Redox-active ligand controlled selectivity of vanadium oxidation on Au(100)

Tempas, Christopher D.; Morris, Tobias W.; Wisman, David L.; Le, Duy; Din, Naseem Ud; Williams, Colin J.; Wang, Miao; Polezhaev, Alexander V.; Rahman, Talat S.; Caulton, Kenneth G.; Tait, Steven L.

doi:10.1039/c7sc04752e

Cited by 24 publications

(16 citation statements)

References 88 publications

(65 reference statements)

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“…Taking Pt SACs as an example, powdered MgO, Al 2 O 3 , and CeO 2 were used as supports to anchor a Pt single atom with a ligand 3,6‐di‐2‐pyridyl‐1,2,4,5tetrazine (DPTZ) [222] . The nitrogen bidentate binding pockets in DPTZ can coordinate Pt and prevent aggregation, owing to its electron‐accepting capability of stabilizing a non‐zero oxidation state Pt [223] . The Pt−DPTZ SACs were synthesized by impregnating DPTZ and Pt precursor H 2 PtCl 6 ⋅6H 2 O on different supports in one step.…”

Section: Understanding Of Active Centermentioning

confidence: 99%

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

Wang

Liu

2020

ChemCatChem

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Single‐atom catalysts (SACs) have been rising recently as a new frontier in the catalysis field. Due to maximum atom utilization efficiency and tunable electronic structures, SACs exhibit highly distinctive catalytic performance from bulk counterparts. SACs with high metal loading will facilitate practical applications. To that end, this Review focuses on recent strategies to maximize metal loading. An appropriate substrate, mainly heteroatom‐doped carbon materials, is the key to avoiding aggregation or sintering during synthetic procedures. The coordination site construction and spatial confinement strategies are adopted to prepare SACs with high metal loading. Advanced characterization techniques with atomic resolution are indispensable for identification of the exact structure of SACs. This is true, especially for the applications and challenges in developing in situ/operando characterization techniques at the atomic level, which are discussed in this Review. Moreover, it is fundamentally necessary to investigate the active center structure, which facilitates any design of efficient SACs that can maximize single‐atom catalytic activity. Furthermore, this Review highlights challenges and prospects for development of SACs.

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Section: Understanding Of Active Centermentioning

confidence: 99%

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

Wang

Liu

2020

ChemCatChem

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“…[3] These assemblies have demonstrated the ability to facilitateh igher selectivitya si llustrated by the reactiono fm olecular oxygen with V-dipyridyl tetrazine (DPTZ)c hains (Scheme 1) compared to vanadium nanoparticles. [6] The V-DPTZ complex consumes O 2 to produce ah ighly uniform vanadyl product (V=O) through am echanism of atomico xygen spillovert ot he support surface. [6] Our aim is to design as ystem in which two metal centers would be in close proximity to one another,e nabling the cooperative reactivity of these metals on as ingle molecular adsorbate.…”

Section: Introductionmentioning

confidence: 99%

“…[6] The V-DPTZ complex consumes O 2 to produce ah ighly uniform vanadyl product (V=O) through am echanism of atomico xygen spillovert ot he support surface. [6] Our aim is to design as ystem in which two metal centers would be in close proximity to one another,e nabling the cooperative reactivity of these metals on as ingle molecular adsorbate. This stems from an umber of examples, in molecular chemistry,w here the reactivityo facomplex relies on two metals cooperatively activating as ubstrate either in ab imetallic complex or as two equivalents of am onometallic species.…”

Section: Introductionmentioning

confidence: 99%

“…Our previous work has demonstrated the ability of our systems to form highly ordered and regular single‐site metal assemblies . These assemblies have demonstrated the ability to facilitate higher selectivity as illustrated by the reaction of molecular oxygen with V‐dipyridyl tetrazine (DPTZ) chains (Scheme ) compared to vanadium nanoparticles . The V‐DPTZ complex consumes O 2 to produce a highly uniform vanadyl product (V=O) through a mechanism of atomic oxygen spillover to the support surface …”

Section: Introductionmentioning

confidence: 99%

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Multi‐electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces

Morris

Huerfano

Wang

et al. 2019

Chemistry A European J

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Metal-ligandc omplexation at surfaces utilizing redox-activel igands has been demonstrated to produce uniform single-site metals centers in regular coordination networks. Twok ey design considerations are the electron storage capacity of the ligand and the metal-coordinating pockets on the ligand.I na ne ffort to move towardg reater complexity in the systems, particularly dinuclear metal centers, we designed and synthesized tetraethyltetra-aza-anthraquinone, TAAQ, which has superior electrons toragec apabilities and four ligatingpocketsinadiverging geometry.Cyclic voltammetry studies of the free ligand demonstrate its ability to undergo up to af our-electron reduction. Solution-based studies with an analogousl igand, diethyldi-aza-anthraqui-none, demonstrate these redoxc apabilities in am olecular environment. Surface studies conducted on the Au(111)s urface demonstrate TAAQ'sa bility to complex with Fe. This complexation can be observed at different stoichiometric ratios of Fe:TAAQ as Fe 2p core level shifts in X-ray photoelectron spectroscopy.S canning tunneling microscopy experiments confirmed the formation of metal-organic coordination structures. The striking feature of these structures is their irregularity,w hich indicates the presence of multiple local binding motifs. Density functional theory calculations confirm severale nergetically accessible Fe:TAAQ isomers, which accounts for the non-uniformity of the chains.

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“…[1][2][3][4] As MONs can be controlled by rational design of its constituents, they are envisioned to be applicable in very different fields ranging from catalysis over nanoelectronics to memory devices. [5][6][7][8][9] MONs are usually obtained from self-assembly on metal surfaces. While suitable precursor molecules are deposited from gas phase, 10 the metal atoms involved can be either co-deposited or provided by substrate atoms.…”

Section: Introductionmentioning

confidence: 99%

Bonding Motifs in Metal–Organic Compounds on Surfaces

et al. 2018

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The bonds in metal organic networks on surfaces govern the resulting geometry as well as the electronic properties. Here, we study the nature of these bonds by forming phenazine-copper complexes on a copper surface by means of atomic manipulation. The structures are characterized by a combination of scanning probe microscopy and density functional theory calculations. We observed an increase of the molecule-substrate distance upon covalent bond formation and an out-of-plane geometry that is in direct contradiction with the common expectation that these networks are steered by coordination bonds. Instead, we find that a complex energy balance of hybridization with the substrate, inhomogeneous Pauli repulsion, and elastic deformation drives the phenazine-copper interaction. Most remarkably, this attractive interaction is not driven by electron acceptor properties of copper but is of completely different donation/back-donation mechanism between molecular π-like orbitals and sp-like metal states. Our findings show that the nature of bonds between constituents adsorbed on surfaces does not have to follow the common categories.

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Redox-active ligand controlled selectivity of vanadium oxidation on Au(100)

Abstract: Selective oxidation of V is observed when coordinated with a redox-active ligand, forming a single VO product.

Cited by 24 publications

References 88 publications

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure

Multi‐electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces

Bonding Motifs in Metal–Organic Compounds on Surfaces

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