Composite non-noble system with bridging oxygen for catalyzing Tafel-type alkaline hydrogen evolution.

Using hydrogen as a fuel is an effective way to combat energy crisis and at the same time reduce greenhouse gas emission. Alkaline hydrogen evolution reaction (HER) is one important way to obtain green hydrogen, which however is energy intensive and is difficult to obtain high efficiencies even when using state-of-the-art noble metal catalysts. Here, we report a three-component catalytic system using only non-noble elements, consisting of cobalt oxide clusters and single molybdenum atoms supported on oxyanion-terminated two-dimensional MXene, which enabled the unusual generation of hydrogen by a kinetically fast Volmer-Tafel process in an alkaline electrolyte. The key feature of this catalyst is that the three components are connected by bridging oxygen, which serves to immediately adsorb H* produced during water dissociation on cobalt oxide and relay it to the molybdenum single-atom catalyst. On the Mo atom, due to this unique coordination environment, the relayed H* intermediates directly combine and desorb, realizing H2 generation through an unusual Tafel pathway. The presence of bridging oxygen increases the acidity of the catalyst as Brønsted acid with the reversible adsorption and donation of a proton, thus eliminating the need for acid addition and ensuring excellent and sustainable alkaline HER performance. The performance of our catalyst is comparable to that of the commercial noble metal catalyst PtRu/C. Our work makes a significant contribution to designing efficient non-noble catalysts for alkaline HER electrocatalysis.

Genuine divalent magnesium-ion storage and fast diffusion kinetics in metal oxides at room temperature.

Rechargeable magnesium batteries represent a viable alternative to lithium-ion technology that can potentially overcome its safety, cost, and energy density limitations. Nevertheless, the development of a competitive room temperature magnesium battery has been hindered by the sluggish dissociation of electrolyte complexes and the low mobility of Mg2+ ions in solids, especially in metal oxides that are generally used in lithium-ion batteries. Herein, we introduce a generic proton-assisted method for the dissociation of the strong Mg-Cl bond to enable genuine Mg2+ intercalation into an oxide host lattice; meanwhile, the anisotropic Smoluchowski effect produced by titanium oxide lattices results in unusually fast Mg2+ diffusion kinetics along the atomic trough direction with a record high ion conductivity of 1.8 × 10-4 S ⋅ cm-1 on the same order as polymer electrolyte. The realization of genuine Mg2+ storage and fast diffusion kinetics enabled a rare high-power Mg-intercalation battery with inorganic oxides. The success of this work provides important information on engineering surface and interlayer chemistries of layered materials to tackle the sluggish intercalation kinetics of multivalent ions.

Engineering Structural Janus MXene-nanofibrils Aerogels for Season-Adaptive Radiative Thermal Regulation.

Aerogels have provided a significant platform for passive radiation-enabled thermal regulation, arousing extensive interest due to their capabilities of radiative cooling or heating. However, there still remains challenge of developing functionally integrated aerogels for sustainable thermal regulation in both hot and cold environment. Here, Janus structured MXene-nanofibrils aerogel (JMNA) is rationally designed via a facile and efficient way. The achieved aerogel presents the characteristic of high porosity (≈98.2%), good mechanical strength (tensile stress of ≈2 MPa, compressive stress of ≈115 kPa), and macroscopic shaping property. Based on the asymmetric structure, the JMNA with switchable functional layers can alternatively enable passive radiative heating and cooling in winter and summer, respectively. As a proof of concept, JMNA can function as a switchable thermal-regulated roof to effectively enable the inner house model to maintain >25 °C in winter and <30 °C in hot summer. This design of Janus structured aerogels with compatible and expandable capabilities is promising to widely benefit the low-energy thermal regulation in changeable climate.

Two-Dimensional Molecular Sheets of Transition Metal Oxides toward Wearable Energy Storage.

Flexible and wearable electronics have recently sparked intense interest in both academia and industry because they can greatly revolutionize human lives by impacting every aspect of our daily routine. Therefore, developing compatible energy storage devices has become one of the most important research frontiers in this field. Particularly, the development of flexible electrodes is of great significance when considering their essential role in the performance of these devices. Although there is no doubt that transition metal oxide nanomaterials are suitable for providing electrochemical energy storage, individual oxides generally cannot be developed into freestanding electrodes because of their intrinsically low mechanical strength.Two-dimensional sheets with genuine unilamellar thickness are perfect units for the assembly of freestanding and mechanically flexible devices, as they have the advantages of low thickness and good flexibility. Therefore, the development of metal oxide materials into a two-dimensional sheet morphology analogous to graphene is expected to solve the above-mentioned problems. In this Account, we summarize the recent progress on two-dimensional molecular sheets of transition metal oxides for wearable energy storage applications. We start with our understanding of the principle of producing two-dimensional metal oxides from their bulk-layered counterparts. The unique layered structure of the precursors inspired the exploration of their interlayer chemistry, which helps us to understand the processes of swelling and delamination. Rational methods for tuning the chemical composition, size/thickness, and surface chemistry of the obtained nanosheets and how physicochemical properties of the nanosheets can be modulated are then briefly introduced. Subsequently, the orientational alignment of the anisotropic sheets and the origins of their liquid-crystalline characteristics are discussed, which are of vital importance for their subsequent macroscopic assembly. Finally, macroscopic electrodes with geometric diversity ranging from one-dimensional macroscopic fibers to two-dimensional films/papers and three-dimensional monolithic foams are summarized. The intrinsically low mechanical stiffness of metal oxide sheets can be effectively overcome by wisely designing the assembly mode and sheet interfaces to obtain decent mechanical properties integrated with superior electrochemical performance, thereby providing critical advantages for the fabrication of wearable energy storage devices.We expect that this Account will stimulate further efforts toward fundamental research on interface engineering in metal oxide sheet assembly and facilitate wide applications of their designed assemblies in future new-concept energy conversion devices and beyond. In the foreseeable future, we believe that there will be a big explosion in the application of transition metal oxide sheets in flexible electronics.

Molecularly Thin Nitride Sheets Stabilized by Titanium Carbide as Efficient Bifunctional Electrocatalysts for Fiber-Shaped Rechargeable Zinc-Air Batteries.

With the ever-increasing growth in next-generation flexible and wearable electronics, fiber-shaped zinc-air batteries have attracted considerable attention due to their advantages of high energy density and low cost, though their development, however, has been seriously hampered by the unavailability of efficient electrocatalysts. In this work, we designed a trimetallic nitride electrocatalyst in an unusual molecular sheet form, which was stabilized by metallic titanium carbide sheets. Besides the expected elevation in catalytic activity toward the oxygen evolution reaction, the material simultaneously unlocked excellent catalytic activity for oxygen reduction reaction with the half-wave potential as small as 0.84 V. A flexible fiber-shaped zinc-air battery, employing the designed electrocatalyst as the air cathode and a gel as the electrolyte, demonstrated an enhanced and durable electrochemical performance, outputting a competitive energy density of 627 Wh kgzn-1. This work opens new avenues for utilizing two-dimensional sheets in future wearable and portable device applications.

Managing Locally Excited and Charge-Transfer Triplet States to Facilitate Up-Conversion in Red TADF Emitters That Are Available for Both Vacuum- and Solution-Processes.

Developing red thermally activated delayed fluorescence (TADF) emitters for high-performance OLEDs is still facing great challenge. Herein, three red TADF emitters, pDBBPZ-DPXZ, pDTBPZ-DPXZ, and oDTBPZ-DPXZ, are designed and synthesized with same donor-acceptor (D-A) backbone with different peripheral groups attaching on the A moieties. Their lowest triplet states change from locally excited to charge transfer character leading to significantly enhance reverse intersystem crossing process. In particular, oDTBPZ-DPXZ exhibits efficient TADF feature and exciton utilization. It not only achieves an external quantum efficiency (EQE) of 20.1 % in red vacuum-processed OLED, but also realize a high EQE of 18.5 % in a solution-processed OLED, which is among the best results in solution-processed red TADF OLEDs. This work provides an effective strategy for designing red TADF molecules by managing energy level alignments to facilitate the up-conversion process and thus enhance exciton harvesting.

A Dopant Replacement-Driven Molten Salt Method toward the Synthesis of Sub-5-nm-Sized Ultrathin Nanowires.

The high-temperature molten-salt method is an important inorganic synthetic route to a wide variety of morphological phenotypes. However, its utility is limited by the fact that it is typically incapable of producing ultrathin (<5 nm diameter) nanowires, which have a crucial role in novel nanotechnology applications. Herein, a rapid molten salt-based synthesis of sub-5-nm-sized nanowires of hexagonal tungsten oxide (h-WO3 ) that is critically dependent on a substantial proportion of molybdenum (Mo) dopant is described. This dopant-driven morphological transition in tungsten oxide (WO3 ) may be attributable to the collapse of layered structure, followed by nanocluster aggregation, coalescence, and recrystallization to form ultrathin nanowires. Interestingly, due to the structural properties of h-WO3 , the thus-formed ultrathin nanowires are demonstrated to be excellent photocatalysts for the production of ammonia (NH3 ) from nitrogen (N2 ) and water. The ultrathin nanowires exhibit a high photocatalytic NH3 -production activity with a rate of 370 µmol g-1 h-1 and an apparent quantum efficiency of 0.84% at 420 nm, which is more than twice that obtained from the best-performing Mo-doped W18 O49 nanowire catalysts. It is envisaged that the dopant replacement-driven synthetic protocol will allow for rapid access to a series of ultrathin nanostructures with intriguing properties and increase potential applications.

Ti3C2 Sheets with an Adjustable Surface and Feature Sizes to Regulate the Chemical Stability.

Tuning the feature sizes and surface moiety groups of a two-dimensional (2D) sheet material has been regarded as the most effective strategy for achieving desired physical and chemical properties. The newly emerging transition-metal carbide or nitride sheets, generally referred to as MXenes, are of interest to the research community owing to their versatile behavior. While the chemical stability of MXenes is of pivotal importance to their real applications, a systematic study of examining the effect of their surface and lateral size on the resulting chemical stability is still lacking. Herein, by systematically varying the synthesis parameters, we obtained both regular and ultrasmall Ti3C2 sheets with different surfaces, namely, Al oxyanions or OH/F. To investigate the chemical stability and sustainability of each Ti3C2 sheet in an oxidizing environment, including an ambient atmosphere and a H2O2 medium, the evolution of phase, morphology, and optical behavior was carefully studied. The sheets covered with Al oxyanions had greater structural stability than those covered with the other species considered in this study, which may be due to the Al oxyanions acting like a shield and passivating the surface in the oxidizing atmosphere. Regarding the effect of feature size, thinner sheets or those with smaller lateral dimensions showed improved oxidation resistance, which could be due to the difficulty encountered in the structural recrystallization from Ti3C2 to oxidized product TiO2. This study provides a deeper understanding of MXenes and a method to efficiently engineer structures with desired performances.

Size-Independent Fast Ion Intercalation in Two-Dimensional Titania Nanosheets for Alkali-Metal-Ion Batteries.

Compared to lithium ions, the fast redox intercalation of large-radius sodium or potassium ions into a solid lattice in non-aqueous electrolytes is an elusive goal. Herein, by regulating the interlayer structure of stacked titania sheets through weakened layer-to-layer interactions and a robustly pillared gallery space, the two-dimensional channel between neighboring sheets was completely open to guest intercalation, allowing fast intercalation that was practically irrespective of the carrier-ion sizes. Regardless of employing regular Li or large-radius Na and K ions, the material manifested zero strain-like behavior with no significant change in both host structure and interlayer space, enabling comparable capacities for all tested ions along with excellent rate behaviors and extraordinarily long lifetimes, even with 80-µm-thick electrodes. The result highlights the importance of interlayer structural features for unlocking the electrochemical activity of a layered material.

Red/Near-Infrared Thermally Activated Delayed Fluorescence OLEDs with Near 100 % Internal Quantum Efficiency.

Developing red thermally activated delayed fluorescence (TADF) emitters, attainable for both high-efficient red organic light-emitting diodes (OLEDs) and non-doped deep red/near-infrared (NIR) OLEDs, is challenging. Now, two red emitters, BPPZ-PXZ and mDPBPZ-PXZ, with twisted donor-acceptor structures were designed and synthesized to study molecular design strategies of high-efficiency red TADF emitters. BPPZ-PXZ employs the strictest molecular restrictions to suppress energy loss and realizes red emission with a photoluminescence quantum yield (ΦPL ) of 100±0.8 % and external quantum efficiency (EQE) of 25.2 % in a doped OLED. Its non-doped OLED has an EQE of 2.5 % owing to unavoidable intermolecular π-π interactions. mDPBPZ-PXZ releases two pyridine substituents from its fused acceptor moiety. Although mDPBPZ-PXZ realizes a lower EQE of 21.7 % in the doped OLED, its non-doped device shows a superior EQE of 5.2 % with a deep red/NIR emission at peak of 680 nm.

Flexible Lithium-Ion Fiber Battery by the Regular Stacking of Two-Dimensional Titanium Oxide Nanosheets Hybridized with Reduced Graphene Oxide.

Increasing interest has recently been devoted to developing small, rapid, and portable electronic devices; thus, it is becoming critically important to provide matching light and flexible energy-storage systems to power them. To this end, compared with the inevitable drawbacks of being bulky, heavy, and rigid for traditional planar sandwiched structures, linear fiber-shaped lithium-ion batteries (LIB) have become increasingly important owing to their combined superiorities of miniaturization, adaptability, and weavability, the progress of which being heavily dependent on the development of new fiber-shaped electrodes. Here, we report a novel fiber battery electrode based on the most widely used LIB material, titanium oxide, which is processed into two-dimensional nanosheets and assembled into a macroscopic fiber by a scalable wet-spinning process. The titania sheets are regularly stacked and conformally hybridized in situ with reduced graphene oxide (rGO), thereby serving as efficient current collectors, which endows the novel fiber electrode with excellent integrated mechanical properties combined with superior battery performances in terms of linear densities, rate capabilities, and cyclic behaviors. The present study clearly demonstrates a new material-design paradigm toward novel fiber electrodes by assembling metal oxide nanosheets into an ordered macroscopic structure, which would represent the most-promising solution to advanced flexible energy-storage systems.

Rapid Synthesis of Sub-5 nm Sized Cubic Boron Nitride Nanocrystals with High-Piezoelectric Behavior via Electrochemical Shock.

A key challenge in current superhard materials research is the design of novel superhard nanocrystals (NCs) whereby new and unexpected properties may be predicted. Cubic boron nitride (c-BN) is a superhard material which ranks next to diamond; however, downsizing c-BN material below the 10 nm scale is rather challenging, and the interesting new properties of c-BN NCs remain unexplored and wide open. Herein we report an electrochemical shock method to prepare uniform c-BN NCs with a lateral size of only 3.4 ± 0.6 nm and a thickness of only 0.74 ± 0.3 nm at ambient temperature and pressure. The fabrication process is simple and fast, with c-BN NCs produced in just a few minutes. Most interestingly, the NCs exhibit excellent piezoelectric performance with a large recordable piezoelectric coefficient of 25.7 pC/N, which is almost 6 times larger than that from bulk c-BN and even competitive to conventional piezoelectric materials. The phenomenon of enhancement in the piezoelectric properties of BN NCs might arise from the nanoscale surface effect and nanoscale shape effect of BN NCs. This work paves an interesting route for exploring new properties of superhard NCs.

Trace H2 O2 -Assisted High-Capacity Tungsten Oxide Electrochromic Batteries with Ultrafast Charging in Seconds.

A recent technological trend in the field of electrochemical energy storage is to integrate energy storage and electrochromism functions in one smart device, which can establish efficient user-device interactions based on a friendly human-readable output. This type of newly born energy storage technology has drawn tremendous attention. However, there is still plenty of room for technological and material innovation, which would allow advancement of the research field. A prototype Al-tungsten oxide electrochromic battery with interactive color-changing behavior is reported. With the assistance of trace amount of H2 O2 , the battery exhibits a specific capacity almost seven times that for the reported electrochromic batteries, up to 429 mAh g(-1) . Fast decoloration of the reduced tungsten oxide affords a very quick charging time of only eight seconds, which possibly comes from an intricate combination of structure and valence state changes of tungsten oxide. This unique combination of features may further advance the development of smart energy storage devices with suitability for user-device interactions.

Organic-Base-Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance.

The delamination of titanium carbide sheets, an intriguing class of two-dimensional materials, has been critically dependent on the extraction of interlayer Al in acidic media, such as concentrated hydrofluoric acid (HF) or a mixture of hydrochloric acid (HCl) and a fluoride salt. Herein, we report an organic-base-driven intercalation and delamination of titanium carbide that takes advantage of the amphoteric nature of interlayer Al. The resulting aluminum-oxoanion-functionalized titanium carbide sheets manifested unusually strong optical absorption in the near-infrared (NIR) region with a mass extinction coefficient as high as 29.1 L g-1 cm-1 at 808 nm. Thus, the performance of this material is comparable or even superior to that of state-of-the-art photoabsorption materials, including gold-based nanostructures, carbon-based materials, and transition-metal dichalcogenides. Preliminary studies show that the titanium carbide sheets serve as efficient photothermal agents against tumor cells.

Macroscopic and Strong Ribbons of Functionality-Rich Metal Oxides from Highly Ordered Assembly of Unilamellar Sheets.

The strong interest in macroscopic graphene and/or carbon nanotube (CNT) fiber has highlighted that anisotropic nanostructured materials are ideal components for fabricating fiber assemblies. Prospectively, employing two-dimensional (2D) crystals or nanosheets of functionality-rich transition metal oxides would notably enrich the general knowledge for desirable fiber constructions and more importantly would greatly broaden the scope of functionalities. However, the fibers obtained up to now have been limited to carbon-related materials, while those made of 2D crystals of metal oxides have not been achieved, probably due to the intrinsically low mechanical stiffness of a molecular sheet of metal oxides, which is only few hundredths of that for graphene. Here, using 2D titania sheets as an illustrating example, we present the first successful fabrication of macroscopic fiber of metal oxides composed of highly aligned stacking sheets with enhanced sheet-to-sheet binding interactions. Regardless of the intrinsically weak Ti-O bond in molecular titania sheets, the optimal fiber manifested mechanical performance comparable to that documented for graphene or CNTs. This work provided important hints for devising optimized architecture in macroscopic assemblies, and the rich functionalities of titania promises fibers with limitless promise for a wealth of innovative applications.

Facile synthesis of α-Fe2O3 nanodisk with superior photocatalytic performance and mechanism insight.

Intrinsic short hole diffusion length is a well-known problem for α-Fe2O3 as a visible-light photocatalytic material. In this paper, a nanodisk morphology was designed to remarkably enhance separation of electron-hole pairs of α-Fe2O3. As expected, α-Fe2O3 nanodisks presented superior photocatalytic activity toward methylene blue degradation: more than 90% of the dye could be photodegraded within 30 min in comparison with a degradation efficiency of 50% for conventional Fe2O3 powder. The unique multilayer structure is thought to play a key role in the remarkably improved photocatalytic performance. Further experiments involving mechanism investigations revealed that instead of high surface area, ·OH plays a crucial role in methylene blue degradation and that O·2- may also contribute effectively to the degradation process. This paper demonstrates a facile and energy-saving route to fabricating homogenous α-Fe2O3 nanodisks with superior photocatalytic activity that is suitable for the treatment of contaminated water and that meets the requirement of mass production.

Synergy of W18O49 and polyaniline for smart supercapacitor electrode integrated with energy level indicating functionality.

Supercapacitors are important energy storage technologies in fields such as fuel-efficient transport and renewable energy. State-of-the-art supercapacitors are capable of supplanting conventional batteries in real applications, and supercapacitors with novel features and functionalities have been sought for years. Herein, we report the realization of a new concept, a smart supercapacitor, which functions as a normal supercapacitor in energy storage and also communicates the level of stored energy through multiple-stage pattern indications integrated into the device. The metal-oxide W18O49 and polyaniline constitute the pattern and background, respectively. Both materials possess excellent electrochemical and electrochromic behaviors and operate in different potential windows, -0.5-0 V (W18O49) and 0-0.8 V (polyaniline). The intricate cooperation of the two materials enables the supercapacitor to work in a widened, 1.3 V window while displaying variations in color schemes depending on the level of energy storage. We believe that our success in integrating this new functionality into a supercapacitor may open the door to significant opportunities in the development of future supercapacitors with imaginative and humanization features.

Gigantic swelling of inorganic layered materials: a bridge to molecularly thin two-dimensional nanosheets.

Platy microcrystals of a typical layered material, protonated titanate, have been shown to undergo an enormous degree of swelling in aqueous solutions of various amines, including tertiary amines, quaternary ammonium hydroxides, and primary amines. Introducing these solutions expanded the crystal gallery height by up to ~100-fold. Through systematic analysis, we determined that ammonium ion intercalation is predominantly affected by the acid-base equilibrium and that the degree of swelling or inflow of H2O is controlled by the osmotic pressure balance between the gallery and the solution environment, both of which are relatively independent of electrolyte identity but substantially dependent on molarity. In solutions of tertiary amines and quaternary ammonium hydroxides, the uptake of ammonium ions increases nearly linearly with increasing external concentration before reaching a saturation plateau, i.e., ~40% relative to the cation-exchange capacity of the crystals used. The only exception is tetrabutylammonium ions, which yield a lower saturation value, ~30%, owing to steric effects. The swelling behaviors in some primary amine solutions differ as a result of the effect of attractive forces between amine solute molecules on the solution osmotic pressure. Although the swelling is essentially colligative in nature, the stability of the resultant swollen structure is heavily dependent on the chemical nature of the guest ions. Intercalated ions of higher polarity and smaller size help stabilize the swollen structure, whereas ions of lower polarity and larger size lead readily to exfoliation. The insight gained from this study sheds new light on both the incorporation of guest molecules into a gallery of layered structures in general and the exfoliation of materials into elementary single-layer nanosheets.

Optical-Cavity-Incorporated Colorful All-Solid-State Electrochromic Devices for Dual Anti-Counterfeiting.

The fusion of electrochromic technology with optical resonant cavities presents an intriguing innovation in the electrochromic field. However, this fusion is mainly achieved in liquid electrolyte-based or sol-gel electrolyte-based electrochromic devices, but not in all-solid-state electrochromic devices, which have broader industrial applications. Here, a new all-solid-state electrochromic device is demonstrated with a metal-dielectric-metal (MDM) resonant cavity, which can achieve strong thin-film interference effects through resonance, enabling the device to achieve unique structural colors that have rarely appeared in reported all-solid-state electrochromic devices, such as yellow green, purple, and light red. The color gamut of the device can be further expanded due to the adjustable optical constants of the electrochromic layer. What is more, this device exhibits remarkable cycling stability (maintaining 84% modulation capability after 7200 cycles), rapid switching time (coloration in 2.6 s and bleaching in 2.8 s), and excellent optical memory effect (only increasing by 13.8% after almost 36 000 s). In addition, this exquisite structural design has dual-responsive anti-counterfeiting effects based on voltage and angle, further demonstrating the powerful color modulation capability of this device.

Covalently bridging graphene edges for improving mechanical and electrical properties of fibers.

Assembling graphene sheets into macroscopic fibers with graphitic layers uniaxially aligned along the fiber axis is of both fundamental and technological importance. However, the optimal performance of graphene-based fibers has been far lower than what is expected based on the properties of individual graphene. Here we show that both mechanical properties and electrical conductivity of graphene-based fibers can be significantly improved if bridges are created between graphene edges through covalent conjugating aromatic amide bonds. The improved electrical conductivity is likely due to extended electron conjugation over the aromatic amide bridged graphene sheets. The larger sheets also result in improved π-π stacking, which, along with the robust aromatic amide linkage, provides high mechanical strength. In our experiments, graphene edges were bridged using the established wet-spinning technique in the presence of an aromatic amine linker, which selectively reacts to carboxyl groups at the graphene edge sites. This technique is already industrial and can be easily upscaled. Our methodology thus paves the way to the fabrication of high-performance macroscopic graphene fibers under optimal techno-economic and ecological conditions.