bluuebunny/crossref_metadata_2025_split huggingface dataset:
Measuring DNA Charge Transport on a Surface Using a Redox Modulated Fluorescence Intensity Strategy with DNA SAMs
Authors: Ma Tianxiao , Ma Tianxiao 
Published: July 2022

The double stranded DNA helix has drawn great attention across different research areas. Various types of platforms have been used to study DNA charge transfer (CT) system. Two types of DNA CT platforms are considered as the most effective: the photoinduced CT in solution with assembled donor and acceptor and electrochemistry on ground state CT in a DNA self-assembled monolayer (SAM)1. We will show a new approach for the study of DNA CT on gold surface by studying the redox modulated fluorescence signal of a co-deposited double-stranded DNA assemblies labeled with Methylene Blue (MB) or AlexaFluoro488 (AF488). We demonstrate a method that can optically distinguish between the two mechanisms of the MB redox on DNA-modified surface: namely either DNA CT mediated reduction or the direct reduction of MB by the gold surface2. Given the fact that the studies on DNA-mediated electrochemistry on surface has been mainly using electrochemical measurements and we still do not fully understand the full picture of the DNA CT, we believe that this study will provide a fresh opinion and facilitate understanding on the DNA CT mechanism on electrode surface.
Reference:

Arnold, A. R.; Grodick, M. A.; Barton, J. K. DNA Charge Transport: From Chemical Principles to the Cell. Cell Chem. Biol.
2016, 23 (1), 183–197.

Pheeney, C. G.; Barton, J. K. DNA Electrochemistry with Tethered Methylene Blue. Langmuir
2012, 28 (17), 7063–7070.

Muren, N. B.; Olmon, E. D.; Barton, J. K. Solution, Surface, and Single Molecule Platforms for the Study of DNA-Mediated Charge Transport. Chem. Chem. Phys.
2012, 14 (40), 13754–13771.
Lithium-Ion Battery Second Life: Cell Performance Assessment for Stationary Energy Storage Applications
Authors: Platt Alison , Fatih Khalid , Brueckner Shawn , Yuan Xiao-Zi , Jang Darren , Fuller Eric 
Published: July 2022

Repurposing electric vehicle (EV) lithium-ion batteries (LIBs) for second-life applications in stationary energy storage has developed considerable interest. With EV sales continuously rising, some critical materials used in LIBs risk supply shortages, while the volume of spent batteries could begin to overwhelm the facilities capable of disposing or recycling them. EV batteries typically reach end-of-life (EOL) when the capacity fades by 20-30%; although this is EOL exclusively for automotive applications, there still remains plenty of residual energy storage available that can be further utilized for less demanding applications. If viable, this could have significant impact in satisfying economic and environmental concerns as the trend toward greener and more sustainable energy solutions gains momentum. Extending the lifespan of retired EV LIBs can potentially supplement and soften the demand for total product, relaxing the strain on newly manufactured product and changing the standard of practice in the value chain. This lifecycle expansion could also be beneficial with respect to environmental impact by reducing raw material extraction and processing, landfill disposal or recycling, and improving resource sustainability.
Existing public work on the reuse of EV batteries has mostly been exploratory, including feasibility studies, techno-economic analyses, and promotional demonstrations. Although necessary as part of the framework to move forward, these investigations lack the data to demonstrate the reliability of EV batteries for second-life applications. The work presented herein utilizes the International Electrotechnical Commission (IEC) standard 62620:2014 to evaluate the compliance, in terms of both capability and longevity, of EOL EV cells for energy storage applications.
Battery modules were obtained from consumer-utilized 2012 and 2014 Nissan Leafs and characterization tests were applied to determine the present state of health. Cells were electrically isolated and the IEC Standard’s electrical tests were applied using a de-rated capacity as the new nominal capacity, based on the characterization results. One of the seven IEC Standard tests included a 500-cycle endurance test in which a C/2 charge and discharge rate was applied. Electrochemical impedance spectroscopy was measured periodically throughout the endurance test. Results on the compliance of these cells for stationary energy storage applications will be presented and discussed.
Artificial Synapse Based on 1D/2D Hybrid Heterostructure
Authors: Eo Jung Sun , Shin Jaeho , Eo Jung Sun 
Published: July 2022

Molecular functional devices have been investigated through the study of molecular structure and its corresponding discrete orbital states since it determines the transport behaviors. [1,2] In contrast to the conventional strategy, we have demonstrated a novel strategy and design rule for realizing molecular-scale functions based on the energy band engineering in molecular heterojunction with two-dimensional (2D) semiconductors [3,4]. Recently, we have designed molecular heterojunction selector and the nonlinearity design rule with the role of the molecular dipole moment orientation which controls the band bending of the 2D semiconductor [4]. Likewise, various role of the molecular self-assembled monolayer (SAM) in hybrid heterostructure device with 2D semiconductor can give a novel and diverse functionality to the device that it can be a powerful platform for the next-generation functional devices. We implemented ferrocene substituted alkanethiol SAMs, which is a redox active molecule [5], in 2D MoS2 field-effect transistor (FET) structure. The redox state (oxidation or reduction) of the SAM is controlled through the gate bias and the oxidized molecular states (Fc -> Fc+) can act as a localized gate at the interface between molecule/2D semiconductor (MoS2) which the conductance of the n-type MoS2 channel can be modulated. This MoS2 FET with non-volatile multistate MoS2 channel can be suggested as electrochemically programmed molecular heterojunction artificial synapse.
[1] L. A. Bumm, J. J. Arnold, M. T. Cygan, T. D. Dunbar, T. P. Burgin, L. Jones, D. L. Allara, J. M. Tour, P. S. Weiss, Science 271, 1705 (
1996),.
[2] H. Song, Y. Kim, Y. H. Jang, H. Jeong, M. A. Reed, T. Lee, Nature 462, 1039 (
2009).
[3] J. Shin, S. Yang, Y. Jang, J. S. Eo, T.-W. Kim, T. Lee, C.-H. Lee, G. Wang, Nat. Commun. 11, 1 (2020).
[4] J. S. Eo, J. Shin, S. Yang, T. Jeon, J. Lee, S. Choi, C.-H. Lee, G. Wang, Adv. Sci. 2101390 (2021).
[5] Y. Zhao, S. Bertolazzi, M. S. Maglione, C. Rovira, M. Mas-Torrent, P. Samori, Adv. Mater. 32, 2000740 (2020).
Characterization of Garnet-Type Li6SrLa2Bi2O12 Solid Electrolyte for LiCoO2 Cathode Composite in All-Solid-State Battery
Authors: Sugimura Yuta , Akimoto Keigo , Inada Ryoji 
Published: July 2022

Together with the development of inorganic solid lithium (Li) ion conducting materials for the use as solid electrolytes, the formation of intimate solid-solid interface between electrode active material and solid electrolyte is pivotal for realizing high performance all-solid-state Li-ion batteries (LiBs) with high safety and reliability. Oxide-based solid electrolytes have the advantages of good chemical stability and ease of handling, but for many of them, the high temperature processing is required for the densification, which may cause undesired side reactions with electrode active materials during the processing.
Although garnet-type oxide solid electrolyte Li6SrLa2Bi2O12 (LSLBO) has lower ionic conductivity than widely studied garnet-type Li7La3Zr2O12 (LLZO), LSLBO can be sintered at much lower temperatures than LLZO [1,2]. Therefore, there is a possibility to suppress the side reaction with electrode active materials during high-temperature sintering for fabricating oxide-based all-solid-state LiBs.
In this study, we prepared dense LSLBO or composites of LiCoO2 (LCO) cathode and LSLBO by hot pressing (HP). LSLBO densified at 750 °C for 1 hour showed high relative density of 95%. The densification temperature of LSLBO by HP confirmed in this work is 100–150 °C lower than Bi-doped LLZO with the formula of Li6La3ZrBiO12 (LLZBO) [3, 4]. Bulk and total (bulk + grain conductivity) ionic conductivity of LSLBO fabricated by HP attained to 2.1 × 10-4 and 1.1 × 10-4 S/cm at room temperature, which is much higher than LSLBO prepared by a conventional furnace sintering (FS) [1] and spark plasma sintering (SPS) [2]. The electrochemical stability of LSLBO at an electrical potential from 3 to 6 V vs. Li/Li+ was also confirmed by measuring the cyclic voltammogram.
From XRD analysis of mixed LSLBO and LCO powders after annealing, LSLBO and LCO were found to be thermally compatible at temperature below 800 °C and LCO-LSLBO composite densified at 700 °C for 1 hour by HP showed mixed conducting properties with both electronic and ionic conductivity of 10-5-10-4 S/cm at room temperature. From galvanostatic charge and discharge testing of sintered LCO-LSLBO composite sheet, we found that electrochemical performance of LCO is not degraded by co-sintering with LSLBO. These results suggest that LSLBO solid electrolyte can be applied for LCO cathode composite in oxide-based all-solid-state LiBs.

References

1. R. Murugan, W. Weppner, P. Schmid-Beurmann and V. Thangadurai, Mater. Sci. Eng. B 143, 14–20 (2007).
2. Y. Gao, X. Wang, Q. Sun, Z. Zhuang and Q. Fang, Front. Mater. Sci. 6(3), 216–224 (2012).
3. M. Wang and J. Sakamoto, Ionics 24, 1861–1868 (2018).
4. D. K. Schwanz, A. Villa, M. Balasubramanian, B Helfrecht and E. E. Marinero, AIP Adv. 10, 035204 (2020).
A Sobering Examination of the Feasibility of Aqueous Aluminum Batteries
Authors: Pastel Glenn 
Published: July 2022

Aqueous aluminum (Al) batteries are posited to be a cheap and energy dense alternative to conventional Li-ion chemistries, but an aqueous electrolyte mediating trivalent aluminum cations (Al3+) warrants greater scrutiny. This study provides a rigorous examination of aqueous Al electrolytes, with the first compelling evidence for a dynamic octahedral solvation structure around the Al3+, without Al-OTf contact ion pairs, even at high concentrations. This solvation behavior and the concomitant, transient electrostatic hydrolysis of Al-OH2 ligands contrasts strongly with previously reported water-in-salt electrolytes, and occurs due to the high charge density of the Lewis acidic Al3+. Nuclear magnetic resonance spectroscopy and other physicochemical measurements quantitatively reveal how species activity evolves with concentration and temperature. This new understanding exposes practical concerns related to the corrosiveness of the acidic aqueous solutions, the degree of hydration of aluminum trifluoromethanesulfonate (Al(OTf)3) salt, and the grossly insufficient reductive stability of the proposed electrolytes (>1 V between HER onset and Al3+/Al). Collectively, these factors constitute multiple fundamental barriers to the feasibility of rechargeable aqueous Al batteries.
Table of Contents: We assess the challenges associated with aqueous aluminum electrolyte by investigating the solvation structure of the Al3+ Lewis acid in Al(OTf)3-H2O solutions. The deprotonation of water ligands in the first solvation sheath leads to early onset of hydrogen evolution in super-concentrated aqueous aluminum electrolyte.

Figure 1
(Digital Presentation) Performance Improvement of Nickel-Rich Layered Cathodes for Li Batteries Based on Modified Solid State Reaction
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Yang Jen-Hao 
Published: July 2022

Lithiated metal oxides with layered structure used as the cathode may provide a high capacity and stable cycle retention, which is a desired property for lithium-ion batteries. Among them, NMC composed of Ni, Mn and Co as transition metal ions is considered a promising positive electrode. Due to high cost and toxicity of Co, Ni-rich layered oxide with substitution of Ni for Co content shows high capacity and adequate cycling performance. Recently, the fabrication of NMC adopting single-crystal (grain size: 1~6 μm) process tends to give better long-term performance than ones with particles in nanometer range.
In this study, LiNi0.8Mn0.1Co0.1O2 (NMC811) with substitution of Ni/Mn for Co were selected as the Ni-rich layered cathode investigated. Due to the low melting point of Li2CO3, the heating temperature/time of powder mixture become crucial to control the adequate grain size of to achieve better retention. The value of the I(003) /I(104) ratio in XRD pattern represent cation mixing in layered structure. And this parameter is closely related to its electrochemical properties. Discussion will be carried out based on the results of XRD analysis and the charge–discharge profiles and cycling performance.
Targeted Synthesis of Metal Dual Atom Electrocatalysts
Authors: Barrio Jesus , Pedersen Angus , Feng Jingyu , Titirici Magda , Stephens Ifan Erfyl Lester 
Published: July 2022

Natural enzymes present within their structure active centres composed of earth-abundant metals in atomic proximity. Such active sites, dual atom catalysts, display a unique efficiency in catalytic processes such as the nitrogen conversion to ammonia, the production of ethylene through C-C coupling, or the oxygen reduction reaction in fuel cells amongst others.1,2 Theoretical calculations suggest that the high catalytic activity of dual atom catalysts arises from the different binding mode of reactant molecules to that of metal foils and single atom catalysts, which allows to break transition scaling relationships.3 Nevertheless, the experimental synthesis and characterisation of this class of materials is highly challenging.4 It is particularly difficult to avoid the formation of single atom catalysts or nanoparticles. In this work we show a general approach to fabricate bioinspired Fe dual atom catalysts in a nitrogen doped carbon support; we test the catalyst for the oxygen reduction reaction under acidic conditions. The catalyst exhibited an activity of 2.4 ± 0.3 A g-1
carbon at 0.8 V versus a reversible hydrogen electrode in acidic media, comparable to the most active in the literature. The two-step procedure leads to well defined Fe-based dimers. We characterised these materials by means of X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy. Our general approach providing a new towards targeted synthesis of dual atom electrocatalysts for energy-critical reactions.
References
(1) Chen, J. G.; Crooks, R. M.; Seefeldt, L. C.; Bren, K. L.; Bullock, R. M.; Darensbourg, M. Y.; Holland, P. L.; Hoffman, B.; Janik, M. J.; Jones, A. K.; Kanatzidis, M. G.; King, P.; Lancaster, K. M.; Lymar, S. V; Pfromm, P.; Schneider, W. F.; Schrock, R. R. Beyond Fossil Fuel–Driven Nitrogen Transformations. Science
2018, 360, eaar6611
(2) Lee, C. C.; Hu, Y.; Ribbe, M. W. Vanadium Nitrogenase Reduces CO. Science
2010, 329, 642
(3) Singh, A. R.; Montoya, J. H.; Rohr, B. A.; Tsai, C.; Vojvodic, A.; Nørskov, J. K. Computational Design of Active Site Structures with Improved Transition-State Scaling for Ammonia Synthesis. ACS Catal.
2018, 8, 4017–4024
(4) Pedersen, A.; Barrio, J.; Li, A.; Jervis, R.; Brett, D. J. L.; Titirici, M. M.; Stephens, I. E. L. Dual-Metal Atom Electrocatalysts: Theory, Synthesis, Characterization, and Applications. Adv. Energy Mater.
2021, 2102715

Figure 1
What Nanomaterials Can Do for Energy Storage: Production of Charged, Individualised Nanomaterials (CINs) As Novel Materials for Electrochemical Energy Storage Devices
Authors: Shutt Rebecca Roisin Christine , Miller Thomas Samuel , Howard Chris Anthony 
Published: July 2022

Electrochemical energy storage devices, such as batteries and supercapacitors, allow us to store electrical energy as chemical energy. They are a vital component of the UK’s plans to achieve net-zero carbon emissions by 2050.1 Nanomaterials offer properties such as short ion diffusion distances, high percolation to form conductive networks, and structural frameworks that can withstand mechanical stresses from successive volume expansion-contraction cycles on insertion-deinsertion of guest ions. Thanks to these properties, incorporation of nanomaterials into electrochemical energy storage devices could allow them to store more energy, last longer, and cope with the load cycles required for grid storage.2 However, the use of nanomaterials in commercial devices is limited by their low density and tendency to agglomerate. In addition, established synthesis methods such as high energy sonication and Hummer’s method yield nanomaterials with properties that fall short of those predicted theoretically, by resulting in a distribution of few-layer materials, and introducing defects that might not benefit electrochemical performance.
This work uses highly reducing solutions, such as alkali metal-ammonia solutions or sodium naphthalide solutions, and subsequent spontaneous dissolution in polar aprotic solvents, to individualise nanomaterials and introduce negative charge to the surface in a single step (Figure 1).3,4 This produces exclusively monolayer, pristine, negatively-charged, individualised nanomaterials (CINs). This synthesis route can be applied to a wide range of materials, such as layered materials like graphite and transition metal dichalcogenides, as well as carbon nanotubes and other carbonaceous materials. The negative charge introduced can be used in subsequent synthesis steps to add functionality, grow nanoparticles, and control assembly into 3D structure. Using starting materials such as graphite, carbon nanotubes, and phosphorus,5 this work presents the application of these methods to investigate what new materials can be made. Furthermore, their electrochemical performance in batteries and supercapacitors is discussed.

References

1HM Government, Dep. Business, Energy Ind. Strateg., 2020, 1–38.

2E. Pomerantseva, F. Bonaccorso, X. Feng, Y. Cui, Y. Gogotsi, Science, 2019, 366, 969.

3P. L. Cullen, K. M. Cox, M. K. Bin Subhan, L. Picco, O. D. Payton, D. J. Buckley, T. S. Miller, S. A. Hodge, N. T. Skipper, V. Tileli, C. A. Howard, Nat. Chem., 2017, 9, 244–249.

4A. Clancy, J. Melbourne, M. S. P. Shaffer, J. Mater. Chem. A, 2015, 3, 16708–16715.

5M. C. Watts, L. Picco, F. S. Russell-Pavier, P. L. Cullen, T. S. Miller, S. P. Bartus, O. D. Payton, N. T. Skipper, V. Tileli, C. A. Howard, Nature, 2019, 568, 216–220.

Figure 1
(Digital Presentation) Hydrophilic and Hydrophobic Carbon Nanotubes Combined into a Buckypaper As an Electrode for Li-O2 Batteries
Authors: Leal Silva Jean Felipe , Doubek Gustavo , Maciel Filho Rubens 
Published: July 2022

With the decreasing costs of wind and solar power, these two energy sources are set to gain a sizeable share of the electricity market in the next years. To cope with the intermittency of these electricity sources, grid operators are required to develop new, inexpensive, and efficient energy storage facilities. One of the technologies being considered for such application is the Li-O2 battery, whose main advantage compared to state-of-the-art lithium-ion batteries is the prospect of higher energy density which might lead to decreased installation costs. Nevertheless, these batteries depend upon efficient mass transport of O2 inside the electrode to present suitable power density. In this work, a mix of hydrophilic and hydrophobic carbon nanotubes (CNT) was used to produce an O2 electrode with enhanced mass transport properties. Hydrophobic CNT were prepared via thermal treatment under Ar atmosphere at 850 °C for 2 h. Hydrophilic CNT were prepared via refluxing in 7 mol L-1 HNO3 solution for 4 h (~120 °C). Raman spectroscopy was used to analyze the quality of both types of CNT. Different proportions of hydrophobic and hydrophilic CNT were dispersed in solution with a surfactant using a probe sonicator. The solution was filtered using a 0.22 μm membrane and vacuum to produce a buckypaper. Batteries were assembled in a glove box using a Li electrode, a separator membrane (glass fiber), and the buckypaper as the O2 electrode. Galvanostatic discharge tests were carried out at different currents to analyze the impact of different qualities of CNT used in the making of the O2 electrode in the increasing demand for O2 in the battery at high currents. Scanning electron microscopy images were used to compare the morphology of the different electrodes before and after discharge. Results are expected to demonstrate a new method to increase the mass transport rates for O2 in Li-O2 batteries.
The authors gratefully acknowledge the support from FAPESP (the Sao Paulo Research Foundation, Grant Numbers 2018/16663-2 and 2017/11958-1), Shell, the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation, and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001.
Li Host Carbon Materials As the Negative Electrode for a Li-Metal Battery – Mechanistic and Practical Assessment
Authors: Zhou Bingxin , Fang Baizeng , Stosevski Ivan , Bonakdarpour Arman , Wilkinson David P. 
Published: July 2022

The lithium metal anode is highly valued in the development of high-energy density storage devices owing to its high specific capacity. However, the growth of lithium dendrites and high-volume expansion during the charging process creates significant issues for commercial application. To regulate the lithium deposition behavior various methods have been proposed among which carbon-based materials are being widely investigated because of their unique advantages including high conductivity, along with the material availability and ease of operation. However, current literature on lithium deposition in carbonaceous hosts have contradictory conclusions and further investigation is needed1–4.
Herein, pure hollow core-carbon spheres (PHCCSs), deposited on copper foil (PHCCS@Cu), are used to study the lithium deposition behavior with respect to this type of structure. It is demonstrated that lithium shows some initial and limited intercalation into the PHCCSs and then plates on its external walls and the top-surface of the hollow core carbon structures during the charging process. Figure 1 shows initial lithium insertion followed by lithium deposition with a greater amount of charging. A possible mechanism of lithium deposition inside the PHCCSs is discussed from the aspect of lithium-ion transport and lithium deposition site preference. The application potential of PHCCSs from the point of view of lithium metal volumetric capacity (VC) are also discussed.

References

G. Zheng et al., Nat. Nanotechnol., 9, 618–623 (2014) http://dx.doi.org/10.1038/nnano.2014.152.

D. Lin et al., Nat. Nanotechnol., 11 (2016).

K. Yan et al., Nat. Energy, 1, 16010 (2016).

W. Ye et al., Adv. Energy Mater., 10, 1–10 (2020).

Figure 1