Tuning the energetics and tailoring the optical properties of silver clusters confined in zeolites

The integration of metal atoms and clusters in well-defined dielectric cavities is a powerful strategy to impart new properties to them that depend on the size and geometry of the confined space as well as on metal-host electrostatic interactions. Here, we unravel the dependence of the electronic properties of metal clusters on space confinement by studying the ionization potential of silver clusters embedded in four different zeolite environments over a range of silver concentrations. Extensive characterization reveals a strong influence of silver loading and host environment on the cluster ionization potential, which is also correlated to the cluster's optical and structural properties. Through fine-tuning of the zeolite host environment, we demonstrate photoluminescence quantum yields approaching unity. This work extends our understanding of structure property relationships of small metal clusters and applies this understanding to develop highly photoluminescent materials with potential applications in optoelectronics and bioimaging

A Contribution of the HAWC Observatory to the TeV era in the High Energy Gamma-Ray Astrophysics: The case of the TeV-Halos

We present a short overview of the TeV-Halos objects as a discovery and a relevant contribution of the High Altitude Water \v{C}erenkov (HAWC) observatory to TeV astrophysics. We discuss history, discovery, knowledge, and the next step through a new and more detailed analysis than the original study in 2017. TeV-Halos will contribute to resolving the problem of the local positron excess observed on the Earth. To clarify the latter, understanding the diffusion process is mandatory.Comment: Work presented in the 21st International Symposium on Very High Energy Cosmic Ray Interactions(ISVHECRI 2022) as part of the Ph. D. Thesis of Ramiro Torres-Escobedo (SJTU, Shanghai, China). Accepted for publication in SciPost Physics Proceedings (ISSN 2666-4003). 11 pages, 3 Figures. Short overview of HAWC and TeV Halos objects until 202

Efficient Emission in Halide Layered Double Perovskites: The Role of Sb3+ Substitution in Cs4Cd1–xMnxBi2Cl12 Phosphors

Layered halide perovskites and double perovskites optoelectronic properties have recently been the subject of intense research. Layered double perovskites represent the merging of both worlds, and as such, have the potential to further expand the already vast space of optoelectronic properties and applications of halide perovskites. Despite having more than 40 known members, to date, only the -oriented layered double perovskites: Cs4Cd1–xMnxBi2Cl12, have shown efficient photoluminescence (PL). In this work, we replaced Bi with Sb to further investigate the electronic structure and PL properties of these materials, resulting in two new families of layered inorganic perovskites alloys with full solubility. The first family, Cs4Cd1–xMnSb2Cl12, exhibits a PL emission at 605 nm ascribed to Mn2+ centers in octahedral coordination, and a maximum photoluminescence quantum yield PLQY of 28.5%. The second family of alloys, also with full solubility, Cs4Cd0.8Mn0.2(Sb1–yBiy)2Cl12, contains a fixed amount of Mn2+ and Cd2+ cations but different concentrations of the trivalent metals. This variability allows the tuning of the PL emission from 603 nm to 614 nm. We show that the decreased efficiency of the Cs4Cd1–xMnxSb2Cl12family compared to Cs4Cd1–xMnxBi2Cl12, is mostly due to a decreased spin-orbit coupling in Sb and the subsequent increased electronic delocalization compared to the Bi alloys, reducing the energy transfer to Mn2+ centers. This work lays out a roadmap to understand and achieve high photoluminescence efficiencies in layered double perovskites.</p

Atomic scale reversible opto-structural switching of few atom luminescent silver clusters confined in LTA zeolites

Luminescent silver clusters (AgCLs) stabilized inside partially Ag exchanged Na LTA zeolites show a remarkable reversible on-off switching of their green-yellowish luminescence that is easily tuned by a hydration and dehydration cycle, making them very promising materials for sensing applications. We have used a unique combination of photoluminescence (PL), UV-visible-NIR Diffuse Reflectance (DRS), X-ray absorption fine structure (XAFS), Fourier Transform-Infrared (FTIR) and electron spin resonance (ESR) spectroscopies to unravel the atomic-scale structural changes responsible for the reversible optical behavior of the confined AgCLs in LTA zeolites. Water coordinated, diamagnetic, tetrahedral AgCLs [Ag4(H2O)4]2+ with Ag atoms positioned along the axis of the sodalite six-membered rings are at the origin of the broad and intense green-yellowish luminescence in the hydrated sample. Upon dehydration, luminescent [Ag4(H2O)4]2+ clusters are transformed into non-luminescent (dark), diamagnetic, octahedral AgCLs [Ag6(OF)14]2+ with Ag atoms interacting strongly with zeolite framework oxygen (OF) of the sodalite four-membered rings. This highly responsive on-off switching reveals that besides quantum confinement and molecular-size, coordinated water and framework oxygen ligands strongly affect the organization of AgCLs valence electrons and play a crucial role in the opto-structural properties of AgCLs.status: publishe

The Roles of the Structure and Basic Sites of Sodium Titanates on Transesterification Reactions to Obtain Biodiesel

Sodium titanates were evaluated as heterogeneous catalysts for biodiesel production. Materials were prepared using an experimental design considering NaOH and TiO2 concentrations and hydrothermal and calcination temperatures as input variables. Materials characterization was carried out by DRX-Rietveld refinement, CO2-TPD, and XPS. Statistical analysis of the experimental results indicates that the calcination temperature is the most influential factor in the formation of sodium titanates with high catalytic performance in transesterification reactions. Further analysis of the oil-to-biodiesel conversion revealed that the catalytic activity of sodium titanates is directly correlated to the catalyst associated species and to the density of medium-strong basic sites on the surface of the material, obtaining up to 95% conversion to biodiesel at 60 &deg;C using 3.6% weight catalyst with respect to oil

Origin of the bright photoluminescence of few-atom silver clusters confined in LTA zeolites

Silver (Ag) clusters confined in matrices possess remarkable luminescence properties, but little is known about their structural and electronic properties. We characterized the bright green luminescence of Ag clusters confined in partially exchanged Ag-Linde Type A (LTA) zeolites by means of a combination of x-ray excited optical luminescence-extended x-ray absorption fine structure, time-dependent-density functional theory calculations, and time-resolved spectroscopy. A mixture of tetrahedral Ag4(H2O) x 2+ (x = 2 and x = 4) clusters occupies the center of a fraction of the sodalite cages. Their optical properties originate from a confined two-electron superatom quantum system with hybridized Ag and water O orbitals delocalized over the cluster. Upon excitation, one electron of the s-type highest occupied molecular orbital is promoted to the p-type lowest unoccupied molecular orbitals and relaxes through enhanced intersystem crossing into long-lived triplet states.status: publishe

Combined dark matter searches towards dwarf spheroidal galaxies with Fermi-LAT, HAWC, H.E.S.S., MAGIC, and VERITAS

Cosmological and astrophysical observations suggest that 85\% of the total matter of the Universe is made of Dark Matter (DM). However, its nature remains one of the most challenging and fundamental open questions of particle physics. Assuming particle DM, this exotic form of matter cannot consist of Standard Model (SM) particles. Many models have been developed to attempt unraveling the nature of DM such as Weakly Interacting Massive Particles (WIMPs), the most favored particle candidates. WIMP annihilations and decay could produce SM particles which in turn hadronize and decay to give SM secondaries such as high energy $\gamma$ rays. In the framework of indirect DM search, observations of promising targets are used to search for signatures of DM annihilation. Among these, the dwarf spheroidal galaxies (dSphs) are commonly favored owing to their expected high DM content and negligible astrophysical background. In this work, we present the very first combination of 20 dSph observations, performed by the Fermi-LAT, HAWC, H.E.S.S., MAGIC, and VERITAS collaborations in order to maximize the sensitivity of DM searches and improve the current results. We use a joint maximum likelihood approach combining each experiment's individual analysis to derive more constraining upper limits on the WIMP DM self-annihilation cross-section as a function of DM particle mass. We present new DM constraints over the widest mass range ever reported, extending from 5 GeV to 100 TeV thanks to the combination of these five different $\gamma$-ray instruments