Fourier transform ion cyclotron resonance studies of sputtered metal cluster ions: The chemistry of Cun+ with O2

Irion, Manfred P.; Selinger, A.

doi:10.1016/0009-2614(89)87309-9

Cited by 42 publications

(26 citation statements)

References 22 publications

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“…[14] The bias of copper and silver against high oxidation states also accounts for the lack of reactivity of Cu 2 + and Ag 2 + toward O 2 . [12,15] The efficiency of cluster degradation decreases when changing M from Cu to Ag and completely vanishes for Au (Table 1). [7] Presumably, the high ionization energy of gold, IE(Au) = 9.23 eV, strongly disfavors the generation of Au + in comparison to Cu + and Ag + (IE(Cu) = 7.73 and IE(Ag) = 7.58 eV).…”

Section: Dedicated To Professor Lutz F Tietzementioning

confidence: 93%

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM⁺

2003

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The activation and functionalization of methane constitute continuing challenges for catalysis. One example of their industrial realization is given by the Degussa process for the large-scale production of hydrogen cyanide from methane and ammonia using platinum as heterogeneous catalyst [Eq. (1)].Our aim is the development of a gas-phase model for this process that may enhance the current mechanistic knowledge [1,2] and thus ultimately contribute to rational catalyst improvement. So far, atomic Pt + , homonuclear clusters Pt m + as well as small heteronuclear clusters Pt m Au n + ions have been studied. [3][4][5][6][7] Whereas all the homonuclear Pt m + clusters investigated achieve CH 4 activation in the first reaction step, [8,9] the C À N coupling of the resulting carbene species Pt m CH 2 + with NH 3 only works for m = 1. [3][4][5] In contrast, the dinuclear cluster mediates CÀN bond formation if one platinum atom is replaced by a gold atom.[6] This finding was ascribed to a particularly well-balanced binding situation in the PtAuCH 2 + species. The bonding is strong enough to afford spontaneous activation of CH 4 on the one hand but does not prevent the CH 2 fragment from coupling with NH 3 on the other.[6] Recent results have shown, however, that the larger bimetallic Pt m Au n + clusters do not mediate the coupling step between the CH 2 moiety and NH 3 , thus pointing to special features of PtAu + . [10] To further elucidate the remarkable role of the second metal in the dinuclear cluster, we have extended our studies to PtCu + and PtAg + . The change from gold to its lighter congeners copper and silver is straightforward in view of their electronic and chemical similarities (note, however, that gold is distinguished from both copper and silver by the operation of much stronger relativistic effects [11] ). As with PtAu + , the reactions with CH 4 , O 2 , and NH 3 are investigated; for comparison, the reactivities of Cu 2 + and Ag 2 + are included

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Section: Dedicated To Professor Lutz F Tietzementioning

confidence: 93%

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM⁺

2003

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“…Furthermore, through a piezoelectric valve mounted close-by, neon is pulsed in to a maximum of about 10-4 mbar, taking away any remaining energy. There is evidence that by the time their reactions are being studied, cluster ions have in fact achieved room temperature [6,10]. By the application of an RF ejection pulse, single sizes may be selected.…”

Section: Methodsmentioning

confidence: 99%

FTMS studies of sputtered metal cluster ions (IV): size-selective effects in the chemistry of Fe+ n with NH3 and Pd+ n with D2 or C2H4

Irion

Selinger

Schnabel

1991

Z Phys D - Atoms, Molecules and Clusters

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Abstract. Fe, + and Pd, + clusters up to n = 19 and n = 25, respectively, are produced in an external ion source by sputtering of the respective metal foils with Xe ÷ primary ions at 20 keV. They are transferred to the ICR cell of a home-built Fourier transform mass spectrometer, where they are thermalized to nearly room temperature and stored for several tens of seconds. During this time, their reactions with a gas leaked in at low level are studied. Thus in the presence of ammonia, most Fe, + clusters react by simply adsorbing intact NH a molecules. Only Fe~ ions show dehydrogenation/adsorption to Fe4(NH)~ + intermediates (m = 1, 2) that in a complex scheme go on adsorbing complete NH3 units. To clarify the reaction scheme, one has to isolate each species in the ion cell, which often requires the ejection of ions very close in mass. This led to the development of a special isolation technique that avoids the use of isotopicatly pure metal sampies. Pd,, + cluster ions (n = 2...9) dehydrogenate C2H4 in general to yield Pd,(C2Hz) +, yet Pd~" appear totally unreactive. Towards D2, Pd~-ions seem inert, whereas Pd~-adsorb up to two molecules.

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“…Due to the fact, that clusters are of great relevance for fundamental research and due to the progress made by experimentalists and theoreticians during the last few years, the study of clusters has become an increasingly active area in physics and physical chemistry [1][2][3][4][5][6][7][8][9][10][11]. Clusters are of great technological importance as well, and they seem to be almost ubiquitous in materials science and chemistry.…”

Section: A Brief Survey Of Clustersmentioning

confidence: 99%

“…The LIF-method enables detection of NH(a) depletion, NH(X) production and of the chemical products. NH is isoelectronic with carbene (CH 2 ) and oxygen atoms (0) and thus a comparison of its reactions with those of CH 2 and 0 is possible.…”

Section: Introductionmentioning

confidence: 99%

“…Its elementary reactions are problems, which can be attacked from both the theoretical and experimental sides. The first excited state (a 1.1) of NH has a long lifetime (To = 1.7 s) [2,3] due to the forbidden transition to the electronic ground state (X 3L -). The first excited state (a1.1) and the electronic ground state eL-) can be detected by laser-induced fluorescence (LIF) with high sensitivity.…”

Section: Introductionmentioning

confidence: 99%

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Reactivity and Electronic Structures of Isolated Clusters

Rademann¹

1990

Ber Bunsenges Phys Chem

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Some aspects of recent advances in the study of isolated clusters and their size dependent properties are reviewed. Reliable techniques for cluster generation and detection are briefly discussed. Methods for studying physical properties and electronic structures of isolated clusters and cluster ions are addressed in the context of relevant fundamental questions. Progress concerned with the exploration of solvated organic clusters, the interrogation of transition metal cluster reactivities and the investigation of electronic structures of metal clusters is documented by selected examples. In some cases, relations between isolated cluster properties and condensed phase behaviour are indicated.

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Fourier transform ion cyclotron resonance studies of sputtered metal cluster ions: The chemistry of Cun+ with O2

Cited by 42 publications

References 22 publications

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM⁺

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM⁺

FTMS studies of sputtered metal cluster ions (IV): size-selective effects in the chemistry of Fe+ n with NH3 and Pd+ n with D2 or C2H4

Reactivity and Electronic Structures of Isolated Clusters

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Fourier transform ion cyclotron resonance studies of sputtered metal cluster ions: The chemistry of Cun+ with O2

Cited by 42 publications

References 22 publications

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM+

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM+

FTMS studies of sputtered metal cluster ions (IV): size-selective effects in the chemistry of Fe+ n with NH3 and Pd+ n with D2 or C2H4

Reactivity and Electronic Structures of Isolated Clusters

Contact Info

Product

Resources

About

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM⁺

Coupling of Methane and Ammonia by Dinuclear Bimetallic Platinum–Coinage‐Metal Cations PtM⁺