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Showing papers in "Nature Materials in 2016"


Journal ArticleDOI
TL;DR: In this article, a plant-inspired shape morphing system is presented, where a composite hydrogel architecture is encoded with localized, anisotropic swelling behavior controlled by the alignment of cellulose fibrils along prescribed four-dimensional printing pathways.
Abstract: Shape-morphing systems can be found in many areas, including smart textiles, autonomous robotics, biomedical devices, drug delivery and tissue engineering. The natural analogues of such systems are exemplified by nastic plant motions, where a variety of organs such as tendrils, bracts, leaves and flowers respond to environmental stimuli (such as humidity, light or touch) by varying internal turgor, which leads to dynamic conformations governed by the tissue composition and microstructural anisotropy of cell walls. Inspired by these botanical systems, we printed composite hydrogel architectures that are encoded with localized, anisotropic swelling behaviour controlled by the alignment of cellulose fibrils along prescribed four-dimensional printing pathways. When combined with a minimal theoretical framework that allows us to solve the inverse problem of designing the alignment patterns for prescribed target shapes, we can programmably fabricate plant-inspired architectures that change shape on immersion in water, yielding complex three-dimensional morphologies.

2,122 citations


Journal ArticleDOI
TL;DR: This work reports the first activation and optimization of the basal plane of monolayer 2H-MoS2 for HER by introducing sulphur (S) vacancies and strain, which allows it to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.
Abstract: Molybdenum disulphide is a promising non-precious catalyst for hydrogen evolution because it contains active edge sites and an inert basal plane. Introducing sulphur vacancies and strain now leads to activation and optimization of the basal plane. As a promising non-precious catalyst for the hydrogen evolution reaction (HER; refs 1,2,3,4,5), molybdenum disulphide (MoS2) is known to contain active edge sites and an inert basal plane1,6,7,8. Activating the MoS2 basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS2 for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bind directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔGH) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Proper combinations of S-vacancy and strain yield the optimal ΔGH = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.

1,938 citations


Journal ArticleDOI
TL;DR: This Review will cover materials and devices designed for mimicking the skin's ability to sense and generate biomimetic signals.
Abstract: Skin plays an important role in mediating our interactions with the world. Recreating the properties of skin using electronic devices could have profound implications for prosthetics and medicine. The pursuit of artificial skin has inspired innovations in materials to imitate skin's unique characteristics, including mechanical durability and stretchability, biodegradability, and the ability to measure a diversity of complex sensations over large areas. New materials and fabrication strategies are being developed to make mechanically compliant and multifunctional skin-like electronics, and improve brain/machine interfaces that enable transmission of the skin's signals into the body. This Review will cover materials and devices designed for mimicking the skin's ability to sense and generate biomimetic signals.

1,681 citations


Journal ArticleDOI
TL;DR: It is found that cell spreading, proliferation, and osteogenic differentiation of mesenchymal stem cells (MSCs) are all enhanced in cells cultured in gels with faster relaxation, highlighting stress relaxation as a key characteristic of cell-ECM interactions and as an important design parameter of biomaterials for cell culture.
Abstract: Natural extracellular matrices (ECMs) are viscoelastic and exhibit stress relaxation. However, hydrogels used as synthetic ECMs for three-dimensional (3D) culture are typically elastic. Here, we report a materials approach to tune the rate of stress relaxation of hydrogels for 3D culture, independently of the hydrogel's initial elastic modulus, degradation, and cell-adhesion-ligand density. We find that cell spreading, proliferation, and osteogenic differentiation of mesenchymal stem cells (MSCs) are all enhanced in cells cultured in gels with faster relaxation. Strikingly, MSCs form a mineralized, collagen-1-rich matrix similar to bone in rapidly relaxing hydrogels with an initial elastic modulus of 17 kPa. We also show that the effects of stress relaxation are mediated by adhesion-ligand binding, actomyosin contractility and mechanical clustering of adhesion ligands. Our findings highlight stress relaxation as a key characteristic of cell-ECM interactions and as an important design parameter of biomaterials for cell culture.

1,528 citations


Journal ArticleDOI
TL;DR: In this paper, stable magnetic skyrmions at room temperature in ultrathin transition metal ferromagnets with magnetic transmission soft X-ray microscopy were observed and demonstrated.
Abstract: Magnetic skyrmions are topologically protected spin textures that exhibit fascinating physical behaviours and large potential in highly energy-efficient spintronic device applications. The main obstacles so far are that skyrmions have been observed in only a few exotic materials and at low temperatures, and fast current-driven motion of individual skyrmions has not yet been achieved. Here, we report the observation of stable magnetic skyrmions at room temperature in ultrathin transition metal ferromagnets with magnetic transmission soft X-ray microscopy. We demonstrate the ability to generate stable skyrmion lattices and drive trains of individual skyrmions by short current pulses along a magnetic racetrack at speeds exceeding 100 m s(-1) as required for applications. Our findings provide experimental evidence of recent predictions and open the door to room-temperature skyrmion spintronics in robust thin-film heterostructures.

1,364 citations


Journal ArticleDOI
TL;DR: The role of surface ligands in tuning and rationally designing properties of functional nanomaterials and their importance for biomedical and optoelectronic applications is focused on and an assessment of application-targeted surface engineering is concluded.
Abstract: All nanomaterials share a common feature of large surface-to-volume ratio, making their surfaces the dominant player in many physical and chemical processes. Surface ligands - molecules that bind to the surface - are an essential component of nanomaterial synthesis, processing and application. Understanding the structure and properties of nanoscale interfaces requires an intricate mix of concepts and techniques borrowed from surface science and coordination chemistry. Our Review elaborates these connections and discusses the bonding, electronic structure and chemical transformations at nanomaterial surfaces. We specifically focus on the role of surface ligands in tuning and rationally designing properties of functional nanomaterials. Given their importance for biomedical (imaging, diagnostics and therapeutics) and optoelectronic (light-emitting devices, transistors, solar cells) applications, we end with an assessment of application-targeted surface engineering.

1,247 citations


Journal ArticleDOI
TL;DR: In this paper, the photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors, which is a potentially scalable and economically feasible technology for converting solar energy into hydrogen.
Abstract: Photocatalytic water splitting using semiconductors is attractive for converting solar energy into hydrogen. An efficient and scalable system based on particulate photocatalyst sheets is now shown to exhibit energy conversion efficiency exceeding 1%. Photocatalytic water splitting using particulate semiconductors is a potentially scalable and economically feasible technology for converting solar energy into hydrogen1,2,3. Z-scheme systems based on two-step photoexcitation of a hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) are suited to harvesting of sunlight because semiconductors with either water reduction or oxidation activity can be applied to the water splitting reaction4,5. However, it is challenging to achieve efficient transfer of electrons between HEP and OEP particles6,7. Here, we present photocatalyst sheets based on La- and Rh-codoped SrTiO3 (SrTiO3:La, Rh; ref. 8) and Mo-doped BiVO4 (BiVO4:Mo) powders embedded into a gold (Au) layer. Enhancement of the electron relay by annealing and suppression of undesirable reactions through surface modification allow pure water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency of 1.1% and an apparent quantum yield of over 30% at 419 nm. The photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors.

1,190 citations


Journal ArticleDOI
TL;DR: A rapidly excreted NIR-II fluorophore based on a synthetic 970-Da organic molecule (CH1055) that allowed targeted molecular imaging of tumours in vivo when conjugated with anti-EGFR Affibody and allowed precise image-guided tumour-removal surgery.
Abstract: Fluorescent imaging of biological systems in the second near-infrared window (NIR-II) can probe tissue at centimetre depths and achieve micrometre-scale resolution at depths of millimetres. Unfortunately, all current NIR-II fluorophores are excreted slowly and are largely retained within the reticuloendothelial system, making clinical translation nearly impossible. Here, we report a rapidly excreted NIR-II fluorophore (∼90% excreted through the kidneys within 24 h) based on a synthetic 970-Da organic molecule (CH1055). The fluorophore outperformed indocyanine green (ICG)—a clinically approved NIR-I dye—in resolving mouse lymphatic vasculature and sentinel lymphatic mapping near a tumour. High levels of uptake of PEGylated-CH1055 dye were observed in brain tumours in mice, suggesting that the dye was detected at a depth of ∼4 mm. The CH1055 dye also allowed targeted molecular imaging of tumours in vivo when conjugated with anti-EGFR Affibody. Moreover, a superior tumour-to-background signal ratio allowed precise image-guided tumour-removal surgery. A renally cleared, water-soluble dye emitting in the near-infrared-imaging (NIR)-II window outperforms a clinically approved NIR-I dye in the in vivo imaging of tumours and their nearby blood and lymphatic vasculatures.

1,160 citations


Journal ArticleDOI
TL;DR: This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin- film transistors, solar cells, diodes and memories.
Abstract: Optical transparency, tunable conducting properties and easy processability make metal oxides key materials for advanced optoelectronic devices. This Review discusses recent advances in the synthesis of these materials and their use in applications. Metal oxides (MOs) are the most abundant materials in the Earth's crust and are ingredients in traditional ceramics. MO semiconductors are strikingly different from conventional inorganic semiconductors such as silicon and III–V compounds with respect to materials design concepts, electronic structure, charge transport mechanisms, defect states, thin-film processing and optoelectronic properties, thereby enabling both conventional and completely new functions. Recently, remarkable advances in MO semiconductors for electronics have been achieved, including the discovery and characterization of new transparent conducting oxides, realization of p-type along with traditional n-type MO semiconductors for transistors, p–n junctions and complementary circuits, formulations for printing MO electronics and, most importantly, commercialization of amorphous oxide semiconductors for flat panel displays. This Review surveys the uniqueness and universality of MOs versus other unconventional electronic materials in terms of materials chemistry and physics, electronic characteristics, thin-film fabrication strategies and selected applications in thin-film transistors, solar cells, diodes and memories.

1,098 citations


Journal ArticleDOI
TL;DR: In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics and research on its environmental impact is becoming increasingly relevant.
Abstract: In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

952 citations


Journal ArticleDOI
TL;DR: Advanced structural ceramics are playing a key role in addressing these challenges in vehicle propulsion systems and will be a major source of inspiration for the next generation of autonomous vehicles.
Abstract: Humankind's aerospace aspirations are placing unprecedented demands on vehicle propulsion systems. Advanced structural ceramics are playing a key role in addressing these challenges.

PatentDOI
TL;DR: This work describes the synthesis and crystal structures of three porous ZIFs that are expanded analogues of zeolite A; their cage walls are functionalized, and their metal ions can be changed without changing the underlying LTA topology.
Abstract: The disclosure provides for multivariant zeolitic imidazolate frameworks (ZIFs), methods of making thereof, and methods of use therefrom.

Journal ArticleDOI
TL;DR: The excitation spectrum of α-RuCl3 is proposed as a prime candidate for fractionalized Kitaev physics, and dynamical response measurements above interlayer energy scales are naturally accounted for in terms of deconfinement physics expected for QSLs.
Abstract: Inelastic neutron scattering characterization shows that α-RuCl3 is close to an experimental realization of a Kitaev quantum spin liquid on a honeycomb lattice. The collective excitations provide evidence for deconfined Majorana fermions.

Journal ArticleDOI
TL;DR: The AFM/FM system is shown to be a promising building block for SOT devices as well as providing an attractive pathway towards neuromorphic computing.
Abstract: Spin-orbit torque (SOT)-induced magnetization switching shows promise for realizing ultrafast and reliable spintronics devices. Bipolar switching of the perpendicular magnetization by the SOT is achieved under an in-plane magnetic field collinear with an applied current. Typical structures studied so far comprise a nonmagnet/ferromagnet (NM/FM) bilayer, where the spin Hall effect in the NM is responsible for the switching. Here we show that an antiferromagnet/ferromagnet (AFM/FM) bilayer system also exhibits a SOT large enough to switch the magnetization of the FM. In this material system, thanks to the exchange bias of the AFM, we observe the switching in the absence of an applied field by using an antiferromagnetic PtMn and ferromagnetic Co/Ni multilayer with a perpendicular easy axis. Furthermore, tailoring the stack achieves a memristor-like behaviour where a portion of the reversed magnetization can be controlled in an analogue manner. The AFM/FM system is thus a promising building block for SOT devices as well as providing an attractive pathway towards neuromorphic computing.

Journal ArticleDOI
TL;DR: By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, this work is able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.
Abstract: Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co(2+) and Mo(4+) centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.

Journal ArticleDOI
TL;DR: A strategy to design tough transparent and conductive bonding of synthetic hydrogels containing 90% water to non-porous surfaces of diverse solids, including glass, silicon, ceramics, titanium and aluminium is reported.
Abstract: In many animals, the bonding of tendon and cartilage to bone is extremely tough (for example, interfacial toughness ∼800 J m(-2); refs ,), yet such tough interfaces have not been achieved between synthetic hydrogels and non-porous surfaces of engineered solids. Here, we report a strategy to design tough transparent and conductive bonding of synthetic hydrogels containing 90% water to non-porous surfaces of diverse solids, including glass, silicon, ceramics, titanium and aluminium. The design strategy is to anchor the long-chain polymer networks of tough hydrogels covalently to non-porous solid surfaces, which can be achieved by the silanation of such surfaces. Compared with physical interactions, the chemical anchorage results in a higher intrinsic work of adhesion and in significant energy dissipation of bulk hydrogel during detachment, which lead to interfacial toughness values over 1,000 J m(-2). We also demonstrate applications of robust hydrogel-solid hybrids, including hydrogel superglues, mechanically protective hydrogel coatings, hydrogel joints for robotic structures and robust hydrogel-metal conductors.

Journal ArticleDOI
TL;DR: An integrated organic functional material design process that incorporates theoretical insight, quantum chemistry, cheminformatics, machine learning, industrial expertise, organic synthesis, molecular characterization, device fabrication and optoelectronic testing is reported.
Abstract: A high-throughput virtual screening approach is used to select molecules with efficient, thermally activated delayed fluorescence. The good performance of several selected emitters in organic LED applications has also been confirmed experimentally.

Journal ArticleDOI
TL;DR: Soft microrobots consisting of photoactive liquid-crystal elastomers can be driven by structured monochromatic light to perform sophisticated biomimetic motions and multiple gaits, mimicking either symplectic or antiplectic metachrony of ciliate protozoa are confirmed.
Abstract: Microorganisms move in challenging environments by periodic changes in body shape. In contrast, current artificial microrobots cannot actively deform, exhibiting at best passive bending under external fields. Here, by taking advantage of the wireless, scalable and spatiotemporally selective capabilities that light allows, we show that soft microrobots consisting of photoactive liquid-crystal elastomers can be driven by structured monochromatic light to perform sophisticated biomimetic motions. We realize continuum yet selectively addressable artificial microswimmers that generate travelling-wave motions to self-propel without external forces or torques, as well as microrobots capable of versatile locomotion behaviours on demand. Both theoretical predictions and experimental results confirm that multiple gaits, mimicking either symplectic or antiplectic metachrony of ciliate protozoa, can be achieved with single microswimmers. The principle of using structured light can be extended to other applications that require microscale actuation with sophisticated spatiotemporal coordination for advanced microrobotic technologies.

Journal ArticleDOI
TL;DR: It is shown that efficient charge injection and the presence of naturally occurring sulfur vacancies are responsible for the observed increase in catalytic activity of the 2H basal planes of monolayer MoS2 nanosheets.
Abstract: The excellent catalytic activity of metallic MoS2 edges for the hydrogen evolution reaction (HER) has led to substantial efforts towards increasing the edge concentration. The 2H basal plane is less active for the HER because it is less conducting and therefore possesses less efficient charge transfer kinetics. Here we show that the activity of the 2H basal planes of monolayer MoS2 nanosheets can be made comparable to state-of-the-art catalytic properties of metallic edges and the 1T phase by improving the electrical coupling between the substrate and the catalyst so that electron injection from the electrode and transport to the catalyst active site is facilitated. Phase-engineered low-resistance contacts on monolayer 2H-phase MoS2 basal plane lead to higher efficiency of charge injection in the nanosheets so that its intrinsic activity towards the HER can be measured. We demonstrate that onset potentials and Tafel slopes of ∼-0.1 V and ∼50 mV per decade can be achieved from 2H-phase catalysts where only the basal plane is exposed. We show that efficient charge injection and the presence of naturally occurring sulfur vacancies are responsible for the observed increase in catalytic activity of the 2H basal plane. Our results provide new insights into the role of contact resistance and charge transport on the performance of two-dimensional MoS2 nanosheet catalysts for the HER.

Journal ArticleDOI
TL;DR: It is shown that N-heterocyclic carbene (NHC) Ir(III) complexes can serve as both deep blue emitters and efficient hole-conducting EBLs, and both the facial and the meridional isomers of the dopant have high efficiencies that arise from the unusual properties of the NHC ligand.
Abstract: N-Heterocyclic carbene Ir(III) complexes, used as deep blue phosphorescent emitters and as electron-blocking dopants in organic LEDs, allow the realization of devices with very high brightness and reduced efficiency roll-off.

Journal ArticleDOI
TL;DR: It is found that nanomaterial velocity reduces 1000-fold as they enter and traverse the liver, leading to 7.5 times morenanomaterial interaction with hepatic cells relative to peripheral cells.
Abstract: The liver and spleen are major biological barriers to translating nanomedicines because they sequester the majority of administered nanomaterials and prevent delivery to diseased tissue. Here we examined the blood clearance mechanism of administered hard nanomaterials in relation to blood flow dynamics, organ microarchitecture and cellular phenotype. We found that nanomaterial velocity reduces 1,000-fold as they enter and traverse the liver, leading to 7.5 times more nanomaterial interaction with hepatic cells relative to peripheral cells. In the liver, Kupffer cells (84.8 ± 6.4%), hepatic B cells (81.5 ± 9.3%) and liver sinusoidal endothelial cells (64.6 ± 13.7%) interacted with administered PEGylated quantum dots, but splenic macrophages took up less material (25.4 ± 10.1%) due to differences in phenotype. The uptake patterns were similar for two other nanomaterial types and five different surface chemistries. Potential new strategies to overcome off-target nanomaterial accumulation may involve manipulating intra-organ flow dynamics and modulating the cellular phenotype to alter hepatic cell interactions.

Journal ArticleDOI
TL;DR: The synthesis of 2D gallium nitride (GaN) via a migration-enhanced encapsulated growth (MEEG) technique utilizing epitaxial graphene is demonstrated and it is established that graphene plays a critical role in stabilizing the direct-bandgap, 2D buckled structure.
Abstract: A method to synthesize 2D layers of gallium nitride on SiC is reported. Epitaxial graphene preliminarily grown on SiC allows intercalation of gallium atoms on the SiC substrate and stabilizes the 2D gallium nitride islands formed by ammonolysis. The spectrum of two-dimensional (2D) and layered materials ‘beyond graphene’ offers a remarkable platform to study new phenomena in condensed matter physics. Among these materials, layered hexagonal boron nitride (hBN), with its wide bandgap energy (∼5.0–6.0 eV), has clearly established that 2D nitrides are key to advancing 2D devices1. A gap, however, remains between the theoretical prediction of 2D nitrides ‘beyond hBN’2,3 and experimental realization of such structures. Here we demonstrate the synthesis of 2D gallium nitride (GaN) via a migration-enhanced encapsulated growth (MEEG) technique utilizing epitaxial graphene. We theoretically predict and experimentally validate that the atomic structure of 2D GaN grown via MEEG is notably different from reported theory2,3,4. Moreover, we establish that graphene plays a critical role in stabilizing the direct-bandgap (nearly 5.0 eV), 2D buckled structure. Our results provide a foundation for discovery and stabilization of 2D nitrides that are difficult to prepare via traditional synthesis.

Journal ArticleDOI
TL;DR: This paper reports the ability of the metamaterial platform to detect ultralow-molecular-weight biomolecules at picomolar concentrations using a standard affinity model streptavidin-biotin.
Abstract: Optical sensor technology offers significant opportunities in the field of medical research and clinical diagnostics, particularly for the detection of small numbers of molecules in highly diluted solutions. Several methods have been developed for this purpose, including label-free plasmonic biosensors based on metamaterials. However, the detection of lower-molecular-weight (<500 Da) biomolecules in highly diluted solutions is still a challenging issue owing to their lower polarizability. In this context, we have developed a miniaturized plasmonic biosensor platform based on a hyperbolic metamaterial that can support highly confined bulk plasmon guided modes over a broad wavelength range from visible to near infrared. By exciting these modes using a grating-coupling technique, we achieved different extreme sensitivity modes with a maximum of 30,000 nm per refractive index unit (RIU) and a record figure of merit (FOM) of 590. We report the ability of the metamaterial platform to detect ultralow-molecular-weight (244 Da) biomolecules at picomolar concentrations using a standard affinity model streptavidin-biotin.

Journal ArticleDOI
TL;DR: H hierarchical metamaterials with disparate three-dimensional features spanning seven orders of magnitude, from nanometres to centimetres are demonstrated, enabled by a high-resolution, large-area additive manufacturing technique with scalability not achievable by two-photon polymerization or traditional stereolithography.
Abstract: Materials with three-dimensional micro- and nanoarchitectures exhibit many beneficial mechanical, energy conversion and optical properties. However, these three-dimensional microarchitectures are significantly limited by their scalability. Efforts have only been successful only in demonstrating overall structure sizes of hundreds of micrometres, or contain size-scale gaps of several orders of magnitude. This results in degraded mechanical properties at the macroscale. Here we demonstrate hierarchical metamaterials with disparate three-dimensional features spanning seven orders of magnitude, from nanometres to centimetres. At the macroscale they achieve high tensile elasticity (>20%) not found in their brittle-like metallic constituents, and a near-constant specific strength. Creation of these materials is enabled by a high-resolution, large-area additive manufacturing technique with scalability not achievable by two-photon polymerization or traditional stereolithography. With overall part sizes approaching tens of centimetres, these unique nanostructured metamaterials might find use in a broad array of applications.

Journal ArticleDOI
TL;DR: A new approach to designing crosslinked, rigid polymer nanofilms with enhanced microporosity by manipulating the molecular structure is reported, showing outstanding separation performance in organic solvents.
Abstract: Here it is shown how ultrathin and microporous polymer membranes, fabricated using sterically contorted monomers, can achieve enhanced performance for solvent-based separations.

Journal ArticleDOI
TL;DR: The results presented here constitute the first step towards the development of a new rechargeable battery technology using calcium anodes, and the reversibility of the process on cycling has been ascertained.
Abstract: The development of a rechargeable battery technology using light electropositive metal anodes would result in a breakthrough in energy density. For multivalent charge carriers (M(n+)), the number of ions that must react to achieve a certain electrochemical capacity is diminished by two (n = 2) or three (n = 3) when compared with Li(+) (ref. ). Whereas proof of concept has been achieved for magnesium, the electrodeposition of calcium has so far been thought to be impossible and research has been restricted to non-rechargeable systems. Here we demonstrate the feasibility of calcium plating at moderate temperatures using conventional organic electrolytes, such as those used for the Li-ion technology. The reversibility of the process on cycling has been ascertained and thus the results presented here constitute the first step towards the development of a new rechargeable battery technology using calcium anodes.

Journal ArticleDOI
TL;DR: The results reveal a platform based on porous covalent organic frameworks for proton conduction and achieve proton conductivities that are 2-4 orders of magnitude higher than those of microporous and non-porous polymers.
Abstract: Progress over the past decades in proton-conducting materials has generated a variety of polyelectrolytes and microporous polymers. However, most studies are still based on a preconception that large pores eventually cause simply flow of proton carriers rather than efficient conduction of proton ions, which precludes the exploration of large-pore polymers for proton transport. Here, we demonstrate proton conduction across mesoporous channels in a crystalline covalent organic framework. The frameworks are designed to constitute hexagonally aligned, dense, mesoporous channels that allow for loading of N-heterocyclic proton carriers. The frameworks achieve proton conductivities that are 2-4 orders of magnitude higher than those of microporous and non-porous polymers. Temperature-dependent and isotopic experiments revealed that the proton transport in these channels is controlled by a low-energy-barrier hopping mechanism. Our results reveal a platform based on porous covalent organic frameworks for proton conduction.

Journal ArticleDOI
TL;DR: Robust propagation along reconfigurable pathways defined by synthetic gauge fields within a topological photonic metacrystal domains is demonstrated and provides a framework for freely steering electromagnetic radiation within photonic structures.
Abstract: The discovery of topological photonic states has revolutionized our understanding of electromagnetic propagation and scattering. Endowed with topological robustness, photonic edge modes are not reflected from structural imperfections and disordered regions. Here we demonstrate robust propagation along reconfigurable pathways defined by synthetic gauge fields within a topological photonic metacrystal. The flow of microwave radiation in helical edge modes following arbitrary contours of the synthetic gauge field between bianisotropic metacrystal domains is unimpeded. This is demonstrated in measurements of the spectrum of transmission and time delay along the topological domain walls. These results provide a framework for freely steering electromagnetic radiation within photonic structures.

Journal ArticleDOI
TL;DR: An efficient strategy for achieving large-area single-crystalline graphene by letting a single nucleus evolve into a monolayer at a fast rate is demonstrated by locally feeding carbon precursors to a desired position of a substrate composed of an optimized Cu-Ni alloy.
Abstract: Wafer-scale single-crystalline graphene monolayers are highly sought after as an ideal platform for electronic and other applications. At present, state-of-the-art growth methods based on chemical vapour deposition allow the synthesis of one-centimetre-sized single-crystalline graphene domains in ∼12 h, by suppressing nucleation events on the growth substrate. Here we demonstrate an efficient strategy for achieving large-area single-crystalline graphene by letting a single nucleus evolve into a monolayer at a fast rate. By locally feeding carbon precursors to a desired position of a substrate composed of an optimized Cu-Ni alloy, we synthesized an ∼1.5-inch-large graphene monolayer in 2.5 h. Localized feeding induces the formation of a single nucleus on the entire substrate, and the optimized alloy activates an isothermal segregation mechanism that greatly expedites the growth rate. This approach may also prove effective for the synthesis of wafer-scale single-crystalline monolayers of other two-dimensional materials.

Journal ArticleDOI
TL;DR: A large negative LMR with the field-steering properties specific to the chiral anomaly is observed in the half-Heusler GdPtBi, and the scheme of creating Weyl nodes from quadratic bands suggests that the Chiral anomaly may be observable in a broad class of semimetals.
Abstract: The Dirac and Weyl semimetals are unusual materials in which the nodes of the bulk states are protected against gap formation by crystalline symmetry. The chiral anomaly, predicted to occur in both systems, was recently observed as a negative longitudinal magnetoresistance (LMR) in Na3Bi (ref. ) and in TaAs (ref. ). An important issue is whether Weyl physics appears in a broader class of materials. We report evidence for the chiral anomaly in the half-Heusler GdPtBi. In zero field, GdPtBi is a zero-gap semiconductor with quadratic bands. In a magnetic field, the Zeeman energy leads to Weyl nodes. We have observed a large negative LMR with the field-steering properties specific to the chiral anomaly. The chiral anomaly also induces strong suppression of the thermopower. We report a detailed study of the thermoelectric response function αxx of Weyl fermions. The scheme of creating Weyl nodes from quadratic bands suggests that the chiral anomaly may be observable in a broad class of semimetals.