Vacuum Ultraviolet Photoionization Studies of PtCH2 and H‐Pt‐CH3: A Potential Energy Surface for the Pt+CH4 Reaction

Perera, Manori; Metz, Ricardo B.; Kostko, Oleg; Ahmed, Musahid

doi:10.1002/ange.201207931

Cited by 9 publications

(5 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Platinum has been extensively studied for methane activation. The neutral, cationic, and anionic Pt atomic and cluster species Pt n (n = 1-24), [24] Pt n + (n = 1-21), [23,25] and Pt n À (n = 2- 5,7,11,12) [23,25] all can activate methane in the gas phase, for example: [26,27] Pt q þ CH 4 ! ½HPtCH 3 q ð2aÞ…”

mentioning

confidence: 99%

“…Methane activation by free Pt atom and Pt + ion [Reaction (2)] was extensively studied [26,27] and it has been recently realized that the neutral (Pt) and cationic (Pt + ) reaction systems follow a similar mechanism, in which the oxidative addition of one CÀH bond to Pt atom [Reaction (2a)] is facile (barrierless for Pt and a tiny barrier for Pt + ). [27d] The natural charge on the Pt atom in PtAl 2 O 4 À is only À0.06 j e j , so the PtAl 2 O 4 À cluster can be considered to be composed of a neutral Pt atom and a "support" cluster anion (Al 2 O 4 À ).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

et al. 2014

View full text Add to dashboard Cite

Identification and mechanistic study of thermal methane conversion mediated by gas-phase species is important for finding potentially useful routes for direct methane transformation under mild conditions. Negatively charged oxide species are usually inert with methane. This work reports an unexpected result that the bi-metallic oxide cluster anions PtAl2 O4 (-) can transform methane into a stable organic compound, formaldehyde, with high selectivity. The clusters are prepared by laser ablation and reacted with CH4 in an ion trap reactor. The reaction is characterized by mass spectrometry and density functional theory calculations. It is found that platinum rather than oxygen activates CH4 at the beginning of the reaction. The Al2 O4 (-) moiety serves as the support of Pt atom and plays important roles in the late stage of the reaction. A new mechanism for selective methane conversion is provided and new insights into the surface chemistry of single Pt atoms may be obtained from this study.

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

et al. 2014

View full text Add to dashboard Cite

show abstract

“…The neutral, cationic, and anionic Pt atomic and cluster species Pt n (n = 1-24), [24] Pt n + (n = 1-21), [23,25] and Pt n À (n = 2- 5,7,11,12) [23,25] all can activate methane in the gas phase, for example: [26,27] Pt q þ CH 4 ! The neutral, cationic, and anionic Pt atomic and cluster species Pt n (n = 1-24), [24] Pt n + (n = 1-21), [23,25] and Pt n À (n = 2- 5,7,11,12) [23,25] all can activate methane in the gas phase, for example: [26,27] Pt q þ CH 4 !…”

mentioning

confidence: 99%

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

Zhao

Yuan

et al. 2014

Angewandte Chemie

View full text Add to dashboard Cite

Identification and mechanistic study of thermal methane conversion mediated by gas-phase species is important for finding potentially useful routes for direct methane transformation under mild conditions. Negatively charged oxide species are usually inert with methane. This work reports an unexpected result that the bi-metallic oxide cluster anions PtAl 2 O 4 À can transform methane into a stable organic compound, formaldehyde, with high selectivity. The clusters are prepared by laser ablation and reacted with CH 4 in an ion trap reactor. The reaction is characterized by mass spectrometry and density functional theory calculations. It is found that platinum rather than oxygen activates CH 4 at the beginning of the reaction. The Al 2 O 4 À moiety serves as the support of Pt atom and plays important roles in the late stage of the reaction. A new mechanism for selective methane conversion is provided and new insights into the surface chemistry of single Pt atoms may be obtained from this study.

show abstract

“…These molecules are challenging to describe with electronic structure theory due to the number of unpaired electrons and many low-lying electronic states (often having different electron spin states), as well as the difficulty of accurately treating electron correlation and Combination of the photoionization results with guided ion beam measurements of the Pt + + CH4 potential energy surface (102) allowed for a derivation of a potential energy surface for the neutral reaction ( Figure 5(b)). IE(H-Pt-CH3)=8.89±0.03 eV and IE(PtCH2)=8.78 ±0.03 eV were determined for species formed by reacting laser-ablated Pt with methane (103). This reveals that formation of H-Pt-CH3 is 164 kJ/mol exoergic, and the overall reaction is only 9 kJ/mol endoergic.…”

Section: Transition Metal Oxides and Carbidesmentioning

confidence: 99%

Vacuum Ultraviolet Photoionization of Complex Chemical Systems

Kostko

Bandyopadhyay²,

Ahmed

2016

Annu. Rev. Phys. Chem.

Self Cite

View full text Add to dashboard Cite

Tunable vacuum ultraviolet (VUV) radiation coupled to mass spectrometry is applied to the study of complex chemical systems. The identification of novel reactive intermediates and radicals is revealed in flame, pulsed photolysis, and pyrolysis reactors, leading to the elucidation of spectroscopy, reaction mechanisms, and kinetics. Mass-resolved threshold photoelectron photoion coincidence measurements provide unprecedented access to vibrationally resolved spectra of free radicals present in high-temperature reactors. Photoionization measurements in water clusters, nucleic acid base dimers, and their complexes with water provide signatures of proton transfer in hydrogen-bonded and π-stacked systems. Experimental and theoretical methods to track ion-molecule reactions and fragmentation pathways in intermolecular and intramolecular hydrogen-bonded systems in sugars and alcohols are described. Photoionization of laser-ablated molecules, clusters, and their reaction products inform thermodynamics and spectroscopy that are relevant to astrochemistry and catalysis. New directions in coupling VUV radiation to interrogate complex chemical systems are discussed.

show abstract

Vacuum Ultraviolet Photoionization Studies of PtCH₂ and H‐Pt‐CH₃: A Potential Energy Surface for the Pt+CH₄ Reaction

Cited by 9 publications

References 28 publications

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

Vacuum Ultraviolet Photoionization of Complex Chemical Systems

Contact Info

Product

Resources

About

Vacuum Ultraviolet Photoionization Studies of PtCH2 and H‐Pt‐CH3: A Potential Energy Surface for the Pt+CH4 Reaction

Cited by 9 publications

References 28 publications

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl2O4− Cluster Anions

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl2O4− Cluster Anions

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl2O4− Cluster Anions

Vacuum Ultraviolet Photoionization of Complex Chemical Systems

Contact Info

Product

Resources

About

Vacuum Ultraviolet Photoionization Studies of PtCH₂ and H‐Pt‐CH₃: A Potential Energy Surface for the Pt+CH₄ Reaction

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions

Thermal Methane Conversion to Formaldehyde Promoted by Single Platinum Atoms in PtAl₂O₄⁻ Cluster Anions