Unprecedented and highly stable lithium storage capacity of (001) faceted nanosheet-constructed hierarchically porous TiO2/rGO hybrid architecture for high-performance Li-ion batteries

Active crystal facets can generate special properties for various applications. Herein, we report a (001) faceted nanosheet-constructed hierarchically porous TiO₂/rGO hybrid architecture with unprecedented and highly stable lithium storage performance. Density functional theory calculations show that the (001) faceted TiO₂ nanosheets enable enhanced reaction kinetics by reinforcing their contact with the electrolyte and shortening the path length of Li⁺ diffusion and insertion-extraction. The reduced graphene oxide (rGO) nanosheets in this TiO₂/rGO hybrid largely improve charge transport, while the porous hierarchy at different length scales favors continuous electrolyte permeation and accommodates volume change. This hierarchically porous TiO₂/rGO hybrid anode material demonstrates an excellent reversible capacity of 250 mAh g^–1 at 1 C (1 C = 335 mA g^–1) at a voltage window of 1.0–3.0 V. Even after 1000 cycles at 5 C and 500 cycles at 10 C, the anode retains exceptional and stable capacities of 176 and 160 mAh g^–1, respectively. Moreover, the formed Li₂Ti₂O₄ nanodots facilitate reversed Li⁺ insertion-extraction during the cycling process. The above results indicate the best performance of TiO₂-based materials as anodes for lithium-ion batteries reported in the literature.     

Anisotropic alignments of hierarchical Li2SiO3/TiO2 @nano-C anode//LiMnPO4@nano-C cathode architectures for full-cell lithium-ion battery

We report on low-cost fabrication and high-energy density of full-cell lithium-ion battery (LIB) models. Super-hierarchical electrode architectures of Li₂SiO₃/TiO₂@nano-carbon anode (LSO.TO@nano-C) and high-voltage olivine LiMnPO₄@nano-carbon cathode (LMPO@nano-C) are designed for half- and full-system LIB-CR2032 coin cell models. On the basis of primary architecture-power-driven LIB geometrics, the structure keys including three-dimensional (3D) modeling superhierarchy, multiscale micro/nano architectures and anisotropic surface heterogeneity affect the buildup design of anode/cathode LIB electrodes. Such hierarchical electrode surface topologies enable continuous in-/out-flow rates and fast transport pathways of Li⁺-ions during charge/discharge cycles. The stacked layer configurations of pouch LIB-types lead to excellent charge/discharge rate, and energy density of 237.6 Wh kg⁻¹. As the most promising LIB-configurations, the high specific energy density of hierarchical pouch battery systems may improve energy storage for long-driving range of electric vehicles. Indeed, the anisotropic alignments of hierarchical electrode architectures in the large-scale LIBs provide proof of excellent capacity storage and outstanding durability and cyclability. The full-system LIB-CR2032 coin cell models maintain high specific capacity of ∼89.8% within a long-term life period of 2000 cycles, and average Coulombic efficiency of 99.8% at 1C rate for future configuration of LIB manufacturing and commercialization challenges.     

Precise fabrication of single-atom alloy co-catalyst with optimal charge state for enhanced photocatalysis

While the surface charge state of co-catalysts plays a critical role for boosting photocatalysis, studies on surface charge regulation via their precise structure control remain extremely rare. Herein, metal-organic framework (MOF) stabilized bimetallic Pd@Pt nanoparticles, which feature adjustable Pt coordination environment and a controlled structure from core-shell to single-atom alloy (SAA), have been fabricated. Significantly, apart from the formation of a Mott-Schottky junction in a conventional way, we elucidate that Pt surface charge regulation can be alternatively achieved by changing its coordination environment and the structure of the Pd@Pt co-catalyst, where the charge between Pd and Pt is redistributed. As a result, the optimized Pd₁₀@Pt₁/MOF composite, which involves an unprecedented SAA co-catalyst, exhibits exceptionally high photocatalytic hydrogen production activity, far surpassing its corresponding counterparts.     

Light-driven directional ion transport for enhanced osmotic energy harvesting

Light-driven ion (proton) transport is a crucial process both for photosynthesis of green plants and solar energy harvesting of some archaea. Here, we describe use of a TiO₂/C₃N₄ semiconductor heterojunction nanotube membrane to realize similar light-driven directional ion transport performance to that of biological systems. This heterojunction system can be fabricated by two simple deposition steps. Under unilateral illumination, the TiO₂/C₃N₄ heterojunction nanotube membrane can generate a photocurrent of about 9 μA/cm², corresponding to a pumping stream of ∼5500 ions per second per nanotube. By changing the position of TiO₂ and C₃N₄, a reverse equivalent ionic current can also be realized. Directional transport of photogenerated electrons and holes results in a transmembrane potential, which is the basis of the light-driven ion transport phenomenon. As a proof of concept, we also show that this system can be used for enhanced osmotic energy generation. The artificial light-driven ion transport system proposed here offers a further step forward on the roadmap for development of ionic photoelectric conversion and integration into other applications, for example water desalination.     

Efficient interlayer charge release for high-performance layered thermoelectrics

Many layered superlattice materials intrinsically possess large Seebeck coefficient and low lattice thermal conductivity, but poor electrical conductivity because of the interlayer transport barrier for charges, which has become a stumbling block for achieving high thermoelectric performance. Herein, taking BiCuSeO superlattice as an example, it is demonstrated that efficient interlayer charge release can increase carrier concentration, thereby activating multiple Fermi pockets through Bi/Cu dual vacancies and Pb codoping. Experimental results reveal that the extrinsic charges, which are introduced by Pb and initially trapped in the charge-reservoir [Bi₂O₂]²⁺ sublayers, are effectively released into [Cu₂Se₂]²⁻ sublayers via the channels bridged by Bi/Cu dual vacancies. This efficient interlayer charge release endows dual-vacancy- and Pb-codoped BiCuSeO with increased carrier concentration and electrical conductivity. Moreover, with increasing carrier concentration, the Fermi level is pushed down, activating multiple converged valence bands, which helps to maintain a relatively high Seebeck coefficient and yield an enhanced power factor. As a result, a high ZT value of ∼1.4 is achieved at 823 K in codoped Bi_0.90Pb_0.06Cu_0.96SeO, which is superior to that of pristine BiCuSeO and solely doped samples. The present findings provide prospective insights into the exploration of high-performance thermoelectric materials and the underlying transport physics.     

Microfluidic reactors for visible-light photocatalytic water purification assisted with thermolysis

Photocatalytic water purification using visible light is under intense research in the hope to use sunlight efficiently, but the conventional bulk reactors are slow and complicated. This paper presents an integrated microfluidic planar reactor for visible-light photocatalysis with the merits of fine flow control, short reaction time, small sample volume, and long photocatalyst durability. One additional feature is that it enables one to use both the light and the heat energy of the light source simultaneously. The reactor consists of a BiVO₄-coated glass as the substrate, a blank glass slide as the cover, and a UV-curable adhesive layer as the spacer and sealant. A blue light emitting diode panel (footprint 10 mm × 10 mm) is mounted on the microreactor to provide uniform irradiation over the whole reactor chamber, ensuring optimal utilization of the photons and easy adjustments of the light intensity and the reaction temperature. This microreactor may provide a versatile platform for studying the photocatalysis under combined conditions such as different temperatures, different light intensities, and different flow rates. Moreover, the microreactor demonstrates significant photodegradation with a reaction time of about 10 s, much shorter than typically a few hours using the bulk reactors, showing its potential as a rapid kit for characterization of photocatalyst performance.     

Protein sensing by nanofluidic crystal and its signal enhancement

Nanofluidics has a unique property that ionic conductance across a nanometer-sized confined space is strongly affected by the space surface charge density, which can be utilized to construct electrical read-out biosensor. Based on this principle, this work demonstrated a novel protein sensor along with a sandwich signal enhancement approach. Nanoparticles with designed aptamer onside are assembled in a suspended micropore to form a 3-dimensional network of nanometer-sized interstices, named as nanofluidic crystal hereafter, as the basic sensing unit. Proteins captured by aptamers will change the surface charge density of nanoparticles and thereby can be detected by monitoring the ionic conductance across this nanofluidic crystal. Another aptamer can further enlarge the variations of the surface charge density by forming a sandwich structure (capturing aptamer/protein/signal enhancement aptamer) and the read-out conductance as well. The preliminary experimental results indicated that human α-thrombin was successfully detected by the corresponding aptamer modified nanofluidic crystal with the limit of detection of 5 nM (0.18 μg/ml) and the read-out signal was enhanced up to 3 folds by using another thrombin aptamer. Being easy to graft probe, facile and low-cost to prepare the nano-device, and having an electrical read-out, the present nanofluidic crystal scheme is a promising and universal strategy for protein sensing.     

A highly efficient atomically thin curved PdIr bimetallene electrocatalyst

The multi-metallene with an ultrahigh surface area has great potential in precise tuning of surface heterogeneous d-electronic correlation by surface strain effect for the distinctive surface electronic structure, which is a brand new class of promising 2D electrocatalyst for sustainable energy device application. However, achieving such an atomically thin multi-metallene still presents a great challenge. Herein, we present a new synthetic method for an atomic-level palladium-iridium (PdIr) bimetallene with an average thickness of only ∼1.0 nm for achieving superior catalysis in the hydrogen evolution reaction (HER) and the formic acid oxidation reaction (FAOR). The curved PdIr bimetallene presents a top-ranked high electrochemical active area of 127.5 ± 10.8 m² g_Pd+Ir⁻¹ in the reported noble alloy materials, and exhibits a very low overpotential, ultrahigh activity and improved stability for HER and FAOR. DFT calculation reveals that the PdIr bimetallene herein has a unique lattice tangential strain, which can induce surface distortion while concurrently creating a variety of concave-convex featured micro-active regions formed by variously coordinated Pd sites agglomeration. Such a strong strain effect correlates the abnormal on-site active 4d¹⁰-t_2g-orbital Coulomb correlation potential and directly elevates orbital-electronegativity exposure within these active regions, resulting in a preeminent barrier-free energetic path for significant enhancement of FAOR and HER catalytic performance.     

Robust sulfonated poly (ether ether ketone) nanochannels for high-performance osmotic energy conversion

The membrane-based reverse electrodialysis (RED) technique has a fundamental role in harvesting clean and sustainable osmotic energy existing in the salinity gradient. However, the current designs of membranes cannot cope with the high output power density and robustness. Here, we construct a sulfonated poly (ether ether ketone) (SPEEK) nanochannel membrane with numerous nanochannels for a membrane-based osmotic power generator. The parallel nanochannels with high space charges show excellent cation-selectivity, which could further be improved by adjusting the length and charge density of nanochannels. Based on numerical simulation, the system with space charge shows better conductivity and selectivity than those of a surface-charged nanochannel. The output power density of our proposed membrane-based device reaches up to 5.8 W/m² by mixing artificial seawater and river water. Additionally, the SPEEK membranes exhibit good mechanical properties, endowing the possibility of creating a high-endurance scale-up membrane-based generator system. We believe that this work provides useful insights into material design and fluid transport for the power generator in osmotic energy conversion.     

Anthropogenic monoterpenes aggravating ozone pollution

Monoterpenes have been known to have a critical influence on air quality and climate change through their impact on the formation of fine particles. Here we present field evidence that monoterpene oxidations largely enhanced local ozone production in a regional site in eastern China. The observed monoterpene was most likely from biomass burning rather than biogenic emissions, as indicated by the high correlation with CO at night-time, and the observed ratio of these two species was consistent with previously determined values from biomass burning experiments. Fast monoterpene oxidations were determined experimentally based on direct radical measurements, leading to a daily ozone enhancement of 4–18 parts per billion by volume (ppb), which was 6%–16% of the total ozone production, depending on the speciation of monoterpenes. It demonstrates that the previously overlooked anthropogenic monoterpenes make an important contribution to O₃ production in eastern China. The role could possibly be important at similar locations across China and other parts of the world that are characterized by massive emissions, especially where there are high NO_x levels. Our results highlight that anthropogenic monoterpenes should be taken into account when proceeding with the coordinated mitigation of O₃ and particulate matter pollution.     

Recent advances in the synthesis of hierarchically mesoporous TiO2 materials for energy and environmental applications

Because of their low cost, natural abundance, environmental benignity, plentiful polymorphs, good chemical stability and excellent optical properties, TiO₂ materials are of great importance in the areas of physics, chemistry and material science. Much effort has been devoted to the synthesis of TiO₂ nanomaterials for various applications. Among them, mesoporous TiO₂ materials, especially with hierarchically porous structures, show great potential owing to their extraordinarily high surface areas, large pore volumes, tunable pore structures and morphologies, and nanoscale effects. This review aims to provide an overview of the synthesis and applications of hierarchically mesoporous TiO₂ materials. In the first section, the general synthetic strategies for hierarchically mesoporous TiO₂ materials are reviewed. After that, we summarize the architectures of hierarchically mesoporous TiO₂ materials, including nanofibers, nanosheets, microparticles, films, spheres, core-shell and multi-level structures. At the same time, the corresponding mechanisms and the key factors for the controllable synthesis are highlighted. Following this, the applications of hierarchically mesoporous TiO₂ materials in terms of energy storage and environmental protection, including photocatalytic degradation of pollutants, photocatalytic fuel generation, photoelectrochemical water splitting, catalyst support, lithium-ion batteries and sodium-ion batteries, are discussed. Finally, we outline the challenges and future directions of research and development in this area.     

Repulsion-based model for contact angle saturation in electrowetting

We introduce a new model for contact angle saturation phenomenon in electrowetting on dielectric systems. This new model attributes contact angle saturation to repulsion between trapped charges on the cap and base surfaces of the droplet in the vicinity of the three-phase contact line, which prevents these surfaces from converging during contact angle reduction. This repulsion-based saturation is similar to repulsion between charges accumulated on the surfaces of conducting droplets which causes the well known Coulombic fission and Taylor cone formation phenomena. In our model, both the droplet and dielectric coating were treated as lossy dielectric media (i.e., having finite electrical conductivities and permittivities) contrary to the more common assumption of a perfectly conducting droplet and perfectly insulating dielectric. We used theoretical analysis and numerical simulations to find actual charge distribution on droplet surface, calculate repulsion energy, and minimize energy of the total system as a function of droplet contact angle. Resulting saturation curves were in good agreement with previously reported experimental results. We used this proposed model to predict effect of changing liquid properties, such as electrical conductivity, and system parameters, such as thickness of the dielectric layer, on the saturation angle, which also matched experimental results.     

Erosion in vent plugs,the effect of vent diameter

Erosion in vent plugs is studied in a 37 mm. Gun which has been cut off at the end of the chamber. Plugs with vent diameters from 0.04 to 0.63 inches and vent lengths from one to four inches are held in the position normally occupied by the projectile. The weight losses due to erosion are in fair agreement with values calculated from heat transfer theory, assuming melting of the surface, for charges of propellant powder above a minimum value. The weight loss due to melting increases as the weight of charge, the web thickness, the length of the vent, and the gas temperature are increased, and decreases as the vent diameter and the melting point of the metal are increased. The minimum charge to produce melting increases rapidly with increases in vent diameter, but the maximum pressure corresponding to this charge increases only slightly. For charges below this minimum, the erosion is shown to be of a chemical nature by the significant decrease due to the elimination of sulphur from the black powder primer.     

Reductive surface synthesis of gold nanoparticles on silicate glass and their biochemical sensor applications

Gold nanoparticles (Au NPs) were directly synthesized on the surface of polyvinylsilazane (PVSZ, -[(vinyl)SiH-NH₂]-) without use of extra reductive additives. The reductive Si-H functional groups on the surface of cured PVSZ acted as surface bound reducing agents to form gold metal when contacted with an aqueous Au precursor (HAuCl₄) solution, leading to formation of Au NPs adhered to silicate glass surface. The Au NPs-silicate platforms were preliminarily tested to detect Rhodamine B (1 μM) by surface enhanced Raman scattering. Furthermore, gold microelectrode obtained by post-chemical plating was used as an integrated amperometric detection element in the polydimethylsilane-glass hybrid microfluidic chip.     

Integration of bio-inspired lanthanide-transition metal cluster and P-doped carbon nitride for efficient photocatalytic overall water splitting

Photosynthesis in nature uses the Mn₄CaO₅ cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo₃ (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn₄O₅ cluster. Anchoring LnCo₃ on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo₃/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo₃ for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O−O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting.     

Integrating plasmonic diagnostics and microfluidics

Plasmonics is generally divided into two categories: surface plasmon resonance (SPR) of electromagnetic modes propagating along a (noble) metal/dielectric interface and localized SPRs (LSPRs) on nanoscopic metallic structures (particles, rods, shells, holes, etc.). Both optical transducer concepts can be combined with and integrated in microfluidic devices for biomolecular analyte detections, with the benefits of small foot-print for point-of-care detection, low-cost for one-time disposal, and ease of being integrated into an array format. The key technologies in such integration include the plasmonic chip, microfluidic channel fabrication, surface bio-functionalization, and selection of the detection scheme, which are selected according to the specifics of the targeting analytes. This paper demonstrates a few examples of the many versions of how to combine plasmonics and integrated microfluidics, using different plasmonic generation mechanisms for different analyte detections. One example is a DNA sensor array using a gold film as substrate and surface plasmon fluorescence spectroscopy and microscopy as the transduction method. This is then compared to grating-coupled SPR for poly(ethylene glycol) thiol interaction detected by angle interrogation, gold nanohole based LSPR chip for biotin-strepavidin detection by wavelength shift, and gold nanoholes/nanopillars for the detection of prostate specific antigen by quantum dot labels excited by the LSPR. Our experimental results exemplified that the plasmonic integrated microfluidics is a promising tool for understanding the biomolecular interactions and molecular recognition process as well as biosensing, especially for on-site or point-of-care diagnostics.     

Achieving ultrahigh electrochemical performance by surface design and nanoconfined water manipulation

The effects of nanoconfined water and the charge storage mechanism are crucial to achieving the ultrahigh electrochemical performance of two-dimensional transition metal carbides (MXenes). We propose a facile method to manipulate nanoconfined water through surface chemistry modification. By introducing oxygen and nitrogen surface groups, more active sites were created for Ti₃C₂ MXene, and the interlayer spacing was significantly increased by accommodating three-layer nanoconfined water. Exceptionally high capacitance of 550 F g^–1 (2000 F cm^–3) was obtained with outstanding high-rate performance. The atomic scale elucidation of the layer-dependent properties of nanoconfined water and pseudocapacitive charge storage was deeply probed through a combination of ‘computational and experimental microscopy’. We believe that an understanding of, and a manipulation strategy for, nanoconfined water will shed light on ways to improve the electrochemical performance of MXene and other two-dimensional materials.     

A Cross-National Study of Computer News Sites: Global News, Local Sites

The Internet is not only an object of and a tool for study; it is also both simultaneously global and local. In order to address how global and how local it is, this study compares the news content of 1 week from four different computer news web sites in four different countries (using four different languages). These sites use the same code base and all strive to be the same in terms of computer culture. They are global in their reach and in the news they cover, yet they are all local in terms of language and geography. They are ideal locales to study how forces of the global and the local play out on the highly connected Internet, using Google language tools for translation. Findings were surprising in that they showed very little in terms of a pattern of any sort. This is similar to a 1953 UNESCO study of newspapers, but strange in that given the passing of 50 years and the connectedness of the Internet, greater overlap was expected. Link destinations for stories that were on more than one site were also examined, and the Japanese site had more in common with the American site while the two European sites were more alike in this lens. This is also surprising, given that an East/West split was expected. Little work in this specific area was found, and this study highlights some of the questions and methodological difficulties that need to be addressed.     

A Cross-National Study of Computer News Sites: Global News,Local Sites

The Internet is not only an object of and a tool for study; it is also both simultaneously global and local. In order to address how global and how local it is, this study compares the news content of 1 week from four different computer news web sites in four different countries (using four different languages). These sites use the same code base and all strive to be the same in terms of computer culture. They are global in their reach and in the news they cover, yet they are all local in terms of language and geography. They are ideal locales to study how forces of the global and the local play out on the highly connected Internet, using Google language tools for translation. Findings were surprising in that they showed very little in terms of a pattern of any sort. This is similar to a 1953 UNESCO study of newspapers, but strange in that given the passing of 50 years and the connectedness of the Internet, greater overlap was expected. Link destinations for stories that were on more than one site were also examined, and the Japanese site had more in common with the American site while the two European sites were more alike in this lens. This is also surprising, given that an East/West split was expected. Little work in this specific area was found, and this study highlights some of the questions and methodological difficulties that need to be addressed.     

Free space propagation measurements at 75 megacycles

In alkaline fixing baths with a low concentration of thiosulfate, the course of the fixing reaction before development was found to be different at different heights of a film strip in the vertical position. A probable explanation was proposed, and the phenomenon was used to extend, for post-fixation development, the density curve to lower exposures.In an acid Elon bath the reduction of silver on the latent image competes with its reduction elsewhere more favorably at lower temperatures than at higher temperatures. The presence of oxidation products retards the first reaction in favor of the second.