RESUMEN

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. We present a 532 nm ultrashort-pulse laser setup to process the inner parts of 15 m long beam vacuum tubes of the Large Hadron Collider (LHC). Picosecond pulses at a repetition rate of 200 kHz are guided through an optical fiber toward an inchworm robot traveling inside the beam pipe. The system was installed, characterized, and tested for reliability. First surface treatments achieved the required scan precision. Cu2O-dominated nano-features were observed when processing at high average laser power (5 W) and slow scanning speed (5 mm s-1) in nitrogen flow, and the maximum SEY of copper was decreased from 2.1 to 0.7.

RESUMEN

Over 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 CxDy molecules. XPS was implemented to estimate the phase composition of the films. The maximal SEY was found to decrease linearly with the fraction of the graphitic phase in the films. These results are supported by Raman scattering and UPS measurements. The graphitic phase decreases almost linearly for hydrogen and deuterium concentrations between 12% and 46% (at.), but abruptly decreases when the concentration reaches 53%. This vanishing of the graphitic phase is accompanied by a strong increase of SEY and the Tauc gap. These results suggest that the SEY is not dictated directly by the concentration of H/D, but by the fraction of the graphitic phase in the film. The results are supported by an original model used to calculate the SEY of films consisting of a mixture of graphitic and polymeric phases.

Asunto(s)

RESUMEN

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(p-benzoate)pyrene)2 Zr6(µ3-O)4(µ3-OH)4(H2O)4(OH)4 with linkers and nodes arranged to satisfy a csq 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 (µ3-hydroxos) and node-ligated proton donors (terminal hydroxos), via simple coordination at open Zr(IV) sites, or via dissociative coordination to Zr(IV) as NH2- and protonation of a node-based µ3-oxo. Ammonia adsorption occurs via both reversible and irreversible processes. The latter are of particular interest for protection and mitigation. Notably, the unexpected dissociative adsorption occurs only with nodes that have been fully dehydrated and irreversibly structurally distorted via thermal pre-treatment-a finding that is supported by density functional theory calculations. Differentiating and ranking the relative importance of the many modes of adsorption was facilitated, in part, by the availability of variants of NU-1000 that replace the majority of terminal aqua and hydroxo ligands with nonstructural formate ligands, auxiliary ditopic linkers, or both. The study provides insights into the chemical basis for both reversible and irreversible uptake of ammonia by Zr-MOFs and related compounds. The unexpectedly rich variety of sorption motifs suggest the criteria for designing or choosing MOFs that are optimal for specific ammonia-centric applications.

RESUMEN

Antimony telluride (Sb2Te3) thin films were prepared by a room temperature Metal-Organic Chemical Vapor Deposition (MOCVD) process using antimony chloride (SbCl3) and bis(trimethylsilyl)telluride (Te(SiMe3)2) 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 Sb2Te3 films on Si(111).

RESUMEN

Engendering 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. At a macroscopic level, the hopping behavior leads to diffusive charge transport and is quantifiable as an apparent diffusion coefficient, Dhopping. Theory suggests that the csq topology of NU-1000, together with its characteristic one-dimensional mesopores, will result in direction-dependent, that is, anisotropic, electrical conductivity. Detailed computations suggest that the governing factor is the strength of electronic coupling between pairs of linkers sited in the a,b plane of the MOF versus the mesopore-aligned c axis of the crystal. The notion has been put to the test experimentally by configuring the MOF as an array of selectively oriented, electrode-supported crystallites, where the rodlike crystallites are either oriented largely normal to the electrode (requiring redox hopping along the c direction) or mainly parallel (requiring redox hopping mainly through the a,b plane). The orientations are preselected by preparing MOF films either via interfacial solvothermal synthesis or via electrophoretic deposition. In semiquantitative accord with computational predictions, Dhopping is up to ∼3500 times larger in the c direction than through the a,b plane. In addition to their fundamental significance, the findings have clear implications for the design and optimization of MOFs for electrocatalysis and for other applications that rely upon electrical conductivity.

RESUMEN

Acid-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. Extended X-ray absorption fine structure (EXAFS), 31P NMR, N2 physisorption, and X-ray diffraction (XRD) show that the catalyst is structurally stable with time-on-stream and that WO x clusters are necessary for detectable rates, consistent with conventional catalysts for the reaction. PTA and framework stability under these aggressive conditions requires maximal loading of PTA within the NU-1000 framework; materials with lower PTA loading lost structural integrity under the reaction conditions. Initial reaction rates over the NU-1000-supported catalyst were comparable to a control WO x-ZrO2, but the NU-1000 composite material was unusually active toward the transmethylation pathway that requires two adjacent active sites in a confined pore, as created when PTA is confined in NU-1000. This work shows the promise of metal-organic framework topologies in giving access to unique reactivity, even for aggressive reactions such as hydrocarbon isomerization.

RESUMEN

Methyltrioxorhenium (ReO3Me) 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-AlMe3). The growth rate of the smooth Re-Al oxide films, with general stoichiometry RexAlyO3x, has been monitored by in situ quartz crystal microbalance (QCM) and ex situ ellipsometry, and found to be 3.2 Å/cycle. X-ray photoelectron spectroscopy (XPS) revealed the mixed valent composition of the film with Re(III) species being the main component. In addition, ReO3Me has been successfully used to deposit rhenium oxide in NU-1000, a mesoporous zirconium-based metal-organic framework (MOF). The metalated MOF was found to retain porosity and crystallinity and to be catalytically active for ethene hydrogenation.

RESUMEN

The metal-organic framework NU-1000, with Zr6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH3)2(iso-propoxide)]2 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(C2H4)2(acac) (acac = acetylacetonate) and converted to Ir(CO)2 complexes by treatment with CO. Infrared spectra of these supported complexes show that incorporation of Al weakened the electron donor tendency of the MOF. Correspondingly, the catalytic activity of the initial supported iridium complexes for ethylene hydrogenation increased, as did the selectivity for ethylene dimerization. The results of density functional theory calculations with a simplified model of the nodes incorporating Al(iii) ions are in qualitative agreement with some catalyst performance data.

RESUMEN

Post-synthetic modification of the zirconium-based metal-organic framework (MOF) NU-1000 by atomic layer deposition (ALD), using tetramethoxysilane (Si(OMe)4 ) 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 SiOx functionalized material (Si-NU-1000) was found to be catalytically active despite the inactivity of related bulk silicon dioxide (SiO2 ), thus demonstrating the positive effects of having nanosized clusters of SiOx . 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-Al2 O3 . X-ray photoelectron spectroscopy and infrared spectroscopy measurements unmasked the electron donating nature of Si-NU-1000, explaining the unusual electronic properties of the nanosized SiOx clusters and supporting their high catalytic activity.

RESUMEN

An iridium pincer complex has been immobilised in the metal-organic framework NU-1000 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 NU-1000 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. Additionally, the Ir-pincer immobilised inside NU-1000 operated as an efficient heterogenous catalyst under flow conditions.

RESUMEN

Atomic 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. Using in situ QCM analysis, we show outstanding conformal self-limiting growth of FeOx using FeAMD and water at temperatures lower than 200 °C. By annealing thin films of FeOx at 500 °C, we observe the formation of α-Fe2O3, confirming that we can use FeAMD to fabricate thin films of catalytically promising iron oxide materials using moderate growth conditions.

RESUMEN

The 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. The coordinatively unsaturated, 16-electron species 2a and 2b react with CO to give the six-coordinate iridium(III) adducts [IrH(O-SBA-15)(CO)(POCOP)] (7a) and [IrH(O-SBA-15)(CO)(PCP)] (7b). Due to dissimilar electronic properties of the pincer ligands, 7a undergoes reductive elimination of the silanol forming the Ir(I) complex [Ir(CO)(POCOP)] (8a), whereas 7b is stable in oxidation state of III. The homogeneous siloxo carbonyl complexes [IrH((i)Bu-POSS)(CO)(POCOP)] (9a), [IrH((i)Bu-POSS)(CO)(PCP)] (9b), and [IrH(OSiMe3)(CO)(POCOP)] (11a) were prepared to substantiate the reactivity and the characterization of the silica grafted species.

RESUMEN

The 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.

RESUMEN

Complexes 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.