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The development of selective electrocatalysts for the chlorine evolution reaction (CER) is majorly restrained by a scaling relation between the OCl and OOH adsorbates, rendering that active CER catalysts are also reasonably active in the competing oxygen evolution reaction (OER). While theory predicts that the OCl versus OOH scaling relation can be circumvented as soon as the elementary reaction steps in the CER comprise the Cl rather than the OCl adsorbate, it was demonstrated recently that PtN4 sites embedded in a carbon nanotube follow this theoretical prediction. Advanced experimental analyses illustrate that the PtN4 sites also reveal a different reaction kinetics compared to the industrial benchmark of dimensionally stable anodes (DSA). A reverse Volmer–Heyrovsky mechanism was identified, in which the rate-determining Volmer step for small overpotentials is followed by the kinetically limiting Heyrovsky step for larger overpotentials. Since the PtN4 sites excel DSA in terms of activity and chlorine selectivity, we suggest the Cl intermediate as well as the reverse Volmer–Heyrovsky mechanism as the design criteria for the development of next-generation electrode materials beyond DSA. 相似文献
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Stephen Fletcher 《Journal of Solid State Electrochemistry》2009,13(4):537-549
Tafel slopes for multistep electrochemical reactions are derived from first principles. The derivation takes place in two stages. First, Dirac’s perturbation theory is used to solve the Schrödinger equation. Second, current–voltage curves are obtained by integrating the single-state results over the full density of states in electrolyte solutions. Thermal equilibrium is assumed throughout. Somewhat surprisingly, it is found that the symmetry factor that appears in the Butler–Volmer equation is different from the symmetry factor that appears in electron transfer theory, and a conversion formula is given. Finally, the Tafel slopes are compiled in a convenient look-up table. 相似文献
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Josefina Viades-Trejo Alfredo Amigo J. Gracia-Fadrique 《Fluid Phase Equilibria》2006,250(1-2):158-164
A new alternative is presented for activity coefficients at infinite dilution determination via surface tension data of low vapour pressure substances. It was found that experimental data for surfactants follows Volmer's surface equation of state behaviour over the diluted region until the critical micelle concentration. The key operations are: the choice of the same standard conditions for the bulk and the surface phases, the combination of Gibbs and Volmer equations and the use of the symmetric activity coefficients convention. An exact relation between the activity coefficient at infinite dilution and the reciprocal of the critical micelle mole fraction was found which allowed us the verification of the model. 相似文献
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We present an analytical model of transient compressive stress evolution during growth of thin films with high surface and grain boundary diffusivities on substrates. The model provides a closed-form analytical solution which compares well with numerical analysis as well as recent experimental data on transient stress evolution during electrodeposition of Sn films on substrates. 相似文献
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Siavash Riahi Mohammad Reza Ganjali Maryam Hariri Shaghayegh Abdolahzadeh Parviz Norouzi 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,74(1):253-258
In this paper, a sensitive, easy, efficient, and suitable method for the calculation of Kf values of complexation between one derivative of Dansyl chloride [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (DMNP) and Lanthanide(III) (Ln) ions is proposed, using both spectrofluorometric and spectrophotometric methods. Determination of Kf showed that DMNP was mostly selective towards the erbium (III) ion. The validity of the method was also confirmed calculating the Stern–Volmer fluorescence quenching constants (Ksv) that resulted in the same consequence, obtained by calculating the Kf of complexation values. In addition, the UV–vis spectroscopy was applied for the determination of Kf only for the Ln ions that had interactions with DMNP. Finally, the DFT studies were done on Er3+ and the DMNP complex for distinguishing the active sites and estimating the pair wise interaction energy. It can be concluded that this derivative of Dansyl chloride with inherent high fluorescence intensity is a suitable reagent for the selective determination of the Er3+ ion which can be used in constructing selective Er3+ sensors. 相似文献
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Dong Wook Chang Seo‐Yoon Bae Liming Dai Jong‐Beom Baek 《Journal of polymer science. Part A, Polymer chemistry》2013,51(1):168-175
The efficient fluorescence resonance energy transfer (FRET) between amphiphilic dendrimers with oligo(p‐phenylenevinylene) core branches and oligo(ethylene oxide) termini have been observed in micelles. All dendrimers show the critical micelle concentration and lower critical solution temperature as well as fluorescent emission. Tailoring electronic structures of the conjugated amphiphiles for FRET have been conveniently achieved by varying the branch number and/or the conjugated core structure. The Stern‐Volmer constants (KSV) for FRET were found to be 4.51 × 10?5 and 8.78 × 10?5 M for Den 30–40 and Den 50–40, respectively. The effects external stimuli such as solvent and temperature on FRET have been also investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
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Qiang Li Joshua Gies Dr. Xiu-Jun Yu Prof. Dr. Yu Gu Prof. Dr. Andreas Terfort Dr. Martin Kind 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5185-5189
The layer-by-layer (LbL) method is a well-established method for the growth of surface-attached metal–organic frameworks (SURMOFs). Various experimental parameters, such as surface functionalization or temperature, have been identified as essential in the past. In this study, inspired by these recent insights regarding the LbL SURMOF growth mechanism, the impact of reactant solutions concentration on LbL growth of the Cu2(F4bdc)2(dabco) SURMOF (F4bdc2−=tetrafluorobenzene-1,4-dicarboxylate and dabco=1,4-diazabicyclo-[2.2.2]octane) in situ by using quartz-crystal microbalance and ex situ with a combination of spectroscopic, diffraction and microscopy techniques was investigated. It was found that number, size, and morphology of MOF crystallites are strongly influenced by the reagent concentration. By adjusting the interplay of nucleation and growth, we were able to produce densely packed, yet thin films, which are highly desired for a variety of SURMOF applications. 相似文献
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The luminescence lifetime (lum) and the luminescence spectra of the title complex (I) were determined in eight solvents. We found that in spite of former assumptions, the lum of I depends on the concentration of the complex. We determined the self-quenching (k
Q) and Stern–Volmer (K
SV) constants, and the relative values of luminescence quantum yields in eight solvents. There was no measurable self-quenching in 1,2-ethanediol and N,N-dimethylformamide; dynamic self-quenching was found (the concentration dependence of lum and lum was the same) in N,N-dimethylacetamide, dimethylsulfoxide, water, propylene–carbonate, and pyridine. In acetonitrile we found both dynamic and static self-quenching based on the different concentration dependence of lum and lum of I; K
SV and the association constant of I in acetonitrile were computed 相似文献