Experimental study for adsorption and photocatalytic reaction of ethyl methylphosphonate molecule as organophosphorus compound adsorbed at surface of titanium dioxide under UV irradiation in ambient condition

The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO₂ film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO₂. By TiO₂ photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO₂ photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO₂. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO₂ photocatalyst were elucidated.

     

Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+: Experimental and Computational Studies of their Hydricities,Interaction with CO2, and Photochemistry

We prepared two geometric isomers of [Ir(tpy)(ppy)H]⁺, previously proposed as a key intermediate in the photochemical reduction of CO₂ to CO, and characterized their notably different ground‐ and excited‐state interactions with CO₂ and their hydricities using experimental and computational methods. Only one isomer, C‐trans‐[Ir(tpy)(ppy)H]⁺, reacts with CO₂ to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH₃CN/TEOA, a common reactive C‐trans‐[Ir(tpy)(ppy)]⁰ species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO₂ and produces CO with the same catalytic efficiency.     

Simultaneous detection of ammonia and humidity using transmission surface plasmon resonance technique

Abstract

Gas sensing by using the transmission surface plasmon resonance (T-SPR) technique was demonstrated. Polyacrylic acid (PAA)/5-nm-thick gold/40-nm-thick silver/polycarbonate grating substrate structure (Sensor A) responded to ammonia; however, it exhibited a strong humidity dependence. Polyvinyl alcohol (PVA)/5-nm-thick gold/40-nm-thick silver/polycarbonate grating substrate structure (Sensor B) as the sensing material was also prepared and it mainly responded to humidity. The T-SPR properties of Sensors A and B were observed simultaneously by a stacking arrangement that enabled us to obtain the responses by using a single spectrophotometer. The ammonia concentration under various humidity conditions could be accurately obtained by simultaneous measurement of Sensors A and B.     

Dibenzylmagnesium-Initiated Anionic Oligomerizations of trans-Stilbene, 1,1-Diphenylethylene,and α-Methylstyrene in Hexamethylphosphortriamide

trans-Stilbene, 1, 1-diphenylethylene, and α-methylstyrene were allowed to react with dibenzylmagnesium to form their oligomers in hexamethylphosphortriamide (HMPA). One and two molecules of stilbene and 1, 1-diphenylethylene were incorporated into the magnesium carbon bond, and the carbanions obtained in HMPA were stable in analogy with the anionic living polymer having alkali cation as the gegenion in eithers. Intense coloration was observed during the reaction between α-methylstyrene and dibenzylmagnesium as well as in the case of stilbene and 1, 1-diphenylethylene. The low molecular weight products which were formed after a long time in the reaction between α-methylstyrene and dibenzylmagnesium were found to have no magnesium-carbon bond. It was considered that the cleavage of the propagating chain occurred gradually after the rapid propagation had proceeded to consume the monomer.     

Corrigendum to “Constraints on operator ordering from third quantization” [Ann. Phys. 365 (2016) 54–65]

In our previous paper Ohkuwa et al. (2016) corrigendum was found in Eqs. (3.4) and (3.6). However, conclusions of our previous paper are not changed.     

Numerical simulation of cyclic voltammetry for reversible systems with complex stoichiometry

Reversible waves of voltammetry with complex non-unity stoichiometry are studied here based on theory. Numerical simulations were performed for various stoichiometric systems in which coefficients m and q were independently varied from 1 to 4 in a general reaction scheme, mO + ne⁻ ai qR. The calculation results indicate that the peak current function at complex stoichiometry differs from that at simple unity stoichiometry. The relation between the half-wave potential and the formal potential has been partially corrected from that previously reported in the literature. Parameters in the relation between the peak potential and the half-wave potential are unique for each stoichiometric system. The parameter in the relation between the peak potential and the half-peak potential is also presented here.     

On distorted probabilities and m-separable fuzzy measures

Fuzzy measures are used in conjunction with fuzzy integrals for aggregation. Their role in the aggregation is to permit the user to express the importance of the information sources (either criteria or experts). Due to the fact that fuzzy measures are set functions, the definition of such measures requires the definition of 2ⁿ parameters, where n is the number of information sources. To make the definition easier, several families of fuzzy measures have been defined in the literature.In this paper m-separable fuzzy measures are introduced. We present some results on this type of measures and we relate them to some of the previous existing ones. We study generating functions for m-separable fuzzy measures and some properties related to these generating functions.     

Neutron Diffraction Study on the Structure of Aqueous LiNO3 Solutions

Neutron diffraction measurements were carried out at 25 °C for aqueous LiNO₃ heavy water solutions, (*LiNO₃) _x (D₂O)_1?x where x = 0.1, 0.05 and 0.01, in which the ⁶Li/⁷Li isotopic ratios were varied. Structural information on intermolecular nearest neighbor Li⁺···D₂O interactions in the extensive concentration range was derived from the first-order difference function, ?_Li(Q), obtained from the difference in scattering cross sections between ⁶Li- and ⁷Li-enriched sample solutions. The nearest neighbor Li⁺···O distance and coordination number for sample solution with x = 0.1 were determined to be r _LiO = 1.969 (8) Å and n _LiO = 4.12 (6), respectively, corresponding to the four-coordinated Li⁺ ion in the solution. On the other hand, those obtained for the solution with x = 0.01 are r _LiO = 2.00 (2) Å and n _LiO = 6.0 (2), respectively, indicating that hexaaqua Li⁺ is dominant in the dilute solution. These results clearly indicate that a concentration dependence of the hydration number of Li⁺ occurs in the aqueous solutions.     

Spectral parameters and Hamaker constants of silicon hydride compounds and organic solvents

Cyclopentasilane (CPS) and polydihydrosilane, which consist of hydrogen and silicon only, are unique materials that can be used to produce intrinsic silicon film in a liquid process, such as spin coating or an ink-jet method. Wettability and solubility of general organic solvents including the above can be estimated by Hamaker constants, which are calculated according to the Lifshitz theory. In order to calculate a Hamaker constant by the simple spectral method (SSM), it is necessary to obtain absorption frequency and function of oscillator strength in the ultraviolet region. In this report, these physical quantities were obtained by means of an optical method. As a result of examination of the relation between molecular structures and ultraviolet absorption frequencies, which were obtained from various liquid materials, it was concluded that ultraviolet absorption frequencies became smaller as electrons were delocalized. In particular, the absorption frequencies were found to be very small for CPS and polydihydrosilane due to σ-conjugate of their electrons. The Hamaker constants of CPS and polydihydrosilane were successfully calculated based on the obtained absorption frequency and function of oscillator strength.