Showing papers in "Nature Materials in 2019"
TL;DR: This Review describes recent progress in the fundamental understanding of inorganic solid electrolytes by addressing key issues in the areas of multiscale ion transport, electrochemical and mechanical properties, and current processing routes.
Abstract: In the critical area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-density and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorganic solid electrolytes, which lie at the heart of the solid-state battery concept, by addressing key issues in the areas of multiscale ion transport, electrochemical and mechanical properties, and current processing routes. The main electrolyte-related challenges for practical solid-state devices include utilization of metal anodes, stabilization of interfaces and the maintenance of physical contact, the solutions to which hinge on gaining greater knowledge of the underlying properties of solid electrolyte materials. Solid-state batteries are attractive due to their potential safety, energy-density and cycle-life benefits. Recent progress in understanding inorganic solid electrolytes considering multiscale ion transport, electrochemical and mechanical properties, and processing are discussed.
1,087 citations
TL;DR: Progress in the fundamental understanding and design of new multiferroic materials, advances in characterization and modelling tools to describe them, and usage in applications are reviewed.
Abstract: The manipulation of magnetic properties by an electric field in magnetoelectric multiferroic materials has driven significant research activity, with the goal of realizing their transformative technological potential. Here, we review progress in the fundamental understanding and design of new multiferroic materials, advances in characterization and modelling tools to describe them, and the exploration of devices and applications. Focusing on the translation of the many scientific breakthroughs into technological innovations, we identify the key open questions in the field where targeted research activities could have maximum impact in transitioning scientific discoveries into real applications. Magnetoelectric multiferroics, where magnetic properties are manipulated by electric field and vice versa, could lead to improved electronic devices. Here, advances in materials, characterisation and modelling, and usage in applications are reviewed.
1,020 citations
TL;DR: The role of PT symmetry and non-Hermitian dynamics for synthesizing and controlling the flow of light in optical structures is highlighted and a roadmap for future studies and potential applications is provided.
Abstract: Exploiting the interplay between gain, loss and the coupling strength between different optical components creates a variety of new opportunities in photonics to generate, control and transmit light. Inspired by the discovery of real eigenfrequencies for non-Hermitian Hamiltonians obeying parity–time (PT) symmetry, many counterintuitive aspects are being explored, particularly close to the associated degeneracies also known as ‘exceptional points’. This Review explains the underlying physical principles and discusses the progress in the experimental investigation of PT-symmetric photonic systems. We highlight the role of PT symmetry and non-Hermitian dynamics for synthesizing and controlling the flow of light in optical structures and provide a roadmap for future studies and potential applications. This Review discusses recent developments in the area of non-Hermitian physics, and more specifically the special case of non-Hermitian optical systems with parity–time symmetry.
1,010 citations
TL;DR: The challenges in the integration and use in computation of large-scale memristive neural networks are discussed, both as accelerators for deep learning and as building blocks for spiking neural networks.
Abstract: With their working mechanisms based on ion migration, the switching dynamics and electrical behaviour of memristive devices resemble those of synapses and neurons, making these devices promising candidates for brain-inspired computing. Built into large-scale crossbar arrays to form neural networks, they perform efficient in-memory computing with massive parallelism by directly using physical laws. The dynamical interactions between artificial synapses and neurons equip the networks with both supervised and unsupervised learning capabilities. Moreover, their ability to interface with analogue signals from sensors without analogue/digital conversions reduces the processing time and energy overhead. Although numerous simulations have indicated the potential of these networks for brain-inspired computing, experimental implementation of large-scale memristive arrays is still in its infancy. This Review looks at the progress, challenges and possible solutions for efficient brain-inspired computation with memristive implementations, both as accelerators for deep learning and as building blocks for spiking neural networks.
948 citations
TL;DR: A second-order topological insulator in an acoustical metamaterial with a breathing kagome lattice, supporting one-dimensional edge states and zero-dimensional corner states is demonstrated, and shape dependence allows corner states to act as topologically protected but reconfigurable local resonances.
Abstract: Higher-order topological insulators1–5 are a family of recently predicted topological phases of matter that obey an extended topological bulk–boundary correspondence principle. For example, a two-dimensional (2D) second-order topological insulator does not exhibit gapless one-dimensional (1D) topological edge states, like a standard 2D topological insulator, but instead has topologically protected zero-dimensional (0D) corner states. The first prediction of a second-order topological insulator1, based on quantized quadrupole polarization, was demonstrated in classical mechanical6 and electromagnetic7,8 metamaterials. Here we experimentally realize a second-order topological insulator in an acoustic metamaterial, based on a ‘breathing’ kagome lattice9 that has zero quadrupole polarization but a non-trivial bulk topology characterized by quantized Wannier centres2,9,10. Unlike previous higher-order topological insulator realizations, the corner states depend not only on the bulk topology but also on the corner shape; we show experimentally that they exist at acute-angled corners of the kagome lattice, but not at obtuse-angled corners. This shape dependence allows corner states to act as topologically protected but reconfigurable local resonances. A second-order topological insulator in an acoustical metamaterial with a breathing kagome lattice, supporting one-dimensional edge states and zero-dimensional corner states is demonstrated.
591 citations
TL;DR: It is demonstrated theoretically and experimentally that 3D-printed two-dimensional acoustic meta-structures can possess nontrivial bulk topological polarization and host one-dimensional edge and Wannier-type second-order zero-dimensional corner states with unique acoustic properties, and offer possibilities for advanced control of the propagation and manipulation of sound, including within the radiative continuum.
Abstract: Topological systems are inherently robust to disorder and continuous perturbations, resulting in dissipation-free edge transport of electrons in quantum solids, or reflectionless guiding of photons and phonons in classical wave systems characterized by topological invariants. Recently, a new class of topological materials characterized by bulk polarization has been introduced, and was shown to host higher-order topological corner states. Here, we demonstrate theoretically and experimentally that 3D-printed two-dimensional acoustic meta-structures can possess nontrivial bulk topological polarization and host one-dimensional edge and Wannier-type second-order zero-dimensional corner states with unique acoustic properties. We observe second-order topological states protected by a generalized chiral symmetry of the meta-structure, which are localized at the corners and are pinned to 'zero energy'. Interestingly, unlike the 'zero energy' states protected by conventional chiral symmetry, the generalized chiral symmetry of our three-atom sublattice enables their spectral overlap with the continuum of bulk states without leakage. Our findings offer possibilities for advanced control of the propagation and manipulation of sound, including within the radiative continuum.
588 citations
TL;DR: A molecular-level SEI design using a reactive polymer composite is shown to effectively construct a stable SEI layer and suppress electrolyte consumption upon cycling, which effectively suppresses electrolytes consumption in the formation and maintenance of the SEI.
Abstract: The solid–electrolyte interphase (SEI) is pivotal in stabilizing lithium metal anodes for rechargeable batteries. However, the SEI is constantly reforming and consuming electrolyte with cycling. The rational design of a stable SEI is plagued by the failure to control its structure and stability. Here we report a molecular-level SEI design using a reactive polymer composite, which effectively suppresses electrolyte consumption in the formation and maintenance of the SEI. The SEI layer consists of a polymeric lithium salt, lithium fluoride nanoparticles and graphene oxide sheets, as evidenced by cryo-transmission electron microscopy, atomic force microscopy and surface-sensitive spectroscopies. This structure is different from that of a conventional electrolyte-derived SEI and has excellent passivation properties, homogeneity and mechanical strength. The use of the polymer–inorganic SEI enables high-efficiency Li deposition and stable cycling of 4 V Li|LiNi0.5Co0.2Mn0.3O2 cells under lean electrolyte, limited Li excess and high capacity conditions. The same approach was also applied to design stable SEI layers for sodium and zinc anodes. Solid–electrolyte interphase is crucial for stabilizing lithium metal anodes for rechargeable batteries. A molecular-level design using a reactive polymer composite is now shown to effectively construct a stable SEI layer and suppress electrolyte consumption upon cycling.
493 citations
TL;DR: The origins of localized plasmon resonances in few-nanometricre or sub-nanometre gaps between metal nanoparticles and metal films are discussed, as well as recent experimental observations and potential future directions.
Abstract: Ultrathin dielectric gaps between metals can trap plasmonic optical modes with surprisingly low loss and with volumes below 1 nm3. We review the origin and subtle properties of these modes, and show how they can be well accounted for by simple models. Particularly important is the mixing between radiating antennas and confined nanogap modes, which is extremely sensitive to precise nanogeometry, right down to the single-atom level. Coupling nanogap plasmons to electronic and vibronic transitions yields a host of phenomena including single-molecule strong coupling and molecular optomechanics, opening access to atomic-scale chemistry and materials science, as well as quantum metamaterials. Ultimate low-energy devices such as robust bottom-up assembled single-atom switches are thus in prospect.
476 citations
TL;DR: An investigation of the structural and transport properties of bilayer graphene as a function of the twist angle between the layers reveals atomic-scale reconstruction for twist angles smaller than a critical value.
Abstract: Control of the interlayer twist angle in two-dimensional van der Waals (vdW) heterostructures enables one to engineer a quasiperiodic moire superlattice of tunable length scale1–8. In twisted bilayer graphene, the simple moire superlattice band description suggests that the electronic bandwidth can be tuned to be comparable to the vdW interlayer interaction at a ‘magic angle’9, exhibiting strongly correlated behaviour. However, the vdW interlayer interaction can also cause significant structural reconstruction at the interface by favouring interlayer commensurability, which competes with the intralayer lattice distortion10–16. Here we report atomic-scale reconstruction in twisted bilayer graphene and its effect on the electronic structure. We find a gradual transition from an incommensurate moire structure to an array of commensurate domains with soliton boundaries as we decrease the twist angle across the characteristic crossover angle, θc ≈ 1°. In the solitonic regime (θ < θc) where the atomic and electronic reconstruction become significant, a simple moire band description breaks down and the secondary Dirac bands appear. On applying a transverse electric field, we observe electronic transport along the network of one-dimensional topological channels that surround the alternating triangular gapped domains. Atomic and electronic reconstruction at the vdW interface provide a new pathway to engineer the system with continuous tunability. An investigation of the structural and transport properties of bilayer graphene as a function of the twist angle between the layers reveals atomic-scale reconstruction for twist angles smaller than a critical value.
451 citations
TL;DR: The pressure dependence on stripping indicates that creep rather than Li diffusion is the dominant mechanism transporting Li to the interface, which is a major factor limiting the power density of Li anode solid-state cells.
Abstract: A critical current density on stripping is identified that results in dendrite formation on plating and cell failure. When the stripping current density removes Li from the interface faster than it can be replenished, voids form in the Li at the interface and accumulate on cycling, increasing the local current density at the interface and ultimately leading to dendrite formation on plating, short circuit and cell death. This occurs even when the overall current density is considerably below the threshold for dendrite formation on plating. For the Li/Li6PS5Cl/Li cell, this is 0.2 and 1.0 mA cm−2 at 3 and 7 MPa pressure, respectively, compared with a critical current for plating of 2.0 mA cm−2 at both 3 and 7 MPa. The pressure dependence on stripping indicates that creep rather than Li diffusion is the dominant mechanism transporting Li to the interface. The critical stripping current is a major factor limiting the power density of Li anode solid-state cells. Considerable pressure may be required to achieve even modest power densities in solid-state cells. A ceramic electrolyte with a lithium metal anode can offer advantages over liquid electrolytes for Li-ion battery performance. A critical current density on stripping in a solid-state cell is identified, resulting in dendrite formation on plating and failure.
449 citations
TL;DR: The atomic-level design and synthetic strategy provide a platform that facilitates valence control of co-catalyst copper atoms, reversible modulation of the macroscopic optoelectronic properties of TiO2 and enhancement of photocatalytic hydrogen generation activity, extending the boundaries of conventional heterogeneous catalysts.
Abstract: The reversible and cooperative activation process, which includes electron transfer from surrounding redox mediators, the reversible valence change of cofactors and macroscopic functional/structural change, is one of the most important characteristics of biological enzymes, and has frequently been used in the design of homogeneous catalysts. However, there are virtually no reports on industrially important heterogeneous catalysts with these enzyme-like characteristics. Here, we report on the design and synthesis of highly active TiO2 photocatalysts incorporating site-specific single copper atoms (Cu/TiO2) that exhibit a reversible and cooperative photoactivation process. Our atomic-level design and synthetic strategy provide a platform that facilitates valence control of co-catalyst copper atoms, reversible modulation of the macroscopic optoelectronic properties of TiO2 and enhancement of photocatalytic hydrogen generation activity, extending the boundaries of conventional heterogeneous catalysts. Reversible and cooperative activation processes are important characteristics of biological enzymes and can be used in designing catalysts. Highly active TiO2 photocatalysts incorporated with site-specific single copper atoms are now shown to exhibit such a photoactivation process.
TL;DR: Hydrophobicity is proposed as a governing factor in CO2 reduction selectivity and can help explain trends seen on previously reported electrocatalysts.
Abstract: The aqueous electrocatalytic reduction of CO2 into alcohol and hydrocarbon fuels presents a sustainable route towards energy-rich chemical feedstocks. Cu is the only material able to catalyse the substantial formation of multicarbon products (C2/C3), but competing proton reduction to hydrogen is an ever-present drain on selectivity. Here, a superhydrophobic surface was generated by 1-octadecanethiol treatment of hierarchically structured Cu dendrites, inspired by the structure of gas-trapping cuticles on subaquatic spiders. The hydrophobic electrode attained a 56% Faradaic efficiency for ethylene and 17% for ethanol production at neutral pH, compared to 9% and 4% on a hydrophilic, wettable equivalent. These observations are assigned to trapped gases at the hydrophobic Cu surface, which increase the concentration of CO2 at the electrode–solution interface and consequently increase CO2 reduction selectivity. Hydrophobicity is thus proposed as a governing factor in CO2 reduction selectivity and can help explain trends seen on previously reported electrocatalysts. Aqueous electrocatalytic reduction of CO2 into alcohol and hydrocarbon fuels is a sustainable route towards energy-rich chemical feedstocks. A superhydrophobic surface of hierarchically structured Cu dendrites exhibits a significant increase in CO2 reduction selectivity.
TL;DR: In this paper, reversible modulation of MoS2 films that is consistent with local 2H-1T' phase transitions by controlling the migration of Li+ ions with an electric field is presented.
Abstract: Coupled ionic-electronic effects present intriguing opportunities for device and circuit development. In particular, layered two-dimensional materials such as MoS2 offer highly anisotropic ionic transport properties, facilitating controlled ion migration and efficient ionic coupling among devices. Here, we report reversible modulation of MoS2 films that is consistent with local 2H-1T' phase transitions by controlling the migration of Li+ ions with an electric field, where an increase/decrease in the local Li+ ion concentration leads to the transition between the 2H (semiconductor) and 1T' (metal) phases. The resulting devices show excellent memristive behaviour and can be directly coupled with each other through local ionic exchange, naturally leading to synaptic competition and synaptic cooperation effects observed in biology. These results demonstrate the potential of direct modulation of two-dimensional materials through field-driven ionic processes, and can lead to future electronic and energy devices based on coupled ionic-electronic effects and biorealistic implementation of artificial neural networks.
TL;DR: The progress in disorder control for graphene and TMDs is discussed, as well as in van der Waals heterostructures realized by combining these materials with hexagonal boron nitride.
Abstract: Realizing the full potential of any materials system requires understanding and controlling disorder, which can obscure intrinsic properties and hinder device performance. Here we examine both intrinsic and extrinsic disorder in two-dimensional (2D) materials, in particular graphene and transition metal dichalcogenides (TMDs). Minimizing disorder is crucial for realizing desired properties in 2D materials and improving device performance and repeatability for practical applications. We discuss the progress in disorder control for graphene and TMDs, as well as in van der Waals heterostructures realized by combining these materials with hexagonal boron nitride. Furthermore, we showcase how atomic defects or disorder can also be harnessed to provide useful electronic, optical, chemical and magnetic functions.
TL;DR: In this paper, pressure-induced changes in the magnetic order of atomically thin van der Waals crystals are revealed and attributed to changes in stacking arrangement, and the interlayer ferromagnetic ground state is established in bulk CrI3 but not observed in native exfoliated thin films.
Abstract: Stacking order can influence the physical properties of two-dimensional van der Waals materials1,2. Here we applied hydrostatic pressure up to 2 GPa to modify the stacking order in the van der Waals magnetic insulator CrI3. We observed an irreversible interlayer antiferromagnetic-to-ferromagnetic transition in atomically thin CrI3 by magnetic circular dichroism and electron tunnelling measurements. The effect was accompanied by a monoclinic-to-rhombohedral stacking-order change characterized by polarized Raman spectroscopy. Before the structural change, the interlayer antiferromagnetic coupling energy can be tuned up by nearly 100% with pressure. Our experiment reveals the interlayer ferromagnetic ground state, which is established in bulk CrI3 but not observed in native exfoliated thin films. The observed correlation between the magnetic ground state and the stacking order is in good agreement with first principles calculations3–8 and suggests a route towards nanoscale magnetic textures by moire engineering3,9. Pressure-induced changes in the magnetic order of atomically thin van der Waals crystals are revealed and attributed to changes in the stacking arrangement.
TL;DR: It was demonstrated that isolated Pt species can adopt a range of local coordination environments and oxidation states, which evolve in response to varied environmental conditions, which showed a strong influence on the chemical reactivity.
Abstract: The use of oxide-supported isolated Pt-group metal atoms as catalytic active sites is of interest due to their unique reactivity and efficient metal utilization. However, relationships between the structure of these active sites, their dynamic response to environments and catalytic functionality have proved difficult to experimentally establish. Here, sinter-resistant catalysts where Pt was deposited uniformly as isolated atoms in well-defined locations on anatase TiO2 nanoparticle supports were used to develop such relationships. Through a combination of in situ atomic-resolution microscopy- and spectroscopy-based characterization supported by first-principles calculations it was demonstrated that isolated Pt species can adopt a range of local coordination environments and oxidation states, which evolve in response to varied environmental conditions. The variation in local coordination showed a strong influence on the chemical reactivity and could be exploited to control the catalytic performance.
TL;DR: MRPs in situ report the sequential occurrence of oxidative stress, lysosomal damage and cellular apoptosis, which precedes clinical manifestation of AKI (decreased glomerular filtration), allowing MRPs to non-invasively detect the onset of cisplatin-induced AKI at least 36 h earlier than the existing imaging methods.
Abstract: Drug-induced acute kidney injury (AKI) with a high morbidity and mortality is poorly diagnosed in hospitals and deficiently evaluated in drug discovery. Here, we report the development of molecular renal probes (MRPs) with high renal clearance efficiency for in vivo optical imaging of drug-induced AKI. MRPs specifically activate their near-infrared fluorescence or chemiluminescence signals towards the prodromal biomarkers of AKI including the superoxide anion, N-acetyl-β-d-glucosaminidase and caspase-3, enabling an example of longitudinal imaging of multiple molecular events in the kidneys of living mice. Importantly, they in situ report the sequential occurrence of oxidative stress, lysosomal damage and cellular apoptosis, which precedes clinical manifestation of AKI (decreased glomerular filtration). Such an active imaging mechanism allows MRPs to non-invasively detect the onset of cisplatin-induced AKI at least 36 h earlier than the existing imaging methods. MRPs can also act as exogenous tracers for optical urinalysis that outperforms typical clinical/preclinical assays, demonstrating their clinical promise for early diagnosis of AKI. Chemiluminescent molecular renal probes have been developed and are shown to be capable of non-invasive real-time imaging of early-stage oxidative stress biomarkers of drug-induced acute kidney injury, and high renal clearance.
TL;DR: The facile water droplet printing on superamphiphobic surfaces is leveraged to create rewritable surface charge density gradients that stimulate droplet propulsion under ambient conditions17 and without the need for additional energy input.
Abstract: The directed, long-range and self-propelled transport of droplets on solid surfaces is crucial for many applications from water harvesting to bio-analysis1-9. Typically, preferential transport is achieved by topographic or chemical modulation of surface wetting gradients that break the asymmetric contact line and overcome the resistance force to move droplets along a particular direction10-16. Nonetheless, despite extensive progress, directional droplet transport is limited to low transport velocity or short transport distance. Here we report the high-velocity and ultralong transport of droplets elicited by surface charge density gradients printed on diverse substrates. We leverage the facile water droplet printing on superamphiphobic surfaces to create rewritable surface charge density gradients that stimulate droplet propulsion under ambient conditions17 and without the need for additional energy input. Our strategy provides a platform for programming the transport of droplets on flat, flexible and vertical surfaces that may be valuable for applications requiring a controlled movement of droplets17-19.
TL;DR: The combined action of WF tuning and interface engineering can lead to substantial performance improvements in MXene-modified perovskite solar cells, as shown by the 26% increase of power conversion efficiency and hysteresis reduction with respect to reference cells without MXene.
Abstract: To improve the efficiency of perovskite solar cells, careful device design and tailored interface engineering are needed to enhance optoelectronic properties and the charge extraction process at the selective electrodes. Here, we use two-dimensional transition metal carbides (MXene Ti3C2Tx) with various termination groups (Tx) to tune the work function (WF) of the perovskite absorber and the TiO2 electron transport layer (ETL), and to engineer the perovskite/ETL interface. Ultraviolet photoemission spectroscopy measurements and density functional theory calculations show that the addition of Ti3C2Tx to halide perovskite and TiO2 layers permits the tuning of the materials’ WFs without affecting other electronic properties. Moreover, the dipole induced by the Ti3C2Tx at the perovskite/ETL interface can be used to change the band alignment between these layers. The combined action of WF tuning and interface engineering can lead to substantial performance improvements in MXene-modified perovskite solar cells, as shown by the 26% increase of power conversion efficiency and hysteresis reduction with respect to reference cells without MXene. Addition of MXenes in the halide perovskite film, in the electron transport layer and at the interface between these layers is shown to enhance the efficiency of and reduce hysteresis in perovskite solar cells.
TL;DR: This Comment discusses relevant issues for industrial-scale graphene synthesis, one of the critical aspects for the future graphene industry.
Abstract: The past few years have witnessed significant development in graphene research, yet a number of challenges remain for its commercialization and industrialization. This Comment discusses relevant issues for industrial-scale graphene synthesis, one of the critical aspects for the future graphene industry.
TL;DR: A nonlinear anomalous Hall effect, allowed for certain point group symmetries, is observed in metallic WTe2, and can be understood as an AHE induced by the bias current, which generates an out-of-plane magnetization.
Abstract: The Hall effect occurs only in systems with broken time-reversal symmetry, such as materials under an external magnetic field in the ordinary Hall effect and magnetic materials in the anomalous Hall effect (AHE)1. Here we show a nonlinear AHE in a non-magnetic material under zero magnetic field, in which the Hall voltage depends quadratically on the longitudinal current2-6. We observe the effect in few-layer Td-WTe2, a two-dimensional semimetal with broken inversion symmetry and only one mirror line in the crystal plane. Our angle-resolved electrical measurements reveal that the Hall voltage maximizes (vanishes) when the bias current is perpendicular (parallel) to the mirror line. The observed effect can be understood as an AHE induced by the bias current, which generates an out-of-plane magnetization. The temperature dependence of the Hall conductivity further suggests that both the intrinsic Berry curvature dipole and extrinsic spin-dependent scatterings contribute to the observed nonlinear AHE.
TL;DR: Pressure tuning of magnetic order in the two-dimensional magnet CrI3 is demonstrated and pressure-induced changes in the magnetic order of bilayer and trilayer van der Waals crystals are revealed and attributed toChanges in the stacking arrangement.
Abstract: The physical properties of two-dimensional van der Waals crystals can be sensitive to interlayer coupling. For two-dimensional magnets1–3, theory suggests that interlayer exchange coupling is strongly dependent on layer separation while the stacking arrangement can even change the sign of the interlayer magnetic exchange, thus drastically modifying the ground state4–10. Here, we demonstrate pressure tuning of magnetic order in the two-dimensional magnet CrI3. We probe the magnetic states using tunnelling8,11–13 and scanning magnetic circular dichroism microscopy measurements2. We find that interlayer magnetic coupling can be more than doubled by hydrostatic pressure. In bilayer CrI3, pressure induces a transition from layered antiferromagnetic to ferromagnetic phase. In trilayer CrI3, pressure can create coexisting domains of three phases, one ferromagnetic and two antiferromagnetic. The observed changes in magnetic order can be explained by changes in the stacking arrangement. Such coupling between stacking order and magnetism provides ample opportunities for designer magnetic phases and functionalities. Pressure-induced changes in the magnetic order of bilayer and trilayer van der Waals crystals are revealed and attributed to changes in the stacking arrangement.
TL;DR: It is reported that resorcinol–formaldehyde resins, widely used inexpensive polymers, act as efficient semiconductor photocatalysts to provide a new basis for H2O2 generation and shows significant potential as a new artificial photosynthesis system.
Abstract: Artificial photosynthesis is a critical challenge in moving towards a sustainable energy future. Photocatalytic generation of hydrogen peroxide from water and dioxygen (H2O +
$$\frac{1}{2}$$
O2 → H2O2, ΔG° = 117 kJ mol–1) by sunlight is a promising strategy for artificial photosynthesis because H2O2 is a storable and transportable fuel that can be used directly for electricity generation. All previously reported powder photocatalysts, however, have suffered from low efficiency in H2O2 generation. Here we report that resorcinol–formaldehyde resins, widely used inexpensive polymers, act as efficient semiconductor photocatalysts to provide a new basis for H2O2 generation. Simple high-temperature hydrothermal synthesis (~523 K) produces low-bandgap resorcinol–formaldehyde resins comprising π-conjugated and π-stacked benzenoid–quinoid donor–acceptor resorcinol couples. The resins absorb broad-wavelength light up to 700 nm and catalyse water oxidation and O2 reduction by the photogenerated charges. Simulated sunlight irradiation of the resins stably generates H2O2 with more than 0.5% solar-to-chemical conversion efficiency. Therefore, this metal-free system shows significant potential as a new artificial photosynthesis system. Generation of hydrogen peroxide from water and dioxygen is promising for artificial photosynthesis but photocatalysts suffer from low efficiency. Resorcinol–formaldehyde resins exhibit stable H2O2 generation with more than 0.5% solar-to-chemical conversion efficiency.
TL;DR: The application of machine learning models in the design, synthesis and characterisation of molecules at different stages in the drug discovery and development process has considerable implications for developing future therapies and their targeting.
Abstract: A variety of machine learning methods such as naive Bayesian, support vector machines and more recently deep neural networks are demonstrating their utility for drug discovery and development. These leverage the generally bigger datasets created from high-throughput screening data and allow prediction of bioactivities for targets and molecular properties with increased levels of accuracy. We have only just begun to exploit the potential of these techniques but they may already be fundamentally changing the research process for identifying new molecules and/or repurposing old drugs. The integrated application of such machine learning models for end-to-end (E2E) application is broadly relevant and has considerable implications for developing future therapies and their targeting. This Perspective describes the application of machine learning models in the design, synthesis and characterisation of molecules at different stages in the drug discovery and development process.
TL;DR: A unified picture of anionic redox in A-rich-TMOs is designed here to identify the electronic origin of this irreversibility and to propose new directions to improve the cycling performance of the electrodes.
Abstract: Anionic redox in Li-rich and Na-rich transition metal oxides (A-rich-TMOs) has emerged as a new paradigm to increase the energy density of rechargeable batteries. Ever since, numerous electrodes delivering extra anionic capacity beyond the theoretical cationic capacity have been reported. Unfortunately, most often the anionic capacity achieved in charge is partly irreversible in discharge. A unified picture of anionic redox in A-rich-TMOs is designed here to identify the electronic origin of this irreversibility and to propose new directions to improve the cycling performance of the electrodes. The electron localization function is introduced as a holistic tool to unambiguously locate the oxygen lone pairs in the structure and follow their participation in the redox activity of A-rich-TMOs. The charge-transfer gap of transition metal oxides is proposed as the pertinent observable to quantify the amount of extra capacity achievable in charge and its reversibility in discharge, irrespective of the material chemical composition. From this generalized approach, we conclude that the reversibility of the anionic capacity is limited to a critical number of O holes per oxygen, hO ≤ 1/3.
TL;DR: 3D printing is now widely used in aerospace, healthcare, energy, automotive and other industries, and is the fastest growing sector, yet its development presents scientific, technological and economic challenges that must be understood and addressed.
Abstract: 3D printing is now widely used in aerospace, healthcare, energy, automotive and other industries. Metal printing, in particular, is the fastest growing sector, yet its development presents scientific, technological and economic challenges that must be understood and addressed.
TL;DR: A cellulosic membrane that relies on sub-nanoscale confinement of ions in oxidized and aligned cellulose molecular chains to enhance selective diffusion under a thermal gradient to demonstrate a flexible and biocompatible heat-to-electricity conversion device via nanoscale engineering based on sustainable materials that can enable large-scale manufacture.
Abstract: Converting low-grade heat into useful electricity requires a technology that is efficient and cost effective. Here, we demonstrate a cellulosic membrane that relies on sub-nanoscale confinement of ions in oxidized and aligned cellulose molecular chains to enhance selective diffusion under a thermal gradient. After infiltrating electrolyte into the cellulosic membrane and applying an axial temperature gradient, the ionic conductor exhibits a thermal gradient ratio (analogous to the Seebeck coefficient in thermoelectrics) of 24 mV K–1—more than twice the highest value reported until now. We attribute the enhanced thermally generated voltage to effective sodium ion insertion into the charged molecular chains of the cellulosic membrane, which consists of type II cellulose, while this process does not occur in natural wood or type I cellulose. With this material, we demonstrate a flexible and biocompatible heat-to-electricity conversion device via nanoscale engineering based on sustainable materials that can enable large-scale manufacture. Generating electricity by low-grade thermal harvesting requires a low-cost technology. Here, by chemically treating wood, aligned cellulose molecular chains form that confine sodium ions in the sub-nanometre channels and enhance selective diffusion, generating differential thermal voltage of 24 mV K–1.
TL;DR: It is proved that the Pockels effect remains strong even in nanoscale devices, and shown as a practical example data modulation up to 50 Gbit s−1.
Abstract: The electro-optical Pockels effect is an essential nonlinear effect used in many applications. The ultrafast modulation of the refractive index is, for example, crucial to optical modulators in photonic circuits. Silicon has emerged as a platform for integrating such compact circuits, but a strong Pockels effect is not available on silicon platforms. Here, we demonstrate a large electro-optical response in silicon photonic devices using barium titanate. We verify the Pockels effect to be the physical origin of the response, with r42 = 923 pm V−1, by confirming key signatures of the Pockels effect in ferroelectrics: the electro-optic response exhibits a crystalline anisotropy, remains strong at high frequencies, and shows hysteresis on changing the electric field. We prove that the Pockels effect remains strong even in nanoscale devices, and show as a practical example data modulation up to 50 Gbit s−1. We foresee that our work will enable novel device concepts with an application area largely extending beyond communication technologies. Electro-optic modulators based on epitaxial barium titanate (BTO) integrated on silicon exhibit speeds up to 50 Gbit s–1 while the Pockels coefficient of the BTO film is found to be approaching the bulk value.
TL;DR: Localize Pt clusters in one zeolite channel, preventing sintering and allowing highly stable and selective catalytic propane dehydrogenation, and could be extended to other crystalline porous materials.
Abstract: Subnanometric metal species (single atoms and clusters) have been demonstrated to be unique compared with their nanoparticulate counterparts. However, the poor stabilization of subnanometric metal species towards sintering at high temperature (>500 °C) under oxidative or reductive reaction conditions limits their catalytic application. Zeolites can serve as an ideal support to stabilize subnanometric metal catalysts, but it is challenging to localize subnanometric metal species on specific sites and modulate their reactivity. We have achieved a very high preference for localization of highly stable subnanometric Pt and PtSn clusters in the sinusoidal channels of purely siliceous MFI zeolite, as revealed by atomically resolved electron microscopy combining high-angle annular dark-field and integrated differential phase contrast imaging techniques. These catalysts show very high stability, selectivity and activity for the industrially important dehydrogenation of propane to form propylene. This stabilization strategy could be extended to other crystalline porous materials. Subnanometre Pt clusters show high catalytic activity, but can sinter and so reduce reactivity. Here, authors localize Pt clusters in one zeolite channel, preventing sintering and allowing highly stable and selective catalytic propane dehydrogenation.
TL;DR: To elucidate the structures of electric double layers at electrochemical interfaces, in situ Raman spectroscopy and ab initio molecular dynamics are combined and two structural transitions of interfacial water at electrified Au single-crystal electrode surfaces are identified.
Abstract: Solid/liquid interfaces are ubiquitous in nature and knowledge of their atomic-level structure is essential in elucidating many phenomena in chemistry, physics, materials science and Earth science1. In electrochemistry, in particular, the detailed structure of interfacial water, such as the orientation and hydrogen-bonding network in electric double layers under bias potentials, has a significant impact on the electrochemical performances of electrode materials2–4. To elucidate the structures of electric double layers at electrochemical interfaces, we combine in situ Raman spectroscopy and ab initio molecular dynamics and distinguish two structural transitions of interfacial water at electrified Au single-crystal electrode surfaces. Towards negative potentials, the interfacial water molecules evolve from structurally ‘parallel’ to ‘one-H-down’ and then to ‘two-H-down’. Concurrently, the number of hydrogen bonds in the interfacial water also undergoes two transitions. Our findings shed light on the fundamental understanding of electric double layers and electrochemical processes at the interfaces. Interfacial water structures in electric double layers under bias potentials can impact the electrochemical performance of electrodes. Two structural transitions of interfacial water at electrified Au single-crystal electrode surfaces have now been identified.