Laser-induced surface structuring is a promising method to suppress electron mulitpacting in the vacuum pipes of particle accelerators. Electrons are scattered inside the rough surface structure, resulting in a low Secondary Electron Yield (SEY) of the material. However, laser processing of internal pipe surfaces with a large aspect ratio is technologically challenging in terms of laser beam guidance and focusing.
View Article and Find Full Text PDFOver the last few years, there has been increasing interest in the use of amorphous carbon thin films with low secondary electron yield (SEY) to mitigate electron multipacting in particle accelerators and RF devices. Previous works found that the SEY increases with the amount of incorporated hydrogen and correlates with the Tauc gap. In this work, we analyse films produced by magnetron sputtering with different contents of hydrogen and deuterium incorporated via the target poisoning and sputtering of CD molecules.
View Article and Find Full Text PDFACS Appl Mater Interfaces
May 2021
Ammonia uptake by high-capacity and high-porosity sorbents is a promising approach to its storage and release, capture and mitigation, and chemical separation. Here, we examined the ammonia sorption behavior of several versions of an archetypal zirconium-based metal-organic framework (MOF) material, NU-1000-a meso- and microporous crystalline compound having the empirical formula (1,3,6,8-tetrakis(-benzoate)pyrene) Zr(μ-O)(μ-OH)(HO)(OH) with linkers and nodes arranged to satisfy a topology. Depending on the thermal treatment protocol used prior to sorption measurements, ammonia can physisorb to NU-1000 via hydrogen-bonding and London-dispersion interactions and chemisorb via Brønsted acid-base reactions with node-integrated proton donors (μ-hydroxos) and node-ligated proton donors (terminal hydroxos), via simple coordination at open Zr(IV) sites, or via dissociative coordination to Zr(IV) as NH and protonation of a node-based μ-oxo.
View Article and Find Full Text PDFAntimony telluride (SbTe) thin films were prepared by a room temperature Metal-Organic Chemical Vapor Deposition (MOCVD) process using antimony chloride (SbCl) and bis(trimethylsilyl)telluride (Te(SiMe)) as precursors. Pre-growth and post-growth treatments were found to be pivotal in favoring out-of-plane and in-plane alignment of the crystallites composing the films. A comprehensive suite of characterization techniques were used to evaluate their composition, surface roughness, as well as to assess their morphology, crystallinity, and structural features, revealing that a quick post-growth annealing triggers the formation of epitaxial-quality SbTe films on Si(111).
View Article and Find Full Text PDFEngendering electrical conductivity in otherwise insulating metal-organic framework (MOF) materials is key to rendering these materials fully functional for a range of potential applications, including electrochemical and photo-electrochemical catalysis. Here we report that the platform MOF, NU-1000, can be made electrically conductive via reversible electrochemical oxidation of a fraction of the framework's tetraphenylpyrene linkers, where the basis for conduction is redox hopping. At a microscopic level, redox hopping is akin to electron self-exchange and is describable by Marcus' well-known theory of electron transfer.
View Article and Find Full Text PDFAcid-catalyzed skeletal C-C bond isomerizations are important benchmark reactions for the petrochemical industries. Among those, o-xylene isomerization/disproportionation is a probe reaction for strong Brønsted acid catalysis, and it is also sensitive to the local acid site density and pore topology. Here, we report on the use of phosphotungstic acid (PTA) encapsulated within NU-1000, a Zr-based metal-organic framework (MOF), as a catalyst for o-xylene isomerization at 523 K.
View Article and Find Full Text PDFACS Appl Mater Interfaces
October 2017
Methyltrioxorhenium (ReOMe) is introduced as the first rhenium atomic layer deposition (ALD) precursor and used to grow rhenium-aluminum oxide thin films in combination with trimethylaluminum (TMA-AlMe). The growth rate of the smooth Re-Al oxide films, with general stoichiometry ReAlO, has been monitored by in situ quartz crystal microbalance (QCM) and ex situ ellipsometry, and found to be 3.2 Å/cycle.
View Article and Find Full Text PDFThe metal-organic framework NU-1000, with Zr-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH)(iso-propoxide)] followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(CH)(acac) (acac = acetylacetonate) and converted to Ir(CO) complexes by treatment with CO.
View Article and Find Full Text PDFPost-synthetic modification of the zirconium-based metal-organic framework (MOF) NU-1000 by atomic layer deposition (ALD), using tetramethoxysilane (Si(OMe) ) as a precursor, led to the incorporation and stabilization of silicon oxide clusters composed of only a few silicon atoms in the framework's pores. The resulting SiO functionalized material (Si-NU-1000) was found to be catalytically active despite the inactivity of related bulk silicon dioxide (SiO ), thus demonstrating the positive effects of having nanosized clusters of SiO . Moreover, Si-NU-1000 showed activity greater than that found for aluminum oxide based catalysts-oxides known for their high acidity-such as an aluminum oxide functionalized MOF (Al-NU-1000) and bulk γ-Al O .
View Article and Find Full Text PDFAn iridium pincer complex has been immobilised in the metal-organic framework using a technique called solvent assisted ligand-incorporation (SALI). The framework proved to be stable under the conditions required to activate the iridium complex and spectroscopic investigations showed formation of the catalytically active iridium dihydride. The Ir-pincer modified is an active catalyst for the condensed phase hydrogenation of a liquid alkene (1-decene and styrene) and shows enhanced activity with respect to a homogeneous analogue.
View Article and Find Full Text PDFAtomic layer deposition (ALD) has been shown to be an excellent method for depositing thin films of iron oxide. With limited iron precursors available, the methods widely used require harsh conditions such as high temperatures and/or the use of oxidants such as ozone or peroxide. This letter aims to show that bis(N,N'-di-t-butylacetamidinato) iron(II) (iron bisamidinate or FeAMD) is an ideal ALD precursor because of its reactivity with water and relative volatility.
View Article and Find Full Text PDFThe dihydride complexes [IrH2(POCOP)] (1a) and [IrH2(PCP)] (1b) (POCOP = 1,3-bis((di-tert-butylphosphino)oxy)benzene; PCP = 1,3-bis((di-tert-butylphosphino)methyl)benzene) react with the surface silanols of mesoporous amorphous silica (SBA-15) to give H2 and the silica-grafted, 16-electron iridium(III) monohydride species [IrH(O-SBA-15)(pincer)] (2a and 2b). These materials contain a single iridium(III) species, that is a highly dispersed, coordinatively unsaturated siloxo hydride complex, as indicated by solid-state spectroscopic data. The siloxo complexes [IrH((i)Bu-POSS)(POCOP)] (3a) and [IrH((i)Bu-POSS)(PCP)] (3b) ((i)Bu-POSS = OSi8O12(i)Bu7) were prepared as soluble analogues of 2a and 2b to support their spectroscopic characterization.
View Article and Find Full Text PDFThe dihydride pincer complex [IrH2(POCOP)] reacts with surface silanols of mesoporous silica (SBA-15) to give the coordinatively unsaturated, yet stable hydridesiloxo Ir(III) species [IrH(O-SBA-15)(POCOP)]. The silica-grafted complex catalyses the hydrogenation of ethene and propene at low temperature and pressure without prior activation.
View Article and Find Full Text PDFComplexes of composition "[Pd(2,9-dimethylphenanthroline)X(2)]" (X = Cl, Br, I) have long been known and they are used as precursors for the synthesis of other derivatives or as catalysts. In the previous literature, they have invariably been described as neutral square planar complexes, but we have found that a second ionic isomer also exists, having composition [Pd(Neoc)(2)X](2)[Pd(2)X(6)], and that the formation of this isomer occurs under a wider range of conditions than that of the neutral one. Retrospectively, the ionic isomer had surely been obtained in most previous reports even if formation of the neutral one was claimed.
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