Catalytic Redox Reactions in the CO/N2O System Mediated by the Bimetallic Oxide‐Cluster Couple AlVO3+/AlVO4+

Wang, Zhe‐Chen; Dietl, Nicolas; Kretschmer, Robert; Weiske, Thomas; Schlangen, Maria; Schwarz, Helmut

doi:10.1002/anie.201105691

Cited by 65 publications

(87 citation statements)

References 90 publications

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“…Theoretical Results. Aiming to provide insights into the molecular origin of Pt catalysis, theoretical calculations have been performed to study the mechanisms of CO oxidation 26,30,65,68,70,74,75,77,80,83 In this study, the unique reactivity of PtAl 3 O 7 − to oxidize two CO molecules consecutively is clearly attributed to the importance of single Pt-atom doping.…”

Section: Introductionmentioning

confidence: 99%

Catalytic CO Oxidation on Single Pt-Atom Doped Aluminum Oxide Clusters: Electronegativity-Ladder Effect

Yuan

Meng

et al. 2015

J. Phys. Chem. C

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Single platinum-atom catalysts exhibit extraordinary activity in a large number of reactions. However, a consensus regarding the molecular origin of Pt catalysis is far from being reached. Here, benefiting from the study of atomic clusters, we propose the Electronegativity-Ladder (E-Ladder) effect to account for the origin of Pt catalysis. The concept was obtained from the study of single Pt-atom doped aluminum oxide clusters PtAl 3 O 5−7 − , which are catalytically active in CO oxidation by molecular O 2 . The undoped aluminum oxide clusters, however, cannot drive such a catalytic cycle. The reactions have been identified by mass spectrometry and density functional theory calculations. The key to drive the cycle lies in the unique structure of PtAl 3 O 6 − , in which the Pt atom that is not fully oxidized can coexist with the highly oxidative oxygen-centered radical (O −• ). After the oxidation of one CO by PtAl 3 O 7 − , the resulting PtAl 3 O 6 − can also oxidize a second CO. The E-Ladder effect originates from the well-fitting electronegativity of the Pt atom (2.28) in between that of the Al atom (1.61) and the O atom (3.44), and this effect promotes the generation of an unpaired electron localized O −• radical, which results in the oxidative nature of PtAl 3 O 6 − toward CO. Thus, the large enthalpy in the catalytic reaction (2CO + O 2 → 2CO 2 ) can be distributed much more evenly into several elementary reactions in the Pt−Al−O system than in the pure Al−O system.

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Section: Introductionmentioning

confidence: 99%

Catalytic CO Oxidation on Single Pt-Atom Doped Aluminum Oxide Clusters: Electronegativity-Ladder Effect

Yuan

Meng

et al. 2015

J. Phys. Chem. C

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“…The reactivity of cationic VAlO 4 + • has been studied previously by both experimen- tal and theoretical studies. 48,49 Methane activation can be achieved by VAlO 4 + • at room temperature and a HAT process shows no observable barrier. 49 The nanocluster VAlO 4 + • is also very reactive toward CO. 48 Figure 10) on the reactivity of these clusters.…”

Section: Cealomentioning

confidence: 99%

“…These cluster systems can serve as a more detailed molecular approach for the understanding of the active sites in catalytic supports and modified catalytic systems. 46,48,49,65,117,[120][121][122][123][124][125][126] The first example of generating, as well as studying, the reactivity of BONCs is reported by He and co-workers: they proposed that the novel AlVO 4 + cluster can activate CH 4 oxidation at room temperature. 49 Additionally, Schwarz and co-workers and He and co-workers report that CH 4 is activated by V 3 PO 10 + .…”

Section: Introductionmentioning

confidence: 99%

“…121,124 The Schwarz group also illustrated the first complete gas phase catalytic cycle conducted by the AlVO 3 + /AlVO 4 + BONC couple through both experimental and theoretical studies. 48 Sauer, Asmis, and co-workers studied the infrared spectroscopy of CeVO 4 + , CeV 2 O 6 + , and Ce 2 VO 5 + BONCs for the first time, indicating interesting structures parallel to the condensed phase VO x /CeO 2 supported materials. 46 They also reported enhanced SO 2 chemical absorption abilities via doping V 4 O 10 cluster with Ti: the enhanced reactivity of V 3 TiO 10 is attributed to charge localization on the outer oxygen atom that binds with the titanium atom.…”

Section: Introductionmentioning

confidence: 99%

“…Note that the unpaired electron is localized not on the rare earth metal centered Ce = O t , but on the main-group metal centered Al-O t • oxygen, as shown inFigure 5. Former studies of charged nanoclusters such as VAlO 4 +• ,48, 49 ScAlO 3 +• , 89, 141 and VAlO 5 −•123 show that the Al-O t • moiety can act as the active site in cationic or anionic BONCs containing transition metals. Here our DFT studies show that the Al-O t • moiety could also be the FIG.…”

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confidence: 99%

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Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C–H bond activation

Wang

Yin

Bernstein

2013

The Journal of Chemical Physics

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Both ceria (CeO2) and alumina (Al2O3) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), CexAlyOz, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C4H10) is studied. The very active species CeAlO4 (●) can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other CexAlyOz NBONCs do not show reactivities toward CO and C4H10. The structures, as well as the reactivities, of CexAlyOz NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO4 (●) NBONC possesses a kite-shaped structure with an OtCeObObAlOt configuration (Ot, terminal oxygen; Ob, bridging oxygen). An unpaired electron is localized on the Ot atom of the AlOt moiety rather than the CeOt moiety: this Ot centered radical moiety plays a very important role for the reactivity of the CeAlO4 (●) NBONC. The reactivities of Ce2O4, CeAlO4 (●), and Al2O4 toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO4 (●) with C4H10 to form the CeAlO4H●C4H9 (●) encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of AlxOy∕MmOn or MmOn∕AlxOy materials are proposed consistent with the presented experimental and theoretical results.

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Synthesis and Structures of Air‐Stable Binuclear Hafnocene Perfluorobutanesulfonate and Perfluorobenzenesulfonate and their Catalytic Application in CC Bond‐Forming Reactions

Zhang

et al. 2013

Adv Synth Catal

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The two air‐stable μ2‐hydroxy‐bridged binuclear hafnocene perfluorobutanesulfonate and perfluorobenzenesulfonate complexes were successfully synthesized. The high catalytic activity and recyclability of these complexes were exemplified for various carbon‐carbon bond formation reactions. Compared with our previously reported hafnocene perfluorooctanesulfonate, these complexes show stronger Lewis acidity and better catalytic activity, and should find broad applications in organic synthesis.magnified image

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Catalytic Redox Reactions in the CO/N₂O System Mediated by the Bimetallic Oxide‐Cluster Couple AlVO₃⁺/AlVO₄⁺

Cited by 65 publications

References 90 publications

Catalytic CO Oxidation on Single Pt-Atom Doped Aluminum Oxide Clusters: Electronegativity-Ladder Effect

Catalytic CO Oxidation on Single Pt-Atom Doped Aluminum Oxide Clusters: Electronegativity-Ladder Effect

Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C–H bond activation

Synthesis and Structures of Air‐Stable Binuclear Hafnocene Perfluorobutanesulfonate and Perfluorobenzenesulfonate and their Catalytic Application in CC Bond‐Forming Reactions

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