen

Baker

Friend

2011

Phys. Chem. Chem. Phys.

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107

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“…Friend and co-workers showed that adsorbed N and NH on Ag(110) could react with styrene to produce 2-phenylaziridine, which is analogous to ethylene epoxidation to form ethylene oxide, elegantly showing how NH can be made to behave similarly to its isoelectronic cousin, atomic O. 138 The calculated symmetric and asymmetric (degenerate) NH 3 vibrational frequencies are 3424 and 3588 cm −1 , respectively. While Ag (111) measurements are not available, it may be useful to compare to EELS measurements on Ag (110), which place these modes at 3320 and 3400 cm −1 .…”

Section: Resultsmentioning

confidence: 99%

“…NH x species on Ag are interesting as they could be useful as synthons for chemical synthesis. Friend and co-workers showed that adsorbed N and NH on Ag(110) could react with styrene to produce 2-phenylaziridine, which is analogous to ethylene epoxidation to form ethylene oxide, elegantly showing how NH can be made to behave similarly to its isoelectronic cousin, atomic O …”

Section: Resultsmentioning

confidence: 99%

Atomic and Molecular Adsorption on Ag(111)

et al. 2018

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The adsorption of atomic (H, C, N, O, S) and molecular (OH, CH x , NH x , CO, NO, CN, N2, HNO, NOH, HCN, x = 1–3) species at 1/4 monolayer coverage on an extended Ag(111) surface was studied using periodic density functional theory. Geometries and energies were calculated self-consistently using the PW91 functional; nonself-consistent energies using the RPBE functional are also provided. We analyze the binding energies, binding geometries, estimated diffusion barriers, harmonic vibrational frequencies, and energetic and geometric deformation parameters of these adsorbates, comparing them to experimental and theoretical results whenever possible. PW91 gives binding energies that match experimental binding energies more closely than RPBE, which consistently predicts weaker binding than PW91. The data were then used to construct and analyze thermochemistry-only potential energy pathways for the hydrocarbon-assisted and hydrogen-assisted selective catalytic reduction (SCR) of nitric oxide (NO). These analyses provide preliminary insights into the possible mechanistic paths of the SCR of NO on Ag(111). Specifically, we show that deep dehydrogenation leading to the formation of atomic intermediates is not favored on Ag(111).

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Silver‐Catalyzed Nitrene Transfer Reactions

Capretto

2010

Silver in Organic Chemistry

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Surface-Mediated NH and N Addition to Styrene on Ag(110)

Cited by 4 publications

References 17 publications

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen

Atomic and Molecular Adsorption on Ag(111)

Silver‐Catalyzed Nitrene Transfer Reactions

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