Methyl orange degradation enhanced by hydrogen spillover onto platinum nanocatalyst surface

Following a thermal reduction method, platinum nanoparticles were synthesized and stabilized by polyvinylpyrrolidone. The colloidal platinum nanoparticles were stable for more than 3 months. The micrograph analysis unveiled that the colloidal platinum nanoparticles were well dispersed with an average size of 2.53 nm. The sol–gel‐based inverse micelle strategy was applied to synthesize mesoporous iron oxide material. The colloidal platinum nanoparticles were deposited on mesoporous iron oxide through the capillary inclusion method. The small‐angle X‐ray scattering analysis indicated that the dimension of platinum nanoparticles deposited on mesoporous iron oxide (Pt‐Fe₂O₃) was 2.64 nm. X‐ray photoelectron spectroscopy (XPS) data showed that the binding energy on Pt‐Fe₂O₃ surface decreased owing to mesoporous support–nanoparticle interaction. Both colloidal and deposited platinum nanocatalysts improved the degradation of methyl orange under reduction conditions. The activation energy on the deposited platinum nanocatalyst interface (2.66 kJ mol^?1) was significantly lowered compared with the one on the colloidal platinum nanocatalyst interface (40.63 ± 0.53 kJ mol^?1).     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Dynamically Induced Excitonic Instability in Pumped Dirac Materials

Driven and non-equilibrium quantum states of matter have attracted growing interest in both theoretical and experimental studies in condensed matter physics. Recent progress in realizing transient collective states in driven or pumped Dirac materials (DMs) is reviewed herein. In particular, the focus is on optically pumped DMs which are a promising platform for transient excitonic instabilities. Optical pumping combined with the linear (Dirac) dispersion of the electronic spectrum offers a knob for tuning the effective interaction between the photoexcited electrons and holes, and thus provides a way of reducing the critical coupling for excitonic instability. As a result, a transient excitonic condensate could be achieved in a pumped DM while it is not feasible in equilibrium. A unifying theoretical framework is provided for describing transient collective states in 2D and 3D DMs. The experimental signatures are described and numerical estimates of the size of the dynamically induced excitonic gaps and the values of the critical temperatures for several specific systems, are summarized. In addition, general guidelines for identifying promising material candidates are discussed. Finally, comments are provided regarding recent experimental efforts in realizing transient excitonic condensate in pumped DMs, and outstanding issues and possible future directions are outlined.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

Kinetics of phenol hydrogenation over supported palladium catalyst

Kinetics of vapor phase hydrogenation of phenol to cyclohexanone over Pd/MgO system has been studied in a flow microreactor under normal atmospheric pressure. The reaction rate is found to be negative order with respect to the partial pressure of phenol and has increased from −0.5 to 0.5 with increasing temperature (473 to 563 K). The apparent activation energy (E_a) of the process is found to be close to 65 kJ per mol. On the basis of kinetic results a surface mechanism is proposed.