H2 Oxidation Mediated by Au1-Doped Vanadium Oxide Cluster Cation AuV2O5+: A Comparative Study with AuCe2O4+

Zhang, Yan; Li, Ziyu; Zhao, Yan‐Xia; Li, Haifang; Ding, Xun‐Lei; Zhang, Huayong; He, Sheng‐Gui

doi:10.1021/acs.jpca.7b02435

Cited by 6 publications

(2 citation statements)

References 62 publications

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“…The pseudo-first-order rate constant ( k 1 ) for the reaction of NiAl 3 O 6 + ( A ) with CH 4 contributing to P1 and P2 is estimated to be 1.8 × 10 –10 cm 3 s –1 molecule –1 , which is very close to the k 1 (1.1 × 10 –10 cm 3 s –1 molecule –1 ) of NiAl 3 O 6 + ( B ) reacting with CH 4 to form P3 and P4 . The reaction efficiencies (Φ = k 1 / k coll ) are estimated as 18 and 12%, respectively. The kinetic isotope effects (KIE = k 1,CH4 / k 1,CD4 ) amount to 1.5 for NiAl 3 O 6 + (A) and 1.4 for NiAl 3 O 6 + (B).…”

Section: Resultsmentioning

confidence: 99%

Thermal Reactions of NiAl₃O₆⁺ and Al₄O₆⁺ with Methane: Reactivity Enhancement by Doping

Sun,

Wei,

Yang

et al. 2024

J. Phys. Chem. A

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Investigation of the reactivity of heteronuclear metal oxide clusters is an important way to uncover the molecular-level mechanisms of the doping effect. Herein, we performed a comparative study on the reactions of CH 4 with NiAl 3 O 6 + and Al 4 O 6 + cluster cations at room temperature to understand the role of Ni during the activation and transformation of methane. Mass spectrometric experiments identify that both NiAl 3 O 6 + and Al 4 O 6 + could bring about hydrogen atom abstraction reaction to generate CH 3 • radical; however, only NiAl 3 O 6 + has the potential to stabilize [CH 3 ] moiety and then transform [CH 3 ] to CH 2 O. Density functional theory calculations demonstrate that the terminal oxygen radicals (O t −• ) bound to Al act as the reactive sites for the two clusters to activate the first C−H bond. Although the Ni atom cannot directly participate in methane activation, it can manipulate the electronic environment of the surrounding bridging oxygen atoms (O b ) and enable such O b to function as an electron reservoir to help O t −• oxidize CH 4 to [H−O−CH 3 ]. The facile reduction of Ni 3+ to Ni + also facilitates the subsequent step of activating the second C−H bond by the bridging "lattice oxygen" (O b 2− ), finally enabling the oxidation of methane into formaldehyde. The important role of the dopant Ni played in improving the product selectivity of CH 2 O for methane conversion discovered in this study allows us to have a possible molecule-level understanding of the excellent performance of the catalysts doping with nickel.

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Section: Resultsmentioning

confidence: 99%

Thermal Reactions of NiAl₃O₆⁺ and Al₄O₆⁺ with Methane: Reactivity Enhancement by Doping

Sun,

Wei,

Yang

et al. 2024

J. Phys. Chem. A

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“…The molecular interactions of H 2 with metal oxide species serve as the simplified models for elucidating the H 2 activation mechanism in relevant catalytic or corrosion processes. Extensive investigations have been conducted employing mass spectrometry or matrix-isolation infrared spectroscopy on the reactions between H 2 and transition metal oxide cations or neutral species. − For instance, MnO, FeO, TaO, CrO 2 , VO 2 , NbO 2 , TaO 2 , and TaO 4 molecules have exhibited the capacity to catalyze the heterolytic cleavage of H 2 via either spontaneous or photoinduced processes. − The H 2 elimination in these reactions leads to the formation of both a metal–H bond and a metal–OH bond.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic and Theoretical Insights into H₂ Activation on Uranium Monoxide: Homolytic H₂ Cleavage Mediated by Intermediate OU(η²-H₂)

Pu,

Fu,

Qin

et al. 2024

Inorg. Chem.

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Elucidating molecular-level interactions between dihydrogen (H 2 ) and uranium oxides reveals fundamental insights into the intrinsic H 2 activation mechanisms underlying processes such as heterogeneous catalysis over uranium oxides and corrosion of uranium induced by H 2 . Herein, the reactions of H 2 with uranium monoxide (UO) molecules have been investigated via a combination of matrix-isolation infrared spectroscopy and quantum chemical calculations. A side-on bonded H 2 complex, OU(η 2 -H 2 ), is identified at 3733.7 and 800.3 cm −1 . This species is regarded as a crucial intermediate along H 2 activation pathways. Bonding analysis reveals cooperative U(π 5f/6d ) → H 2 (σ*) π // backdonation and U ← H 2 (σ) σ donation in OU(η 2 -H 2 ) that facilitate the activation of the H 2 moiety. Upon λ > 550 nm photoirradiation, OU(η 2 -H 2 ) isomerizes into H 2 UO, indicating the homolytic H 2 cleavage on UO. Mechanistic details of H 2 adsorption and dissociation on UO molecules have been further elucidated.

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H2 dissociation by Au1-doped closed-shell titanium oxide cluster anions

Jiang

et al. 2018

Chinese Journal of Chemical Physics

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Dissociation of molecular hydrogen (H 2) is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H 2 dissociation by Au 1-doped closed-shell titanium oxide cluster anions AuTi 3 O 7 − and AuTi 3 O 8 − has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and massselected to react with H 2 in an ion trap reactor. In the reaction of AuTi 3 O 8 − with H 2 , the ion pair Au + −O 2 2− rather than Au + −O 2− is the active site to promote H 2 dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H 2 dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H 2 activation and dissociation.

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H₂ Oxidation Mediated by Au₁-Doped Vanadium Oxide Cluster Cation AuV₂O₅⁺: A Comparative Study with AuCe₂O₄⁺

Cited by 6 publications

References 62 publications

Thermal Reactions of NiAl₃O₆⁺ and Al₄O₆⁺ with Methane: Reactivity Enhancement by Doping

Thermal Reactions of NiAl₃O₆⁺ and Al₄O₆⁺ with Methane: Reactivity Enhancement by Doping

Spectroscopic and Theoretical Insights into H₂ Activation on Uranium Monoxide: Homolytic H₂ Cleavage Mediated by Intermediate OU(η²-H₂)

H2 dissociation by Au1-doped closed-shell titanium oxide cluster anions

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H2 Oxidation Mediated by Au1-Doped Vanadium Oxide Cluster Cation AuV2O5+: A Comparative Study with AuCe2O4+

Cited by 6 publications

References 62 publications

Thermal Reactions of NiAl3O6+ and Al4O6+ with Methane: Reactivity Enhancement by Doping

Thermal Reactions of NiAl3O6+ and Al4O6+ with Methane: Reactivity Enhancement by Doping

Spectroscopic and Theoretical Insights into H2 Activation on Uranium Monoxide: Homolytic H2 Cleavage Mediated by Intermediate OU(η2-H2)

H2 dissociation by Au1-doped closed-shell titanium oxide cluster anions

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H₂ Oxidation Mediated by Au₁-Doped Vanadium Oxide Cluster Cation AuV₂O₅⁺: A Comparative Study with AuCe₂O₄⁺

Thermal Reactions of NiAl₃O₆⁺ and Al₄O₆⁺ with Methane: Reactivity Enhancement by Doping

Thermal Reactions of NiAl₃O₆⁺ and Al₄O₆⁺ with Methane: Reactivity Enhancement by Doping

Spectroscopic and Theoretical Insights into H₂ Activation on Uranium Monoxide: Homolytic H₂ Cleavage Mediated by Intermediate OU(η²-H₂)