bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lithium Bond Chemistry at the Interlayer for High-Performance Lithium Sulfur Batteries
Authors: Duangdangchote Salatan , Phattharasupakun Nutthaphon , Joraleechanchai Nattanon , Sawangphruk Montree 
Published: May 2020

Lithium-sulfur battery (LSB) is a promising candidate as a conventional lithium-ion battery substitute due to its high theoretical specific capacity and high energy density together with additional advantages of low cost, abundance, and environment friendliness. However, LSB is still hindered from commercialize scale due to its many challenges including insulator of reactant sulfur (S8) and final product (Li2S), polysulfide shuttle effect, and volume expansion during cycling. These issues cause the capacity fading and low efficiency in the LSB. To overcome the mentioned above issue as well as improve performances of the LSB, the modified carbon fiber interlayer has introduced between the sulfur cathode and separator in order to suppress the lithium polysulfide intermediates (LPSs) diffusion through the lithium bond. The lithium polysulfide intermediate can occur the chemisorption with functionalized group on the interlayer which can fundamentally explain by density functional theory (DFT) calculations. More interestingly, we also prove that the performance of the LSB is in a correlation with strength of the lithium bond between the interlayers and LPSs. We hope that this study should be a useful information in term of the chemistry of lithium bond which can enhance performance and safe operation of LSBs.1-3

Keywords: Carbon fiber interlayer, Lithium bond, Li-S battery

REFERENCES

1. 1. Duangdangchote, S.; Krittayavathananon, A.; Phattharasupakun, N.; Joraleechanchai, N.; Sawangphruk, M. Chem
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2. 2. Maihom, T.; Kaewruang, S.; Phattharasupakun, N.; Chiochan, P.; Limtrakul, J.; Sawangphruk, M. J
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2018,
122 (13), 7033-7040.
3. 3. Kosasang, S.; Ma, N.; Duangdangchote, S.; Chiochan, P.; Chanlek, N.; Sawangphruk, M. Carbon
2019,
155, 553-561.

Figure 1
(Invited) Bimetallic Electrocatalysts for Electrochemical CO2 Reduction
Authors: Ismail Ahmed Mohsen , Csapo Edit , Janáky Csaba 
Published: May 2020

Bimetallic nanoparticles (NPs) offer great flexibility to tailor the activity and selectivity in electrocatalytic conversion of carbon dioxide (CO2) to valuable chemicals. Here, we report on the electrocatalytic behavior of Au-Sn, Au-Ag and Au-Pb NPs, to highlight the effect of the intermetallic phase formation and the bimetallic composition in CO2 electroreduction.
Firstly, a series of Au–Sn electrocatalysts with different intermetallic phases were obtained via tin incorporation into the gold lattice through gradual diffusion. Stoichiometric intermetallic phases were formed, and under optimal conditions, two high-value products formed with reasonable current density: formic acid in the liquid phase and syngas in the gas phase. Notably, the phase composition had a massive influence on both the activity and the product distribution. In situ Raman spectroelectrochemistry studies demonstrated that catalytic performance of the AuSn phase was superior to that its parent metals and other bimetallic counterparts.
Secondly, the correlation between the electrocatalytic activity and the composition of Au-Ag alloy NPs was studied. The CO Faradaic efficiency (and thus the forming CO:H2 ratio) was changed linearly by controlling the Au:Ag ratio in the alloy. This trend was attributed to the changes in the electronic properties, as there was a monotonous shift in the Fermi level away from the vacuum level with increasing Au content. This shift correspondingly reduces the binding energy of the intermediates (*COOH and *CO), resulting in the gradually enhanced CO2-reduction activity.
Finally, I will show results gained with Au-Pb electrodes, where the formation of methane (CH4) was demonstrated. Factors underpinning this unusual behavior were studied by both experimental and theoretical means.
(Invited) Highly Durable Platelet-Type Carbon Nanofibers for Oer in Alkaline Electrolyte
Authors: Sato Yuki , Kowalski Damian , Aoki Yoshitaka , Habazaki Hiroki 
Published: May 2020

Porous anodic alumina films formed by anodizing of aluminum in acid electrolytes have a highly ordered, nanopore channels, which have attracted increased attention as template for various nanomaterials. Utilizing this template, platelet-type carbon nanofibers (pCNFs) have been successfully prepared by simply heating a mixture of the template and polymer powders, such as polyvinyl chloride and polyvinyl alcohol, in argon atmosphere via liquefied intermediate of the polymers (1, 2). The graphitization degree of pCNFs increases with annealing temperature, and interestingly, the neighboring reactive carbon edge sites at the sidewall of pCNFs form loops of several carbon layers at above 2000ºC. Here, we demonstrate that such pCNFs with high graphitization degree and loop structure exhibit extremely high oxidation resistance under oxygen evolution reaction (OER) conditions in highly alkaline electrolyte for a zinc-air secondary battery application.
During galvanostatic OER on the state-of-the-art highly active Ca2FeCoO5 electrode with a conventional carbon black conductive agent in 4 mol dm-3 KOH electrolyte consumed the carbon black almost completely within a few days, whereas that with pCNFs annealed at 2400ºC exhibited almost no consumption of the pCNFs even after one month. The carbon nanofibers with platelet structure and high graphitization degree are promising for the air electrode materials in a zinc-air battery.

Acknowledgment

This work was supported in part by the RISING2 (Research and Development Initiative for Science Innovation of New Generation Batteries 2) of the New Energy and Industrial Technology Development Organization (NEDO), Japan.

1. H. Konno, S. Sato, H. Habazaki and M. Inagaki, Carbon, 42, 2756 (2004).
2. H. Habazaki, M. Kiriu, M. Hayashi and H. Konno, Mater. Chem. Phys., 105, 367 (2007).
Electrocatalytic Metallic Nanostructures Prepared By Electrorefining and Cathodic Corrosion
Authors: Michalak Magdalena , Kalisz Justyna , Roguska Agata , Opallo Marcin , Nogala Wojciech 
Published: May 2020

Metallic nanostructures (NS) due to their unique properties are often used as electrocatalytic electrode materials in energy conversion and storage as well as in sensing applications. Their common methods of preparation involve homogeneous synthesis and electrodeposition from solutions containing appropriate precursor and often reducing agent and capping agent (surfactant). The main drawbacks of these methods are restricted yield, waste production and often intrinsic contamination of the surface of obtained NS. Moreover, surface capping ligands affect electrocatalytic activity by hindrance of reactant access to the active sites.
We propose a versatile method of preparation of bare (non-capped) mono- and multi-metallic (Au,1 Cu,2 Ag, Fe) NS by localized electrorefining of polycrystalline raw metals at high efficiency in a controlled manner. Catalytic activities of obtained NS towards oxygen reduction reaction (ORR) in alkaline media, hydrogen evolution (HER) and carbon dioxide reduction (CO2RR) to easily electrooxidizable fuels (formic acid and carbon monooxide) were analyzed by feedback mode scanning electrochemical microscopy (SECM). The morphology and specific activity of obtained NS depend on used support material (indium tin oxide (ITO) and glassy carbon) and other electrorefining parameters such as electrodeposition potential, source velocity and the composition of the electrolyte. The last parameter determines stoichiometry of Faradaic processes. Both gold and copper electrooxidation and electroreduction can follow one electron stoichiometry. ORR in alkaline media and CO2RR occur effectively on NS with highly developed surfaces, containing large number of defects, corners and edges, whereas HER occurs efficiently at crystallographic Cu facets. Bare gold NS also exhibit outstanding plasmonic properties. They were applied as support for surface-enhanced Raman spectroscopy (SERS) of single molecules providing enhancement factor >106.1

Another method of preparation of metallic nanostructures is cathodic corrosion. This approach for platinum was studied by Koper group.3 We used this procedure for platinum ultramicroelectrode treatment. Obtained Pt NS exhibit unique catalytic properties towards electrooxidation of glucose.
References:
1. W. Nogala, P. Kannan, S. Gawinkowski, M. Jönsson-Niedziolka, M. Kominiak, J. Waluk and M. Opallo, Nanoscale, 7, 10767 (2015).
2. M. Michalak, A. Roguska, W. Nogala and M. Opallo, Nanoscale Advances, 1, 2645 (2019).
3. T. Hersbach, Alexei. Yanson and M. Koper, Nature Communications, 7, 12653 (2016).

Figure 1
(Invited) Morphology and Conductivity of Copper Hexacyanoferrate Films
Authors: Hosseini Pouya , Wolkersdörfer Konrad , Wark Michael , Redel Engelbert , Baumgart Helmut , Wittstock Gunther 
Published: May 2020

Metal hexacyanometallates (MHCMs) form a large family of coordination network compounds [1]. They have variable and tunable physical and chemical properties due to the three-dimensional framework of alternating metal knots connected by a non-innocent small bridging ligand forming interconnected channels that can accommodate solvent molecules and counter ions. Therefore, these materials have been comprehensively studied in several different fields, including, functional materials for charge storage, electrocatalysis, electrochromic devices or light harvesting. For the mentioned applications, conductivity is critical, to which i) electronic conductivity by electrons or holes [2], ii) ionic conductivity by mobile alkali ions in the channels of the MHCMs [3], and iii) proton conductivity [4] may contribute. In larger scale for real application, the conductivity depends not only on intrinsic material properties but also on the morphology. Morphology (particularly grain boundaries) plays an important role in determining the pathway of charge carrier transport (electrons and holes) in the film. From first principles it is expected that continuous compact crystalline films will have better electrical conductivity.
Here, we present results on copper hexacyanoferrate which demonstrate particularly well the variation of film morphology and its influence on conductivity as a key functional property. We succeeded in devising a simple method for preparation of metal hexacyanoferrates as a thin continuous film by a combination of sonication-assisted casting and vapor-assisted conversion, without the need for surface pre-treatment. This is especially helpful for coating substrates composed of different materials. Films obtained in this way show conductivities higher than that of powder pellets with equivalent crystal structure. Temperature-dependent and humidity-dependent measurements on powder pellets revealed the activation energies for charge transport as well as the role of zeolitic water in facilitating the charge transfer.

1. Paolella, A.; Faure, C.; Timoshevskii, V.; Marras, S.; Bertoni, G.; Guerfi, A.; Vijh, A.; Armand, M.; Zaghib, K. A Review on Hexacyanoferrate-based Materials for Energy Storage and Smart Windows: Challenges and Perspectives. Mater. Chem. A
2017, 5, 18919–18932.
2. Behera, J. N.; D’Alessandro, D. M.; Soheilnia, N.; Long, J. R. Synthesis and Characterization of Ruthenium and Iron−Ruthenium Prussian Blue Analogues. Mater.
2009, 21, 1922–1926.
3. Ishizaki, M.; Ando, H.; Yamada, N.; Tsumoto, K.; Ono, K.; Sutoh, H.; Nakamura, T.; Nakao, Y.; Kurihara, M. Redox-Coupled Alkali-Metal Ion Transport Mechanism in Binder-Free Films of Prussian Blue Nanoparticles. Mater. Chem. A
2019, 7, 4777–4787.
4. Ohkoshi, S.-I.; Nakagawa, K.; Tomono, K.; Imoto, K.; Tsunobuchi, Y.; Tokoro, H. High Proton Conductivity in Prussian Blue Analogues and the Interference Effect by Magnetic Ordering. Am. Chem. Soc.
2010, 132, 6620–6621.
(Invited) Controlling Free Charge Density Gradients in Ionic Liquid Media
Authors: Blanchard Gary J. 
Published: May 2020

Room Temperature Ionic Liquids (RTILs) have found use in a variety of practical applications, including chemical synthesis and supercapacitor development, but many fundamental issues remain to be resolved in understanding dynamics, organization and the response of these materials to external forces. We have demonstrated that RTILs in contact with a charged surface can exhibit a free charge density gradient (ρf
) that extends over ca. 100 μm. The existence of such a free charge density gradient in a fluid medium is without precedent and needs to be understood. Experimental and theoretical investigations of RTILs have revealed organization of some type over a variety of length scales, ranging from ca. 10 nm to ca. 100 μm. The term “organization” is not well-defined, however. The existence of any type of organization over such a range of length scales is highly unusual for a liquid, particularly so for a macroscopic free charge density gradient in an ionic liquid. Achieving a deeper understanding of this phenomenon is important because of its implications in how we conceptualize and use this class of materials.
We report on experiments that have elucidated the spatial extent of the induced gradient, it's magnitude, and the chemical and structural factors that serve to determine these factors. We also present a model for understanding this gradient that draws on known physical properties of materials such as piezoelectrics. The optical and physical behavior of RTILs draw analogy to piezoelectric properties in solids and the demonstration of this correspondence provides a novel framework for the interpretation of the unexpected phenomena we have reported.
Dimethylenebis-(tetra-decyldimethylammonium Bromide)-Driven Au Nanoparticles: Hg2+ Sensing a Competency
Authors: Kim Hohyeong , Jae-Young Park 
Published: May 2020

Heavy metal ions can cause severe threats to the environment and human health, and the potential sources of substantial metal ions are mining, agriculture, toxic wastes, electronic merchandise, and natural discharge from earth’s crust into the surroundings. This discharge from oceanic and volcanic emissions end up in the contamination of underground water resources and human beings get exposed to the same. Among aforesaid ions, mercury ions are incredibly fatal and may cause serious health problems if consumed by individuals, leading to numerous critical diseases such as harmful effects on immune systems, cancer, organ damage, nervous system damage, etc.
In order to confirm these, it is essential to investigate the influence of the shorter hydrocarbon chain length on the detection performance of metal nanoparticles. In view of that, we selected dimethylenebis-(tetra-decyldimethylammonium bromide) (14–2-14) GS with a shorter hydrocarbon chain length and further investigated sensitivity and selectivity of anisotropic nanoparticles.
(Invited) Hybrid Porphyrin – Polyoxometalate Copolymer for Photo(electro)Chemical Applications: From Flat to Mesoporous ITO Electrodes
Authors: Ruhlmann Laurent , Liang Yiming , Wang Jingjing , Bonnefont Antoine 
Published: May 2020

The development of hybrid polymers incorporating polyoxometalates (POMs) is a promising approach to elaborate new functional materials. To expand the practical applications, their association to a visible-light photosensitizer is needed. In this context, we have developed a method of electropolymerization of POMs based on nucleophilic attack onto the electrogenerated porphyrin dications.
1-2
The formation of hybrid POM-porphyrin copolymeric films (Fig. 1, film I) can be obtained by the electro-oxidation of porphyrin in the presence of the hybrid POM bearing two pyridyl groups (Py-POM-Py)
3
. This process is feasible for various type of POMs such as Dawson, Lindqvist or Keggin type POMs
4-6
. A second methodology is also proposed to form hybrid POM-porphyrin films (Fig. 1, films II or III): first the formation of cationic polyporphyrin electropolymer. Then, by metathesis reaction, the (partial) exchange onto the surface of the initial counter ions by the POMn- or by the nanoparticles stabilized with POMn- (POMn-@M, M = Ag, Au, Pt, etc.).
7
The photovoltaic performances of these hybrid materials have been investigated by photocurrent transient measurements under visible-light illumination
8-10
given by now good efficiency. In order to increase the efficiency, mesoporous ITO electrodes (nanofiber formed by electrospun or porous ITO electrode obtained using a colloidal co-assembly approach) have been used and will be discussed.
1. L. Ruhlmann, A. Schulz, A. Giraudeau, J.-H. Fuhrhop, J. Am. Chem. Soc., 1999, 121, 6664.
2. Z. Huo, J.-P. Gisselbrecht, R. Farha, M. Goldmann, E. Saint-Aman, C. Bucher, L. Ruhlmann, Electrochimica Acta, 2014, 122, 108.
3. D. Schaming, C. Allain, R. Farha, M. Goldmann, S. Lobstein, A. Giraudeau, B. Hasenknopf, L. Ruhlmann, Langmuir, 2010, 26, 5101.
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5. Z. Huo, I. Azcarate, R. Farha, M.Goldmann, H. Xu, B. Hasenknopf, E. Lacôte, L. Ruhlmann, J. solid State Electrochemistry, 2015, 19, 2611.
6. Z. Huo,D. Zang,S. Yang,R. Farha,M. Goldmann,B. Hasenknopf, H. Xu, L. Ruhlmann, Electrochimica Acta, 2015, 179, 326.
7. Z. Huo,A. Bonnefont, C. Bucher, L Ruhlmann, Electrochimica Acta, 2018, 274, 177.
8. I. Ahmed, R. Farha, M. Goldmann, L. Ruhlmann, Chem. Comm.
2013, 49, 496.
9. I. Ahmed, R. Farha, Z. Huo, C. Allain, X. Wang, H. Xu, M. Goldmann, B. Hasenknopf, L. Ruhlmann, Electrochimica Acta, 2013, 110, 726.
10. I. Azcarate, Z. Huo, R. Farha, M. Goldmann,H. Xu, B. Hasenknopf, E. Lacôte, L. Ruhlmann, Chem. Eur. J.
2015, 21, 8271.

Figure 1
(Invited) Optimizing Iridium Utilization for Oxygen Evolution Reaction – Viability of the Supported Ir Oxide Nanoparticles Strategy
Authors: Claudel Fabien , Abbou Sofyane , Chattot Raphaël , Sola-Hernandez Lluis , Beauger Christian , Peron Jennifer , Maillard Frédéric , Dubau Laetitia 
Published: May 2020

Determining the relationships between structure, oxidation state and oxygen evolution reaction (OER) activity is fundamental to design improved anode catalysts for polymer electrolyte membrane water electrolyser (PEMWE) devices. To date, Ir-based electrocatalysts are the best compromise between activity and stability. According to the scarcity of Ir on the Earth crust, the deployment of PEMWE technology cannot overlook an optimized utilization of Ir loading. Following the successful approach in proton-exchange membrane fuel cells (PEMFC) consisting of using carbon-supported Pt nanoparticles instead of Pt-blacks, we investigated supported Ir oxide nanoparticles. The nature of the support appears to be crucial since high-surface area carbon supports are rapidly degraded in the operating conditions of a PEMWE anode (E > 1.6 V vs. the reversible hydrogen electrode, T = 80 °C). We opted for alternative support materials based on doped tin oxide. In this contribution, a wide and sound library of Ir oxide materials differing from each other by the presence/absence of support and by the Ir architecture has been studied by identical location transmission electron microscopy, X-ray photoelectron spectroscopy, inductively coupled plasma mass spectrometry and electrochemical techniques (Figure 1). It allowed us to establish trends on the viability of supported Ir oxide catalysts in the harsh PEMWE operating conditions [1].
[1] F. Claudel, L. Dubau, G. Berthomé, L. Sola-Hernandez, C. Beauger, L. Piccolo, F. Maillard,

ACS catal.,
2019, 9 (5), 4688–4698.
Surface Engineering of Carbon Nanotubes with Inorganic-Organic Materials for Electrochemical Capacitors.
Authors: N'Diaye Jeanne , Siddiqui Shaheer , Lian Keryn 
Published: May 2020

Composite electrodes comprised of inorganic-organic molecular materials are of great interest in applications such as electrochemical capacitors (ECs). ECs store and release charge via double layer capacitance (EDLC) or pseudocapacitance. The carbon materials used for EDLC has low capacitance, while pseudocapacitive materials such as redox active polymers or metal oxides have long term stability issues. Therefore, anchoring inorganic-organic materials on a carbon substrate can leverage the advantages of both EDLC and pseudocapacitance. Composite electrodes of kegging type polyoxometalates (POM) deposited on polydiallyldimethylammonium chloride (PDDA) via the layer-by-layer assembly has been well established and has shown great promise [1-3] . The issues are the limited operation window and the inert PDDA layer. Suitable alternatives that can complement the redox activity of POMs and enlarge the operating potential window are redox active polymers [4].
The objectives of this work are to: 1) develop and optimize an electroactive inorganic-organic composite electrode based on a carbon nanotube (CNT) substrate modified with polyluminol (CpLum) and H5GeMo11VO40.24H2O (GeMo11V); 2) study the electrochemical behavior of the composite electrode with and without PDDA for electrochemical capacitors; and 3) investigate the interactions between each layer.
GeMo11V was first deposited onto CNT using PDDA as an anchor. The vanadium atom in the kegging structure provided an additional electrochemical redox peak with improved capacitive behavior on the cyclic voltammogram (CV) as seen in figure 1. First, CpLum, and GeMo11V were applied on CNT (CNT-CpLum-GeMo11V), then co-deposited with PDDA (CNT-CpLum-PDDA-GeMo11V). For both composite electrodes, CpLum and GeMo11V contributed to the redox activity leading to a wider potential window. The CV of CNT-CpLum-GeMo11V showed more reversible redox peaks with a slightly reduced GeMo11V contribution compared to CNT-CpLum-PDDA-GeMo11V that had a smoother CV shape. The decrease in GeMo11V contribution was attributed to the smaller amount of positive charge within the CpLum chain needed to anchor the GeMo11V. Each layer had a distinct role in the inorganic-organic composite electrode. The CpLum polymer added additional redox activity in the higher potential range, while PDDA attracted and held the GeMo11V, which provided redox activity in the lower potential range. All three layers had a synergistic interaction and provided enhanced charge storage properties with good rate capability and cycling stability.
REFERENCES
1. M. Genovese, Y. W. Foong and K. Lian, Electrochimica Acta, 199, 261 (2016).
2. M. Genovese and K. Lian, Current Opinion in Solid State and Materials Science, 19, 126 (2015).
3. M. Genovese, Y. W. Foong and K. Lian, Journal of The Electrochemical Society, 162, A5041 (2015).
4. N. Casado, G. Hernández, H. Sardon and D. Mecerreyes, Progress in Polymer Science, 52, 107 (2016).

Figure 1