UiO-66-based metal organic frameworks for the photodegradation of acetaminophen under simulated solar irradiation

This work reports the solvothermal synthesis of UiO-66-based MOFs with three different ligands and its application to the breakdown of aqueous acetaminophen under simulated sunlight. This pharmaceutical is a representative contaminant of emerging concern that enters water bodies mainly through wastewater treatment plant discharges. The synthesis approach of the MOFs was fitted using a zirconium alkoxide as metal cluster precursor and 2-aminoterephthalic and 2,5-dihydroxyterephthalic acids as ligands to prepare UiO-66-NH2 and UiO-66-(OH)2 MOFs, respectively. These new MOFs have enhanced visible light harvesting and narrower band gap than the UiO-66. Among all, UiO-66-NH2 yielded the highest removal of acetaminophen under simulated solar irradiation in batch test. The activity and stability of UiO-66-NH2 were demonstrated for the first time in a continuous flow test, where stable performance was observed upon 30 h on stream. The degradation pathway of acetaminophen was elucidated based on coupling, ring-opening, and oxidation reactions. DFT calculation confirmed that the indirect semiconductor behavior of UiO-66-NH2 upon light excitation occurred through ligand-ligand charge transfer. Overall, promising UiO-66-based MOFs photocatalysts were obtained for effective degradation of acetaminophen with the assistance of solar lightThis research was funded by the National State Research Agency of Spain (project number: PID2019-106186RB-I00/AEI/10.13039/501100011033). Yilan Wang acknowledges the support from the China Scholarship Council (CSC No. 201908610198). We also thank to Prof. Shi Ye for his help with density functional theory calculatio

Degradation of diclofenac in water under LED irradiation using combined g-C3N4/NH2-MIL-125 photocatalysts

This study reports the photocatalytic degradation of diclofenac by hybrid materials prepared by combination of graphitic carbon nitride (g-C3N4) and titanium-metal organic framework (NH2-MIL-125), in different mass proportions (MOF:C3N4 of 25:75, 50:50 and 75:25). The hybrid materials were fully characterized, and their properties compared to those of the individual components, whose presence was confirmed by XRD. The porous structure was the result of the highly microporous character of the MOF and the non-porous one of g-C3N4. The band gap values were very close to that of MOF component. Photoluminescence measurements suggested an increase on the recombination rate associated to the presence of g-C3N4. Photodegradation tests of diclofenac (10 mg·L-1) were performed under UV LED irradiation at 384 nm. The hybrid materials showed higher photocatalytic activity than the individual components, suggesting the occurrence of some synergistic effect. The photocatalyst with a MOF:g-C3N4 ratio of 50:50 yielded the highest conversion rate, allowing complete disappearance of diclofenac in 2 h. Experiments with scavengers showed that superoxide radicals and holes played a major role in the photocatalytic process photodegradation, being that of hydroxyl radicals less significant. From the identification of by-products species, a degradation pathway was proposed for the degradation of diclofenac under the experimental operating conditionsThis work was financially supported by Associate Laboratory LSRELCM - UID/EQU/50020/2020 - funded by national funds through FCT/ MCTES (PIDDAC) and by project POCI-01-0145-FEDER-030674, financed by the ERDF through COMPETE2020 and POCI – and by national funds through FCT (Portugal). This research was also funded by Spanish Ministry of Economy and Competitiveness (project CTQ2016-78576-R, FEDER funds) and the State Research Agency (PID2019- 106186RB-I00/AEI/10.13039/501100011033) (Spain). V. MuelasRamos thanks to MCIU for BES-2017-082613 grant. Authors thank the TEM images from the Centro Nacional de Microscopía Electronica ´ (Spain). Authors would like to acknowledge the use of Servicio General de Apoyo a la Investigacion-SAI ´ for EDX mapping images, Universidad de Zaragoza (Spain) and the Research Support Service of XPS data from University of Málaga (Spain

An upper limit on hypertriton production in collisions of Ar(1.76 AGeV)+KCl

A high-statistic data sample of Ar(1.76 AGeV)+KCl events recorded with HADES is used to search for a hypertriton signal. An upper production limit per centrality-triggered event of $1.04$ x $10^{-3}$ on the $3\sigma$ level is derived. Comparing this value with the number of successfully reconstructed $\Lambda$ hyperons allows to determine an upper limit on the ratio $N_{_{\Lambda}^3H}/N_{\Lambda}$, which is confronted with statistical and coalescence-type model calculations

Inclusive pion and eta production in p+Nb collisions at 3.5 GeV beam energy

Data on inclusive pion and eta production measured with the dielectron spectrometer HADES in the reaction p+93Nb at a kinetic beam energy of 3.5 GeV are presented. Our results, obtained with the photon conversion method, supplement the rather sparse information on neutral meson production in proton-nucleus reactions existing for this bombarding energy regime. The reconstructed e+e-e+e- transverse-momentum and rapidity distributions are confronted with transport model calculations, which account fairly well for both pi0 and eta production.Comment: 12 pages, 9 figures, submitted to Physical Review

Searching a Dark Photon with HADES

We present a search for the e+e- decay of a hypothetical dark photon, also names U vector boson, in inclusive dielectron spectra measured by HADES in the p (3.5 GeV) + p, Nb reactions, as well as the Ar (1.756 GeV/u) + KCl reaction. An upper limit on the kinetic mixing parameter squared epsilon^{2} at 90% CL has been obtained for the mass range M(U) = 0.02 - 0.55 GeV/c2 and is compared with the present world data set. For masses 0.03 - 0.1 GeV/c^2, the limit has been lowered with respect to previous results, allowing now to exclude a large part of the parameter region favoured by the muon g-2 anomaly. Furthermore, an improved upper limit on the branching ratio of 2.3 * 10^{-6} has been set on the helicity-suppressed direct decay of the eta meson, eta-> e+e-, at 90% CL

Medium effects in proton-induced K0K^{0} production at 3.5 GeV

We present the analysis of the inclusive $K^{0}$ production in p+p and p+Nb collisions measured with the HADES detector at a beam kinetic energy of 3.5 GeV. Data are compared to the GiBUU transport model. The data suggest the presence of a repulsive momentum-dependent kaon potential as predicted by the Chiral Perturbation Theory (ChPT). For the kaon at rest and at normal nuclear density, the ChPT potential amounts to $\approx 35$ MeV. A detailed tuning of the kaon production cross sections implemented in the model has been carried out to reproduce the experimental data measured in p+p collisions. The uncertainties in the parameters of the model were examined with respect to the sensitivity of the experimental results from p+Nb collisions to the in-medium kaon potential.Comment: 13 pages, 14 figure

Lambda hyperon production and polarization in collisions of p(3.5 GeV) + Nb

Results on $\Lambda$ hyperon production are reported for collisions of p(3.5 GeV) + Nb, studied with the High Acceptance Di-Electron Spectrometer (HADES) at SIS18 at GSI Helmholtzzentrum for Heavy-Ion Research, Darmstadt. The transverse mass distributions in rapidity bins are well described by Boltzmann shapes with a maximum inverse slope parameter of about $90\,$MeV at a rapidity of $y=1.0$, i.e. slightly below the center-of-mass rapidity for nucleon-nucleon collisions, $y_{cm}=1.12$. The rapidity density decreases monotonically with increasing rapidity within a rapidity window ranging from 0.3 to 1.3. The $\Lambda$ phase-space distribution is compared with results of other experiments and with predictions of two transport approaches which are available publicly. None of the present versions of the employed models is able to fully reproduce the experimental distributions, i.e. in absolute yield and in shape. Presumably, this finding results from an insufficient modelling in the transport models of the elementary processes being relevant for $\Lambda$ production, rescattering and absorption. The present high-statistics data allow for a genuine two-dimensional investigation as a function of phase space of the self-analyzing $\Lambda$ polarization in the weak decay $\Lambda\rightarrow p \pi^-$. Finite negative values of the polarization in the order of $5-20\,\%$ are observed over the entire phase space studied. The absolute value of the polarization increases almost linearly with increasing transverse momentum for $p_t>300\,$MeV/c and increases with decreasing rapidity for $y < 0.8$.Comment: accepted by Eur. Phys. J.

Subthreshold Xi- Production in Collisions of p(3.5 GeV)+Nb

Results on the production of the double-strange cascade hyperon $\mathrm{\Xi^-}$ are reported for collisions of p\,(3.5~GeV)\,+\,Nb, studied with the High Acceptance Di-Electron Spectrometer (HADES) at SIS18 at GSI Helmholtzzentrum for Heavy-Ion Research, Darmstadt. For the first time, subthreshold $\mathrm{\Xi^-}$ production is observed in proton-nucleus interactions. Assuming a $\mathrm{\Xi^-}$ phase-space distribution similar to that of $\mathrm{\Lambda}$ hyperons, the production probability amounts to $P_{\mathrm{\Xi^-}}=(2.0\,\pm0.4\,\mathrm{(stat)}\,\pm 0.3\,\mathrm{(norm)}\,\pm 0.6\,\mathrm{(syst)})\times10^{-4}$ resulting in a $\mathrm{\Xi^-/(\Lambda+\Sigma^0)}$ ratio of $P_{\mathrm{\Xi^-}}/\ P_{\mathrm{\Lambda+\Sigma^0}}=(1.2\pm 0.3\,\mathrm{(stat)}\pm0.4\,\mathrm{(syst)})\times10^{-2}$. Available model predictions are significantly lower than the estimated$\mathrm{\Xi^-}$ yield.Comment: 6 pages, 3 figure