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| Open AccessAccessing five oxidation states of uranium in a retained ligand framework
Understanding and exploiting the redox properties of uranium is of great importance but stabilizing both low and high valent uranium ions in a preserved ligand environment remains challenging. Here, the authors report the synthesis and characterisation of a series of uranium(II–VI) complexes supported by a tripodal tris(amido)arene ligand.
- Chong Deng
- , Jiefeng Liang
- & Wenliang Huang
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Article
| Open AccessUnusual nuclear exchange within a germanium-containing aromatic ring that results in germanium atom transfer
Controlled atomic delivery is a desirable synthetic process. Here a germanium-substituted phenyl anion is shown to act as a germanium atom transfer reagent and demonstrated by the preparation of well-defined molecular germanium species.
- Ryohei Nishino
- , Norihiro Tokitoh
- & Yoshiyuki Mizuhata
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Article
| Open AccessPrecise cooperative sulfur placement leads to semi-crystallinity and selective depolymerisability in CS2/oxetane copolymers
CS2 promises easy access to degradable sulfur-rich polymers, but ring-opening copolymerisation using CS2 is challenging due to low linkage selectivity and small-molecule by-products. Here, the authors report a cooperative Cr(III)/K catalyst which selectively delivers poly(dithiocarbonates) from CS2 and oxetanes.
- Christoph Fornacon-Wood
- , Bhargav R. Manjunatha
- & Alex J. Plajer
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Article
| Open AccessActinide inverse trans influence versus cooperative pushing from below and multi-center bonding
Actinide-ligand bonds with high multiplicities remain poorly understood. Here, the authors investigate covalency in actinide complexes and identify terminal O and N ligands that are triply to quadruply bonded to the actinide, facilitated by electrostatic, steric, and covalent interactions.
- Laura C. Motta
- & Jochen Autschbach
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Article
| Open AccessAtomic stiffness for bulk modulus prediction and high-throughput screening of ultraincompressible crystals
Fast and accurate prediction of bulk moduli for diverse materials is challenging. Here, the authors introduce the concept of atomic stiffness to accelerate bulk modulus prediction and high-throughput screening of ultra-incompressible crystals.
- Ruihua Jin
- , Xiaoang Yuan
- & Enlai Gao
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Article
| Open AccessA squarate-pillared titanium oxide quantum sieve towards practical hydrogen isotope separation
Hydrogen isotope separation is key for developing technologies. Here authors present a squarate-pillared titanium oxide quantum sieve for deuterium separation, displaying impressive separation performance, cost-effective green scalable synthesis, and stability.
- Qingqing Yan
- , Jing Wang
- & Jiangfeng Du
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Article
| Open AccessAccessing parity-forbidden d-d transitions for photocatalytic CO2 reduction driven by infrared light
This study demonstrates the effectiveness and generality of utilizing ultrathin Cu-based hydrotalcite-like hydroxy salts as catalysts for infrared light-driven CO2 reduction based on their d-d orbital transition mechanism.
- Xiaodong Li
- , Li Li
- & Xinliang Feng
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Article
| Open AccessA cost-effective, ionically conductive and compressible oxychloride solid-state electrolyte for stable all-solid-state lithium-based batteries
Ionic conductivity > 1 mS cm−1 at 25 °C, compressibility enabling > 90% density at 250 − 350 MPa, and cost < $50/kg are desirable for inorganic solid-state electrolytes. Here, the authors report Li1.75ZrCl4.75O0.5 as a solid-state electrolyte capable of satisfying these requirements simultaneously.
- Lv Hu
- , Jinzhu Wang
- & Cheng Ma
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Article
| Open AccessAltering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine
Despite the distinct electronic properties of the wide variety Cm3+ compounds that have been prepared to date, no singlecrystal structural characterization of a complex containing a Cm−C bond has been reported. Here the authors report the synthesis of a Cm complex bearing trimethylsilylcyclopentadienyl and 4,4’-bipyridine ligands with a low energy emission and identify the 4,4’-bipyridine ligand as the primary quenching agent.
- Brian N. Long
- , María J. Beltrán-Leíva
- & Thomas E. Albrecht-Schönzart
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Article
| Open AccessCarbon neutral hydrogen storage and release cycles based on dual-functional roles of formamides
The search for new carbon-based hydrogen storage materials attracts scientists from various disciplines. Now, carbon-neutral hydrogen storage-release is reported based on dual-functional roles of formamides and uses non-noble, Fe-based catalyst.
- Duo Wei
- , Xinzhe Shi
- & Matthias Beller
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Article
| Open AccessDirect determination of high-order transverse ligand field parameters via µSQUID-EPR in a Et4N[160GdPc2] SMM
Single molecule magnets (SMMs) are molecules with magnetic states separated by an energy barrier. These two (or more) states can serve as basis for quantum information processing, but this requires a detailed understanding of the ligand field of the molecule that forms the SMM. Here, Taran et al use a combination of two experimental techniques, µSQUID and EPR, to precisely measure the higher-order ligand field parameters.
- Gheorghe Taran
- , Eufemio Moreno-Pineda
- & Wolfgang Wernsdorfer
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Article
| Open AccessLigand effect on switching the rate-determining step of water oxidation in atomically precise metal nanoclusters
Surface modification using organic molecules is crucial for tailoring the physicochemical properties of electrocatalysts. In this study, we employ atomically precise Au25 nanoclusters with different ligands to identify the ligand effect on switching rate-limiting steps of oxygen evolution reaction.
- Zhihe Liu
- , Hua Tan
- & Jianping Xie
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Article
| Open AccessThe curious case of the structural phase transition in SnSe insights from neutron total scattering
The thermoelectric properties of SnSe are attributed to a high-temperature phase transition, whose nature has not been resolved. Here the authors probe the transition at different length scales using neutron pair distribution function analysis and diffraction data, revealing a dynamic order-disorder nature, and shedding light on previous discrepancies.
- Bo Jiang
- , Jennifer Neu
- & Theo Siegrist
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Article
| Open AccessCritical roles of metal–ligand complexes in the controlled synthesis of various metal nanoclusters
Metal-thiolate complexes are the precursors to atomically precise metal nanoclusters. Here, the authors show that the extent of metal-ligand interaction is key to controlling the size and uniformity in the synthesis of metal nanoclusters.
- Ji Soo Kim
- , Hogeun Chang
- & Jungwon Park
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Article
| Open AccessThe double protonation of dihapto-coordinated benzene complexes enables dearomatization using aromatic nucleophiles
Coordination of benzene by a tungsten complex can minimize the formation of oligomeric aromatic products in Friedel-Crafts Arylation. Here the authors show that coordinating benzene to tungsten through two carbons (dihapto-coordination) enables a rarely observed double protonation of the bound benzene, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.
- Justin T. Weatherford-Pratt
- , Jacob A. Smith
- & W. Dean Harman
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Article
| Open AccessChemical design of electronic and magnetic energy scales of tetravalent praseodymium materials
Trivalent lanthanides are typically described using an ionic picture that leads to localized magnetic moments. Here authors show that the “textbook” description of lanthanides fails for Pr4+ ions where the hierarchy of single-ion energy scales can be tailored to explore correlated phenomena in quantum materials.
- Arun Ramanathan
- , Jensen Kaplan
- & Henry S. La Pierre
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Article
| Open AccessIsolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations
Tetrylones show unique electronic properties and display potantial as soluble molecular allotropes, but until now, the chemistry of Tetrylone homologs remains underexplored. Here, the authors describe the synthesis of a family of antimony(I) and bismuth(I) cations supported by a bis silylene ligand and explore their reactivity.
- Xuyang Wang
- , Binglin Lei
- & Zhenbo Mo
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Article
| Open AccessAnion redox as a means to derive layered manganese oxychalcogenides with exotic intergrowth structures
Low temperature chemical transformations of solids using high-energy intermediates have enabled the synthesis of a new series of layered oxide chalcogenide containing oxidised chalcogenide dimers promising a new range of solids.
- Shunsuke Sasaki
- , Souvik Giri
- & Simon J. Clarke
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Article
| Open AccessArchitector for high-throughput cross-periodic table 3D complex building
Rare-earth and actinide complexes are critical for a wealth of clean-energy applications but Three dimensional (3D) structural generation and prediction for these organometallic systems remains challenging. Here, the authors propose a high-throughput in-silico synthesis code for s-, p-, d-, and f-block mononuclear organometallic complexes.
- Michael G. Taylor
- , Daniel J. Burrill
- & Ping Yang
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Article
| Open AccessComplex phase transitions and phase engineering in the aqueous solution of an isopolyoxometalate cluster
Complex phase transitions including gelation in dilute aqueous solutions of polyanionic clusters ([Mo7O24]6−) in the presence of (Fe(NO3)3) and attributed to the counterion association and overcharging on the clusters, have been identified.
- Zhi-Da Wang
- , Song Liang
- & Hong-Ying Zang
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Article
| Open AccessA step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl
Replicating the seminal reactions of transition metals with p-block species is often very challenging. Here, the authors present a step-for-step main-group replica of the historical Fischer carbene synthesis, providing bora-Fischer carbene species.
- Marcel Härterich
- , Alexander Matler
- & Holger Braunschweig
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Article
| Open AccessDirect synthesis of oxalic acid via oxidative CO coupling mediated by a dinuclear hydroxycarbonylcobalt(III) complex
Oxidative coupling of CO is a straightforward but currently underdeveloped economically benign synthetic route to target α-diketones. Here, the authors synthesize a rare coplanar dinuclear hydroxycarbonylcobalt(III) complex and demonstrate that the Co – carboxylate bonds can be easily cleaved leading to the formation of oxalic acid.
- Yingzhuang Xu
- , Songyi Li
- & Huayi Fang
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Article
| Open AccessBoosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries
Compositional tuning is a standard procedure to improve the ionic conductivity of inorganic superionic conductors. Here, the authors report (electro)chemical stable composite halide solid electrolytes applying a nanostructure approach that promotes interfacial superionic conductivity.
- Hiram Kwak
- , Jae-Seung Kim
- & Yoon Seok Jung
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Article
| Open AccessDesigned Rubredoxin miniature in a fully artificial electron chain triggered by visible light
Living organisms regulate their energy demand by managing electron trafficking in complex transport chains. Here, the authors pioneer a fully artificial electron chain triggered by visible light using designed proteins, unlocking possibilities in bioengineering.
- Marco Chino
- , Luigi Franklin Di Costanzo
- & Vincenzo Pavone
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Article
| Open AccessRapid determination of solid-state diffusion coefficients in Li-based batteries via intermittent current interruption method
The galvanostatic intermittent titration technique (GITT) is the state-of-the-art method for determining the Li+ diffusion coefficients in battery materials. Here, authors propose the intermittent current interruption method as a reliable, accurate and faster alternative to GITT-based methods.
- Yu-Chuan Chien
- , Haidong Liu
- & Matthew J. Lacey
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Article
| Open AccessReal-time insight into the multistage mechanism of nanoparticle exsolution from a perovskite host surface
The separation of nanoparticles from oxide hosts by exsolution forms the basis for catalytic and energy-related applications. Here, the authors elucidate the multistep mechanism of exsolution at perovskite surfaces by combining real-time electron microscopy and computational methods.
- Eleonora Calì
- , Melonie P. Thomas
- & David J. Payne
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Article
| Open AccessEpitaxially grown silicon-based single-atom catalyst for visible-light-driven syngas production
Despite the natural abundance and promising properties of Si, there are few examples of crystalline Si-based catalysts. Here, the authors report an epitaxial growth method to construct Co single atoms on Si for light driven CO2 reduction to syngas.
- Huai Chen
- , Yangyang Xiong
- & Zhenyu Yang
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Article
| Open AccessArene C–H borylation strategy enabled by a non-classical boron cluster-based electrophile
Electrophilic borylation of sterically hindered arenes is a challenging transformation. Here, authors report a metal-free electrophilic C–H borylation of hindered arenes using a boron cluster reagent producing valuable aryl boronic esters.
- Sangmin Kim
- , Joseph W. Treacy
- & Alexander M. Spokoyny
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Article
| Open AccessUnderstanding the evolution of lithium dendrites at Li6.25Al0.25La3Zr2O12 grain boundaries via operando microscopy techniques
Lithium metal penetration into solid-state electrolytes is a major drawback for developing all-solid-state batteries. Here, authors, via operando force microscopy, demonstrate that the trapping of electrons in garnet-type solid-state electrolyte grain boundaries is the origin of cell failure.
- Chao Zhu
- , Till Fuchs
- & Rüdiger Berger
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Article
| Open AccessCharacterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst
The characterization of nickel (Ni)‐centred paramagnetic states relevant to [NiFe] hydrogenases is rare in mononuclear Ni hydrogen evolution catalysts. Here, the authors report the spectroscopic and synthetic characterization of NiI and NiIII states in an organometallic Ni hydrogen evolution catalyst.
- Sagnik Chakrabarti
- , Soumalya Sinha
- & Liviu M. Mirica
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Article
| Open AccessRegioselective protein oxidative cleavage enabled by enzyme-like recognition of an inorganic metal oxo cluster ligand
Metal-catalysed oxidation of proteins varies in selectivity and depends on the surface residues to direct the reaction. Here, the authors use polyoxometalate clusters as inorganic ligands for Cu ions, enabling the regioselective oxidative cleavage of a protein via reactive oxygen species in the vicinity of its binding sites.
- Shorok A. M. Abdelhameed
- , Francisco de Azambuja
- & Tatjana N. Parac-Vogt
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Article
| Open AccessQuantification of gas-accessible microporosity in metal-organic framework glasses
Glasses derived from meltable metal-organic frameworks (MOFs) offer great potential for gas separation and solid state ionics. Here, the authors quantify the porosity of a series of MOF glasses by cryogenic carbon dioxide gas sorption and propose design principles for rational tuning the glasses‘ pore size and pore volume.
- Louis Frentzel-Beyme
- , Pascal Kolodzeiski
- & Sebastian Henke
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| Open AccessChemoselective carbene insertion into the N−H bonds of NH3·H2O
Converting low-cost inorganic chemicals into value-added organic chemicals is a longstanding goal in chemistry. Here the authors describe a silver-catalysed chemoselective carbene N−H insertion reaction, providing access to primary amines from aqueous ammonia and diazo compounds.
- Zhaohong Liu
- , Yong Yang
- & Xihe Bi
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Article
| Open AccessUnlocking the hidden chemical space in cubic-phase garnet solid electrolyte for efficient quasi-all-solid-state lithium batteries
Conventional compositions of garnet solid electrolytes have limited access to the cubic phase for a high Li content of 7.0, which is beneficial for stability against Li metals. Here, the authors unlock the hidden chemical space via a high entropy strategy, enabling stable long-term battery cycling.
- Sung-Kyun Jung
- , Hyeokjo Gwon
- & Ju-Sik Kim
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Article
| Open AccessData-driven design of molecular nanomagnets
Three decades of research in molecular nanomagnets have enabled the preparation of compounds displaying magnetic memory at liquid nitrogen temperature. Here, the authors provide an innovative framework for the design of molecular magnets based on data mining, and develop an interactive dashboard to visualize the dataset.
- Yan Duan
- , Lorena E. Rosaleny
- & Alejandro Gaita-Ariño
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Article
| Open AccessCatalytic nitrogen fixation using visible light energy
The development of a nitrogen fixation process that relies on the renewable energy, such as visible light, is an important goal in sustainable chemistry. Here, authors establish an iridium and molybdenum-catalysed ammonia formation from dinitrogen driven by visible light under ambient reaction conditions.
- Yuya Ashida
- , Yuto Onozuka
- & Yoshiaki Nishibayashi
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Article
| Open AccessA charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages
Diatomic actinide molecules are ideal models for studying rare multiple-bond motifs. Here, the authors report host-guest structures of metastable charged U≡N diatoms confined in fullerene cages and stabilized by coordinative electron transfer.
- Qingyu Meng
- , Laura Abella
- & Ning Chen
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Article
| Open AccessPhosphorylation disrupts long-distance electron transport in cytochrome c
Electron transfer between mitochondrial cytochrome c and subunit of cytochrome bc1 can proceed at long distance. Here the authors investigate further the mechanism and show phosphorylation regulation of the interactions between the protein partners in the electron transport chain.
- Alexandre M. J. Gomila
- , Gonzalo Pérez-Mejías
- & Anna Lagunas
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Article
| Open AccessA linear Di-coordinate boron radical cation
The stabilization of low-coordinate boron radicals is challenging, as they tend to form strong chemical bonds. Here the authors report the isolation and structural characterization of a dicoordinate boron radical featuring a π-donating amino and a π-accepting carbene ligand.
- Yu-Jiang Lin
- , Wei-Chun Liu
- & Ching-Wen Chiu
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Article
| Open AccessAzide-functionalized ligand enabling organic–inorganic hybrid dielectric for high-performance solution-processed oxide transistors
Low cost and low power consumption of transistors are needed for the development of internet of things. Here Chung et al. develop a high performance n-type oxide thin film transistor by introducing a ligand for crosslinking nanoparticles and polymers, obtaining a near-ideal hybrid dielectric layer.
- Juhyeok Lee
- , Syed Zahid Hassan
- & Dae Sung Chung
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Article
| Open AccessDesign and directed evolution of noncanonical β-stereoselective metalloglycosidases
Metallohydrolases are ubiquitous enzymes. Here the authors show the design and biochemical characterisation of metalloglycosidase by constructing a hydrolytically active Zn-binding site within a barrel-shaped outer membrane protein OmpF.
- Woo Jae Jeong
- & Woon Ju Song
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Article
| Open AccessSingle atom catalysts in Van der Waals gaps
A family of single-atom catalysts synthesized by intercalating metal single atoms into the van der Waals gap of two-dimensional SnS2 is reported. The materials are applied as hydrogen evolving catalysts with good durability and overpotential.
- Huaning Jiang
- , Weiwei Yang
- & Yongji Gong
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Article
| Open AccessWater-stable porous Al24 Archimedean solids for removal of trace iodine
The removal of radioactive elements is important to human health and sustainable development. Here, the authors reveal the synthesis of water-stable Archimedean solids based on the earth-abundant element for the fast removal of trace iodine.
- Ya-Jie Liu
- , Yi-Fan Sun
- & Jian Zhang
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Article
| Open AccessElectrically regulating nonlinear optical limiting of metal-organic framework film
Nonlinear optical properties of metal-organic framework can be tuned for potential optical applications. Here the authors demonstrate an enhancement the nonlinear absorption coefficient of MOF film by applying external electric field.
- Zhi-Zhou Ma
- , Qiao-Hong Li
- & Jian Zhang
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Article
| Open AccessDirect synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand
Direct conversion of dinitrogen to organonitrogen compounds is a challenging goal in nitrogen fixation chemistry. Here, the authors report the catalytic formation of cyanate anion from dinitrogen under ambient conditions using a molybdenum complex.
- Takayuki Itabashi
- , Kazuya Arashiba
- & Yoshiaki Nishibayashi
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Article
| Open AccessBiferroelectricity of a homochiral organic molecule in both solid crystal and liquid crystal phases
Ferroelectricity normally exists in either solid crystals or liquid crystals. Here, the authors report a homochiral organic compound which shows ferroelectricity in both solid crystal and liquid crystal phases.
- Xian-Jiang Song
- , Xiao-Gang Chen
- & Wei-Qiang Liao
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Article
| Open AccessA medium-entropy transition metal oxide cathode for high-capacity lithium metal batteries
Structural instability is a major drawback of high-capacity lithium-based battery cathodes. Here, the authors report a cathode active material with a medium-entropy state created by partial cation disordering capable of restraining the structural evolution in the high-capacity operated spinel phase.
- Yi Pei
- , Qing Chen
- & Cheng-Yan Xu
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Article
| Open AccessOrganic radicals stabilization above 300 °C in Eu-based coordination polymers for solar steam generation
Organic radicals have potential applications in a variety of fields, including energy conversion. Here, the authors report Eu-based coordination polymers that enable the stabilization of organic radicals up to 350 °C; these systems can be used to enhance solar steam generation.
- Xinhe Ye
- , Lai-Hon Chung
- & Jun He
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Article
| Open AccessRapid and efficient hydrogen clathrate hydrate formation in confined nanospace
Clathrate hydrates are crystalline solids physically resembling ice, in which small molecules (typically gases) are trapped inside cages of hydrogen bonded, frozen water molecules. Here authors present the rapid formation of hydrogen clathrates by using activated carbon substrates.
- Judit Farrando-Perez
- , Rafael Balderas-Xicohtencatl
- & Joaquin Silvestre-Albero