Electrocatalysis articles within Nature Chemistry

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  • News & Views |

    Understanding the ways by which metal-containing catalysts carry out a reaction is a chemical puzzle. Now, investigations of a multi-metallic molecular system uncover how the self-assembly of molecular catalysts facilitates cooperation between active species and improves the conversion of water to hydrogen gas.

    • Ana Sonea
    •  & Jeffrey J. Warren

  • 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

  • Article |

    Although the light-driven generation of hydrogen from water is a promising approach to renewable fuels, the H–H bond formation step represents a persistent mechanistic question. Now light-harvesting molecular catalysts have been shown to self-assemble into nanoscale aggregates that feature improved efficiency for photoelectrochemical H2 evolution.

    • Isaac N. Cloward
    • , Tianfei Liu
    •  & Alexander J. M. Miller

  • 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

  • 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

  • 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

  • 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 |

    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
    | 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

  • Review Article |

    The light-driven conversion of abundant resources such as CO2 and H2O into chemical fuels for energy storage is crucial to end our dependence on fossil fuels. This Review highlights how molecular catalysts and photosensitizers can be grafted onto metal–organic frameworks to combine the advantages of both classes of compounds. Different synthetic strategies are discussed, along with their advantages and limitations.

    • P. M. Stanley
    • , J. Haimerl
    •  & J. Warnan

  • Article |

    The facile release of corrosive HCl gas and plasticizers from poly(vinyl chloride) (PVC) makes it a challenging material to recycle. Now, it has been shown that PVC waste can be directly used as a halogen source to synthesize chloroarenes. This paired electro(de)chlorination is mediated by a phthalate plasticizer already contained in PVC waste.

    • Danielle E. Fagnani
    • , Dukhan Kim
    •  & Anne J. McNeil

  • 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 |

    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 |

    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

  • 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 |

    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 |

    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 |

    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 |

    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

  • 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 |

    Finely tuned interactions in the second coordination sphere of enzymes or homogeneous catalysts can be essential for their function. Now, this concept has been applied to the surface of a catalytic material, utilizing pairs of Cu atoms for the selective electrochemical fixation of CO2.

    • Benjamin S. Natinsky
    •  & Chong Liu

  • Article |

    MoS2 single layers spontaneously undergo a slow oxygen substitution reaction under ambient conditions giving rise to solid-solution-type 2D molybdenum oxy-sulfide crystals. The oxygen substitution sites of the 2D MoS2−xOx crystals act as efficient single-atom catalytic centres for the hydrogen evolution reaction.

    • János Pető
    • , Tamás Ollár
    •  & Levente Tapasztó

  • News & Views |

    Specific forms of nitrogen doping can endow carbon-based metal-free materials with electrocatalytic activity. Now, introducing sp-hybridized nitrogen atoms into some acetylenic sites of ultra-thin graphdiyne — a highly π-conjugated lamellar carbon allotrope — has led to excellent oxygen reduction reaction activity.

    • Yao Zheng
    •  & Shi-Zhang Qiao

  • Article |

    Heteroatom doping is a widely used modification method for carbon-based catalysts. Now, chemically defined sp-hybridized nitrogen atoms have been selectively introduced to the acetylene groups in ultrathin graphdiynes, resulting in good catalytic activity for the oxygen reduction reaction in both alkaline and acidic media.

    • Yasong Zhao
    • , Jiawei Wan
    •  & Dan Wang

  • 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 phase in which a crystal exists can have a direct influence over its properties; however, it is usually difficult to control during synthesis. Now it has been shown that micrometre-sized metallic 1T′-MoS2- and 1T′-MoSe2-layered crystals can be prepared in high phase purity on a large scale, and that they display promising electrocatalytic activity towards the hydrogen evolution reaction.

    • Yifu Yu
    • , Gwang-Hyeon Nam
    •  & Hua Zhang

  • 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

  • Article |

    Water oxidation is key to the production of chemical fuels from electricity. Now, guided by theory, NiCoFeP oxyhydroxide catalysts have been developed that require an overpotential lower than that required by IrO2. In situ soft X-ray absorption studies of neutral-pH NiCoFeP catalysts indicate formation of Ni4+, which is favourable for water oxidation.

    • Xueli Zheng
    • , Bo Zhang
    •  & Edward H. Sargent

  • 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

  • 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 |

    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

  • 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 |

    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

  • Article |

    Surfaces decorated with nanoparticles are typically prepared by depositing particles on the substrate. Instead, particles have now been grown in situ directly from perovskites, by exsolution through judicious tuning of the materials’ compositions, particularly their nonstoichiometry. This approach enables control over particle composition, size, surface coverage and anchorage.

    • Dragos Neagu
    • , George Tsekouras
    •  & John T. S. Irvine

  • 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 |

    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

  • 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 |

    Methods that fix atmospheric nitrogen to ammonia under mild conditions could offer a more environmentally benign alternative to the Haber–Bosch process. Now, a Ru-loaded electride, [Ca24Al28O64]4+(e−)4, is reported that acts as an efficient electron donor and reversible hydrogen store, and is demonstrated to function as an efficient catalyst for ammonia synthesis.

    • Masaaki Kitano
    • , Yasunori Inoue
    •  & Hideo Hosono

  • Article |

    Copper and bipyridine (bpy) self-assemble in aqueous solutions at high pH into an active electrocatalyst for the oxidation of water to O2, one of the great challenges in energy catalysis. These solutions contain primarily (bpy)Cu(OH)2, and are robust and active catalysts, albeit at high overpotentials.

    • Shoshanna M. Barnett
    • , Karen I. Goldberg
    •  & James M. Mayer

  • Article |

    Adsorbed carbon monoxide typically acts to poison the oxidation of alcohols on heterogeneous catalysts and electrocatalysts. Here, it is shown that carbon monoxide that has been adsorbed irreversibly on a Au(111) surface can act as a promoter for this process by enhancing the scission of C–H bonds in the alcohol to yield the corresponding aldehyde.

    • Paramaconi Rodriguez
    • , Youngkook Kwon
    •  & Marc T. M. Koper

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