Concept: Galvanic cell
Economical and efficient carbon capture, utilization, and sequestration technologies are a requirement for successful implementation of global action plans to reduce carbon emissions and to mitigate climate change. These technologies are also essential for longer-term use of fossil fuels while reducing the associated carbon footprint. We demonstrate an O2-assisted Al/CO2 electrochemical cell as a new approach to sequester CO2 emissions and, at the same time, to generate substantial amounts of electrical energy. We report on the fundamental principles that guide operations of these cells using multiple intrusive electrochemical and physical analytical methods, including chronopotentiometry, cyclic voltammetry, direct analysis in real-time mass spectrometry, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy, and coupled thermogravimetric analysis-Fourier transform infrared spectroscopy. On this basis, we demonstrate that an electrochemical cell that uses metallic aluminum as anode and a carbon dioxide/oxygen gas mixture as the active material in the cathode provides a path toward electrochemical generation of a valuable (C2) species and electrical energy. Specifically, we show that the cell first reduces O2 at the cathode to form superoxide intermediates. Chemical reaction of the superoxide with CO2 sequesters the CO2 in the form of aluminum oxalate, Al2(C2O4)3, as the dominant product. On the basis of an analysis of the overall CO2 footprint, which considers emissions associated with the production of the aluminum anode and the CO2 captured/abated by the Al/CO2-O2 electrochemical cell, we conclude that the proposed process offers an important strategy for net reduction of CO2 emissions.
Significance: Thioredoxin, glutaredoxin and peroxiredoxin systems play critical roles in a large number of redox sensitive cellular processes. These systems are linked to each other by coupled redox cycles and common reaction intermediates into a larger network. Given the scale and connectivity of this network, computational approaches are required to analyze its dynamics and organization. Recent Advances: Theoretical advances, as well as new redox proteomic methods, have led to the development of both top-down and bottom-up systems biology approaches to analyze the these systems and the network as a whole. Top-down approaches have been based on modifications to the Nernst equation or on graph theoretical approaches while bottom-up approaches have been based on kinetic or stoichiometric modeling techniques. Critical issues: This review will consider the rationale behind these approaches and focus on their advantages and limitations. Further, the review will discuss modeling standards to ensure model accuracy and availability. Future Directions: Top-down and bottom-up approaches have distinct strengths and limitations in describing cellular redoxin networks. The availability of methods to overcome these limitations, together with the adoption of common modeling standards, is expected to increase the pace of model-led discovery within the redox biology field.
A facile and scalable synthesis method has been developed for TiO2/graphene nanostructured composites as high-performance anode materials for Li-ion batteries. Through a moderate reaction between tetrabutyl titanate and oxalic acid, an amorphous flower-like intermediate of hydroxyl titanium oxalate attached to graphene oxide nanosheets can be firstly prepared; by following calcination, the intermediate converts to the final product TiO2/graphene nanocomposite. The ultra-small size of TiO2 nanoparticles, the unique flower-like nanostructure of TiO2 with a high surface area, and the excellent electrical conductivity of graphene nanosheets that support TiO2 endow the TiO2/graphene nanocomposite with outstanding electrochemical performance. The nanocomposite can deliver a charge capacity of 230 mA h g-1 at 0.1C, and demonstrates superior high-rate charge-discharge capability and cycling stability at charge/discharge rates up to 50C in a half cell configuration. Full cell measurement using the TiO2/graphene as the anode material and spinel LiMnO2 as the cathode material exhibits good high-rate performance and cycling stability, indicating that the TiO2/graphene nanocomposite has a practical application potential in advanced Li-ion batteries.
During the 1790s, Alexander von Humboldt (1769-1859), who showed an early interest in many facets of natural philosophy and natural history, delved into the controversial subject of galvanism and animal electricity, hoping to shed light on the basic nature of the nerve force. He was motivated by his broad worldview, the experiments of Luigi Galvani, who favored animal electricity in more than a few specialized fishes, and the thinking of Alessandro Volta, who accepted specialized fish electricity but was not willing to generalize to other animals, thinking Galvani’s frog experiments flawed by his use of metals. Differing from many German Naturphilosophen, who shunned “violent” experiments, the newest instruments, and detailed measurement, Humboldt conducted thousands of galvanic experiments on animals and animal parts, as well as many on his own body, some of which caused him great pain. He interpreted his results as supporting some but not all of the claims made by both Galvani and Volta. Notably, because of certain negative findings and phenomenological differences, he remained skeptical about the intrinsic animal force being qualitatively identical to true electricity. Hence, he referred to a “galvanic force,” not animal electricity, in his letters and publications, a theoretical position he would abandon with Volta’s help early in the new century.
Surface engineering of sponge-like Si particles is necessary to alleviate the large volume expansion of Si during the lithiation-delithiation process and to mitigate the unwanted interfacial reactions upon cycling. The sponge-like Si structuring and introduction of double layers consisting of carbon and polyimide enabled us to make high performance Si anode materials exhibiting a high specific capacity and highly stable cycling.
Layered P2-Na(x)[Ni(1/3)Mn(2/3)]O(2) (0 < x < 2/3) is investigated as a cathode material for Na-ion batteries. A combination of first principles computation, electrochemical and synchrotron characterizations is conducted to elucidate the working mechanism for the improved electrochemical properties. The reversible phase transformation from P2 to O2 is observed. New configurations of Na-ions and vacancy are found at x = 1/3 and 1/2, which correspond to the intermediate phases upon the electrochemical cycling process. The mobility of Na-ions is investigated using the galvanostatic intermittent titration technique (GITT) and the Na diffusion barriers are calculated by the Nudged Elastic Band (NEB) method. Both techniques prove that the mobility of Na-ions is faster than Li-ions in the O3 structure within the 1/3 < x < 2/3 concentration region. Excellent cycling properties and high rate capability can be obtained by limiting the oxygen framework shift during P2-O2 phase transformation, suggesting that this material can be a strong candidate as a sustainable low-cost Na-ion battery cathode.
Substrate leveling is an essential but neglected instrumental technique of scanning electrochemical microscopy (SECM). In this technical note, we provide an effective substrate leveling method based on the current feedback mode of SECM. By using an air-bearing rotary stage as the supporter of electrolytic cell, the current feedback presents a periodic waveform signal which can be used to characterize the levelness of the substrate. Tuning the adjusting screws of the tilt stage, substrate leveling can be completed in minutes by observing the decreased current amplitude. The obtained high-quality SECM feedback curves and images prove this leveling technique is valuable in not only SECM studies but also electrochemical machining.
An electrochemical cell based on the reversible oxygen reduction reaction: 2Li(+) + 2e (-) + O2↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells.
Biofouling is a major problem caused by bacteria colonizing abiotic surfaces, such as medical devices. Biofilms are formed as the bacterial metabolism adapts to an attached growth state. We studied whether bacterial metabolism, hence biofilm formation, can be modulated in electrochemically active surfaces using the conducting conjugated polymer poly(3,4-ethylenedioxythiophene) (PEDOT). We fabricated composites of PEDOT doped with either heparin, dodecyl benzene sulfonate or chloride, and identified the fabrication parameters so that the electrochemical redox state is the main distinct factor influencing biofilm growth. PEDOT surfaces fitted into a custom-designed culturing device allowed for redox switching in Salmonella cultures, leading to oxidized or reduced electrodes. Similarly large biofilm growth was found on the oxidized anodes and on conventional polyester. In contrast, biofilm was significantly decreased (52-58%) on the reduced cathodes. Quantification of electrochromism in unswitched conducting polymer surfaces revealed a bacteria-driven electrochemical reduction of PEDOT. As a result, unswitched PEDOT acquired an analogous electrochemical state to the externally reduced cathode, explaining the similarly decreased biofilm growth on reduced cathodes and unswitched surfaces. Collectively, our findings reveal two opposing effects affecting biofilm formation. While the oxidized PEDOT anode constitutes a renewable electron sink that promotes biofilm growth, reduction of PEDOT by a power source or by bacteria largely suppresses biofilm formation. Modulating bacterial metabolism using the redox state of electroactive surfaces constitutes an unexplored method with applications spanning from antifouling coatings and microbial fuel cells to the study of the role of bacterial respiration during infection.
The ability of crystalline Si to photo-assist the V3+/V2+ cathodic reaction under simulated solar irradiation, combined with the effect of Bi have led to important electrochemical improvements. Besides the photo-voltage supplied by the photovoltaics, additional decrease in the onset potentials, high reversibility of the V3+/V2+ redox pair and improvement in the electro-kinetics have been attained thanks to the addition of Bi. In fact, Bi0 deposition has shown to slightly decrease the photocurrent, but the significant betterment in the charge transfer, reflected in the overall electrochemical performance clearly justifies its use as additive in a photo-assisted system for maximizing the efficiency of solar charge to battery.