Conversion of Methane to Methanol: Nickel, Palladium, and Platinum (d<sup>9</sup>) Cations as Catalysts for the Oxidation of Methane by Ozone at Room Temperature

Božović, Andrea; Feil, S.; Koyanagi, Gregory K.; Viggiano, Albert A.; Zhang, Xinhao; Schlangen, Maria; Schwarz, Helmut; Böhme, Diethard K.

doi:10.1002/chem.201000627

Cited by 93 publications

(49 citation statements)

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“…The genuine gas‐phase catalytic oxidation CH 4 →CH 3 OH by MO + was realized quite some time ago for FeO + 34a and, more recently, for NiO + and PdO + 67. On the basis of computational and experimental studies, it was shown that NiO + , owing to its easy availability and high selectivity, is a rather promising candidate, and experiments that use NiO‐ or FeO‐doped zeolites as catalyst for the oxygenation of CH 4 under ambient conditions are also encouraged by computational and (for iron and copper) experimental investigations 68…”

Section: The Conversion Of Methane To Methanol: a Long‐time Conundmentioning

confidence: 99%

Chemistry with Methane: Concepts Rather than Recipes

2011

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Four seemingly simple transformations related to the chemistry of methane will be addressed from mechanistic and conceptual points of view: 1) metal-mediated dehydrogenation to form metal carbene complexes, 2) the hydrogen-atom abstraction step in the oxidative dimerization of methane, 3) the mechanisms of the CH(4)→CH(3)OH conversion, and 4) the initial bond scission (C-H vs. O-H) as well as the rate-limiting step in the selective CH(3)OH→CH(2)O oxidation. State-of-the-art gas-phase experiments, in conjunction with electronic-structure calculations, permit identification of the elementary reactions at a molecular level and thus allow us to unravel detailed mechanistic aspects. Where appropriate, these results are compared with findings from related studies in solution or on surfaces.

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Section: The Conversion Of Methane To Methanol: a Long‐time Conundmentioning

confidence: 99%

Chemistry with Methane: Concepts Rather than Recipes

2011

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“…2d, 4, 12, 20 For example, MO . + can be generated through the oxidation of M + by, for example, O 3 ,21 N 2 O,22, 23 and other terminal oxygen sources, and Fourier transform ion‐cyclotron resonance (FTICR) mass spectrometry has often been employed to perform the IMRs 24. To achieve an efficient conversion of M + to MO .…”

Section: Resultsmentioning

confidence: 99%

Thermal Activation of Methane and Ethene by Bare MO^.+ (M=Ge, Sn, and Pb): A Combined Theoretical/Experimental Study

Chen

Wang

Schlangen

et al. 2011

Chemistry A European J

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The thermal ion/molecule reactions (IMRs) of the Group 14 metal oxide radical cations MO(·+) (M=Ge, Sn, Pb) with methane and ethene were investigated. For the MO(·+)/CH(4) couples abstraction of a hydrogen atom to form MOH(+) and a methyl radical constitutes the sole channel. The nearly barrier-free process, combined with a large exothermicity as revealed by density functional theory (DFT) calculations, suggests a fast and efficient reaction in agreement with the experiment. For the IMR of MO(·+) with ethene, two competitive channels exist: hydrogen-atom abstraction (HAA) from and oxygen-atom transfer (OAT) to the organic substrate. The HAA channel, yielding C(2)H(3·) and MOH(+) predominates for the GeO(·+)/ethene system, while for SnO(·+) and PbO(·+) the major reaction observed corresponds to the OAT producing M(+) and C(2)H(4)O. The DFT-derived potential-energy surfaces are consistent with the experimental findings. The behavior of the metal oxide cations towards ethene can be explained in terms of the bond dissociation energies (BDEs) of MO(+)-H and M(+)-O, which define the hydrogen-atom affinity of MO(+) and the oxophilicity of M(+), respectively. Since the differences among the BDEs(MO(+)-H) are rather small and the hydrogen-atom affinities of the three radical cations MO(·+) exceed the BDE(CH(3)H) and BDE(C(2)H(3)-H), hydrogen-atom abstraction is possible thermochemically. In contrast, the BDEs(M(+)-O) vary quite substantially; consequently, the OAT channel becomes energetically less favorable for GeO(·+) which exhibits the highest oxophilicity among these three group 14 metal ions.

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“…1930-1980, a golden age for ionic studies in vacuum. The selection of major subjects omits important topics such as development of ion/ion collisions, 27) the demonstration of catalytic reaction in the gas phase, 28) and the measurement of collision cross sections 29) and many others.…”

Section: Ion Chemistrymentioning

confidence: 99%

Through a Glass Darkly: Glimpses into the Future of Mass Spectrometry

Cooks

Mueller

2013

Mass Spectrometry

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The paper has three parts, (i) a brief overview of the main achievements made using mass spectrometry across all the fields of science, (ii) a survey of some of the topics currently being pursued most activity, including both applications and fundamental studies, and (iii) some hints as to what the future of mass spectrometry might hold with particular emphasis on revolutionary changes in the subject. Emphasis is given to ambient methods of ionization and their use in disease diagnosis and to their use in combination with miniature mass spectrometers for in-situ measurements. Special attention goes to the chemical aspects of mass spectrometry, including its emerging role as a preparative method based on accelerated bimolecular reaction rates in solution and on ion soft landing as a means of surface tailoring. In summary, the paper covers the proud history, vibrant present and expansive future of mass spectrometry.Keywords: ion chemistry, history of mass spectrometry, reaction rates, ion reactivity, mechanisms, instrumentation (Received October 12, 2012; Accepted October 16, 2012) Mass spectrometry may be defined, broadly, as the science and technology of ions. As such, it is a subject of enormous scope. The achievements of 20th century mass spectrometry now have come into focus. In rapid succession these include the measurement of mass/charge ratios of ions, 1) the discovery of isotopes, 2) and the utilization of isotope ratio measurements, 3) the measurements of mass defects, 4) and fundamental understanding of ionization, 5) fragmentation mechanisms 6) and the measurement of bond energies. 7) All this was achieved in the first half of the century and was made possible by advances in instrumentation including ionization methods, detectors and most importantly mass analyzers such as double focusing sector instruments. In the second half-century, organic mass spectrometry grew rapidly, starting with applications to petroleum distillates and moving quickly to natural products, steroids, and small-molecule drugs. 8) Gas chromatography/mass spectrometry was a key technology in early studies of biological systems. 9) Advances in instrumentation again fueled these advances, with ion optics becoming a significant scientific technology especially in Japan.10) A preoccupation with improving mass resolution and mass range became established and different types of mass analyzers were introduced for this purpose, including time-of-flight instruments 11) and quadrupole ion traps. 12) This quest drove biological mass spectrometry and propelled the development of ionization methods that were increasingly successful in handling both solid samples (desorption methods) 13)

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Conversion of Methane to Methanol: Nickel, Palladium, and Platinum (d⁹) Cations as Catalysts for the Oxidation of Methane by Ozone at Room Temperature

Cited by 93 publications

References 58 publications

Chemistry with Methane: Concepts Rather than Recipes

Chemistry with Methane: Concepts Rather than Recipes

Thermal Activation of Methane and Ethene by Bare MO^.+ (M=Ge, Sn, and Pb): A Combined Theoretical/Experimental Study

Through a Glass Darkly: Glimpses into the Future of Mass Spectrometry

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Conversion of Methane to Methanol: Nickel, Palladium, and Platinum (d9) Cations as Catalysts for the Oxidation of Methane by Ozone at Room Temperature

Cited by 93 publications

References 58 publications

Chemistry with Methane: Concepts Rather than Recipes

Chemistry with Methane: Concepts Rather than Recipes

Thermal Activation of Methane and Ethene by Bare MO.+ (M=Ge, Sn, and Pb): A Combined Theoretical/Experimental Study

Through a Glass Darkly: Glimpses into the Future of Mass Spectrometry

Contact Info

Product

Resources

About

Conversion of Methane to Methanol: Nickel, Palladium, and Platinum (d⁹) Cations as Catalysts for the Oxidation of Methane by Ozone at Room Temperature

Thermal Activation of Methane and Ethene by Bare MO^.+ (M=Ge, Sn, and Pb): A Combined Theoretical/Experimental Study