Fundamental Structural and Electronic Understanding of Palladium Catalysts on Nitride and Oxide Supports.

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single-atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non-metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non-metal and metal oxide). Through thorough oxidation state investigations by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), CO-DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd-N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity.

Effect of atmosphere and relative humidity on photodegradation of clopidogrel under artificial solar and indoor light irradiation.

Knowledge of the chemical stability of active pharmaceutical ingredients (APIs) is an important issue in the drug development process. This work describes a methodical approach and a comprehensive protocol for forced photodegradation studies of solid clopidogrel hydrogen sulfate (Clp) under artificial sunlight and indoor irradiation at different relative humidities (RHs) and atmospheres. The results showed that, at low RHs (up to 21%), this API was relatively resistant to simulated sunlight as well as indoor light. However, at higher RHs (between 52% and 100%), more degradation products were formed, and the degradation rate increased with rising RH. The influence of oxygen on the degradation was relatively low, and most degradation reactions proceeded even in humid argon atmosphere. The photodegradation products (DP) were analyzed with two different HPLC systems (LC-UV, LC-UV-MS) and selected impurities were separated by a semi-preparative HPLC and identified by high resolution mass spectrometry (ESI-TOF-MS) and 1H NMR techniques. Based on the obtained results, a light induced degradation pathway could be proposed for Clp in solid state.

In situ monitoring of Pt nanoparticle formation in ethylene glycol solution by SAXS-influence of the NaOH to Pt ratio.

The temporal evolution of Pt nanoparticle formation in ethylene glycol solution from H(2)PtCl(6)·6H(2)O at 90 °C for different molar ratios of NaOH to Pt (84, 6.5, and 2) in the presence or absence of poly(N-vinyl-2-pyrrolidone) (PVP) as protecting agent was followed in situ by small-angle X-ray scattering (SAXS). The SAXS profiles were analyzed regarding particle size and size distribution using the Guinier approximation and the indirect Fourier transform technique (IFT). The NaOH to Pt ratio has an influence on the integral nanoparticle formation rate as well as on the metal reduction rate and the ratio of nucleation to growth reactions. The fastest nanoparticle formation rate was observed for the NaOH/Pt ratio of 6.5. The obtained results indicate that the differences in the particle formation rate might be due to differences in the reduction rate of the formed Pt complexes. In alkaline reaction media (NaOH/Pt = 84 or 6.5), small nanoparticles with a relatively narrow size distribution were formed. Therefore, it is assumed that for these NaOH/Pt ratios the particle formation is dominated by nucleation reactions. Additionally, the in situ studies point out that nanoparticles prepared at the NaOH/Pt ratio of 84 do not grow further after attaining a certain particle size. For a NaOH to Pt ratio of 2, that means in acidic medium, particle formation should be dominated by growing processes and, therefore, larger particles are formed accompanied by a broader particle size distribution. The influence of PVP on the nanoparticle formation rate is relatively low. However, in acidic medium, the presence of PVP is necessary in order to protect the formed nanoparticles from irreversible aggregation reactions.

Construction of amorphous SiO2 modified ß-Bi2O3 porous hierarchical microspheres for photocatalytic antibiotics degradation.

This work describes the synthesis of porous hierarchical microspheres composed of amorphous SiO2 and crystalline ß-Bi2O3 (BSO) via a simple solvothermal process and subsequent calcination. Complementary physicochemical methods were applied to study the function of amorphous SiO2, as well as the phase composition and morphology evolution of as-synthesized samples as a function of calcination temperature. The presence of amorphous SiO2 contributed to form hierarchically structured ß-Bi2O3 with enhanced thermostability. Moreover, the degradation of tetracycline hydrochloride (TC) under visible light irradiation was employed as a model reaction to evaluate the photocatalytic activity of as prepared materials. In consequence, both phase composition and morphology were found to be significant parameters for adjusting the photocatalytic performance of the synthesized samples. The fastest TC degradation at a low dosage of catalyst (0.2 g L-1) was observed for the sample annealed at 400℃ which contains a highly crystalline ß-Bi2O3 phase. The synergistic effect of the porous structure, excellent light absorption, and higher charge carrier separation and transfer efficiency is believed to be the reason for the optimal photocatalytic activity. This study offers a new method toward the fabrication of hierarchical porous structured ß-Bi2O3 with enhanced thermostability for various applications.

Facile synthesis of supported Ru-Triphos catalysts for continuous flow application in selective nitrile reduction.

The selective catalytic hydrogenation of nitriles represents an important but challenging transformation for many homogeneous and heterogeneous catalysts. Herein, we report the efficient and modular solid-phase synthesis of immobilized Triphos-type ligands in very high yields, involving only minimal work-up procedures. The corresponding supported ruthenium-Triphos catalysts are tested in the hydrogenation of various nitriles. Under mild conditions and without the requirement of additives, the tunable supported catalyst library provides selective access to both primary amines and secondary imines. Moreover, the first application of a Triphos-type catalyst in a continuous flow process is presented demonstrating high catalyst life-time over at least 195 hours without significant activity loss.

Experimental and theoretical investigations of the influence of carbon on a Ho3+-TiO2 photocatalyst with Vis response.

Due to their photon up-converting capability, lanthanide ions are ideal candidates dopants for semiconductors for developing visible light-driven photocatalytic activity. Of particular relevance, the low luminescence efficiency of Ln-based nanoparticles is one of the main factors that limits their further applications. Carbon, which is present on the surface of all TiO2 photocatalysts, can be responsible for luminescence quenching processes and, thus, decreasing the photocatalytic activity of TiO2. This article presents a systematic experimental and theoretical study of the effects of carbon on the photocatalytic performance of Ho3+-modified TiO2. Ho3+-TiO2 photocatalysts modified with various carbon contents (from 0.5 to 20 mol.%) were successfully prepared using a simple hydrothermal method. As-obtained samples were characterized by UV-Vis diffuse reflectance spectroscopy (DRS/UV-Vis), X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), N2 adsorption measurements, photoluminescent spectroscopy (PL), field-emission scanning electron microscopy (FE-SEM) and scanning transmission microscopy (STEM). The photodegradation efficiency of phenol was estimated for visible light (λ > 420 nm and λ > 455 nm). The XPS and XRD analyses and theoretical calculations revealed that the substitutional doping of holmium and carbon in the TiO2 anatase structure resulted in the appearance of a new sub-band-gap. Changes in the material texture, BET surface area and pore volume can be easily controlled via carbon content in samples. Doping of the Ho3+-TiO2 photocatalysts with carbon resulted in quenching of the emission of Ho3+ and, thus, the photodegradation of phenol, was observed in samples containing smaller amounts of carbon. Sixty minutes of irradiation resulted in 89% of phenol degradation under visible light (λ > 420 nm).

Polyoxoanions Derived from [gamma-SiO(4)W(10)O(32)](8-)-Containing Oxo-Centered Dinuclear Chromium(III) Carboxylato Complexes: Synthesis and Single-Crystal Structural Determination of [gamma-SiO(4)W(10)O(32)(OH)Cr(2)(OOCCH(3))(2)(OH(2))(2)](5-).

The previously unknown heteropolyoxometalates [gamma-SiO(4)W(10)O(32)(OH)Cr(2)(OOCR)(2)(OH(2))(2)](5-) (R = H, CH(3)) have been prepared by the reaction of [gamma-SiO(4)W(10)O(32)](8-) with [Cr(OH(2))(6)](3+) in formate or acetate buffer solution. Isolation of these new Cr(III)-substituted polyoxometalates was accomplished both as Cs(+) salts and as the Bu(4)N(+) salt for the acetate-containing anion. The compounds were characterized by elemental analysis, UV/vis, IR, and ESR spectroscopy, and cyclic voltammetry. The single-crystal X-ray structural analysis of (Bu(4)N)(3)H(2)[gamma-SiO(4)W(10)O(32)(OH)Cr(2)(OOCCH(3))(2)(OH(2))(2)].3H(2)O [P2(1)2(1)2(1); a = 17.608(12), b = 20.992(13), c = 24.464(11) Å; Z = 4; R = 0.057 for 6549 observed independent reflections] reveals that the two corner-linked CrO(6) octahedra are additionally bridged by two acetate groups, demonstrating the relationship to the well-studied oxo-centered trinuclear carboxylato complexes of Cr(III).

Transient and steady state investigation of selective and non-selective reaction pathways in the oxidative dehydrogenation of propane over supported vanadia catalysts.

Mechanistic aspects of the formation of C3H6, CO and CO2 in the oxidative dehydrogenation of propane over VOx/gamma-Al2O3 materials have been investigated by means of steady state and transient isotopic tests. The materials possessed highly dispersed and polymerised VOx species as well as bulk-like V2O5. Propene was primarily formed via oxidative dehydrogenation of propane by lattice oxygen of VOx species. It was suggested that non-selective consecutive propene oxidation is initiated by the breaking of the C-C bond in the molecule by the lattice oxygen, forming formaldehyde as a side product, which is further oxidised to CO and CO2. The following order of initial steady state propene selectivity (at a zero degree of propane conversion) as a function of the nature of VOx species was established: a mixture of bulk-like V2O5 and polymerised VOx>polymerised VOx>highly dispersed VOx species. The low propene selectivity over highly dispersed VOx species was explained by the fact that these species do not fully cover the bare acidic surface of gamma-Al2O3 where propene adsorption and further oxidation take place. Thus, two different locations of COx formation were considered: (i) in the vicinity of acidic sites of the support and (ii) on VOx species. The propene selectivity over samples possessing polymerised VOx species and bulk-like V2O5 strongly decreased with an increasing degree of propane conversion. Contrarily, highly dispersed VOx species showed the lowest ability for consecutive propene oxidation.