bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Transformation of 2,5-Diphenyltellurophene
Authors: Shida Naoki , Komatsuzaki Yusuke , Seferos Dwight , Nishiyama Hiroki , Tomita Ikuyoshi , Inagi Shinsuke 
Published: February 2020

Tellurphene-containing materials are attracting great attention in a wide range of chemistry field. Due to the metalloid nature of tellurium, tellurophene shows unique reactivity. Previous report revealed that the 2,5-diphenyltellurophene (PT) reacted with halogen sources to give its dihalogen adducts PT-X2
(Seferos et al., Dalton Trans. 2015, 44, 2092.) (Figure, upper). In this reaction, the oxidation state of tellurium-center changed from Te(II) to Te(IV), in other word, tellurium transformed into the hypervalent state. Interestingly, dehalogenation also occurred by the irradiation of the lights to give an original Te(II)-centered tellurophene.
In this study, we have investigated the electrochemical transformation of PT (Figure, lower). The spectroelectrochemistry measurements have successfully revealed that the oxidation of PT in the presence of halides (F-, Cl-, Br-) gave the corresponding hypervalent tellurium compound, PT-X2
. In addition, the electrochemical reduction of PT-X2
resulted in the recovery of PT. In the course of Te(II)/Te(IV) redox cycle, there were no trace of side reaction, evidenced by the existence of isobestic points in absorption spectra. The bulk electrolysis of PT was also succeeded to give PT-X2
in sufficient yield.

Figure 1
Electrochemical Studies of Cysteine
Authors: Worosz Matthew A. , Cheek Graham T. 
Published: February 2020

Introduction
L-Cysteine is an important amino acid because of its role in various biochemical pathways (1). The sulfhydryl functional group gives L-cysteine significant redox characteristics, prompting an investigation of its electrochemical behavior in various media and electrode surfaces. The interaction of protein cysteine residues with Zn2+ (“zinc fingers”) also suggested a voltammetric study of the effect of Zn2+ on L-cysteine electrochemistry.

Experimental
L-Cysteine was obtained from Sigma-Aldrich. Electrochemical experiments were carried out using a Gamry Interface 1000 potentiostat and Gamry Framework software. Potentials are referenced against a Ag/AgCl reference electrode. Platinum and glassy carbon electrodes were obtained from BASi. Gold electrodes were purchased from eDAQ.

Results and Discussion
The voltammetric behavior of 5 mM Zn2+ in 0.10 M KNO3 is shown in the figure. Zinc deposition at -1.0 V was not very distinct, and there was no well-defined stripping peak. Addition of equimolar L-cysteine produced a definite stripping peak at -0.8 V, evidently an effect of complexation of Zn2+ by L-cysteine. The L-cysteine voltammetry was also affected by the presence of Zn2+. At platinum and gold with no addition of Zn2+, oxidation of L-cysteine occurred as merged peaks at +0.8 and +1.0 V (2), with no oxidation feature at +0.6 V. Even with Zn2+ added to L-cysteine n solution, an initial positive-going scan gave no +0.6 V peak, and scanning through the zinc reduction/stripping region was necessary to produce the +0.6 V feature on the second sweep to more positive potentials as shown in the figure. The stripping of the zinc layer from the gold surface may produce a renewed gold surface which allows strong adsorption of L-cysteine on gold. In general, L-cysteine is known to interact strongly with gold surfaces (3).

References

C. K. Mathews, K. E. Van Holde, D. R. Appling, and S. J. Anthony-Cahill, Biochemistry, 4th Edition, Pearson Canada, Toronto, 2013.

J. Koryta and J. Pradac, J. Electroanal. Chem., 1968, 17, 185-189.

A. J. Tudos, P. J. Vandeberg, and D. C. Johnson, Analytical Chem., 1995, 67, 552-556.

Figure 1. Cyclic voltammograms at gold (1 mm diameter) in aqueous 0.10 M KNO3. 100 mV/s.
[ Dashed line : 5.0 mM ZnSO4 ] [ Solid line : 5.0 mM ZnSO4 + 5.3 mM L-cysteine ]

Figure 1
Rationalized Onion-like Non-PGM Catalyst Development for Oxygen Reduction Reaction
Authors: Narvaez Villarrubia Claudia Wuillma , Yen Hung-Ju , Chen Gen , Li Hombo , Zhou Ming , Jiang Ying-Bing , Artyushkova Kateryna , Atanassov Plamen , Gupta Gautam , Wu Gang , Wang Hsing-Lin 
Published: February 2020

Fuel cell technology is a green alternative to conventional combustion engine technology. At the cathode of the fuel cell, the oxygen reduction reaction (ORR) takes place. The state-of-the-art catalysts for this reaction are platinum (Pt)-based materials. At the fuel cell’s anode, Pt-based catalyst is also needed. The limited activation and reduction of oxygen on the cathode force to increase the loading of Pt-catalysts when compared to the anode. As a result, the practical fuel cell application is constrained by the expensive and volatile price of the Pt-market; the Pt-catalysts represent the 40% of the cost of the fuel cell.
The development of inexpensive non-Pt catalysts are the center of investigation in the last decades and the development of non-Pt group metal (Non-PGM) catalysts, nitrogen-doped carbon materials, are promising alternatives. These are, typically, synthesized from metal salts and organic nitrogen and carbon precursors. The precursors are pyrolyzed at elevated temperatures, in an inert environment, to form the active structures for oxygen reuction catalysis. N-doped onion-like carbon nanostructures have being developed to achieve ORR catalysis. However, the mechanism of formation of these structures is not very well understood nor controlled.
In this research, we aimed to rationally control the active site nanoarchitectures for ORR in acid media. Onion-like nanoarchitectures are developed as catalytic structures by handling the chemistry of the carbon and nitrogen precursors and the reaction leading to the formation of the onion-like nanostructures. These structures are inserted in a carbon-based conductive matrix that serves as electron collector. Results show these controlled nanoarchitectures are promising Non-PGM materials for ORR catalysis.

Steele, B. C. H.; Heinzel, A. Materials for Fuel-Cell Technologies. Nature 2001, 414, 345–352.

Shao, Y. Y.; Liu, J.; Wang, Y.; Lin, Y. H. Novel Catalyst Support Materials for PEM Fuel Cells: Current Status and Future Prospects. J. Mater. Chem. 2009, 19, 46–59.

Wu, G.; Nelson, M.; Ma, S.; Meng, H.; Cui, G.; Shen, P. K. Carbon. 2011, 49, 3972-3982.
(Invited) Plasmon-Induced Charge Separation: Mechanisms and Applications
Authors: Tatsuma Tetsu , Nishi Hiroyasu 
Published: February 2020

Plasmonic nanoparticles, which are characterized by strong light absorption, scattering, and their controllability, attract much attention as new photofunctional materials. Plasmonic metal nanoparticles in contact with semiconductor exhibit charge separation under visible and near infrared light, i.e. plasmon-induced charge separation (PICS, Fig. 1).1 PICS involves carrier transfer from plasmonic nanoparticles (e.g. gold or silver nanoparticles) to semiconductor (e.g. TiO2)1-3 due to external photoelectric effect, hot carrier injection, or interfacial electron transition. In addition, PICS and/or accompanying redox reactions are accelerated by localized electric field (i.e. optical near field).4,5

PICS attracts increasing attention, because it can be applied to wet1 or solid-state6 photovoltaics under visible and near infrared light. It is also applied to photocatalysis1 and LSPR sensors,7 in which stable gold nanoparticles are used. In the case where less stable silver nanoparticles are used, PICS gives rise to oxidative dissolution of silver to silver ions. This process can be applied to multicolor photochromism,8 near infrared photochromism,9 single nanoparticle multicolor changes,5 and photomorphing hydrogels.10

1. Y. Tian and T. Tatsuma, J. Am. Chem. Soc., 127, 7632 (2005).
2. T. Tatsuma, Bull. Chem. Soc. Jpn., 86, 1 (2013).
3. E. Kazuma and T. Tatsuma, Adv. Mater. Interfaces, 1, 1400066 (2014).
4. E. Kazuma, N. Sakai, and T. Tatsuma, Chem. Commun., 47, 5777 (2011).
5. I. Tanabe and T. Tatsuma, Nano Lett., 12, 5418 (2012).
6. Y. Takahashi and T. Tatsuma, Appl. Phys. Lett., 99, 182110 (2011).
7. T. Tatsuma, Y. Katagi, S. Watanabe, K. Akiyoshi, T. Kawawaki, H. Nishi, and E. Kazuma, Chem. Commun., 51, 6100 (2015).
8. Y. Ohko, T. Tatsuma, T. Fujii, K. Naoi, C. Niwa, Y. Kubota, and A. Fujishima, Nat. Mater.,
2, 29 (2003).
9. E. Kazuma, and T. Tatsuma, Chem. Commun., 48, 1733 (2012).
10. T. Tatsuma, K. Takada, and T. Miyazaki, Adv. Mater., 19, 1249 (2007).

Figure 1
Structure, Electronic Properties and Electrochemical Behavior of a Boron-Doped Diamond/Quartz Optically Transparent Electrode
Authors: Swain Greg M , Jarosova Romana , Wachter Naihara , Munson Catherine 
Published: February 2020

This presentation will review the morphology, microstructure, chemistry, electronic properties and electrochemical behavior of a boron-doped nanocrystalline diamond (BDD) thin film grown on quartz. Diamond optically transparent electrodes (OTEs) are useful for transmission spectroelectrochemical measurements offering excellent stability during anodic and cathodic polarization and exposure to a variety of chemical environments.1,2 An example will be shown of how the OTE in a spectroelectrochemical measurement can be used to study the redox mechanism of the model analyte, chlorpromazine.1 We will also report on the characterization of the BDD OTE by AFM, optical spectroscopy, Raman spectroscopic mapping, AC Hall Effect measurements, XPS and electrochemical methods. Cyclic voltammetry was used to investigate the background current response as a function of potential, scan rate and electrolyte composition. Cyclic voltammetry and digital simulation were used to determine the heterogeneous electron-transfer rate constants (ko) for IrCl6
2-/3-, Fe(CN)6
3-/4-, ferrocene carboxylic acid, Ru(NH3)6
3+/2+ and methyl viologen. The diamond OTE supports relatively rapid electron transfer for a wide range of redox systems with formal potentials from ca. 0.9 to -1.0 V vs. Ag/AgCl. Capacitance-potential measurements were made in aqueous electrolyte solutions and ionic liquids to better understand the organization of electrified interfaces formed at this electrode. The work constitutes the first comprehensive study of the relationship between the physical and chemical structure and electronic properties of a diamond OTE, and the electrode’s electrochemical activity.
1. Stotter, J; Zak J; Behler Z; Show Y; Swain GM. Optical and Electrochemical Properties of Optically Transparent, Boron-Doped Diamond Thin Films on Quartz. Anal. Chem. 2002, 74, 5924-5930.
2. Stotter J; Show Y; Wang S; Swain GM. Comparison of the Electrical, Optical and Electrochemical Properties of Diamond and Indium Tin Oxide Thin-Film Electrodes. Chem. Mater. 2005, 17, 4880-4888.
Tunable Electrocatalytic Performance of Metal Nanocrystals By Tailoring Surface Electronic Structures
Authors: Xiong Yujie 
Published: February 2020

Nanocrystals of noble metals have been widely used as electrocatalysts in various reaction systems. As heterogeneous electrocatalytic reactions take place at catalyst surface, the efficiency relies on the interactions of surface with reaction species. For this reason, the electrocatalytic performance can be tuned by tailoring the surface electronic structures of solid materials. In this talk, I will demonstrate a new approach to maneuvering the surface electronic structures through interfacial or interatomic charge polarization between noble metals and other materials. The charge polarization provides a versatile tool for tailoring the charge densities and d-band centers of surface catalytic sites. Leveraging chemical bonding, we have developed methods for forming material interfaces at atomic precision in core-shell or alloy nanostructures, which allows to implementing the charge polarization mechanism in multiple electrocatalytic systems. The number of active sites and their activity can be controlled by altering the interfacial dimensions. It is anticipated that this work will provide insights into the rational design of hybrid catalytic nanomaterials through interface engineering.

References.

1. Du, N.; Wang, C.; Wang, X.; Lin, Y.; Jiang, J.; Xiong, Y.*,
Adv. Mater.

2016
,
28, 2077-2084.
2. Ma, L.; Wang, C.; Xia, B. Y.; Mao, K.; He, J.; Wu, X.; Xiong, Y.;* Lou, X. W.*, Angew. Chem. Int. Ed.
2015, 54, 5666-5671.
3. Bai, S.; Wang, C.; Deng, M.; Gong, M.; Bai, Y.; Jiang, J.; Xiong, Y.*, Angew. Chem. Int. Ed.
2014, 53, 12120-12124.
4. Ma, L.; Wang, C.; Gong, M.; Liao, L.; Long, R.; Wang, J.; Wu, D.; Zhong, W.; Kim, M.;* Chen, Y.; Xie, Y.; Xiong, Y.*, ACS Nano
2012, 6, 9797-9806.
5. Liu, D.; Xie, M.; Wang, C.;* Liao, L.; Qiu, L.; Ma, J.; Huang, H.; Long, R.; Jiang, J.;* Xiong, Y.*, Nano Res. DOI: 10.1007/s12274-016-1053-6.
Integrating Enzymes into Cytochrome c –Based Multilayer Architectures – General Considerations and Example with Fructose Dehydrogenase
Authors: Lisdat Fred , Wollenberger Ulla , Kano Kenji , Wettstein Christoph 
Published: February 2020

The creation of artificial electron transfer (ET) chains based on the defined arrangement of enzymes and redox proteins on electrode surfaces represents an interesting field in bioelectronics1. One approach exploits the self exchange properties of cytochrome c (cyt c) to build up new sensing electrodes2.
In this study we have investigated the ET reaction of the flavin-dependent enzyme fructose dehydrogenase (FDH) with the redox protein cyt c. Two different pH optima are detected for the reaction of both proteins in solution - at acidic and neutral pH. When one reaction partner - cyt c - is immobilized on a thiol-modified gold electrode and FDH is in solution ET proceeds efficiently at neutral pH which can be concluded from well-shaped catalytic currents obtained in cyclic voltammetry. In addition, a defined dependence on the substrate concentration has been found. In acidic media the reaction can also be verified but appears to be less efficient.
Furthermore, it can be demonstrated that both partners can be assembled in a stable multilayer architecture, using the biopolymer DNA as a negatively charged polyelectrolyte building block. The defined layered deposition of DNA and a mixture of FDH and cyt c is confirmed by surface plasmon resonance (SPR) measurements. Prepared on electrodes, substantial catalytic currents are recorded upon addition of fructose. The response can be enhanced by the number of layers deposited on the surface. This shows that an artificial signal chain can be constructed through multiple protein layers.
FDH is not the only enzyme which can be immobilized and connected to the electrode by means of the redox protein cyt c. Cellobiose dehydrogenase, sulfite oxidase or billirubin oxidase are other examples3,4. This may indicate that cyt c based multilayers can have some general applicability when some preconditions are fullfilled.
1. Feifel et al , in Biosensors Based on Aptamers and Enzymes, Springer 2014, 140, 253-298
2. Lisdat et al., Chemical Communications 3 2009, 274-283.
3. Feifel et al., Angew. Chemie 126(22) 2014 5782-86
4 Dronov et al. JACS 2008 130(4) 1122.
Electrochemical Reduction of Atrazine at Carbon and Silver Cathodes
Authors: Martin Erin Theresa , Peters Dennis G 
Published: February 2020

Since its introduction in the 1950s, atrazine (6-chloro-N2-ethyl-N4-(1-methylethyl)-1,3,5-triazine-2,4-diamine) has become one of the mostly widely used pesticides in the world. Although atrazine has been banned in the European Union since 2004, it is still applied extensively in the US, and can be detected in water sources, soil, and even air.1 Environmental persistence of atrazine and its metabolites has caused contamination to spread away from regions of herbicide application, and some studies have shown evidence of endocrine disruption in amphibians exposed to these chemicals.1 For these reasons, the degradation of atrazine to less environmentally harmful compounds is of great concern.
In this study, we have employed electrochemical reduction for the degradation of atrazine at different cathode materials. Previous electrochemical studies of atrazine have been performed at mercury cathodes, and were successful in both the detection of atrazine by means of square-wave voltammetry and its degradation through controlled-potential (bulk) electrolyses.2-4 At mercury cathodes, long electrolyses resulted in both the breaking of the carbon–halogen bond and reduction of the triazine ring.4 To avoid the use of mercury, we have explored the use of carbon and silver cathodes; glassy carbon provides a simple, environmentally friendly alternative, whereas silver has been shown to be catalytic for the cleavage of carbon–halogen bonds. Reduction of atrazine at carbon and silver cathodes, respectively, in dimethylformamide (DMF) containing 0.050 M tetramethylammonium tetrafluoroborate (TMABF4), results in a single cyclic voltammetry peak at –1.77 or –1.62 V vs. a Cd(Hg) reference electrode. Investigations of the products arising from controlled-potential electrolysis by means of gas chromatography–mass spectrometry indicate the presence of dechlorinated atrazine (N2-ethyl-N4-(1-methylethyl)-1,3,5-triazine-2,4-diamine) after electrolyses at both carbon and silver cathodes.

References

1. Jablonowski, N. D.; Schäffer, A. Environ. Sci. Pollut. Res.
2011, 18, 328–331.
2. dos Santos, L. B. O.; Silva, M. S. P.; Masini, J. C. Anal. Chim. Acta
2005, 528, 21–27.
3. Maleki, N.; Absalan, A.; Farjami, S. E. Anal. Chim. Acta
2007, 581, 37–41.
4. Caetano, J.; Homem-de-Mello, P.; da Silva, A. B. F.; Ferreira, A. G.; Avaca, L. A. J. Electroanal. Chem.
2007, 608, 47–51.

Figure 1
Characterization of the Electrochemical Behavior of a Li-Bi Reference Electrode for the Molten LiCl-Li
Authors: Phillips William , Merwin Augustus , Singh Vickram , Chidambaram Dev 
Published: February 2020

In order to maximize uranium resources and minimize the need to store radioactive material in geologic repositories, it is necessary to reprocess used nuclear fuel (UNF) to recycle the fissile material and transuranic isotopes that remain. The pyroprocessing operation developed by Argonne National Laboratory as part of the integral fast reactor project was designed to accomplish this goal while minimizing the risk of proliferation (1). Inclusion of oxide based UNF from the current light water reactor fleet into the metallic fuel based fast reactor cycle will require electrolytic oxide reduction in a LiCl-Li2O electrolyte (2). As a side reaction during the electroreduction of U, Li is codeposited on the cathode surface and subsequently dissolves, forming a ternary LiCl-Li2O-Li electrolyte (3, 4). The presence of metallic Li in the electrolyte negates the possibility of using the reference electrodes typically used for molten salt electrochemistry. The Li-Bi couple has been used as a reference electrode previously but has not yet been well characterized (5, 6). This work investigates the stability of the Li-Bi reference couple in varying solution chemistries typical of those found during electrolytic reduction of UO2.
Acknowledgements: This work was performed under the auspices of the Department of Energy (DOE) under contracts DE-NE0008262 and DE-NE0008236, and the US Nuclear Regulatory Commission (NRC) under contracts NRCHQ-11-G-38-0039, NRC-HQ-10-G-38-0027, NRC-HQ-13-G-38-0027. W.P. and A.M acknowledge the Fellowship Award from the USNRC. Dr. Kenny Osborne serves as the program manager for the DOE award and Ms. Nancy Hebron-Isreal serves as the grants program officer for the NRC awards.
References:
1. J. J. Laidler, J. E. Battles, W. E. Miller, J. P. Ackerman, E. L. Carls, Development of Pyroprocessing Technology. Progress in Nuclear Energy
31, 131-140 (1997).
2. S. D. Herrmann, S. X. Li, M. F. Simpson, S. Phongikaroon, Electrolytic Reduction of Spent Nuclear Oxide Fuel as Part of an Integral Process to Separate and Recover Actinides from Fission Products. Separation Science and Technology
41, 1965-1983 (2006).
3. T. Takenaka, K. Shigeta, H. Masuhama, K. Kubota, Influence of Some Factors upon Electrodeposition of Liquid Li and Mg. ECS Transactions
49, 441-448 (2009).
4. A. S. Dworkin, H. R. Bronstein, M. A. Bredig, Miscibility of Metals with Salts. VI. Lithium-Lithium Halide Systems. The Journal of Physical Chemistry
66, 572-573 (1962).
5. M. Iizuka, Y. Sakamura, T. Inoue, Electrochemical reduction of (U-40Pu-5Np)O2 in molten LiCl electrolyte. Journal of Nuclear Materials
359, 102-113 (2006).
6. X. Ning et al., Self-healing Li-Bi liquid metal battery for grid-scale energy storage. Journal of Power Sciences
275, 370-376 (2015).
CO Gas Production by CO2 Gas Decomposition in Molten Salt Electrolysis
Authors: Suzuki Ryosuke O. , Matsuura Fumiya , Natsui Shungo , Kikuchi Tatsuya 
Published: February 2020

If CO2 gas can be efficiently decomposed, the produced carbon can be used as the raw material of the reducing agent of iron ore. Oxygen can be also used as the blowing gas into converters. In addition, CO gas can be used as an effective fuel in industrial plants. Thus, all the products arising from CO2 decomposition can become raw materials or energy resources.
The decomposition of CO2 gas to carbon or CO gas by electrolysis is examined via the use of a combination of CaCl2-CaO melt as a media and ZrO2 solid-state electrolyte as anode. The schematic of the reactor used in this study is shown in Figure.
CO2 gas is injected through the cathodic pipe, and it is reduced near the cathode by metallic Ca that is electrochemically deposited from CaO, leading to formation of carbon or CO gas. However, CO2 gas partially dissolves to form CO3
2- with coexistence of CaO in the melt. CO3
2- precipitates carbon on the cathode. A part of carbon reacts with the blown CO2 gas to form CO gas. These two mechanisms work for effective CO2 decomposition.
The anode contained 8 mol% Y2O3 to ensure stability of the ZrO2 cubic crystal structure. By means of utilizing platinum paste as the conductor inside the ZrO2 tube instead of carbon powder, its tube can work as a good anode, and a large amount of CO gas is stably produced in the exhaust gas.
At a higher electrolysis temperature, CO2 gas is preferentially converted to CO gas. At 1273 K, the conversion ratio approached the maximum value of 88.2%.
The highest concentration of CO gas is generated by application of a cell voltage of 2.55 V, which is lower than the theoretical decomposition voltage of CaO, E
0
CaO (2.65 V at 1173 K). Therefore, CO2 gas decomposes preferentially via the decomposition reaction of carbonate ions.
We believe that our approach can contribute in reducing atmospheric CO2.

Figure 1
Transport Properties of Ionic Liquid Mixtures Containing Heterodications
Authors: Lall-Ramnarine Sharon , Fernandez Eddie , Rodriguez Chanele , Wei Sujun , Dhiman Surajdevparkash , Wishart James F. 
Published: February 2020

Ionic liquid (IL) mixtures are gaining popularity as a means to access the attractive properties of individual ILs while minimizing less desirable characteristics that impede their large scale adoption. We report here on the transport properties of ionic liquid mixtures that incorporate a series of asymmetrical dications including heterodications. The dicationic ILs were designed to bear triphenyl phosphonium and trimethyl ammonium cationic sites bridged to methylimidazolium, and methylpyrrolidinium cationic sites by a carbon chain, with the Bis(trifluoromethylsulfonyl)imide (NTf2) anion. IL mixtures containing 10%, 25% and 50% dicationic NTf2 by weight with alkoxyalkyl- methylimidazolium and methylpyrrolidinium NTf2 ILs were prepared. The IL mixtures were characterized for their transport properties (temperature dependent conductivity and viscosity) and thermal properties including melting point, glass transition point, and thermal degradation point. The work at BNL was supported by the BNL Office of Educational Programs and the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under contract DE- SC0012704.