Electrochemistry articles within Nature Chemistry

Featured

  • Article |

    Developing a stable metallic lithium anode is necessary for next-generation batteries; however, lithium is prone to corrosion, a process that must be better understood if practical devices are to be created. A Kirkendall-type mechanism of lithium corrosion has now been observed. The corrosion is fast and is governed by a galvanic process.

    • Dingchang Lin
    • , Yayuan Liu
    •  & Yi Cui

  • Article |

    The use of Li or Na as electrodes in Li-Na alloy–O2 batteries creates formidable challenges for both safety and stability because of their oxidative corrosion and the growth of dendrites and cracks on their surface. Now, an aprotic bimetal Li-Na alloy–O2 battery with high cycling stability has been developed using a Li-Na eutectic alloy anode and an electrolyte additive.

    • Jin-ling Ma
    • , Fan-lu Meng
    •  & Qing Jiang

  • Article |

    The polyoxoanion [P2W18O62]6− has been shown to reversibly accept up to 18 electrons upon reduction in aqueous solution. The resulting highly reduced solution can then be used either for the on-demand generation of hydrogen over a catalyst bed, or as a high-energy-density electrolyte in a redox flow battery.

    • Jia-Jia Chen
    • , Mark D. Symes
    •  & Leroy Cronin

  • Article |

    On copper catalysts, Cuδ+ sites play a key role in the electrochemical reduction of CO2 to C2 hydrocarbons, however, they are prone to being reduced (to Cu0) themselves. Now, a Cuδ+-based catalyst is reported that is stable for in excess of ~40 hours while electrochemically reducing CO2 to multi-carbon hydrocarbons and that exhibits a Faradaic efficiency for C2 of ~80%.

    • Yansong Zhou
    • , Fanglin Che
    •  & Edward H. Sargent

  • Article |

    The [4Fe4S]2+ cluster-containing DNA-repair enzyme MUTYH helps safeguard the integrity of Watson–Crick base pairing and the human genetic code. The MUTYH [4Fe4S]2+ cluster mediates DNA redox signalling and DNA lesion identification. Now, a MUTYH pathologic variant associated with catastrophic [4Fe4S]2+ cluster redox degradation, impairment of DNA signalling and human colonic tumorigenesis has been identified.

    • Kevin J. McDonnell
    • , Joseph A. Chemler
    •  & Stephen B. Gruber

  • Article |

    Calcium-ion batteries are potentially attractive alternatives to lithium-ion batteries, but remain largely unexplored because of low performance. A reversible calcium alloying/de-alloying reaction with the tin anode has now been coupled with the intercalation/de-intercalation of hexafluorophosphate in the graphite cathode to enable a calcium-ion battery that operates stably at room temperature.

    • Meng Wang
    • , Chunlei Jiang
    •  & Hui-Ming Cheng

  • Article |

    Mg-based batteries possess potential advantages over their lithium counterparts; however, the use of reversible oxidation-resistant, carbonate-based electrolytes has been hindered because of their undesirable electrochemical reduction reactions. Now, by engineering a Mg2+-conductive artificial interphase on a Mg electrode surface, which prevents such reactivity, highly reversible Mg deposition/stripping in carbonate-based electrolytes has been demonstrated.

    • Seoung-Bum Son
    • , Tao Gao
    •  & Chunmei Ban

  • Article |

    Heterometallic nanomaterials in unusual crystal phases that are impossible to form in the bulk state can show interesting physical and chemical properties. Here, crystal-phase heterostructured 4H/fcc Au nanowires are used as seeds to epitaxially grow a variety of binary and ternary hybrid noble metal nanostructures on the phase boundary.

    • Qipeng Lu
    • , An-Liang Wang
    •  & Hua Zhang

  • News & Views |

    Water-oxidation catalysts that are fast and efficient in strong acid are rare even though there are several benefits for systems working at low pH. Such catalysts usually feature expensive noble metals such as ruthenium and iridum; however, an electrocatalytic system that is exceptionally efficient and based on cobalt has now been developed.

    • Qiushi Yin
    •  & Craig L. Hill

  • Article |

    Electrochemical water oxidation in acidic media is a promising water-splitting technique, but typically requires noble metal catalysts. Now, two polyoxometalate salts based on earth-abundant metals have shown excellent catalytic performance for the oxygen evolution reaction. The barium salt of a cobalt-phosphotungstate polyanion outperformed the state-of-the-art IrO2 catalyst at pHs lower than 1.

    • Marta Blasco-Ahicart
    • , Joaquín Soriano-López
    •  & J. R. Galan-Mascaros

  • Article |

    Understanding how oxygen-evolution reaction (OER) catalysts work is important for the development of efficient energy storage technologies. It has now been shown that lattice oxygen participates in O2 generation during the OER on some highly active metal oxides and that this behaviour becomes more prevalent with greater metal–oxygen covalency.

    • Alexis Grimaud
    • , Oscar Diaz-Morales
    •  & Yang Shao-Horn

  • Article |

    FeFe hydrogenases are highly efficient H2 producing enzymes; however, they can be inactivated by O2. Now, a mechanism for O2 diffusion within FeFe hydrogenases and its reactions at the active site of the enzyme has been proposed. These findings could help with the design of hydrogenase mutants with increased resistance to oxidative damage.

    • Adam Kubas
    • , Christophe Orain
    •  & Christophe Léger

  • News & Views |

    Chemists have long been fascinated by electron delocalization, from both a fundamental and applied perspective. Macrocyclic oligomers containing fused ferrocenes provide a new structural framework — containing strongly interacting metal centres — that is capable of supporting substantial charge delocalization.

    • Rebecca A. Musgrave
    •  & Ian Manners

  • Article |

    Cyclic molecules often exhibit unusual properties; consider for example the resonance stabilization energy of benzene or the strong cation binding of crown ethers. Now, a family of rings comprising varying numbers of directly linked ferrocenes has been prepared. These compounds are highly symmetric in solution and undergo rapid ‘oxidation-state isomerism’ when charged.

    • Michael S. Inkpen
    • , Stefan Scheerer
    •  & Nicholas J. Long

  • News & Views |

    Combining conventional transition-metal oxidation with oxygen oxidation in 'lithium-excess' materials is a recently discovered route to improving the capacity of lithium-ion batteries. Now two studies, one experimental and one theoretical, have investigated the processes, states and structures involved.

    • Claude Delmas

  • Article |

    The chemistry of the transition metals within the oxide cathodes of lithium-ion batteries typically limits their capacity, however, reversible oxygen redox could potentially break this limit. It is now demonstrated that Li-excess and cation disorder create specific environments around oxygen atoms that lead to labile oxygen electrons that participate in the practical capacity of cathodes.

    • Dong-Hwa Seo
    • , Jinhyuk Lee
    •  & Gerbrand Ceder

  • Article |

    Designing improved catalysts is predicated on understanding how they work. Now, by positioning three ruthenium centres in a macrocyclic framework, a remarkable acceleration of catalytic water oxidation has been achieved. Detailed mechanistic studies revealed that the catalyst operates through the ‘water nucleophilic attack’ pathway—similar to the natural oxygen-evolving cluster of photosystem II.

    • Marcus Schulze
    • , Valentin Kunz
    •  & Frank Würthner

  • Article |

    The energy that can be stored in lithium-ion batteries is typically limited by the redox chemistry of the transition metals within the cathodes. Now it is shown that for Li1.2[Ni2+0.13Co3+0.13Mn4+0.54]O2, a 3d-transition-metal oxide that breaks this limit, Li-ion extraction is charge compensated not just by transition-metal oxidation but also through the generation of localized electron-holes on oxygen.

    • Kun Luo
    • , Matthew R. Roberts
    •  & Peter G. Bruce

  • Article |

    Li+-selective solid electrolytes may enable next-generation battery systems, such as Li–S and Li–O2. Now, in an exemplar system, it is shown that a resistive interphase forms at the interface between solid and liquid electrolytes, termed the solid-liquid electrolyte interphase (SLEI). An in situ study of this undesirable effect is supported by state-of-the-art surface analysis.

    • Martin R. Busche
    • , Thomas Drossel
    •  & Jürgen Janek

  • News & Views |

    The use of renewable resources as providers to the electrical grid is hampered by the intermittent and irregular nature in which they generate energy. Electrical energy storage technology could provide a solution and now, by using an iterative design process, a promising anolyte for use in redox flow batteries has been developed.

    • Wei Wang
    •  & Vince Sprenkle

  • Article |

    The analysis of circulating cell-free nucleic acids (cfNA) in the blood of cancer patients permits the analysis of tumour mutations without requiring invasive sampling of tissue. Now, the development of an electrochemical assay that uses a collection of clamp molecules to sequester interfering cfNAs enables the accurate detection of mutated sequences in serum collected from people with lung cancer or melanoma.

    • Jagotamoy Das
    • , Ivaylo Ivanov
    •  & Shana O. Kelley

  • Article |

    Better understanding of the chemistry of rechargeable metal–oxygen batteries is needed to fulfil their potential. It is now shown that proton phase-transfer catalysts drive Na–O2 batteries, transporting superoxide between the electrode surface and the electrolyte as HO2. The chemistry uncovered gives rise to the system's high reversible capacity.

    • Chun Xia
    • , Robert Black
    •  & Linda F. Nazar

  • Article |

    The maximum attainable capacity of the Li–O2 battery is limited by the passivation of its cathode by electronically insulating Li2O2. It is now shown that electrolyte additives, which activate solution-mediated growth of Li2O2, make it possible to circumvent this fundamental limitation, leading to design rules for additive selection.

    • Nagaphani B. Aetukuri
    • , Bryan D. McCloskey
    •  & Alan C. Luntz

  • Review Article |

    Energy storage using batteries offers a solution to the intermittent nature of energy production from renewable sources; however, such technology must be sustainable. This Review discusses battery development from a sustainability perspective, considering the energy and environmental costs of state-of-the-art Li-ion batteries and the design of new systems beyond Li-ion. Images: batteries, car, globe: © iStock/Thinkstock.

    • D. Larcher
    •  & J-M. Tarascon

  • Article |

    The mechanism of O2 reduction in aprotic solvents is important for the operation of Li–O2 batteries but is not well understood. A single unified mechanism is now described that regards previous models as limiting cases. It shows that the solubility of the intermediate LiO2 is a critical factor that dictates the mechanism, emphasizing the importance of the solvent.

    • Lee Johnson
    • , Chunmei Li
    •  & Peter G. Bruce

  • Article |

    The oxygen reduction reaction limits fuel cell performance and currently requires costly electrocatalysts with high platinum content to achieve adequate power densities. Now a silver–cobalt surface alloy electrocatalyst has been developed for the oxygen reduction reaction that is stable in alkaline electrolytes and is more economical than traditional platinum-based materials.

    • Adam Holewinski
    • , Juan-Carlos Idrobo
    •  & Suljo Linic

  • Article |

    Hydrogenases are efficient and promising catalysts for fuel cells; however, they suffer from oxygen sensitivity and deactivation at high potentials. Integration of hydrogenases into redox-active hydrogels provides a redox buffer and a self-activated oxygen-scavenging mechanism. This tandem protection makes the hydrogenase a possible alternative to noble metal catalysts.

    • Nicolas Plumeré
    • , Olaf Rüdiger
    •  & Wolfgang Lubitz

  • Article |

    The widespread use of fuel cells requires improved catalysts to reduce oxygen efficiently at the cathode. It is shown that model, well-characterized size-selected PtxY nanoparticles can be synthesized by the gas aggregation technique, and that they are highly active for this reaction.

    • Patricia Hernandez-Fernandez
    • , Federico Masini
    •  & Ib Chorkendorff

  • News & Views |

    The ordered one-dimensional nanochannels found in covalent organic frameworks (COFs) could render them able to conduct protons. However, the frameworks' instability in acid has thus far precluded any practical implementations. Now, a strategy to overcome this instability has enabled proton conduction using a COF for the first time.

    • Hong Xu
    •  & Donglin Jiang

  • Article |

    FeFe hydrogenases, the enzymes that oxidize or produce H2, are inactivated under oxidizing conditions. Here, it is shown that this inactivation results from H2 binding to coordination positions that are normally blocked by intrinsic CO ligands. This flexibility of the active site prevents irreversible oxidative damage.

    • Vincent Fourmond
    • , Claudio Greco
    •  & Christophe Léger

  • Article |

    Light-driven proton pumps are used in biology to create a proton gradient that can be subsequently converted into chemical energy. Here, an artificial light-harvesting system based on a membrane doped with a spiropyran is described. Irradiation with UV light generates a proton flux across the membrane and results in the generation of an electrical current.

    • Xiaojiang Xie
    • , Gastón A. Crespo
    •  & Eric Bakker

  • Article |

    Non-noble-metal-based MoS2 nanostructures are hydrogen evolution catalysts whose active sites are known to be located at the edges. Supported thiomolybdate [Mo3S13]2− nanoclusters have now been prepared that exhibit a structural motif similar to that of MoS2 edges. The nanoclusters, synthesized by a scalable route, demonstrate a high turnover frequency.

    • Jakob Kibsgaard
    • , Thomas F. Jaramillo
    •  & Flemming Besenbacher

  • News & Views |

    The rechargeable Li–O2 battery has low energy efficiency, which is mainly due to kinetic difficulties in the electrochemical oxidation of the insulating discharge product, Li2O2. Now a redox mediator, acting as an electron–hole transfer agent, has been used to promote this oxidation reaction.

    • Yonggang Wang
    •  & Yongyao Xia

  • Article |

    Recharging Li–O2 batteries requires oxidation of the discharge product solid Li2O2. Now a redox-mediating molecule is shown to assist this process by transferring electron–holes between solid Li2O2 and the positive electrode in a non-aqueous Li–O2 cell. This allows the cell to be charged at rates that are otherwise impossible.

    • Yuhui Chen
    • , Stefan A. Freunberger
    •  & Peter G. Bruce

  • News & Views |

    The electrolysis of water provides a link between electrical energy and hydrogen, a high-energy-density fuel and a versatile energy carrier, but the process is expensive. Splitting the electrolysis reaction into two steps through an electrochemical 'buffer' offers a new way to think about improving the cost and efficiency of electrolysers.

    • Thomas E. Mallouk

  • Article |

    Using a polyoxometalate as an electron-coupled-proton buffer, the decoupling of the water oxidation and proton reduction half reactions of electrolytic water splitting is achieved. This allows O2 and H2 to be produced separately in both time and space. The implications of these findings for electrolyser design and low-cost hydrogen production from water are discussed.

    • Mark D. Symes
    •  & Leroy Cronin

  • News & Views |

    Tying molecules together in a link results in tremendous stabilization of the radical species they can form. Six clearly distinguishable charged states — which can be interconverted reversibly — have now been observed in a densely cationic system.

    • David B. Amabilino

  • News & Views |

    During photosynthesis, the oxygen-evolving complex oxidizes water to produce molecular oxygen. Now, a possible role for the calcium ion in this complex has been proposed based on the electrochemical properties of a series of synthetic heterometallic clusters.

    • Sarah A. Cook
    •  & A. S. Borovik

  • News & Views |

    Hydrogen–oxygen alkaline fuel cells are promising devices for the 'hydrogen economy' but their oxidation of hydrogen fuel is slow compared with that of acidic fuel cells. More efficient electrocatalysts have now been prepared in which the adsorption of hydroxyl groups onto the electrode surface is controlled through suitable promoters.

    • Marc T. M. Koper

  • Article |

    The presence of Ca2+ is essential for the activity of the oxygen-evolving complex (OEC) of Photosystem II, although its exact role is still unclear. Now, electrochemical measurements of structural mimics of the OEC — based on mixed-metal trimanganese dioxido complexes — reveal a correlation between the Lewis acidity of the redox-inactive metal and the reduction potential of the complex.

    • Emily Y. Tsui
    • , Rosalie Tran
    •  & Theodor Agapie

  • Article |

    Hydrogen is an attractive alternative to fossil fuels, but the slow rate of the hydrogen oxidation reaction in alkaline fuel cells hinders their development. It is now proposed that bifunctional materials can be devised to offer the optimal balance between hydrogen and hydroxyl adsorption, thus significantly reducing the amount of precious metal on the anode.

    • Dusan Strmcnik
    • , Masanobu Uchimura
    •  & Nenad M. Markovic

  • Article |

    Electricity can be produced by the oxidation of hydrogen in fuel cells, but the best catalyst for this is platinum, a precious metal of low abundance. Now a molecular complex of iron, a very abundant, inexpensive metal, has been rationally designed for the oxidation of H2 at room temperature.

    • Tianbiao Liu
    • , Daniel L. DuBois
    •  & R. Morris Bullock

  • News & Views |

    The reversible reduction and evolution of oxygen are the key processes to be mastered before high-energy rechargeable lithium–air batteries can be successfully created. Now an advance towards this goal has been achieved with the synthesis of a pyrochlore catalyst that benefits from a mesoporous structure and oxygen deficiencies.

    • Fangyi Cheng
    •  & Jun Chen

  • Article |

    The lithium–O2 battery can theoretically provide energy densities that greatly exceed that of Li-ion, but it requires more efficient catalysts (or ‘promoters’) than carbon for oxygen reduction and evolution. Here, we report a tailor-made mesoporous metallic oxide that results in high reversible capacities and operates over many cycles.

    • Si Hyoung Oh
    • , Robert Black
    •  & Linda F. Nazar

  • Article |

    Efficient hydrogen-evolving catalysts comprising readily available elements are needed if hydrogen is to be adopted as a clean alternative to fossil fuels. Now, a diimine–dioxime cobalt complex has been covalently attached to a carbon nanotube electrode to yield an active and robust electrocatalyst for hydrogen generation (55,000 turnovers in seven hours) from aqueous solutions.

    • Eugen S. Andreiadis
    • , Pierre-André Jacques
    •  & Vincent Artero

  • Article |

    So far, reports of molecular electrochemical water oxidation have involved catalytic transition metal complexes. Now it is demonstrated that water can be oxidized, and oxygen evolved, using a simple organic, flavin derivative.

    • Ekaterina Mirzakulova
    • , Renat Khatmullin
    •  & Ksenija D. Glusac

Browse broader subjects

Browse narrower subjects

Browse Electrochemistry across other nature.com journals