Electrochemistry articles within Nature Chemistry

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  • Article |

    Although metal-free catalysts, featuring defined active sites, represent alternatives to scarce or problematic metals, metal-free compounds rarely show activities as promising as metal-based materials. Now deprotonated 2-thiolimidazole is shown to serve as a metal-free electrocatalyst for selective acetylene hydrogenation and achieves competitive performances with metal-based catalysts.

    • Lei Zhang
    • , Rui Bai
    •  & Jian Zhang

  • Research Briefing |

    Ether-based electrolytes are desired for lithium metal batteries owing to their low reduction potentials; however, they suffer from low anodic stability. Strategic methylation of ether solvents is shown to extend their electrochemical stability and facilitate the formation of LiF-rich interphases, enabling high-voltage lithium metal batteries while avoiding the use of fluorinated solvents.

  • Article |

    Lithium metal batteries are an attractive energy storage technology, but their development relies on the complex interplay between the components’ chemical, physical and mechanical properties. Now, selective methylation of dimethoxyethane ether electrolytes is shown to improve electrolyte, electrode and solid–electrolyte interphase stabilities to enable high-performance 4.3 V lithium metal batteries.

    • Ai-Min Li
    • , Oleg Borodin
    •  & Chunsheng Wang

  • Article |

    Electrolysers can upgrade CO2 into high-value chemicals, but there are few tools capable of tracking the reactions that occur within these devices during operation. Now an electrolysis optical coherence tomography platform has been developed to visualize the electrochemical conversion of CO2 to CO, plus the movement of components, within the device.

    • Xin Lu
    • , Chris Zhou
    •  & Curtis P. Berlinguette

  • News & Views |

    Electrocatalytic transformations often involve the concerted transfer of electrons and protons at electrode interfaces; however, these processes are not well understood. Now, experiments on an electrode that features well-defined molecular sites deepen fundamental understanding of such transfers to pave the way for future catalysts.

    • Siyuan L. Xie
    •  & Eva M. Nichols

  • Article
    | Open Access

    Although surface-bound molecular catalysts offer well-defined active sites on heterogeneous supports, it is challenging to identify key radical intermediates in the reaction mechanism. Now, a characterization method has been developed that combines film electrochemistry and EPR spectroscopy to track radical intermediates in real time, exemplified by alcohol oxidation with a surface-immobilized nitroxide.

    • Maryam Seif-Eddine
    • , Samuel J. Cobb
    •  & Maxie M. Roessler

  • Article |

    Although interfacial proton-coupled electron transfers are critical reaction steps in chemical and biological processes, studies investigating these reactions are complicated by surface heterogeneity. Now, interfacial proton-coupled electron transfer kinetics are studied and modelled at isolated, well-defined active sites to provide a foundation for understanding complex reactions involved in energy conversion and catalysis.

    • Noah B. Lewis
    • , Ryan P. Bisbey
    •  & Yogesh Surendranath

  • News & Views |

    Gas bubble accumulation at interfaces is a barrier to achieving more efficient electrochemical devices. A clever model system to understand bubble formation during electrochemical hydrogen evolution now reveals similarities between the forces at play during their detachment from the catalyst surface and those involved in wine climbing up a glass.

    • Gaurav Ashish Kamat
    •  & Michaela Burke Stevens

  • News & Views |

    Although Li–O2 batteries offer high theoretical energy storage capacities, few approach these limits. Now, a class of redox mediators is shown to send the discharge reaction from the electrode surface into the electrolyte solution, boosting device capacities and providing selection criteria for future efforts.

    • Zhangquan Peng

  • Article |

    Although gas bubble dynamics during electrochemical processes dramatically affect performance, the fundamental understanding and manipulation of such dynamics have been limited. Now, electrolyte composition is found to be a key factor in inducing a solutal Marangoni instability that impacts both H2 gas detachment and coalescence between H2 microbubbles.

    • Sunghak Park
    • , Luhao Liu
    •  & Marc T. M. Koper

  • Article |

    Understanding interfacial and cellular electron transport is essential for guiding efficiency optimization in microbe–semiconductor biohybrids for energy conversion. A multimodal imaging platform that combines optical imaging and photocurrent mapping can now interrogate such electron-transport pathways at the single-cell level, uncovering different roles of hydrogenases and a microbe’s large electron-uptake capacity.

    • Bing Fu
    • , Xianwen Mao
    •  & Peng Chen

  • Article |

    Although Li–O2 batteries offer high theoretical capacities, redox mediators are necessary to control intermediate reaction kinetics and to limit electrode passivation. Now it has been shown that a family of triarylmethyl cations can rival top-performing quinone-based redox mediators. Cations with sluggish catalytic rates were found to suppress surface-mediated O2 reduction and achieve higher capacitances.

    • Erik J. Askins
    • , Marija R. Zoric
    •  & Ksenija D. Glusac

  • Article |

    Ultra-high-capacity Li–air batteries have low Coulombic efficiency and degrade during re-charging, resulting in a poor cycle life. Redox mediators enable improvements but only at undesirably high potentials. The origin of this high potential and the impact of purported reactive intermediates has now been elucidated by resolving the charging mechanism using Marcus theory.

    • Sunyhik Ahn
    • , Ceren Zor
    •  & Peter G. Bruce

  • Article
    | Open Access

    The electrochemical reduction of carbon dioxide to propylene requires multiple C–C coupling steps and the transfer of 18 electrons, posing kinetic and thermodynamic barriers. Now the electrosynthesis of propylene from carbon dioxide using copper nanocrystals has been demonstrated, with analysis revealing that the key step for its formation is probably the coupling between carbon dioxide or carboxyl with intermediates involved in the ethylene pathway.

    • Jing Gao
    • , Alimohammad Bahmanpour
    •  & Michael Grätzel

  • Article |

    Kinetic isotope effect studies can provide valuable insights into the complex mechanisms of the oxygen reduction reaction; however, inaccessibility to ultra-high-purity D2O has made this difficult. Now, a methodology to prepare ultra-pure D2O has been developed and inverse kinetic isotope effects have subsequently been measured for the oxygen reduction reaction on platinum single-crystal surfaces, providing mechanistic insights.

    • Yao Yang
    • , Rishi G. Agarwal
    •  & Héctor D. Abruña

  • News & Views |

    Aqueous organic redox flow batteries are promising for low-cost and large-scale energy storage, but the redox-active molecules they rely on degrade prematurely. Now, a facile electrochemical protocol to regenerate them has been proposed, resulting in extended battery lifetimes.

    • Antoni Forner-Cuenca

  • Article |

    Aqueous organic redox flow batteries offer a safe and inexpensive solution to the problem of storing electricity produced from intermittent renewables. However, decomposition of the redox-active organic molecules that they rely on limits their lifetimes, preventing commercialization. Now it has been shown that these redox molecules can be electro-recomposed in situ, rejuvenating their function.

    • Yan Jing
    • , Evan Wenbo Zhao
    •  & Michael J. Aziz

  • Article |

    Nickel-rich layered oxides, such as NCM622, are promising cathode materials for lithium batteries, but chemo-mechanical failures hinder their practical application. Now the solid-state synthesis of NCM622 has been studied using multiscale in situ techniques, and kinetic competition between precursor decomposition and lithiation has been observed to lead to spatially heterogeneous intermediates and the formation of defects that are detrimental to cycling.

    • Hyeokjun Park
    • , Hayoung Park
    •  & Kisuk Kang

  • News & Views |

    The electronic structure of an electrode can affect the electron transfer rate of electrochemical processes at its surface. Now, it has been shown that varying the ‘twist’ angle between two stacked layers of graphene modifies the bilayer electronic structure and provides a new dimension to control interfacial redox activity.

    • Oluwasegun J. Wahab
    •  & Patrick R. Unwin

  • Article |

    Carbonic anhydrase enzymatically catalyses CO2 hydration, and its effect on enzymatic and heterogeneous CO2 reduction has now been studied. Through the co-immobilization of carbonic anhydrase, it has been shown that faster CO2 hydration kinetics are beneficial for enzymatic catalysis (using formate dehydrogenase) but detrimental for heterogeneous catalysts, such as gold.

    • Samuel J. Cobb
    • , Vivek M. Badiani
    •  & Erwin Reisner

  • Article |

    Controlling the crystallographic registry of layered materials through interlayer twist angles has introduced a distinctive degree of freedom for tuning their electronic behaviour. Now, the interfacial electrochemical kinetics of solution-phase redox complexes at twisted bilayer graphene electrodes have been modulated by the angle-dependent tuning of moiré-derived flat bands.

    • Yun Yu
    • , Kaidi Zhang
    •  & D. Kwabena Bediako

  • Article |

    The use of ammonia as an alternative fuel relies on its electrochemical conversion to dinitrogen in a fuel cell. Now a stable metal–metal bonded diruthenium complex is shown to spontaneously produce dinitrogen from ammonia under ambient conditions and is also able to electrocatalyse the oxidation of ammonia to dinitrogen at low potentials.

    • Michael J. Trenerry
    • , Christian M. Wallen
    •  & John F. Berry

  • News & Views |

    Aziridines — three-membered nitrogen-containing heterocycles — are important synthetic targets, but N-alkyl aziridines are difficult to synthesize. Now, an electrochemical method, involving a dicationic intermediate, enables the coupling of alkenes and amines.

    • Tiffany Piou
    •  & Louis-Charles Campeau

  • Article |

    Self-propelled artificial chemical swimmers have previously been developed for chemical sensing. Now, hybrid bioelectrochemical swimmers, capable of translating chiral molecular information into macroscopic motion, have been developed. Diastereomeric interactions between enantiopure oligomers immobilized on the swimmer and a chiral molecule present in solution control the trajectory of the device.

    • Serena Arnaboldi
    • , Gerardo Salinas
    •  & Alexander Kuhn

  • Article |

    Super-concentrated water-in-salt electrolytes enable high-voltage aqueous batteries, but have considerable drawbacks such as high viscosity, low conductivity and slow kinetics. Now a concentration-dependent association between CO2 and TFSI– has been discovered and leveraged to decouple the interphasial responsibility of an aqueous electrolyte from its bulk properties, making high-voltage aqueous Li-ion batteries practical in dilute salt-in-water electrolytes.

    • Jinming Yue
    • , Jinkai Zhang
    •  & Liquan Chen

  • Article |

    The use of anionic redox chemistry in high-capacity Li-rich cathodes is being hampered by voltage hysteresis, the origin of which remains obscure. Now it has been shown that sluggish ligand-to-metal charge transfer kinetically traps an intermediate Fe4+ species and is responsible for voltage hysteresis in the prototypical Li-rich cation-disordered rock-salt Li1.17Ti0.33Fe0.5O2.

    • Biao Li
    • , Moulay Tahar Sougrati
    •  & Jean-Marie Tarascon

  • Article |

    Molecular catalysts can be made more practical by anchoring them onto electrode surfaces, but such systems are less stable than standard heterogeneous electrocatalysts. Now, supramolecular hosts bound to electrode surfaces have enabled the immobilization of molecular electrocatalysts through host–guest interactions. Desorbed or degraded guest molecules can be replaced with fresh guest molecules, extending their lifetimes.

    • Laurent Sévery
    • , Jacek Szczerbiński
    •  & S. David Tilley

  • Article |

    Excising hydrogen adjacent to a carbonyl group—one of the most basic and widely employed transformations in organic synthesis—is traditionally achieved using metals and/or stoichiometric oxidants. Now, it has been shown that an electrochemically driven approach removes such requirements, resulting in a more sustainable and easily scalable method with wide substrate scope.

    • Samer Gnaim
    • , Yusuke Takahira
    •  & Phil S. Baran

  • Article |

    Redox mediators are important for improving the rechargeability of metal–air batteries, however, how they affect singlet oxygen formation and hence parasitic chemistry is unclear, hindering strategies for their improvement. Now, the mechanism of mediated peroxide and superoxide oxidation is elucidated, explaining how redox mediators either enhance or suppress singlet oxygen formation.

    • Yann K. Petit
    • , Eléonore Mourad
    •  & Stefan A. Freunberger

  • Thesis |

    We’re in the middle of an energy revolution, argues Bruce C. Gibb, and chemistry is an integral part of it.

    • Bruce C. Gibb

  • Article |

    Moving towards renewable energy sources requires pathways for efficiently converting electricity to chemicals, and gas-fed CO2 electrolysers show promise. Now, the layer-by-layer assembly of a weak-acid cation exchange layer has been shown to affect the local pH in a bipolar-membrane-based gas-fed CO2 electrolyser, improving the conversion efficiency of CO2 to CO by suppressing the competing hydrogen evolution reaction.

    • Zhifei Yan
    • , Jeremy L. Hitt
    •  & Thomas E. Mallouk

  • Article |

    Efficient and stable water oxidation catalysts are important if photoelectrochemical cells are to be used to provide clean and sustainable solar fuels. A water oxidation catalyst that operates at neutral pH has now been developed that features ruthenium coordination oligomers anchored onto the surfaces of graphitic materials through CH–π interactions.

    • Md Asmaul Hoque
    • , Marcos Gil-Sepulcre
    •  & Antoni Llobet

  • Article |

    A general method for the enantioselective hydrocyanation of alkenes has been a long-standing synthetic challenge. Now, using a dual electrocatalytic approach that combines two synergistic redox catalytic cycles, a wide variety of chiral nitriles can be synthesized from conjugated alkenes in high enantioselectivity.

    • Lu Song
    • , Niankai Fu
    •  & Song Lin

  • Article |

    Conventionally, urea is synthesized via two consecutive processes, N2 + H2 → NH3 followed by NH3 + CO2. Now, an electrocatalyst consisting of PdCu alloy nanoparticles on TiO2 nanosheets has been shown to directly couple N2 and CO2 in H2O to produce urea under ambient conditions.

    • Chen Chen
    • , Xiaorong Zhu
    •  & Shuangyin Wang

  • Article |

    Single-atom catalysts maximize metal atom efficiency and exhibit properties that can be considerably different to their nanoparticle equivalent. Now a general host–guest strategy to make various single-atom catalysts on nitrogen-doped carbon has been developed; the iridium variant electrocatalyses the formic acid oxidation reaction with high mass activity and displays high tolerance to CO poisoning.

    • Zhi Li
    • , Yuanjun Chen
    •  & Yadong Li

  • Article |

    Gene-circuit-based sensors have, to date, largely relied on optical proteins (such as green fluorescent protein) to report the output, which limits the signalling bandwidth. Now, an electrochemical output has been developed and integrated with cell-free gene circuits. This approach enables multiplexing of sensors and introduces the possibility of electronic-based logic, memory and response elements to synthetic biology.

    • Peivand Sadat Mousavi
    • , Sarah J. Smith
    •  & Keith Pardee

  • Article |

    Phase-forming conversion chemistry, like that observed in Li–S and Li–O2 batteries, shows great promise, but these systems suffer some drawbacks, such as practically low cathode areal capacities and electrolyte decomposition. Now, high-energy conversion battery chemistry—based on nitrate/nitrite redox where one of the products is soluble—has been enabled by using nanoparticulate Ni/NiO electrocatalysts.

    • Vincent Giordani
    • , Dylan Tozier
    •  & Dan Addison

  • Article |

    The electroreduction of CO2-derived CO is a promising technology for the sustainable production of value-added chemicals. Now, it is shown how C–N bonds can be formed electrochemically through CO electroreduction on a Cu surface in the presence of amines. The formation of acetamides is observed through nucleophilic addition to a ketene intermediate.

    • Matthew Jouny
    • , Jing-Jing Lv
    •  & Feng Jiao

  • News & Views |

    Interphases that form on the anode surface of lithium-ion batteries are critical for performance and lifetime, but are poorly understood. Now, a decade-old misconception regarding a main component of the interphase has been revealed, which could potentially lead to improved devices.

    • Stefan A. Freunberger

  • Article |

    The solid–electrolyte-interphase layer is extremely important for reversible electrochemical cycling of Li-ion batteries. Now it has been observed that lithium ethylene mono-carbonate, instead of the previously reported lithium ethylene di-carbonate, is the major initial organic species in this layer and it has a high Li-ion conductivity.

    • Luning Wang
    • , Anjali Menakath
    •  & Bryan W. Eichhorn

  • Article |

    The production of ammonia from dinitrogen is a well-studied process; however, the catalytic conversion of ammonia into dinitrogen is underdeveloped. Now, ammonia oxidation has been achieved using ruthenium complexes as catalysts. The production of dinitrogen is observed when ammonium salts are treated with a single-electron oxidant, base and ruthenium catalyst.

    • Kazunari Nakajima
    • , Hiroki Toda
    •  & Yoshiaki Nishibayashi

  • News & Views |

    Aqueous batteries hold promise for large-scale energy storage, but are often maligned because of their low energy densities. Now, a demonstration of halogen conversion–intercalation chemistry inside graphite has blazed a trail for high-energy aqueous batteries.

    • Xianyong Wu
    •  & Xiulei Ji

  • Article |

    While much effort has been devoted to understanding how nanoparticle morphology can be leveraged to improve catalytic activity, engineering their microstructure from first principles to this end has remained difficult. Now a methodology for designing the optimal structure of a solid catalyst with the aim of achieving the highest possible activity for surface-sensitive reactions has been developed.

    • M. Núñez
    • , J. L. Lansford
    •  & D. G. Vlachos

  • 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

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