bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modification of Electrodes for MFC Using Sludge from the Wastewater Treatment Plant
Authors: Ibañez-Redín Glenda Gisela , Chaur Manuel Noe , Bravo Enrique , Lizcano-Valbuena William Hernando 
Published: February 2020

Carbon Vulcan XC 72R was modified using several chemical treatments (oxidation in acidic medium, ethylene glycol, 4-aminopyridine and rubeanic acid treatments) changes in the electrochemical behavior and the surface composition were observed. Pieces of carbon tissue were modified with the carbon materials. The pieces of carbon tissue were electrochemically characterized and used as anodes in a single chamber air cathode MFCs (Microbial Fuel Cells ) inoculated with sludge from the Wastewater Treatment plant of La Voragine, yielding a maximum power density of 15.37 mWm-2 and a maximum current density of 61.25 mAm-2 for the cell with the electrode modified with ethylene glycol. To compare the performance of the anodes were measured anodic polarization curves, which showed better performance for the rubeanic acid modified electrode. The lower performance was obtained for the unmodified electrode followed by electrode modified by chemical oxidation. These results suggest a reduction in biocompatibility by the introduction of negatively charged groups.
The results of the cultivation and isolation of microorganisms in the anode showed a greater affinity of the bacteria for the rubeanic acid modified electrode and the exclusive presence of a microorganism in it. Additionally was observed the presence of redox mediators producing bacteria on the electrode modified by oxidative treatment. The results show the influence of the surface composition on the biofilm composition and probably in the electron transfer mechanism.
The Electrolytic Dissociation of 1,4-Cyclohexanedicarboxylic Acid
Authors: Kvaratskhelia Elene , Kvaratskhelia Ramaz , Kurtanidze Rusudan 
Published: February 2020

Cyclohexanedicarboxylic acids are widely used as the members of the positive resist radiation-sensitive composition, the coating resinous compositions, for production the high-solid polyurethane coatings for such demanding markets as automotive, transportation, maintenance, and aerospace. In this communication the regularities of electrolytic dissociation of trans-1,4-cyclohexanedicarboxylic acid are studied by the suggested by authors original method for calculation the parameters of dissociation of weak multibasic organic acids with the “overlapping” equilibria effect.
For weak dibasic organic acids the law of dilution for both dissociation steps may be expressed as follows:
where K1 and K2 are the thermodynamic dissociation constants of first and second steps, α1 and α2 are the usual degrees of dissociation of these steps, α′
2 is the “partial” degree of dissociation of second step, c is the total (analytical) concentration of acid, F1 and F2are the quotients of the activity coefficients for the corresponding steps:
The values of the activity coefficients were approximated by the Debye-Huckel equation:
where ai is the cation-anion distance of closest approach, A and B are constants depending on the properties of water at given temperature, ziis the charge of ion. Ionic strength .
According to equations [1] and [2] the degrees of dissociation α1, α2 and α′
2can be evaluated successively by iterative solution of following two quadratic equations:
The equilibrium concentrations of the dissociation products: hydrogen ions, mono- and dianions and undissociated acid molecules can be calculated with the aid of the following equations:
The dissociation constants of trans-1,4-cyclohexanedicarboxylic acid have the following values: K1=6.607×10ˉ5; K2=3.802×10ˉ6.
In Tables I the values of α1, α2, α′
2and pH for the dilute solutions of acid are presented.

Table I. The values of the dissociation parameters
of trans-1,4-cyclohexanedicarboxylic acid
at 16ºC

Concentration, M

α1

α2

α′
2

pH

0.00010.00020.00040.00060.00080.0010.0020.0040.0060.0080.01
0.55070.43650.33580.28490.25250.22950.16910.12330.10210.089260.08035
0.034720.018260.0094730.006427
0.004875
0.003932
0.0020140.0010300.0006954
0.0005267
0.0004246
0.063050.041830.028210.022560.019310.017130.011910.008354
0.006811
0.005901
0.005284
4.2364.0463.8663.7643.6933.6393.4743.3143.2213.1563.106

We suggest also the simple empirical equations for fast approximate calculation of the dissociation parameters of trans-1,4-cyclohexanedicarboxylic acid:
Modified Surfaces by Electrodeposition for Energy Devices
Authors: Innocenti Massimo , Lavacchi Alessandro , Vizza Francesco , Di Benedetto Francesco , Zafferoni Claudio , Foresti Maria Luisa 
Published: February 2020

The global environmental concerns and the escalating demand for energy, coupled with a steady progress in renewable energy technologies, are opening up new opportunities for the utilization of renewable energy resources. Electrodeposition is well known for depositing metals and metallic alloys at the industrial level, with a wide range of applications from large area surface treatments to most advanced electronic industries. Electrodeposition of semiconducting materials represents a new challenge, not only from the academic point of view, but also from the economic point of view, since this method presents interesting characteristics for large area, low cost and generally low temperature and soft processing of materials. In this presentation, we exploited alternated electrodeposition of some metals by E-ALD (Electrochemical Atomic Layer Deposition) to obtain thin films, controlling the growth of the structures at the nanometric level. Selective Electrodesorption Based Atomic Layer Deposition (SEBALD [1]) was used to prepare new bimetallic electrodes for fuel cells. This new method of Electrodeposition, recently pointed out in Florence on the base of ECALE method [2], allows to deposit under morphological and compositional control those metals that cannot be deposited at underpotential. We have recently reported the use of nanostructured palladium in the realization of a new “green” and energetically self-sustainable paradigm for the chemical industry based on the electro-oxidation of renewable alcohols [3]. The exploitation of the catalytic properties of palladium toward the oxidation of alcohols strongly depends on the availability of methods capable of generating supported metal nanoparticles with high index facets, as well as selecting size and metal loading. The concomitant control of all these aspects is a major challenge for nanotechnology oriented to catalysis and electrocatalysis.
To achieve these targets we developed a method (Electrochemical Milling and Faceting – ECMF [4]), consisting of an electrochemical post-deposition treatment. Ultimately the purpose of the method is to perform a milling and faceting of the palladium nanoparticles deposited by virtually any known deposition
method.
[1] M. Innocenti, S. Bellandi, E. Lastraioli, F. Loglio, and M. L. Foresti, Langmuir, 2011.
[2] Gregory, B. W.; Stickney, J. L. J. Electronanal. Chem. 1991, 300, 543.
[3] V. Bambagioni, M. Bevilacqua, C. Bianchini, J.
Filippi, A. Lavacchi, A. Marchionni, F. Vizza and P. K.
Shen, ChemSusChem, 3 (2010) 851.
[4] Y.X. Chen, A. Lavacchi, S.P Chen, F. Di Benedetto, M. Bevilacqua, C. Bianchini, P. Fornasiero, M. Innocenti, M. Marelli, W. Oberhauser, .S.G. Sun, F. Vizza.
Angew. Chem. Int. Ed. 2012, 51, 8500 –8504.
Electrochemical Reaction of Tris(1,10-phenanthroline)Iron Complexes in Some Amide-Type Ionic Liquids
Authors: Katayama Yasushi , Yoshihara Mami , Miura Takashi 
Published: February 2020

Electrochemical behavior of a charged species in ionic liquids have been known to depend on the physicochemical properties of the ionic liquids[1-4]. Diffusion of the charged species is affected not only by the viscosity of the ionic liquids but also by the coulombic interaction between the charged species and the ions composing the ionic liquids. Thus, Stokes-Einstein relation is generally inapplicable to diffusion of charge species in ionic liquids. The electron transfer rates are also influenced by the viscosity and the coulombic interaction, which is considered related to the outer component of reorganization energy. Furthermore, the reaction entropy of the redox couples without change of their coordination environment has been found to relate to the coulombic interaction[5,6]. We have reported these results with tris(2,2'-bipyridine) complexes of iron and ruthenium in some ionic liquids. In the present study, electrochemical reactions of tris(1,10-phenanthroline)iron and tris(2,2'-bipyridine)iron complexes were investigated in 1-butyl-1-methylpyrrolidinium (BMP+) and 1-ethyl-3-methylimidazolium (EMI+) bis(trifluoromethylsulfonyl)amide (TFSA–) ionic liquids in order to elucidate the effects of the charge density of the redox species on electrode kinetics and reaction entropy. The diffusion coefficient of [Fe(phen)3]
n+ was smaller than that of [Fe(bpy)3]
n+ (n = 2 and 3) in BMPTFSA and EMITFSA. The ratios of diffusion coefficients of [Fe(phen)3]3+ to [Fe(phen)3]2+ were larger than those of [Fe(bpy)3]3+ to [Fe(bpy)3]2+, indicating the coulombic interaction of TFSA– with [Fe(phen)3]
n+ is weaker than that with [Fe(bpy)3]
n+ since the size of [Fe(phen)3]
n+ is larger than that of [Fe(bpy)3]
n+. The rate constants for [Fe(phen)3]3+/2+ were close to those for [Fe(bpy)3]3+/2+. On the other hand, the reaction entropy for [Fe(phen)3]3+/2+ was smaller than that for [Fe(bpy)3]3+/2+, reflecting the difference in the charge densities.
References
[1] N. Tachikawa, Y. Katayama, and T. Miura, J. Electrochem. Soc., 154, F211 (2007).
[2] N. Tachikawa, Y. Katayama, and T. Miura, Electrochem. Solid-State Lett., 12, F39 (2009).
[3] Y. Toshimitsu, Y. Katayama, and T. Miura, Electrochim. Acta, 82, 43 (2012).
[4] Y. Katayama, Y. Toshimitsu, and T. Miura, J. Electrochem. Soc., 160, H219 (2013).
[5] T. Migita, N. Tachikawa, Y. Katayama, and T. Miura, Electrochemistry, 77, 639 (2009).
[6] Y. Yamato, Y. Katayama, and T. Miura, J. Electrochem. Soc., 160, H309 (2013).
Energy Efficient Capture and Release of Carbon Dioxide in Tetraalkyl Phosphonium and Tetraalkyl Ammonium Ionic Liquids
Authors: Rheinhardt Joseph , Buttry Daniel A. 
Published: February 2020

Described herein is an electrochemical method for the energy efficient capture and release of CO2 that employs electrochemically-generated thiolates as the CO2 capture agents. In N,N-dimethylformamide at glassy carbon electrodes the onset of CO2 reduction precludes capture by electrochemically generated thiolates. This is not the case in tetraalkyl phosphonium and tetraalkyl ammonium ionic liquids. In these media saturated with CO2, electrochemical reduction of disulfides to thiolates proceeds via a two-electron process with potential inversion.1 One-electron reduction of the disulfide results in dissociative electron transfer (DET), the first step of which is the formation of a short-lived radical anion.2 The S–S σ bond of the radical anion is subsequently cleaved leading to a thiolate and a sulfur-based radical.2 Resultant sulfur radicals are reduced at potentials positive of the potential applied for reduction of the corresponding disulfide. Thus, electrochemical thiolate generation is best formulated as a two-electron reduction with concomitant disulfide cleavage.3 In this presentation we will show that the potent, electrochemically generated sulfur nucleophiles capture CO2 via a facile SN2 reaction leading to formation of a thiocarbonate (Scheme 1). We will further demonstrate that the mechanism for the release of CO2 and regeneration of the disulfide is the one-electron Kolbe oxidation of the thiocarbonate followed by coupling of two sulfur radicals (Scheme 2).4 Cyclic voltammograms show that thiocarbonate oxidation occurs at potentials positive of thiolate oxidation. Increases in the peak-to-peak separation between thiolate oxidation and thiocarbonate oxidation have been ameliorated by targeted modifications to the disulfide.
(1) Evans, D. H. Chem. Rev.
2008, 108, 2113–2144.
(2) (a) Antonello, S.; Benassi, R.; Gavioli, G.; Taddei, F.; Maran, F. J. Am. Chem. Soc.
2002, 104, 7529–7538. (b) Meneses, A. B.; Antonello, S.; Arévalo, M. C.; Gonzáles, C. C.; Sharma, J.; Wallette, A. N.; Workentin, M. S.; Maran, F. Chem. Eur. J.
2007, 13, 7983–7995.
(3) Hall, G. B.; Kottani, R.; Felton, G. A. N.; Yamamoto, T.; Evans, D. H.; Glass, R. S.; Lichtenberger, D. L. J. Am. Chem. Soc.
2014, 136, 4012–4018.
(4) Vijh, A. K.; Conway, B. E.; Chem. Rev.
1967, 67, 623–664.
The Composition of the Second Coordination Sphere and Charge Transfer of the Nb(V)/Nb(IV) Redox Couple in Alkali Halide Melts
Authors: Popova Anna V. , Kremenetsky Vyacheslav G. , Kuznetsov Sergey A. 
Published: February 2020

The effect of the second coordination sphere and the working electrode nature on the standard rate constants of charge transfer (k
s) for the Nb(V)/Nb(IV) redox couple in chloride-fluoride and fluoride melts was studied.
The standard rate constants for the Nb(V)/Nb(IV) redox couple were calculated based on cyclic voltammetry data and the Nicholson’s equation.
The following unusual series of the standard rate constants of charge transfer is experimentally determined in chloride-fluoride melts:

k
s (KCl) < k
s (CsCl) < k
s
(NaCl-KCl).
Ab initio calculations carried out by using PC Gamess/Firefly quantum chemical program showed that charge transfer activation energies can actually change in nonmonotonic manner in the series sodium-potassium-cesium, which leads to nonmonotonic change of the charge transfer rate constants in chloride-fluoride melts.
In pure fluoride melts, the following dependence of the standard rate constants was obtained using cyclic voltammetry:

ks
(CsF) < ks
(KF) < ks
(NaF-KF).
It has been established that the standard rate constants of charge transfer increase with increasing temperature, as well as with replacement of the glassy carbon electrode with a platinum one.
Acknowledgments
The work was financially supported by the Russian Foundation for Basic Research (project 12-08-01178-а).
The High Temperature Operation of Lithium Secondary Batteries with Using Ionic Liquids
Authors: Matsumoto Hajime , Kubota Keigo 
Published: February 2020

Ionic liquids (ILs) composed of perfluoroanion such as BF4
− and bis(trifluoromethylsulfonyl)amide (([(CF3SO2)2N]−, Tf2N−) have attracted attention as less flammable and less volatile electrolyte for a lithium secondary battery for past decade. Especially, Tf2N- forms ILs not only 1-ethyl-3-methylimidazolium (C2mim+), but also various aliphatic quaternary ammonium (AQA+). The AQA-Tf2N exhibited large apparent electrochemical windows enough wide to use a solvent free electrolyte for a 4 V-class battery such as a LiCoO2 half-cell. Though the rate properties of the cell at room temperature were much lower than that for a conventional organic solvents, another promising ILs composed of bis(fluoromethylsulfonyl)amide (f2N−) are dramatically improved the rate property of the cells using ILs. However, it should be focused on not only the rate performance but also the actual thermal stability of the cells using ILs, which might not depend on only the thermal stability of ILs.[1]
In this presentation, we would like to show the effect of cationic species of Tf2N--ILs on the cycle stability of a cathode half-cell at high temperature over 100 °C. For this purpose, a conventional LiFePO4 cathode composed of polyvinylidene fluoride (PVDF) (KUREHA, #1120) as binder and acetylene black (AB) as the conductive additive. We found that the rate property of the LiFePO4half-cells were much improved over 85 °C and also the cycle performance of the cells over 100 °C were much depend on the kind of cation in ILs.

Acknowledgements

A part of this work was supported by the R&D project for Li batteries by NEDO of Japan (Li-EAD) and Advanced Low Carbon Technology Research and Development Program (ALCA) of Japan Science and Technology Agency (JST).

Reference

[1] H. Matsumoto, in Electrolytes for Lithium-ion Batteries, eds. T. R. Jow, K. Xu, O. Borodin and M. Ue, Springer, 2014, ch.4 and references therein.
Inorganic-Organic Hybrid Ionic Liquid Electrolytes for Na Secondary Batteries
Authors: Matsumoto Kazuhiko , Taniki Ryosuke , Nohira Toshiyuki , Hagiwara Rika 
Published: February 2020

Sodium secondary batteries are attracting more and more attraction as energy storage devices for stationary use and electric vehicles due to high abundance and low cost of sodium resources as well as the low redox potential of Na+/Na. Ionic liquid electrolytes are attractive to improve the safety issues of sodium secondary batteries, owing to their unique properties such as low flammability and low vapor pressure [1-3]. Our recent works suggest FSA- (FSA- = bis(fluorosulfonyl)amide anion) based ionic liquids, such as Na[FSA]-K[FSA] and Na[FSA]-[C3C1pyrr][FSA] (C3C1pyrr+ = N-propyl-N-methylpyrrolidinium cation) systems, exhibit good physical and electrochemical properties as electrolytes for Na secondary batteries [4-6]. This study will present a new series of inorganic-organic hybrid ionic liquids as electrolytes for Na secondary batteries.
Four FSA salts of organic cations, N6111
+ (hexyltrimethylammonium), N4422
+ (dibutyldimethylammonium), AS[4.5]+ (azoniaspiro[4.5]nonane), and C2C1im+ (1-ethyl-3-methylimidazolium), are mixed with Na[FSA]. In all the cases, a wide liquid temperature range around room temperature was observed in a certain x(Na[FSA]) range. Ionic conductivity and viscosity increase and decrease with decreasing x(Na[FSA]), respectively. The highest ionic conductivity was observed for the Na[FSA]-[C2C1im][FSA] system. Electrochemical windows are around 5 V and Na metal deposition and dissolution are observed at the cathode limit. The efficiency of Na metal deposition and dissolution is improved by increasing temperature due to suppression of dendritic Na metal deposition.
[1] L.G. Chagas, D. Buchholz, L.M. Wu, B. Vortmann, S. Passerini, J. Power Sources, 247 (2014) 377-383.
[2] S.A.M. Noor, P.C. Howlett, D.R. MacFarlane, M. Forsyth, Electrochim. Acta, 114 (2013) 766-771.
[3] D. Monti, E. Jonsson, M.R. Palacin, P. Johansson, J. Power Sources, 245 (2014) 630-636.
[4] C. Ding, T. Nohira, K. Kuroda, R. Hagiwara, A. Fukunaga, S. Sakai, K. Nitta, S. Inazawa, J. Power Sources, 238 (2013) 296-300.
[5] T. Yamamoto, T. Nohira, R. Hagiwara, A. Fukunaga, S. Sakai, K. Nitta, S. Inazawa, J. Power Sources, 217 (2012) 479-484.
[6] C.Y. Chen, K. Matsumoto, T. Nohira, R. Hagiwara, A. Fukunaga, S. Sakai, K. Nitta, S. Inazawa, J. Power Sources, 237 (2013) 52-57.
Synthesis and Characterizations of Cobalt Films Electrochemically Deposited from Aqueous and Non-Aqueous Media
Authors: Dushatinski Thomas , Huff Clay , Abdel-Fattah Tarek M 
Published: February 2020

Optically absorbent materials have applications in both high-resolution optical imaging and photonic conversion systems. In optical imaging, these materials can be used to reduce the amount of parasitic light. Reducing the parasitic light present in a system increases the possible resolution, making highly optically absorbent materials important for advancements in imaging devices, such as telescopes and optical microscopes. Cobalt films convert absorbed light to heat and transfer it effectively because of their thermal conductivity. This property combined with the characteristics of novel non-aqueously deposited cobalt films (NADCFs) has applications in thermal photonic conversion systems. The characteristics of novel NADCFs are much different than traditional aqueously deposited films (ADCFs) and have much better optical absorbance that can be attributed to their microstructures porosity.
The two films were characterized using UV-Vis Spectroscopy to determine percent absorbance, energy dispersive x-ray spectroscopy (EDS) to infer density, and scanning electron microscopy (SEM) to determine microstructure and thickness. SEM micrographs of the cobalt micro-particles differed depending on solvent (Figure 1). The SEM images and EDS spectra together show a less dense accumulation of micro-particles in the NADCFs compared to the ADCFs. Greater porosity in the 180µm thick NADCF compared to the 115µm thick ADCF was confirmed by the transmission of the x-ray beam in EDS to the copper substrate, showing copper peaks. Thicknesses were determined using cross-section analysis in SEM. The optical absorbance of both films as produced were measured. NADCFs had >99% absorbance and the ADCFs had 95% absorbance at 490nm.

References:

[1] Florea, A.; Anicai, L.; Costovici, S.; Golgovici, F.; Visan, T. 2010, Surf.
Interface Anal, 42, 1271-1275
[2] Abdel-Fattah, T.M.; Crooks, R. 2010, ECS Trans, 33, 571
[3] Abdel-Fattah, T.M.; Loftis, J.D. 2010, ECS Trans, 25, 57
[4] Abdel-Fattah, T.M.; Loftis, J.D.; Mahapatro2010, ECS Trans, 25, 57
[5] Abdel-Fattah, T.M.; Loftis, J.D. 2009, ECS Trans. 25, 327
[6] Damiano, B.; Wixtrom, A.; Abdel-Fattah, T. 2012,
ECS Trans.

[7] Jiovannini H.; Amra,C. 1998, Applied Optics. 37(1), 104-105.
"Core-Shell" ORR Nano-Electrocatalysts Based on a PtNi Carbon Nitride "Shell" and Cu NP "Core"
Authors: Di Noto Vito , Negro Enrico , Vezzù Keti , Bertasi Federico 
Published: February 2020

One of the most severe bottlenecks in the operation of proton exchange membrane fuel cells (PEMFCs) is the sluggish kinetics of the Oxygen Reduction Reaction (ORR). Thus, suitable ORR electrocatalysts are required in order to obtain PEMFCs able to yield a sufficiently high performance [1]. State-of-the-art ORR electrocatalysts for application in PEMFCs are obtained by supporting Pt nanocrystals on active carbon supports characterized by a very large surface area [2]. However, despite extensive investigations the performance of these electrocatalysts does not meet yet the strict requirements necessary for a large-scale application of PEMFC technology. A new preparation protocol has been proposed recently to obtain nano-electrocatalysts with a well-controlled chemical composition, based on the pyrolysis and activation of hybrid inorganic-organic precursors. The resulting carbon nitride nano-electrocatalysts thus prepared show an outstanding ORR performance both in “ex-situ” studies and in a single-cell configuration [3]. In this work, a new family of multimetal carbon nitride nano-electrocatalysts is described. The materials are synthesized by pyrolysis of a hybrid inorganic-organic precursor including Pt and Ni atoms impregnating Cu nanoparticles acting as the support. The final ORR electrocatalysts are obtained after an extensive electrochemical dealloying activation process. The products are fully characterized before and after the activation processes. The chemical composition of the electrocatalysts is determined by Inductively-Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and microanalysis. The morphology is investigated by High-Resolution Scanning Electron Microscopy (HR-SEM) and High-Resolution Transmission Electron Microscopy (HR-TEM). The structure is probed by powder X-Ray Diffraction (XRD). The electrochemical performance of the electrocatalysts in the ORR is determined both by “ex-situ” measurements carried out by cyclic voltammetry with the rotating ring disk electrode (CV-TF-RRDE method) and by “in-situ” fuel cell studies in a PEM single-cell configuration. Preliminary results indicate clearly that the proposed electrocatalysts show a remarkable ORR performance, which is significantly enhanced in comparison with the Pt/C reference both in terms of overpotential and selectivity in the 4-electron mechanism of the ORR (see Figure 1).

REFERENCES

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[3] V. Di Noto, E. Negro, Electrochim. Acta
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