Controlled Formation of Fused Metal Chalcogenide Nanoclusters Using Soft Landing of Gaseous Fragment Ions

Gholipour-Ranjbar, Habib; Samayoa-Oviedo, Hugo Y.; Laskin, Julia

doi:10.1021/acsnano.3c05545

“…It should be noted that neutralization of deposited cations via electron transfer from the surface was shown in the case of metal containing cations deposited in higher coverages on FSAM. [14,43] However, a molecular neutralization of the deposited 2 b + prior to reaction with 6 + can be ruled out in our case, since addition of an electron to the quaternary ammonium ion would lead to an unstable hypervalent nitrogen radical, which would immediately decompose and the observed products could not form.…”

Section: Methodsmentioning

confidence: 77%

“…[7][8][9][10][11] Complementary, ion soft-landing of reactive intermediates is a powerful technique to control reactions on surfaces that are not possible in solution or in the bulk solid phase. [12][13][14] Reactive ions, including fragment ions generated by excitation and fragmentation in the gas phase, can be selected by their mass-to-charge ratio and deposited with low kinetic energy onto a surface. [15] Also, synthesis of new compounds using the products of ion molecule reactions in the gas phase has recently been shown.…”

Section: Introductionmentioning

confidence: 99%

Control of Intermediates and Products by Combining Droplet Reactions and Ion Soft‐Landing

Yang,

Urban,

Lorenz

et al. 2023

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Despite being recognized primarily as an analytical technique, mass spectrometry also has a large potential as a synthetic tool, enabling access to advanced synthetic routes by reactions in charged microdroplets or ionic thin layers. Such reactions are special and proceed primarily at surfaces of droplets and thin layers. Partial solvation of the reactants is usually considered to play an important role for reducing the activation barrier, but many mechanistic details still need to be clarified. In our study, we showcase the synergy between two sequentially applied "preparative mass spectrometry" methods: initiating accelerated reactions within microdroplets during electrospray ionization to generate gaseous ionic intermediates in high abundance, which are subsequently mass‐selected and soft‐landed to react with a provided reagent on a substrate. This allows the generation of products at a nanomolar scale, amenable to further characterization. In this proof‐of‐concept study, the contrasting reaction pathways between intrinsically neutral and pre‐charged reagents, respectively, both in microdroplets and in layers generated by ion soft‐landing are investigated. This provides new insights into the role of partially solvated reagents at microdroplet surfaces for increased reaction rates. Additionally, further insights into reactions of ions of the same polarity under various conditions is obtained.

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“…Im ersten Experiment wurden 6.25×10 13 Neutralisierung der deponierten Kationen durch Elektronenübertragung von der Oberfläche im Fall von metallhaltigen Kationen, die in höheren Bedeckungen auf FSAM deponiert wurden, nachgewiesen wurde. [14,43]…”

Section: Ergebnisse Und Diskussionunclassified

“…Dies zeigt, dass 7 b + in einer Kation‐Kation‐Reaktion von 2 b + und 6 + auf der geerdeten Oberfläche gebildet werden kann. Es ist anzumerken, dass die Neutralisierung der deponierten Kationen durch Elektronenübertragung von der Oberfläche im Fall von metallhaltigen Kationen, die in höheren Bedeckungen auf FSAM deponiert wurden, nachgewiesen wurde [14,43] . Eine molekulare Neutralisation des deponierten 2 b + vor der Reaktion mit 6 + kann in unserem Fall jedoch ausgeschlossen werden, da die Anlagerung eines Elektrons an das quaternäre Ammoniumion zu einem instabilen hypervalenten Stickstoffradikal führen würde, das sich sofort zersetzen würde und nicht die beobachteten Produkte bilden könnte.…”

Section: Ergebnisse Und Diskussionunclassified

“…[7][8][9][10][11] Ergänzend dazu ist das "Ion Soft-landing" reaktiver Zwischenprodukte eine leistungsstarke Technik zur Steuerung von Reaktionen auf Oberflächen, die in Lösung oder in der festen Phase nicht möglich sind. [12][13][14] Reaktive Ionen, einschließlich der durch Anregung und Fragmentierung in der Gasphase erzeugten Fragment-Ionen, können anhand Weitere Einzelheiten sind dem Text und der einschlägigen Literatur zu entnehmen. [17] ihres Masse-zu-Ladungsverhältnisses ausgewählt und mit geringer kinetischer Energie auf einer Oberfläche deponiert werden.…”

Section: Introductionunclassified

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Kontrolle von Intermediaten und Endprodukten durch Kombination von Tröpfchenreaktionen und “Ion Soft‐landing”

Yang,

Urban,

Lorenz

et al. 2023

Angewandte Chemie

0

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Despite being recognized primarily as an analytical technique, mass spectrometry also has a large potential as a synthetic tool, enabling access to advanced synthetic routes by reactions in charged microdroplets or ionic thin layers. Such reactions are special and proceed primarily at surfaces of droplets and thin layers. Partial solvation of the reactants is usually considered to play an important role for reducing the activation barrier, but many mechanistic details still need to be clarified. In our study, we showcase the synergy between two sequentially applied "preparative mass spectrometry" methods: initiating accelerated reactions within microdroplets during electrospray ionization to generate gaseous ionic intermediates in high abundance, which are subsequently mass‐selected and soft‐landed to react with a provided reagent on a substrate. This allows the generation of products at a nanomolar scale, amenable to further characterization. In this proof‐of‐concept study, the contrasting reaction pathways between intrinsically neutral and pre‐charged reagents, respectively, both in microdroplets and in layers generated by ion soft‐landing are investigated. This provides new insights into the role of partially solvated reagents at microdroplet surfaces for increased reaction rates. Additionally, further insights into reactions of ions of the same polarity under various conditions is obtained.

show abstract

Controlled Formation of Nanoribbons and Their Heterostructures via Assembly of Mass‐Selected Inorganic Ions

Zhang,

Srot,

Wu

et al. 2024

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Control of nanomaterial dimensions with atomic precision through synthetic methods is essential to understanding and engineering of nanomaterials. For single‐layer inorganic materials, size and shape controls have been achieved by self‐assembly and surface‐catalyzed reactions of building blocks deposited at a surface. However, the scope of nanostructures accessible by such approach is restricted by the limited choice of building blocks that can be thermally evaporated onto surfaces, such as atoms or thermostable molecules. Herein this limitation is bypassed by using mass‐selected molecular ions obtained via electrospray ionization as building blocks to synthesize nanostructures that are inaccessible by conventional evaporation methods. As the first example, micron‐scale production of MoS2 and WS2 nanoribbons and their heterostructures on graphene are shown by the self‐assembly of asymmetrically shaped building blocks obtained from the electrospray. It is expected that judicious use of electrospray‐generated building blocks would unlock access to previously inaccessible inorganic nanostructures.

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Controlled Formation of Fused Metal Chalcogenide Nanoclusters Using Soft Landing of Gaseous Fragment Ions

Cited by 12 publications

References 56 publications

Control of Intermediates and Products by Combining Droplet Reactions and Ion Soft‐Landing

Control of Intermediates and Products by Combining Droplet Reactions and Ion Soft‐Landing

Kontrolle von Intermediaten und Endprodukten durch Kombination von Tröpfchenreaktionen und “Ion Soft‐landing”

Controlled Formation of Nanoribbons and Their Heterostructures via Assembly of Mass‐Selected Inorganic Ions

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