Nitrogen doping in ion-exchangeable layered tantalate towards visible-light induced water oxidation

An ion-exchangeable layered photocatalyst CsCa(2)Ta(3)O(10) was doped with nitrogen. The as-prepared photocatalyst (N-doped CsCa(2)Ta(3)O(10)) is stable and demonstrates high performance for catalyzing water oxidation under visible light irradiation.     

Work distribution function for a Brownian particle driven by a nonconservative force

We derive the distribution function of work performed by a harmonic force acting on a uniformly dragged Brownian particle subjected to a rotational torque. Following the Onsager and Machlup’s functional integral approach, we obtain the transition probability of finding the Brownian particle at a particular position at time t given that it started the journey from a specific location at an earlier time. The difference between the forward and the time-reversed form of the generalized Onsager-Machlup’s Lagrangian is identified as the rate of medium entropy production which further helps us develop the stochastic thermodynamics formalism for our model. The probability distribution for the work done by the harmonic trap is evaluated for an equilibrium initial condition. Although this distribution has a Gaussian form, it is found that the distribution does not satisfy the conventional work fluctuation theorem.     

Dilute Solution Properties of Styrene-N-Butyl Methacrylate (65:35) Copolymer: Short- and Long-Range Interaction of the Polymer Chain

Abstract

Viscosity and light-scattering data on styrene-n-butyl methacrylate (65:35) in chloroform are presented and tested by the two-parameter theoretical relations. The short-range interactions K and A and the long-range interaction parameter B have been calculated by different equations, using intrinsic viscosity and second virial coefficient data. These are then compared to the values of the homopolymer polystyrene. The conformation or the steric factor for the polymer chain has also been calculated. The excluded volume parameter Z, which is related to both the short- and long-range parameters, has been evaluated along with the expansion factor α _n . The higher value of the short-range parameters and the conformation factor compared to the parent styrene homopolymer is attributed to the effect of unlike monomer interactions causing extension of the polymer chain. An increase in the restriction of the internal rotation of side chains about the C-C bonds is also suggested. The excess interaction parameter has a negative value. The expansion factor α _n has been related to the excluded volume factor Z and the coefficient C is in close agreement with the theoretically calculated value of Yamakawa and Tanaka.     

Bis(acetonitrile)bis(acetylacetonato)ruthenium(III) mediated chemical transformations of coordinated 2-methylthioanilide

Chemical reaction of [Ru(III)(acac)(2)(CH(3)CN)(2)]ClO(4) (1) with 2-methylthioaniline, HL(1) in ethanol under basic conditions yielded three new complexes Ru(II)(acac)(2)(L(1b)) (1b), (L(1b) = 4-imino-3-(methylsulfanyl)cyclohexa-2,5-dien-1-one), Ru(III)(acac)(2)(L(1c)) (1c), (HL(1c) = N-(2-methylthiophenyl)formamide) and (acac)(2)Ru(II)(μ-L(1d))Ru(II)(acac)(2) (1d), (L(1d) = 1,4-bis(2-methylthioaniline)-1,4-diazabutadiene) via the intermediate Ru(III)(acac)(2)(L(1a)) (1a, L(1a) = (L(1))(-) = 2-methylthioanilide). The reaction proceeded through temperature induced valence tautomerisation between the Ru(III) center and its 2-methylthioanilide counterpart in 1a with concomitant reduction of ruthenium from +III to +II oxidation state and oxidation of ligand L(1a), resulting in aromatic ring hydroxylation, N-formylation and C-C bond formation reactions. All the complexes have been characterised by their single-crystal X-ray structure determination and various spectroscopic and electrochemical techniques. The identity of complex 1a has been confirmed by X-ray crystal structure determination of complex 2, a phenyl analogue of complex 1a. The complexes (1a-d) showed intense charge transfer (MLCT/LMCT) transition in the long wavelength region. The paramagnetic compounds, 1a and 1c, along with the diamagnetic compound 1b showed two one-electron responses in the ranges, -0.4 to -1.0 V and 0.3 to 1.1 V. The diamagnetic complex 1d displayed two successive one-electron reversible reductions (-1.31 and -1.55 V) and two one-electron reversible oxidation processes (-0.036 and 0.51 V). The redox processes are characterized by EPR spectroscopy and spectroelectrochemistry. The compound 1c has been found to exhibit solvatochromism and concentration dependent aggregation in solution.     

Sodium-alizarin-3-sulphonate as a colloidal electrolyte

Summary During the study of the composition of metal chelates of sodium alizarin-3-sulphonate, it was realized that the colloidal nature of the reagent, especially in concentrated solutions, masks the true composition of the chelate. An investigation of the electrical conductance at various dilutions and temperatures shows that the reagent belongs to the class of colloidal electrolytes. It is recommended that for the study of the composition of chelates involving such chelating agents, extremely dilute solutions should be employed for physicochemical investigation, because under these conditions the reagent would behave as a true electrolyte.     

g-B3C2N3: A Potential Two Dimensional Metal-free Photocatalyst for Overall Water Splitting**

Based on hybrid density functional theory (DFT) calculations, we propose a new two-dimensional (2D) B-C-N material, graphitic- (g- ), with the promising prospect of metal-free photocatalysis. We find it to be a near ultraviolet (UV) absorbing direct band gap (3.69 eV) semiconductor with robust dynamical and mechanical stability. Estimating the band positions with respect to water oxidation and hydrogen reduction potential levels along with a detailed analysis of reaction mechanism of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), we observe that g- monolayer can be efficiently used for hydrogen fuel generation over entire pH range as well as for spontaneous water splitting at basic pH range. Upon biaxial strain application, band positions get realigned along with the free energy change that is involved in HER and OER. Consequently, operational range of pH for OER gets broadened and the proposed material exhibits the ability to perform spontaneous and simultaneous oxidation and reduction even in neutral pH. The combination of pH variation and applied strain can be used as a key to control the reducing and/or oxidizing abilities precisely for diverse photocatalytic reactions to attain environmental sustainability.