On the Origin of the Surprisingly Sluggish Redox Reaction of the N2O/CO Couple Mediated by [Y2O2]+. and [YAlO2]+. Cluster Ions in the Gas Phase

Ma, Jianzhong; Wang, Zhe‐Chen; Schlangen, Maria; He, Sheng‐Gui; Schwarz, Helmut

doi:10.1002/anie.201208559

Cited by 58 publications

(55 citation statements)

References 74 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 catalytic ability of di-nuclear yttrium oxides clusters Y 2 O 3 + c and YAlO 3 + c for CO/N 2 O couple also have been studied by He and co-workers. 11 The oxidation of CO with Y 2 O 3 + c is impeded by an energy barrier. As one yttrium atom of Y 2 O 3 + c was replaced by one aluminum atom, the oxygen radical center was generated leading to the reaction barrier-less.…”

Section: Comparison With Di-nuclear Yttrium Oxide Clustersmentioning

confidence: 99%

“…[34][35][36][37][38] The previous study has pointed out that the YAlO 3 + c cluster contains oxygen radical center and shows better reactivity than homonuclear yttrium oxide cluster Y 2 O 3 + c in CO oxidation. 11 Recently, the terminal oxygen radical was also found in the neutral Y 3 O 5 cluster. 38 In this work, we present our theoretical study on CO oxidations by neutral Y 2 MO 5 (M ¼ Y, Al) clusters employing density functional calculations.…”

Section: Introductionmentioning

confidence: 99%

Catalytic oxidation of CO by N₂O on neutral Y₂MO₅ (M = Y, Al) clusters: a density functional theory study

Fang

et al. 2015

RSC Adv.

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Density functional theory (DFT) calculations are employed to investigate the full catalytic cycle of CO oxidation by N 2 O on yttrium oxide clusters Y 2 MO 5 (M ¼ Y, Al) in the gas-phase. Extensive structural searches show that both the ground-state structures of Y 3 O 5 and Y 2 AlO 5 contain an oxygen radical (O t c)which plays an important role in CO oxidation. Energy profiles are calculated to determine the reaction mechanisms. Molecular electrostatic potential maps (MEPs) and natural bond orbital (NBO) analyses are employed to rationalize the reaction mechanisms. The results indicate that the whole catalytic cycle for the reaction CO + N 2 O / CO 2 + N 2 , conducted by yttrium oxide clusters Y 2 MO 5 (M ¼ Y, Al), is favored both thermodynamically and kinetically. Moreover, compared with the previous report on di-nuclear YAlO 3 + c and Y 2 O 3 + c, it's obvious we can conclude that tri-nuclear Y 3 O 5 and Y 2 AlO 5 exhibit greatly enhanced catalytic activity toward CO/N 2 O couples.

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“…65,125 Studies of BONC ions are becom-ing increasingly widespread: e.g., AuNbO 3 [138][139][140] and AlYO 3 + . 89,141 All the above systems are charged BONCs. Our group has extended BONC studies to neutral systems: in particular, neutral V x Co y O z BONCs are generated in the gas phase and their reactivity toward CO is determined.…”

Section: Introductionmentioning

confidence: 99%

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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On the Origin of the Surprisingly Sluggish Redox Reaction of the N₂O/CO Couple Mediated by [Y₂O₂]^+. and [YAlO₂]^+. Cluster Ions in the Gas Phase

Cited by 58 publications

References 74 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

Catalytic oxidation of CO by N₂O on neutral Y₂MO₅ (M = Y, Al) clusters: a density functional theory study

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

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On the Origin of the Surprisingly Sluggish Redox Reaction of the N2O/CO Couple Mediated by [Y2O2]+. and [YAlO2]+. Cluster Ions in the Gas Phase

Cited by 58 publications

References 74 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

Catalytic oxidation of CO by N2O on neutral Y2MO5 (M = Y, Al) clusters: a density functional theory study

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

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On the Origin of the Surprisingly Sluggish Redox Reaction of the N₂O/CO Couple Mediated by [Y₂O₂]^+. and [YAlO₂]^+. Cluster Ions in the Gas Phase

Catalytic oxidation of CO by N₂O on neutral Y₂MO₅ (M = Y, Al) clusters: a density functional theory study