Site specific and localized structural displacements in open structured multimetallic oxides

Lunkenbein, Thomas; Masliuk, Liudmyla; Plodinec, Milivoj; Algara‐Siller, Gerardo; Jung, Sabrina; Jastak, Mateusz; Kube, Pierre; Trunschke, Annette; Schlögl, Robert

doi:10.1039/c9nr09041j

Cited by 9 publications

(14 citation statements)

References 48 publications

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“…The redistribution of the reducing electron as consequence of relocating the TeO moiety in the hexagonal channels is especially important, given the recent experimental evidence for the irregular positioning of Te columns within the hexagonal channels [59]. As described above, the reducibility of the metal centers, i.e., their ability to form a small polaron, increases with the proximity to a TeO moiety.…”

Section: Atomic Charges and Spin Densities When The Teo Position Varimentioning

confidence: 97%

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

et al. 2021

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With hybrid DFT calculations applied to periodic models of the bulk MoVNbTeO M1 catalyst, we examined how [TeO]2+ species in the hexagonal channels of this material stabilize nearby reduced metal centers. In particular, an S2(Mo) site, with adjacent [TeO]2+ moieties at both sides, is calculated to be reduced to Mo5+. The modeling study presented offers insight into how the redox behavior of V and Mo centers, a crucial aspect of the M1 catalyst for the selective partial oxidation of small hydrocarbons, may be fine-tuned via TeO moieties at various distances from the metal centers. Graphic Abstract TeO moieties in hexagonal channels, adjacent on either side of an S2(Mo) center, stabilize a gap state at the Mo center, facilitating its reduction to Mo5+.

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Section: Atomic Charges and Spin Densities When The Teo Position Varimentioning

confidence: 97%

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

et al. 2021

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“…Not only the oxygen sublattice that appears distorted or displaced but also individual metal sites can be shifted from the ideal equilibrium position. For (Mo,V,Te,Nb)O x such kinds of displacements were observed for metal sites that connect the hexagonal channels (Figure e) . The metal centers are shifted toward the channel sites.…”

Section: Scientific Case For Operando Em Studiesmentioning

confidence: 83%

Section: Scientific Case For Operando Em Studiesmentioning

confidence: 99%

Operando Electron Microscopy of Catalysts: The Missing Cornerstone in Heterogeneous Catalysis Research?

Chee,

Lunkenbein,

Schlögl

et al. 2023

Chem. Rev.

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Heterogeneous catalysis in thermal gas-phase and electrochemical liquid-phase chemical conversion plays an important role in our modern energy landscape. However, many of the structural features that drive efficient chemical energy conversion are still unknown. These features are, in general, highly distinct on the local scale and lack translational symmetry, and thus, they are difficult to capture without the required spatial and temporal resolution. Correlating these structures to their function will, conversely, allow us to disentangle irrelevant and relevant features, explore the entanglement of different local structures, and provide us with the necessary understanding to tailor novel catalyst systems with improved productivity. This critical review provides a summary of the still immature field of operando electron microscopy for thermal gas-phase and electrochemical liquid-phase reactions. It focuses on the complexity of investigating catalytic reactions and catalysts, progress in the field, and analysis. The forthcoming advances are discussed in view of correlative techniques, artificial intelligence in analysis, and novel reactor designs.

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“…AC-1 and AC-2 were subjected to annular bright-field scanning transmission electron microscopy (ABF-STEM) measurements. In these experiments, weak spots derived from the lattice oxygen were detected between the dark spots derived from the constituent metals. , Figure b–e shows representative ABF-STEM images of AC-1 and AC-2 captured along the (001) plane (see Figures S6 and S7 for additional images). Oxygen contrasts in the PU (OC PU ) and Pen (OC Pen ) were measured for 150–200 points, respectively, and were averaged to calculate the OC PU /OC Pen ratio.…”

Section: Resultsmentioning

confidence: 99%

Oxidation Catalysis of Crystalline Mo₃VO_x for the Selective Oxidation of Ethane

Ishikawa,

Shimoda,

Kamachi

et al. 2023

ACS Catal.

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Oxidative dehydrogenation of ethane (ODHE) is an essential reaction in modern society to produce ethylene. The orthorhombic Mo 3 VO x catalyst (MoVO) was reported as one of the best catalysts for this reaction after a particular redox treatment to generate lattice oxygen defects. This study elucidates the location and nature of the defect sites as well as how molecular oxygen is activated toward the ODHE. The insights into the active site formation and guidelines for its design were gained through structural characterization, quantification of oxygen defects, and experimental and theoretical investigation of the reaction mechanisms. Peroxo formed at the defect sites of the bridging oxygen facing the heptagonal channel was found to drive the reaction efficiently.

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Site specific and localized structural displacements in open structured multimetallic oxides

Abstract: Picometer-scale displacements of one metal site and their local distribution in open structured (Mo,V,Te,Nb)Ox are described.

Cited by 9 publications

References 48 publications

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

Operando Electron Microscopy of Catalysts: The Missing Cornerstone in Heterogeneous Catalysis Research?

Oxidation Catalysis of Crystalline Mo₃VO_x for the Selective Oxidation of Ethane

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Site specific and localized structural displacements in open structured multimetallic oxides

Abstract: Picometer-scale displacements of one metal site and their local distribution in open structured (Mo,V,Te,Nb)Ox are described.

Cited by 9 publications

References 48 publications

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

Probing the Positions of TeO Moieties in the Channels of the MoVNbTeO M1 Catalyst: A Density Functional Theory Model Study

Operando Electron Microscopy of Catalysts: The Missing Cornerstone in Heterogeneous Catalysis Research?

Oxidation Catalysis of Crystalline Mo3VOx for the Selective Oxidation of Ethane

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Oxidation Catalysis of Crystalline Mo₃VO_x for the Selective Oxidation of Ethane