Covalent‐Organic‐Framework‐Based Li–CO2 Batteries

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials constructed from designer molecular building blocks that are linked and extended periodically via covalent bonds. Their high stability, open channels, and ease of functionalization suggest that they can function as a useful cathode material in reversible lithium batteries. Here, a COF constructed from hydrazone/hydrazide‐containing molecular units, which shows good CO₂ sequestration properties, is reported. The COF is hybridized to Ru‐nanoparticle‐coated carbon nanotubes, and the composite is found to function as highly efficient cathode in a Li–CO₂ battery. The robust 1D channels in the COF serve as CO₂^– and lithium‐ion‐diffusion channels and improve the kinetics of electrochemical reactions. The COF‐based Li–CO₂ battery exhibits an ultrahigh capacity of 27 348 mAh g^?1 at a current density of 200 mA g^?1, and a low cut‐off overpotential of 1.24 V within a limiting capacity of 1000 mAh g^?1. The rate performance of the battery is improved considerably with the use of the COF at the cathode, where the battery shows a slow decay of discharge voltage from a current density of 0.1 to 4 A g^?1. The COF‐based battery runs for 200 cycles when discharged/charged at a high current density of 1 A g^?1.     

Gram‐Scale Aqueous Synthesis of Stable Few‐Layered 1T‐MoS2: Applications for Visible‐Light‐Driven Photocatalytic Hydrogen Evolution

Most recently, much attention has been devoted to 1T phase MoS₂ because of its distinctive phase‐engineering nature and promising applications in catalysts, electronics, and energy storage devices. While alkali metal intercalation and exfoliation methods have been well developed to realize unstable 1T‐MoS₂, but the aqueous synthesis for producing stable metallic phase remains big challenging. Herein, a new synthetic protocol is developed to mass‐produce colloidal metallic 1T‐MoS₂ layers highly stabilized by intercalated ammonium ions (abbreviated as N‐MoS₂). In combination with density functional calculations, the X‐ray diffraction pattern and Raman spectra elucidate the excellent stability of metallic phase. As clearly depicted by high‐angle annular dark‐field imaging in an aberration‐corrected scanning transmission electron microscope and extended X‐ray absorption fine structure, the N‐MoS₂ exhibits a distorted octahedral structure with a 2a ₀ × a ₀ basal plane superlattice and 2.72 Å Mo–Mo bond length. In a proof‐of‐concept demonstration for the obtained material's applications, highly efficient photocatalytic activity is achieved by simply hybridizing metallic N‐MoS₂ with semiconducting CdS nanorods due to the synergistic effect. As a direct outcome, this CdS:N‐MoS₂ hybrid shows giant enhancement of hydrogen evolution rate, which is almost 21‐fold higher than pure CdS and threefold higher than corresponding annealed CdS:2H‐MoS₂.     

In‐Plane 2H‐1T′ MoTe2 Homojunctions Synthesized by Flux‐Controlled Phase Engineering

The fabrication of in‐plane 2H‐1T′ MoTe₂ homojunctions by the flux‐controlled, phase‐engineering of few‐layer MoTe₂ from Mo nanoislands is reported. The phase of few‐layer MoTe₂ is controlled by simply changing Te atomic flux controlled by the temperature of the reaction vessel. Few‐layer 2H MoTe₂ is formed with high Te flux, while few‐layer 1T′ MoTe₂ is obtained with low Te flux. With medium flux, few‐layer in‐plane 2H‐1T′ MoTe₂ homojunctions are synthesized. As‐synthesized MoTe₂ is characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy. Kelvin probe force microscopy and Raman mapping confirm that in‐plane 2H‐1T′ MoTe₂ homojunctions have abrupt interfaces between 2H and 1T′ MoTe₂ domains, possessing a potential difference of about 100 mV. It is further shown that this method can be extended to create patterned metal–semiconductor junctions in MoTe₂ in a two‐step lithographic synthesis. The flux‐controlled phase engineering method could be utilized for the large‐scale controlled fabrication of 2D metal–semiconductor junctions for next‐generation electronic and optoelectronic devices.     

Bimetal‐Organic‐Framework Derivation of Ball‐Cactus‐Like Ni‐Sn‐P@C‐CNT as Long‐Cycle Anode for Lithium Ion Battery

Metal phosphides are a new class of potential high‐capacity anodes for lithium ion batteries, but their short cycle life is the critical problem to hinder its practical application. A unique ball‐cactus‐like microsphere of carbon coated NiP₂/Ni₃Sn₄ with deep‐rooted carbon nanotubes (Ni‐Sn‐P@C‐CNT) is demonstrated in this work to solve this problem. Bimetal‐organic‐frameworks (BMOFs, Ni‐Sn‐BTC, BTC refers to 1,3,5‐benzenetricarboxylic acid) are formed by a two‐step uniform microwave‐assisted irradiation approach and used as the precursor to grow Ni‐Sn@C‐CNT, Ni‐Sn‐P@C‐CNT, yolk–shell Ni‐Sn@C, and Ni‐Sn‐P@C. The uniform carbon overlayer is formed by the decomposition of organic ligands from MOFs and small CNTs are deeply rooted in Ni‐Sn‐P@C microsphere due to the in situ catalysis effect of Ni‐Sn. Among these potential anode materials, the Ni‐Sn‐P@C‐CNT is found to be a promising anode with best electrochemical properties. It exhibits a large reversible capacity of 704 mA h g^?1 after 200 cycles at 100 mA g^?1 and excellent high‐rate cycling performance (a stable capacity of 504 mA h g^?1 retained after 800 cycles at 1 A g^?1). These good electrochemical properties are mainly ascribed to the unique 3D mesoporous structure design along with dual active components showing synergistic electrochemical activity within different voltage windows.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

Self‐Sensitized Carbon Nitride Microspheres for Long‐Lasting Visible‐Light‐Driven Hydrogen Generation

A new type of metal‐free photocatalyst is reported having a microsphere core of oxygen‐containing carbon nitride and self‐sensitized surfaces by covalently linked polymeric triazine dyes. These self‐sensitized carbon nitride microspheres exhibit high visible‐light activities in photocatalytic H₂ generation with excellent stability for more than 100 h reaction. Comparing to the traditional g‐C₃N₄ with activities terminated at 450 nm, the polymeric triazine dyes on the carbon nitride microsphere surface allow for effective wide‐range visible‐light harvesting and extend the H₂ generation activities up to 600 nm. It is believed that this new type of highly stable self‐sensitized metal‐free structure opens a new direction of future development of low‐cost photocatalysts for efficient and long‐term solar fuels production.     

Excitons and Trions in One‐Photon‐ and Two‐Photon‐Excited MoS2: A Study in Dispersions

Herein, various dispersions of MoS₂ obtained by means of liquid phase exfoliation are spectroscopically, (spectro‐) electrochemically, and microscopically characterized. At the core of these studies are transient absorption assays. Importantly, small‐angle X‐ray scattering measurements are employed to corroborate the exfoliated character of the MoS₂ flakes in dispersion, on the one hand, and to correlate the results with TEM, AFM, and Raman characterization in the solid state, on the other. It is, then, demonstrated that transient absorption spectroscopy responds sensitively not only to changes in the sample preparation but also to instrumental and environmental parameters. It is documented that the spectroscopic features and their underlying lifetimes are tuneable on the femto‐, pico‐, and nanosecond scales by changing, for example, the centrifugation speed, the pump fluence, or the temperature. In other words, transient absorption spectroscopy provides an in situ method to quantitatively characterize liquid dispersions of MoS₂ without facing the problems of reaggregated samples due to their drying for microscopic assays. The most far reaching results stem from resonantly and nonresonantly changing the pump fluence to characterize either single‐ or multiple‐excited‐state species such as excitons, trions, and bi‐/multiexcitons and to follow their formation and deactivation pattern.     

An All‐Stretchable‐Component Sodium‐Ion Full Battery

Stretchable energy‐storage devices receive considerable attention due to their promising applications in future wearable technologies. However, they currently suffer from many problems, including low utility of active materials, limited multidirectional stretchability, and poor stability under stretched conditions. In addition, most proposed designs use one or more rigid components that fail to meet the stretchability requirement for the entire device. Here, an all‐stretchable‐component sodium‐ion full battery based on graphene‐modified poly(dimethylsiloxane) sponge electrodes and an elastic gel membrane is developed for the first time. The battery exhibits reasonable electrochemical performance and robust mechanical deformability; its electrochemical characteristics can be well‐maintained under many different stretched conditions and after hundreds of stretching–release cycles. This novel design integrating all stretchable components provides a pathway toward the next generation of wearable energy devices in modern electronics.     

Wafer‐Scale Fabrication of High‐Performance n‐Type Polymer Monolayer Transistors Using a Multi‐Level Self‐Assembly Strategy

Wafer‐scale fabrication of high‐performance uniform organic electronic materials is of great challenge and has rarely been realized before. Previous large‐scale fabrication methods always lead to different layer thickness and thereby poor film and device uniformity. Herein, the first demonstration of 4 in. wafer‐scale, uniform, and high‐performance n‐type polymer monolayer films is reported, enabled by controlling the multi‐level self‐assembly process of conjugated polymers in solution. Since the self‐assembly process happened in solution, the uniform 2D polymer monolayers can be facilely deposited on various substrates, and theoretically without size limitations. Polymer monolayer transistors exhibit high electron mobilities of up to 1.88 cm² V^?1 s^?1, which is among the highest in n‐type monolayer organic transistors. This method allows to easily fabricate n‐type conjugated polymers with wafer‐scale, high uniformity, low contact resistance, and excellent transistor performance (better than the traditional spin‐coating method). This work provides an effective strategy to prepare large‐scale and uniform 2D polymer monolayers, which could enable the application of conjugated polymers for wafer‐scale sophisticated electronics.