ROS-generating rare-earth coordination networks for photodynamic inactivation of Candida albicans.

Water-ethanol suspensions of 2D coordination network (CN) based on rare earth elements and mixed ligands were evaluated as reactive oxygen species (ROS) generators under UV light irradiation, in contact with a biomimetic substrate (tryptophan) or an O2(1Δg) quencher (1,3-diphenylisobenzofuran; 1,3-DPBF). A combination of bottom-up and top-down strategies was implemented in order to obtain nano-sized CN particles and the subsequent colloidal suspensions were also tested towards photodynamic inactivation of Candida albicans (C. albicans). SEM, TEM, FTIR, and XRD techniques were applied to characterize the solids and ICP-AES was employed to determine the metal content of the colloidal suspensions. Promising results were found indicating that the presence of Tb3+ allows an intersystem crossing suitable for singlet oxygen generation, resulting in the antifungal activity of C. albicans culture upon UV-irradiation.

Controlling CO2 Hydrogenation Selectivity by Metal-Supported Electron Transfer.

Tuning CO2 hydrogenation selectivity to obtain targeted value-added chemicals and fuels has attracted increasing attention. However, a fundamental understanding of the way to control the selectivity is still lacking, posing a challenge in catalyst design and development. Herein, we report our new discovery in ambient pressure CO2 hydrogenation reaction where selectivity can be completely reversed by simply changing the crystal phases of TiO2 support (anatase- or rutile-TiO2 ) or changing metal loadings on anatase-TiO2 . Operando spectroscopy and NAP-XPS studies reveal that the determining factor is a different electron transfer from metal to the support, most probably as a result of the different extents of hydrogen spillover, which changes the adsorption and activation of the intermediate of CO. Based on this new finding, we can not only regulate CO2 hydrogenation selectivity but also tune catalytic performance in other important reactions, thus opening up a door for efficient catalyst development by rational design.

Resolution of intermediate surface species by combining modulated infrared spectroscopy and chemometrics.

In this work, aiming at exploiting the essential particularities of modulation excitation spectroscopy (MES) coupled to phase sensitive detection (PSD) and chemometrics, a data analysis procedure was implemented to analyze phase-resolved infrared (IR) data. The fundamental principle of the proceedings is the application of successive multivariate curve resolution-alternating least squares (MCR-ALS) resolutions to MES-PSD IR data. The applicability of the strategy was evaluated in several cases of simulated data considering the effect of spectral band overlapping and presence of noise. Outcomes related to data-processing are depicted in detail. As a proof of concept, the data resolution approach was validated by resolving an experimental real system related to the adsorption-desorption dynamic of oxalic acid on titanium dioxide by in situ IR spectroscopy in attenuated total reflection (ATR) mode. After data resolution, different oxalate species were assigned to each spectral band and information about the kinetics in terms of phase lag was obtained. In the light of the obtained results, this approach is rather appealing in other research fields, very helpful for the non-chemometric community and foresees manifold applications, specially, in catalytic system investigations.

Molecular structure and thermal stability of the oxide-supported phosphotungstic Wells-Dawson heteropolyacid.

We present, for the first time in the literature, a systematic study of the molecular structure of the Wells-Dawson heteropolyacid H6P2W18O62·24H2O (HPA) dispersed on TiO2, SiO2, ZrO2 and Al2O3. The heteropolyacid-based materials were synthesized through a conventional impregnation method (in aqueous and ethanol media) at a loading that corresponds to the theoretical "monolayer" coverage (dispersion limit loading). The combination of Raman and infrared studies demonstrates the presence of crystals of HPA (regardless of the nature of the medium used during the synthesis) suggesting that the dispersion limit loading was greatly exceeded. In situ temperature programmed spectroscopy analyses demonstrated that the Raman shift of the distinctive W[double bond, length as m-dash]O Raman mode of the phosphotungstic Wells-Dawson heteropolyacid is sensitive to the local environment, that is, the amount of water molecules associated with the structure. Moreover, the aqueous based species associated with such structures are recognizable through infrared spectroscopy.

Methanol adsorption on the beta-Ga2O3 surface with oxygen vacancies: theoretical and experimental approach.

Methanol adsorption on beta-Ga2O3 surface has been studied by Fourier transform infrared spectroscopy (FTIR) and by means of density functional theory (DFT) cluster model calculations. Adsorption sites of tetrahedral and octahedral gallium ions with different numbers of oxygen vacancies have been compared. The electronic properties of the adsorbed molecules have been monitored by computing adsorption energies, optimized geometry parameters, overlap populations, atomic charges, and vibrational frequencies. The gallia-methanol interaction has different behaviors according to the local surface chemical composition. The calculations show that methanol can react in three different ways with the gallia surface giving rise to a nondissociative adsorption, a dissociative adsorption, and an oxidative decomposition. The surface without oxygen vacancies is very reactive and produces the methanol molecule decomposition. The molecule is nondissociatively adsorbed by means of a hydrogen bond between the alcoholic hydrogen atom and a surface oxygen atom and a bond between the alcoholic oxygen atom and a surface gallium atom. Two neighbor oxygen vacancies on tetrahedral gallium sites produce the dissociation of the methanol molecule and the formation of a bridge bond between two surface gallium atoms and the methoxy group.

Infrared spectroscopic study of the carbon dioxide adsorption on the surface of Ga2O3 polymorphs.

The adsorption of CO(2) over a set of gallium (III) oxide polymorphs with different crystallographic phases (alpha, beta, and gamma) and surface areas (12-105 m(2) g(-1)) was studied by in situ infrared spectroscopy. On the bare surface of the activated gallias (i.e., partially dehydroxylated under O(2) and D(2) (H(2)) at 723 K), several IR signals of the O-D (O-H) stretching mode were assigned to mono-, di- and tricoordinated OD (OH) groups bonded to gallium cations in tetrahedral and/or octahedral positions. After exposing the surface of the polymorphs to CO(2) at 323 K, a variety of (bi)carbonate species emerged. The more basic hydroxyl groups were able to react with CO(2), to yield two types of bicarbonate species: mono- (m-) and bidentate (b-) [nu(as)(CO(3)) = 1630 cm(-1); nu(s)(CO(3)) = 1431 or 1455 cm(-1) (for m- or b-); delta(OH) = 1225 cm(-1)]. Together with the bicarbonate groups, IR bands assigned to carboxylate [nu(as)(CO(2)) = 1750 cm(-1); nu(s)(CO(2)) = 1170 cm(-1)], bridge carbonate [nu(as)(CO(3)) = 1680 cm(-1); nu(s)(CO(3)) = 1280 cm(-1)], bidentate carbonate [nu(as)(CO(3)) = 1587 cm(-1); nu(s)(CO(3)) = 1325 cm(-1)], and polydentate carbonate [nu(as)(CO(3)) = 1460 cm(-1); nu(s)(CO(3)) = 1406 cm(-1)] species developed, up to approximately 600 Torr of CO(2). However, only the bi- and polydentate carbonate groups still remained on the surface upon outgassing the samples at 323 K. The total amount of adsorbed CO(2), measured by volumetric adsorption (323 K), was approximately 2.0 micromol m(-2) over any of the polymorphs, congruent with an integrated absorbance of (bi)carbonate species proportional to the surface area of the materials. Upon heating under flowing CO(2) (760 Torr), most of the (bi)carbonate species vanished a T > 550 K, but polydentate groups remained on the surface up to the highest temperature used (723 K). A thorough discussion of the more probable surface sites involved in the adsorption of CO(2) is made.

Hydrogen chemisorption on gallium oxide polymorphs.

The chemisorption of H(2) over a set of gallia polymorphs (alpha-, beta-, and gamma-Ga(2)O(3)) has been studied by temperature-programmed adsorption equilibrium and desorption (TPA and TPD, respectively) experiments, using in situ transmission infrared spectroscopy. Upon heating the gallium oxides above 500 K in 101.3 kPa of H(2), two overlapped infrared signals developed. The 2003- and 1980-cm(-1) bands were assigned to the stretching frequencies of H bonded to coordinatively unsaturated (cus) gallium cations in tetrahedral and octahedral positions [nu(Ga(t)-H) and nu(Ga(o)-H), respectively]. Irrespective to the gallium cation geometrical environment, (i) a linear relationship between the integrated intensity of the whole nu(Ga-H) infrared band versus the Brunauer-Emmett-Teller surface area of the gallia was found and (ii) TPA and TPD results revealed that molecular hydrogen is dissociatively chemisorbed on any bulk gallium oxide polymorph following two reaction pathways. An endothermal, homolytic dissociation occurs over surface cus-gallium sites at T > 450 K, giving rise to Ga-H(I) bonds. The heat and entropy of this type I hydrogen adsorption were determined by the Langmuir's adsorption model as Deltah(I) = 155 +/- 25 kJ mol(-1) and Deltas(I) = 0.27 +/- 0.11 kJ mol(-1) K(-1). In addition, another exothermic, heterolytic adsorption sets in already in the low-temperature region. This type of hydrogen chemisorption involves surface Ga-O-Ga species, originating GaO-H and Ga-H(II) bonds which can only be removed from the gallia surface after heating under evacuation at T > 650 K. The measured desorption energy of this last, second-order process was equal to 77 +/- 10 kJ mol(-1). The potential of the H(2) chemisorption as a tool to measure or estimate the specific surface area of gallia and to discern the nature and proportion of gallium cation coordination sites on the surface of bulk gallium oxides is also analyzed.