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| Open AccessUnravelling the hidden link of lithium halides and application in the synthesis of organocuprates
Organocopper species are widely used in synthetic chemistry. Here the authors study the structure of the anionic complex formed from copper salts and lithium halides, showing it to be a key intermediate in the formation of organocuprates, and also show that Cu(II) precursors can form Gilman reagents.
- Hong Yi
- , Dali Yang
- & Aiwen Lei
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Article
| Open AccessIridium-catalysed regioselective borylation of carboranes via direct B–H activation
Functionalization of the multiple, similar, boron-hydrogen bonds in carboranes is difficult to achieve with selectivity. Here the authors report an iridium-catalysed borylation ofo-carboranes with high yields and regioselectivities.
- Ruofei Cheng
- , Zaozao Qiu
- & Zuowei Xie
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Article
| Open AccessTriamidoamine thorium-arsenic complexes with parent arsenide, arsinidiide and arsenido structural motifs
Advances in actinide chemistry have led to the isolation of a range of uranium–ligand multiple bonds, but analogous thorium complexes are rare. Here, the authors prepare thorium–arsenic complexes that are stabilized by bulky triamidoamine ligands and exhibit ThAsH2, ThAs(H)K, ThAs(H)Th and ThAsTh linkages.
- Elizabeth P. Wildman
- , Gábor Balázs
- & Stephen T. Liddle
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Article
| Open AccessSynthesis and structures of gold and copper carbene intermediates in catalytic amination of alkynes
Metal carbenes are typically highly reactive and unstable species, proposed as intermediates in numerous catalytic processes. Here the authors report the isolation and characterization of gold and copper carbene intermediates involved in catalytic cyclization reactions.
- Jiwei Wang
- , Xiaoming Cao
- & Jun Zhang
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Article
| Open AccessMetal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism
In metal-based molecular motors, the motion is generally triggered by changes in the ligand coordination around the metal centre. Here, the authors synthesize a molecular gear that switches between states through photo- and thermally driven geometrical isomerization around a platinum ion.
- Hitoshi Ube
- , Yoshihiro Yasuda
- & Mitsuhiko Shionoya
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Article
| Open AccessBisguanidinium dinuclear oxodiperoxomolybdosulfate ion pair-catalyzed enantioselective sulfoxidation
Peroxomolybdates can be used as catalysts, but to date have not been employed in catalytic asymmetric transformations. Here the authors report that peroxomolybdates with a chiral bisguanidinium salts are active catalysts for asymmetric sulfoxidation, and furthermore identify the catalytic species.
- Lili Zong
- , Chao Wang
- & Choon-Hong Tan
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Article
| Open AccessRapid and reversible photoinduced switching of a rotaxane crystal
Crystalline phase transition can be used to detect changes in the solid state properties of materials. Here, the authors describe the mechanical response of a crystal composed of ferrocene-containing rotaxane to laser irradiation.
- Kai-Jen Chen
- , Ya-Ching Tsai
- & Masaki Horie
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Article
| Open AccessStille coupling via C–N bond cleavage
The Stille reaction is a long-standing method for the construction of carbon-carbon bonds by coupling aryl halides with organotin compounds. Here the authors report a Stille coupling between aryl ammonium salts and arylstannanes catalysed by nickel.
- Dong-Yu Wang
- , Masatoshi Kawahata
- & Masanobu Uchiyama
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Article
| Open AccessCatalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand
Converting dinitrogen into other nitrogen compounds such as ammonia is a difficult task, especially under mild conditions. Here, the authors report a molecular iron complex capable of reducing dinitrogen to both ammonia and hydrazine in a catalytic process.
- Shogo Kuriyama
- , Kazuya Arashiba
- & Yoshiaki Nishibayashi
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Article
| Open AccessSelective catalytic two-step process for ethylene glycol from carbon monoxide
Conversion of one-carbon feedstocks to more complex structures is vital for the production of bulk chemicals. Here, the authors report a highly selective method for the conversion of carbon monoxide to ethylene glycol by means of an oxamide intermediate.
- Kaiwu Dong
- , Saravanakumar Elangovan
- & Matthias Beller
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Article
| Open AccessMultimetallic catalysed radical oxidative C(sp3)–H/C(sp)–H cross-coupling between unactivated alkanes and terminal alkynes
Cross coupling via the activation of two carbon-hydrogen bonds avoids the need for organometallic coupling partners and associated waste. Here, the authors report a radical process that allows selective coupling between alkynes and non-activated C(sp3)-H groups via a multimetallic catalytic system.
- Shan Tang
- , Pan Wang
- & Aiwen Lei
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Article
| Open AccessMerging rhodium-catalysed C–H activation and hydroamination in a highly selective [4+2] imine/alkyne annulation
C–H activations and hydroaminations are useful synthetic procedures for building up complex, functional molecules. Here, the authors report a single catalyst capable of performing tandem C–H activation and hydroamination, giving access to N-heterocycles via the [4+2] annulation of aromatic imines and alkynes.
- Rajith S. Manan
- & Pinjing Zhao
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Article
| Open AccessPalladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism
Palladium catalyzed allylic substitution reactions typically proceed via an outer sphere mechanism, yielding predominately linear products. Here, the authors report an inner sphere process for the allylic substitution of ketone enolates, giving branched products with up to three contiguous stereocentres.
- Da-Chang Bai
- , Fei-Le Yu
- & Xue-Long Hou
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Article
| Open AccessEfficient hydrogen evolution in transition metal dichalcogenides via a simple one-step hydrazine reaction
Transition metal dichalcogenides are promising hydrogen evolution catalysts however they can require expensive processing steps to enhance their activity. Here, the authors report a one-step activation step in which room temperature hydrazine treatment results in much enhanced electrocatalytic performance.
- Dustin R. Cummins
- , Ulises Martinez
- & Gautam Gupta
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Article
| Open AccessEvidence for a chemical clock in oscillatory formation of UiO-66
Reactions with non-linear kinetics, such as chemical clocks, are reasonably common but only well understood in the liquid phase. Here, the authors report and rationalize a chemical clock reaction taking place in a solidifying metal-organic framework.
- M. G. Goesten
- , M. F. de Lange
- & Jorge Gascon
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Article
| Open AccessLigand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid
Designing catalysts and understanding the influence of ligands for particular transformations remains a highly challenging task. Here, the authors show that bisphosphine ligands can alter the geometry of the active site in silver catalysts, driving protonation and ultimately extrusion of carbon dioxide from formic acid.
- Athanasios Zavras
- , George N. Khairallah
- & Richard A. J. O’Hair
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Article
| Open AccessFast, greener and scalable direct coupling of organolithium compounds with no additional solvents
Cross-coupling reactions typically are carried out under dilute conditions of ethereal solvents. Here, the authors report a method for palladium catalysed cross-coupling of organolithium reagents that avoids the use of any added solvent with reaction times of only minutes.
- Erik B. Pinxterhuis
- , Massimo Giannerini
- & Ben L. Feringa
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Article
| Open AccessA two-step approach to achieve secondary amide transamidation enabled by nickel catalysis
Transamidation reactions are kinetically and thermodynamically challenging because of the stability of the amide starting materials. Here, the authors show a two-step process—activation of a secondary amide, followed by nickel-catalysed C–N bond cleavage—that allows mild and high yielding transamidation.
- Emma L. Baker
- , Michael M. Yamano
- & Neil K. Garg
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Article
| Open AccessEngineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition
The activity of electrocatalysts exhibits a strong dependence on their electronic structures. Here, the authors manipulate the eg filling of perovskite cobaltite LaCoO3nanoparticles by changing particle size and show improved oxygen evolution activity with increased numbers of surface high-spin cobalt ions.
- Shiming Zhou
- , Xianbing Miao
- & Jie Zeng
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Article
| Open AccessSynthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2
Industrial routes to acetic acid use carbon monoxide for the carbonylation of methanol. Here, the authors report a hydrocarboxylation method that instead uses carbon dioxide and hydrogen for the conversion of methanol into acetic acid.
- Qingli Qian
- , Jingjing Zhang
- & Buxing Han
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Article
| Open AccessSupramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production
Self-assembly is robust in creating advanced, homogeneous architectures under mild conditions. Here, the authors describe the generation of the first 3D metal-cored supramolecular organic framework using this strategy and illustrate its capacity in catalysing visible light-induced H2production.
- Jia Tian
- , Zi-Yue Xu
- & Zhan-Ting Li
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Article
| Open AccessIntermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
Sodium-excess metal oxides Na2MO3 are appealing cathode materials for sodium-ion batteries. Here, the authors demonstrate that honeycomb-type cation ordering in Na2RuO3 triggers the oxygen redox reaction via frontier orbital reorganization, increasing the capacity by 1/3 compared with disordered Na2RuO3.
- Benoit Mortemard de Boisse
- , Guandong Liu
- & Atsuo Yamada
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Article
| Open AccessA prolific catalyst for dehydrogenation of neat formic acid
Formic acid is a promising energy carrier for on-demand hydrogen generation. Here, the authors present a robust, reusable iridium catalyst that enables hydrogen release from neat formic acid under mild conditions and in the presence of air.
- Jeff Joseph A. Celaje
- , Zhiyao Lu
- & Travis J. Williams
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Article
| Open AccessCatalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation
The use of N-centred radicals is limited by the difficulties in their preparation. Here, the authors report a photoredox method for the formation of N-centred radicals on hydrazones and their use for the synthesis of heterocyclic compounds through a radical cascade reaction.
- Xiao-Qiang Hu
- , Xiaotian Qi
- & Wen-Jing Xiao
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Article
| Open AccessIterative protecting group-free cross-coupling leading to chiral multiply arylated structures
The Suzuki-Miyaura cross coupling is widely used in industrial and academic settings for the formation of carbon-carbon bonds. Here, the authors report a procedure whereby a molecule with multiple reactive carbon-boron bonds can undergo sequential, selective Suzuki-Miyaura reactions without the need for protecting groups.
- Cathleen M. Crudden
- , Christopher Ziebenhaus
- & Daisuke Imao
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Article
| Open AccessPractical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation
Olefins are employed in many coupling procedures but direct hydrocarbonations of unactivated olefins remain to be developed. Here, the authors report the nickel-catalyzed reductive coupling of olefins with aryl and alky electrophiles under mild conditions and with a broad substrate scope.
- Xi Lu
- , Bin Xiao
- & Lei Liu
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Article
| Open AccessDirect hydrodeoxygenation of raw woody biomass into liquid alkanes
The conversion of renewable lignocellulosic biomass into liquid fuels is attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here, the authors describe the direct hydrodeoxygenation of raw woods into liquid alkanes over a multifunctional Pt/NbOPO4catalyst.
- Qineng Xia
- , Zongjia Chen
- & Yanqin Wang
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Article
| Open AccessElectrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2
There are numerous heterogeneous oxygen reduction reaction catalysts, although synthetic tunability is rare among these materials. Here, the authors report that a conductive metal-organic framework functions as a well-defined, tunable electrocatalyst for the oxygen reduction reaction in alkaline solution.
- Elise M. Miner
- , Tomohiro Fukushima
- & Mircea Dincă
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Article
| Open AccessDesigning high-performance layered thermoelectric materials through orbital engineering
Thermoelectric materials with enhanced performances need to be identified. Here, the authors use the crystal field splitting energy of orbitals as a descriptor to design thermoelectric materials by solid solution maps and strain engineering in layered CaAl2Si2-type Zintl compounds.
- Jiawei Zhang
- , Lirong Song
- & Bo B. Iversen
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Article
| Open AccessOrganic–inorganic supramolecular solid catalyst boosts organic reactions in water
Coordination polymers and metal-organic frameworks are appealing synthetic hosts for mediating reactions. Here, the authors report a mesoscopic metal-organic structure that is shown to accelerate condensation reactions in water in the absence of acid or base, owing to the hydrophobic environment of the host.
- Pilar García-García
- , José María Moreno
- & Avelino Corma
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Article
| Open AccessAtomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis
There is tremendous ongoing effort in the development of electrocatalysts for hydrogen evolution. Here, the authors report that single nickel atoms dispersed on graphitic supports are formed by carbonization of metal-organic frameworks and that they are highly active hydrogen evolution catalysts.
- Lili Fan
- , Peng Fei Liu
- & Xiangdong Yao
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Article
| Open AccessHomochiral D4-symmetric metal–organic cages from stereogenic Ru(II) metalloligands for effective enantioseparation of atropisomeric molecules
Homochiral molecular capsules offer potential applications in chiral separation and stereospecific catalysis. Here, by pre-resolution of Δ/Λ-metalloligand precursors, the authors are able to assemble enantiopure supramolecular cages capable of stereoselective host-guest behaviour.
- Kai Wu
- , Kang Li
- & Cheng-Yong Su
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Article
| Open AccessComputational ligand design in enantio- and diastereoselective ynamide [5+2] cycloisomerization
Using a chiral catalyst to override the innate stereochemical outcome of a diastereoselective process is a challenging task. Here, the authors use theory and experiment to develop a cycloisomerization where the enantioselectivity is driven by the electronic nature of the ligand regardless of the reaction's inherent diastereoselectivity.
- R. N. Straker
- , Q. Peng
- & E. A. Anderson
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Article
| Open AccessPolyoxometalate-based homochiral metal-organic frameworks for tandem asymmetric transformation of cyclic carbonates from olefins
Using a single catalyst to promote multiple distinct reactions without alteration in reaction conditions is an attractive synthetic goal. Here, to this end, the authors have developed a polyoxometalate-based metal-organic framework for the synthesis of cyclic carbonates from olefins.
- Qiuxia Han
- , Bo Qi
- & Chunying Duan
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Article
| Open AccessAcceptorless dehydrogenation of small molecules through cooperative base metal catalysis
Acceptorless dehydrogenation of simple alkanes and alcohols provides useful functionality and typically requires precious metal catalysts. Here, the authors dehydrogenate unactivated alkanes and alcohols at room temperature using earth-abundant metals with hydrogen as the sole by-product.
- Julian G. West
- , David Huang
- & Erik J. Sorensen
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Article
| Open AccessSuppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials
Phosphorescent materials made of purely organic components are typically less efficient than their organometallic counterparts. Here, the authors report a strategy to improve the phosphorescence efficiency of metal-free materials by reducing radiationless transitions by covalently linking into a polymer matrix.
- Min Sang Kwon
- , Youngchang Yu
- & Jinsang Kim
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Article
| Open AccessMesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons
Precious metal free catalysts for aerobic oxidation of hydrocarbons are industrially useful materials. Here, the authors report a mesoporous maganese-cerium oxide solid solution that is highly active for the selective oxidation of C-H bonds in hydrocarbons under mild conditions.
- Pengfei Zhang
- , Hanfeng Lu
- & Sheng Dai
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Article
| Open AccessA biosynthetic model of cytochrome c oxidase as an electrocatalyst for oxygen reduction
An artificial functional mimic of cytochrome coxidase is a long term research goal for the development of oxygen reduction electrocatalysts. Here, the authors use site directed mutants of myoglobin to develop an electrocatalyst for reducing oxygen to water under ambient conditions.
- Sohini Mukherjee
- , Arnab Mukherjee
- & Abhishek Dey
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Article
| Open AccessBio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymes
Activated atmospheric dioxygen is potentially an environmentally friendly oxidant. Here, the authors incorporate a flavin mononucleotide into a water soluble polymer, demonstrating single electron reduction of a metalloporphyrin centre, and subsequent activation of dioxygen for the oxidation of organic substrates.
- Yoann Roux
- , Rémy Ricoux
- & Jean-Pierre Mahy
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Article
| Open AccessCoordinating activation strategy for C(sp3)–H/C(sp3)–H cross-coupling to access β-aromatic α-amino acids
Oxidative coupling of two C(sp3)-H groups is an attractive approach for the formation of carbon-carbon bonds, building structural complexity while avoiding the formation of waste salts. Here, the authors report such a transformation, using a nickel catalyst to functionalise amino acids with benzylic radicals.
- Kaizhi Li
- , Qian Wu
- & Jingsong You
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Article
| Open AccessIn silico prediction and screening of modular crystal structures via a high-throughput genomic approach
High-throughput computation aids design of new functional materials. Here, Yu et al.develop a high-throughput screening method for a group of zeolites with crystalline modular structures which are viewed as having gene-like stacking codes, and identify the most promising structures with desired properties.
- Yi Li
- , Xu Li
- & Jihong Yu
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Article
| Open AccessPlatinum–nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving
Catalysts with improved hydrogen activation and substrate adsorption are required for advanced hydrogenation applications. Here, the authors fabricate metal organic framework coated platinum–nickel catalyst exhibiting enhanced hydrogenation activity and substrate selectivity due to molecular sieving effects.
- Zhi Li
- , Rong Yu
- & Yadong Li
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Article
| Open AccessA porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution
Hydrogen evolution technologies for a future carbon-free energy economy require efficient catalysts which can be implemented on a large scale. Here, the authors prepare a composite electrode from readily available elements, whereby a metal-organic framework boosts catalytic performance by enabling rapid proton transport.
- Idan Hod
- , Pravas Deria
- & Joseph T. Hupp
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Article
| Open AccessNano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution
Metal particles supported on oxide surfaces are widely used catalysts, and the composites are generally formed by deposition or exsolution methods. Here, the authors show that nickel particles exsolved from the parent perovskite exhibit enhanced stability due to a stronger metal–oxide interface.
- Dragos Neagu
- , Tae-Sik Oh
- & John T.S. Irvine
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Article
| Open AccessCovalency-reinforced oxygen evolution reaction catalyst
Perovskites are cost-effective and efficient catalysts for electrocatalytic oxygen evolution, however often lack stability. Here, the authors report a tetravalent iron based quadruple perovskite which is both active and stable, due to the covalent bonding network incorporating many of its iron and copper ions.
- Shunsuke Yagi
- , Ikuya Yamada
- & Shigeo Mori
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Article
| Open AccessCationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids
Many structurally diverse carboxylic acids are available from renewable and petrochemical sources. Here, the authors report a method to reduce carboxylic acids to alcohols using hydrogen, with high selectivity, wherein the carboxylates form active and hydrogen-accepting parts of the catalyst system.
- Masayuki Naruto
- & Susumu Saito
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Article
| Open AccessHybrid glasses from strong and fragile metal-organic framework liquids
The fine interface between crystallinity and amorphicity in synthetic hybrid materials has to-date been relatively under-explored. Here, the authors probe the relationship between amorphisation and melting behaviour in zeolitic metal-organic frameworks as a route towards functional glasses.
- Thomas D. Bennett
- , Jin-Chong Tan
- & G. Neville Greaves
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Article
| Open AccessThe water catalysis at oxygen cathodes of lithium–oxygen cells
The main challenges in lithium-oxygen batteries are the low round-trip efficiency and decaying cycle life. Here, the authors present that a trace amount of water in electrolytes facilitates oxygen cathode reactions, enabling the batteries to be operated with small overpotential and good cycling stability.
- Fujun Li
- , Shichao Wu
- & Haoshen Zhou
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Article
| Open AccessDynamic structural evolution of supported palladium–ceria core–shell catalysts revealed by in situ electron microscopy
There is currently renewed interest in the use of core–shell catalysts for methane combustion. Here, the authors perform anex situ and in situelectron microscopy study to probe the structural evolution of palladium–cerium dioxide catalytic core–shell subunits over a wide temperature range.
- Shuyi Zhang
- , Chen Chen
- & Xiaoqing Pan