Challenges and Opportunities in Preserving Key Structural Features of 3D-Printed Metal/Covalent Organic Framework

Metal-organic framework(MOF)and covalent organic framework(COF)are a huge group of advanced porous materials exhibiting attractive and tunable microstructural features,such as large surface area,tunable pore size,and functional surfaces,which have significant values in various application areas.The emerging 3D printing technology further provides MOF and COFs(M/COFs)with higher designability of their macrostructure and demonstrates large achievements in their performance by shaping them into advanced 3D monoliths.However,the currently available 3D printing M/COFs strategy faces a major challenge of severe destruction of M/COFs’microstructural features,both during and after 3D printing.It is envisioned that preserving the microstructure of M/COFs in the 3D-printed monolith will bring a great improvement to the related applications.In this overview,the 3D-printed M/COFs are categorized into M/COF-mixed monoliths and M/COF-covered monoliths.Their differences in the properties,applications,and current research states are discussed.The up-to-date advancements in paste/scaffold composition and printing/covering methods to preserve the superior M/COF microstructure during 3D printing are further discussed for the two types of 3D-printed M/COF.Throughout the analysis of the current states of 3D-printed M/COFs,the expected future research direction to achieve a highly preserved microstructure in the 3D monolith is proposed.

Electrically-driven ultrafast out-of-equilibrium light emission from hot electrons in suspended graphene/hBN heterostructures

Nanoscale light sources with high speed of electrical modulation and low energy consumption are key components for nanophotonics and optoelectronics.The record-high carrier mobility and ultrafast carrier dynamics of graphene make it promising as an atomically thin light emitter which can be further integrated into arbitrary platforms by van der Waals forces.However,due to the zero bandgap,graphene is difficult to emit light through the interband recombination of carriers like conventional semiconductors.Here,we demonstrate ultrafast thermal light emitters based on suspended graphene/hexagonal boron nitride(Gr/hBN)heterostructures.Electrons in biased graphene are significantly heated up to 2800 K at modest electric fields,emitting bright photons from the near-infrared to the visible spectral range.By eliminating the heat dissipation channel of the substrate,the radiation efficiency of the suspended Gr/hBN device is about two orders of magnitude greater than that of graphene devices supported on SiO2or hBN.Wefurther demonstrate that hot electrons and low-energy acoustic phonons in graphene are weakly coupled to each other and are not in full thermal equilibrium.Direct cooling ofhigh-temperature hot electrons to low-temperature acoustic phonons is enabled by the significant near-field heat transfer at the highly localized Gr/hBN interface,resulting in ultrafast thermal emission with up to 1 GHz bandwidth under electrical excitation.It is found thatsuspending the Gr/hBN heterostructures on the SiO2trenches significantly modifies the light emission due to the formation of the optical cavity and showed a~440%enhancement inintensity at the peak wavelength of 940 nm compared to the black-body thermal radiation.The demonstration of electrically driven ultrafast light emission from suspended Gr/hBNheterostructures sheds the light on applications of graphene heterostructures in photonicintegrated circuits,such as broadband light sources and ultrafast thermo-optic phase modulators.

Modulating surface oxygen species via facet engineering for efficient conversion of nitrate to ammonia

Electrochemical reduction of nitrate,a common pollutant in aquatic environment,to valuable ammonia(NO3-RR) using renewably-sourced electricity has attracted widespread interests,with past efforts mainly focused on designing electrocatalysts with high activity and selectivity.The detailed correlation between catalyst properties and NO3-RR kinetics,nevertheless,is still not fully understood.In this work,we modulate the surface oxygen species of Cu_(2)O via facet engineering,and systematically study the impact of these oxygen species on the NO_(3)^(-)RR activity.Combining advanced spectroscopic techniques,densi ty fu n ctional theory calculations and molecular dynamics simulations,we find that while oxygen vacancies on Cu_(2)O(111) surface promote the adsorption of reactants and reaction intermediates,hydroxyl groups effectively inhibit the side reaction of hydrogen evolution and facilitate the hydrogenation process of NO3-RR.These two effects work in concert to render Cu_(2)O(111) facet the highest NO3-RR activity relative to those from other facets.Our study provides critical insights into the synergistic effect of exposed facets and surface oxygen species on heterogeneous catalysis,and offers a generalizable,facet engineeringbased strategy for improving the performance of a variety of electrocatalysts important for renewable energy conversion.

Applications of carbon nanotubes and graphene for third-generation solar cells and fuel cells

Carbon nanotubes (CNTs) and graphene have attracted great attention since decades ago because of their interesting structure and properties and important application in many areas. They can have high conductivity, high specific surface area, high transparency in the visible range and high mechanical flexibility. They have important application in energy conversion systems including solar cells and fuel cells. They have been extensively studied as the transparent electrode and interfacial materials of organic solar cells (OSCs) and perovskite solar cells (PSCs). They are also used as the catalytic counter electrode of dye-sensitized solar cells (DSSCs). In addition, graphene oxide (GO) is exploited as an auxiliary binder of TiO2 paste for the mesoporous TiO2 layer of DSSCs, and GO and functionalized CNTs are adopted as gelators of gel electrolyte for quasi-solid state DSSCs. CNTs and graphene also have important application in fuel cells. They can be used as catalyst support for the oxidation of fuels or oxygen reduction reaction (ORR). CNTs and graphene, particularly when doped with nitrogen, can be directly used metal-free catalysts. This article provides a brief review on the application of CNTs and graphene in OSCs, PSCs, DSSCs and fuel cells.

Recent Progress of Electrode Materials for Flexible Perovskite Solar Cells

Flexible perovskite solar cells(FPSCs) have attracted enormous interest in wearable and portable electronics due to their high power-per-weight and low cost. Flexible and efficient perovskite solar cells require the development of flexible electrodes compatible with the optoelectronic properties of perovskite. In this review, the recent progress of flexible electrodes used in FPSCs is comprehensively reviewed. The major features of flexible transparent electrodes, including transparent conductive oxides, conductive polymer, carbon nanomaterials and nanostructured metallic materials are systematically compared. And the corresponding modification strategies and device performance are summarized. Moreover, flexible opaque electrodes including metal films, opaque carbon materials and metal foils are critically assessed. Finally, the development directions and difficulties of flexible electrodes are given.

Mechanisms of High Coercivity in Ni/NiO Composite Films by Post Annealing

A coercivity as large as 2.4 kOe has been achieved in the Ni/NiO composite film after an annealing under a magnetic field of 10 kOe and an O_2 partial pressure of 0.001 torr.The coercivity was attributed to the strong exchange coupling of Ni and NiO.Small grain size of Ni and NiO was observed after the post-annealing.The enhanced coercivity is probably associated with the domain wall pinning by local energy minima,the distribution of Ni and NiO,and the domain structure in the interface of Ni/NiO generated under the presence of the magnetic field during the post-annealing.

Visible-light driven room-temperature coupling of methane to ethane by atomically dispersed Au on WO_(3)

Gold(Au)as co-catalyst is remarkable for activating methane(CH4),especially atomically dispersed Au with maximized exposing active sites and specific electronic structure.Furthermore,singlet oxygen(^(1)O_(2))typically manifests a mild redox capacity with a high selectivity to attack organic substrates.Peroxomonosulfate(PMS)favors to produce oxidative species 102 during the photocatalytic reactions.Thus,combining atomic Au as co-catalyst and ^(1)O_(2) as oxidant is an effective strategy to selectively convert CH4.Herein,we synthesized atomically dispersed Au on WO_(3)(Au/WO_(3)),where Au was in the forms of single atoms and clusters.At room temperature,such Au/WO_(3) exhibited enhanced photocata lytic conversion of CH4 to CH3 CH3 with a selectivity,up to 94%,under visible light.The radicals-pathway mechanism of CH4 coupling has also been investigated through detection and trapping experiment of active species.Theoretical calculations further interpret the electronic structure of Au/WO_(3) and tip-enhanced local electric field at the Au sites for promoting CH4 conversion.

Electrospun Nanofibers for New Generation Flexible Energy Storage

As one of the essential components for flexible electronics,flexible electrochemical energy storage(EES)has garnered extensive interests at all levels of materials,devices,and systems.The successful implementation of high-performance flexible EES devices relies on exploring of suitable electrode/electrolyte materials that have both superior electrochemical and mechanical properties.For this function,one-dimensional electrospun nanofibers have emerged as a class of promising building blocks for the key components of flexible EES devices.In this overview,the fundamental principles and technical advances of electrospinning are examined,for both their successes and challenges in controllable fabrication of nanofibers with the desirable chemical compositions,micro/meso-/nanostructures,and therefore resultant properties.The advances in applications of electrospun nanofibers for various key flexible EES devices are critically looked into,including those in supercapacitors,metal-ion batteries,and metal-air batteries.The existing challenges and prospects of these electrospun nanofiber-based flexible EES are discussed,aiming to inspire continued efforts in developing the optimal high-performance and low cost flexible EES devices for long-awaited practical applications.

A review of Mott insulator in memristors:The materials,characteristics,applications for future computing systems and neuromorphic computing

Mott insulator material,as a kind of strongly correlated electronic system with the characteristic of a drastic change in electrical conductivity,shows excellent application prospects in neuromorphological calculations and has attracted significant attention in the scientific community.Especially,computing systems based on Mott insulators can overcome the bottleneck of separated data storage and calculation in traditional artificial intelligence systems based on the von Neumann architecture,with the potential to save energy,increase operation speed,improve integration,scalability,and three-dimensionally stacked,and more suitable to neuromorphic computing than a complementary metal-oxide-semiconductor.In this review,we have reviewed Mott insulator materials,methods for driving Mott insulator transformation(pressure-,voltage-,and temperature-driven approaches),and recent relevant applications in neuromorphic calculations.The results in this review provide a path for further study of the applications in neuromorphic calculations based on Mott insulator materials and the related devices.

Engineering CoMoO_(4) in reduced graphene oxide as superior cathode hosts for advanced room-temperature sodium-sulfur batteries

Promising room-temperature sodium-sulfur(RT Na-S)battery systems rely on purposely designed highperforming and low-cost electrode materials.Nevertheless,there are the challenges of irreversible dissolution and slow redox kinetics of NaPSs in the complete discharge of sulfur capacity.Herein,engineered CoMoO_(4)in reduced graphene oxide(CoMoO_(4)@rGO)is reported as a class of superior cathode hosts for RT Na-S batteries.The CoMoO_(4)@rGO matrix is designed to facilitate the reversible sodiation and desodiation of sulfur,considering the strong chemisorption between sulfur(and short-chain sodium sulfides)and CoMoO_(4),which alleviates the shuttle effect of sodium sulfides and accelerates the electrochemical reaction rate at RT.The obtained S/CoMoO_(4)@rGO cathode with~52%S loading exhibits a high capacity of520.1 mA h g^(-1)after 100 cycles at 0.1 A g^(-1).Moreover,an enhanced long-term performance at high current densities(212.2 mA h g^(-1)at 4 A g^(-1)over 1000 cycles)with high Coulombic efficiency(~100%)is also achieved.This work demonstrates a novel multifunctional additive for RT Na-S battery cathodes,which is expected to promote the long-waited development towards practical applications of RT Na-S batteries.

Texture Engineering to Boost the Thermoelectric Properties

A round 60% of useful energy is wasted in industry, homes, or transportation. Therefore, there has been increasing attention on thermoelectric materials for their ability to harvest waste heat into useful energy. The efficiency of a thermoelectric material depends on its electrical conductivity, Seebeck coefficient, and thermal conductivity in a conflicting manner which results in efficiency optimization challenges. Single crystals and polycrystalline layered materials have comparatively better thermoelectric and mechanical properties in a certain direction. Texture engineering is a special strategy that allows the exploitation of superior material properties in a specific direction. Texturing could be achieved by various sintering and deformation methods, which yield defects improving thermoelectric and mechanical properties. The results show that for(Bi,Sb)_(2)Te_(3), Bi_(2)(Se,Te)_(3), C uSbSe_(2), and SnSe, significant enhancement in the thermoelectric figure of merit is achieved by enhancing the preferred orientation. Texture engineering provides a wide range of strategies to elevate the zT of anisotropic materials to values comparable to those of their single crystalline counterparts.

Crystallization Regulation and Morphological Evolution for HTM-free Tin-Lead (1.28eV) Alloyed Perovskite Solar Cells

There have been huge achievements of all-perovskite tandem solar cells,which recently realized the highest power conversion efficiency of 24.8%.However,the complex device structure and complicated manufacture processes severely restrict the further development of all-perovskite tandem solar cells.In this work,we successfully fabricated high-efficiency hole transport material-free(HTM-free)Sn−Pb alloyed narrow bandgap perovskite solar cells(PSCs)by introducing guanidinium thiocyanate(GASCN)and hydroiodic acid(HI)into the perovskite precursor solution.GASCN and HI play a positive synergy effect during perovskite crystallization process resulting in larger grain size,fewer surface defects,and lower trap density to suppress the Sn^(2+)oxidation degradation.Furthermore,they could effectively adjust the energy level of perovskite materials,reduce the energy level difference between perovskite and ITO resulting in more efficiently transport of free hole charge carriers.As a result,with adding GASCN and HI,the achieved highest power conversion efficiency of HTM-free devices increased from 12.58%to 17.85%,which is one of the highest PCEs among all values reported to date for the HTM-free narrow-bandgap(1.2-1.4 eV)Sn−Pb binary PSCs.Moreover,the optimized device shows improved environmental stability.Our additive strategy manifests a remarkable step towards the facile,cost-efficient fabrication of HTM-free perovskite-based tandem solar cells with both high efficiency and simple fabrication process.

Synergistic effect of K^(+)and PANI in vanadium oxide hydration by interlayer engineering boosts the ammonium ion storage

Aqueous ammonium-ion(NH_(4)^(+))hybrid supercapacitor(AA-HSC),as a new type of energy storage device with great potential,is in the initial stage of rapid development.Based on its special energy storage mechanism,exploiting novel NH_(4)^(+)-hostingmaterials is still a great challenge.Herein,vanadium oxide hydration(VOH)tuned by interlayer engineering of K+/PANI co-intercalation,named KVO/PANI,is designed for AA-HSC.Intercalated PANI can shield interaction between NH_(4)^(+)and V–O layers to some extent and enlarge interlayer space,which improves the efficiency of reversible NH_(4)^(+)(de)insertion.However,K+enhances redox activity and electronic conductivity.The synergistic effect of co-intercalation optimizes intercalation pseudocapacitive behavior during the(de)ammonization process,which is reported in NH_(4)^(+)storage for the first time.Theoretical calculations reveal that the lowered electron transport barrier and enhanced electronic conductivity improveNH_(4)^(+)kinetics and exhibit high capacitance for charge storage.The KVO/PANI can deliver the specific capacitance of 340 F g^(−1) at 0.5 A g^(−1) and retain 177 F g^(−1) at 10 A g^(−1).Pairing with activated carbon,the AA-HSC can achieve a decent energy density of 31.8 Wh kg^(−1).This work gives inorganic/organic co-intercalation that can enhance the NH_(4)^(+)storage of VOH by interlayer engineering.The strategy can be used to design other materials for aqueous energy storage systems.

Dielectric metasurface evolution from bulk to monolayer by strong coupling of quasi-BICs for second harmonic boosting

2D materials are promising candidates as nonlinear optical components for on-chip devices due to their ultrathin structure. In general, their nonlinear optical responses are inherently weak due to the short interaction thickness with light. Recently, there has been great interest in using quasi-bound states in the continuum (q-BICs) of dielectric metasurfaces, which are able to achieve remarkable optical near-field enhancement for elevating the second harmonic generation (SHG) emission from 2D materials. However, most studies focus on the design of combining bulk dielectric metasurfaces with unpatterned 2D materials, which suffer considerable radiation loss and limit near-field enhancement by high-quality q-BIC resonances. Here, we investigate the dielectric metasurface evolution from bulk silicon to monolayer molybdenum disulfide (MoS2), and discover the critical role of meta-atom thickness design on enhancing near-field effects of two q-BIC modes. We further introduce the strongcoupling of the two q-BIC modes by oblique incidence manipulation, and enhance the localized optical field on monolayer MoS2dramatically. In the ultraviolet and visible regions, the MoS2SHG enhancement factor of our design is 105times higher than that of conventional bulk metasurfaces, leading to an extremely high nonlinear conversion efficiency of 5.8%. Our research will provide an important theoretical guide for the design of high-performance nonlinear devices based on 2D materials.

Exploring van der Waals materials with high anisotropy:geometrical and optical approaches

The emergence of van der Waals(vdW)materials resulted in the discovery of their high optical,mechanical,and electronic anisotropic properties,immediately enabling countless novel phenomena and applications.Such success inspired an intensive search for the highest possible anisotropic properties among vdW materials.Furthermore,the identification of the most promising among the huge family of vdW materials is a challenging quest requiring innovative approaches.Here,we suggest an easy-to-use method for such a survey based on the crystallographic geometrical perspective of vdW materials followed by their optical characterization.Using our approach,we found As2S3 as a highly anisotropic vdW material.It demonstrates high in-plane optical anisotropy that is~20%larger than for rutile and over two times as large as calcite,high refractive index,and transparency in the visible range,overcoming the century-long record set by rutile.Given these benefits,As2S3 opens a pathway towards nextgeneration nanophotonics as demonstrated by an ultrathin true zero-order quarter-wave plate that combines classical and the Fabry–Pérot optical phase accumulations.Hence,our approach provides an effective and easy-to-use method to find vdW materials with the utmost anisotropic properties.

Identification of chemical compositions from“featureless”optical absorption spectra:Machine learning predictions and experimental validations

Rapid and accurate chemical composition identification is critically important in chemistry.While it can be achieved with optical absorption spectrometry by comparing the experimental spectra with the reference data when the chemical compositions are simple,such application is limited in more complicated scenarios especially in nano-scale research.This is due to the difficulties in identifying optical absorption peaks(i.e.,from“featureless”spectra)arose from the complexity.In this work,using the ultraviolet-visible(UV-Vis)absorption spectra of metal nanoclusters(NCs)as a demonstration,we develop a machine-learningbased method to unravel the compositions of metal NCs behind the“featureless”spectra.By implementing a one-dimensional convolutional neural network,good matches between prediction results and experimental results and low mean absolute error values are achieved on these optical absorption spectra that human cannot interpret.This work opens a door for the identification of nanomaterials at molecular precision from their optical properties,paving the way to rapid and high-throughput characterizations.

Modeling the effects of salt concentration on aqueous and organic electrolytes

Understanding the thermodynamic properties of electrolyte solutions is of vital importance for a myriad of physiological and technological applications.The mean activity coefficientγ±is associated with the deviation of an electrolyte solution from its ideal behavior and may be obtained by combining the Debye-Hückel(DH)and Born(B)equations.However,the DH and B equations depend on the concentration and temperature-dependent static permittivity of the solutionεr(c,T)and the size of the solvated ions ri,whose experimental data is often not available.Here,we use a combination of molecular dynamics and density functional theory to predictεr(c,T)and ri,which enables us to apply the DH and B equations to any technologically relevant aqueous and nonaqueous electrolyte at any concentration and temperature of interest.

High-Energy Batteries:Beyond Lithium-Ion and Their Long Road to Commercialisation

Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century.While lithium-ion batteries have so far been the dominant choice,numerous emerging applications call for higher capacity,better safety and lower costs while maintaining sufficient cyclability.The design space for potentially better alternatives is extremely large,with numerous new chemistries and architectures being simultaneously explored.These include other insertion ions(e.g.sodium and numerous multivalent ions),conversion electrode materials(e.g.silicon,metallic anodes,halides and chalcogens)and aqueous and solid electrolytes.However,each of these potential“beyond lithium-ion”alternatives faces numerous challenges that often lead to very poor cyclability,especially at the commercial cell level,while lithium-ion batteries continue to improve in performance and decrease in cost.This review examines fundamental principles to rationalise these numerous developments,and in each case,a brief overview is given on the advantages,advances,remaining challenges preventing cell-level implementation and the state-of-the-art of the solutions to these challenges.Finally,research and development results obtained in academia are compared to emerging commercial examples,as a commentary on the current and near-future viability of these“beyond lithium-ion”alternatives.

Nanohollow Carbon for Rechargeable Batteries:Ongoing Progresses and Challenges

Among the various morphologies of carbon-based materials,hollow carbon nanostructures are of particular interest for energy storage.They have been widely investigated as electrode materials in different types of rechargeable batteries,owing to their high surface areas in association with the high surface-to-volume ratios,controllable pores and pore size distribution,high electrical conductivity,and excellent chemical and mechanical stability,which are beneficial for providing active sites,accelerating electrons/ions transfer,interacting with electrolytes,and giving rise to high specific capacity,rate capability,cycling ability,and overall electrochemical performance.In this overview,we look into the ongoing progresses that are being made with the nanohollow carbon materials,including nanospheres,nanopolyhedrons,and nanofibers,in relation to their applications in the main types of rechargeable batteries.The design and synthesis strategies for them and their electrochemical performance in rechargeable batteries,including lithium-ion batteries,sodium-ion batteries,potassium-ion batteries,and lithium–sulfur batteries are comprehensively reviewed and discussed,together with the challenges being faced and perspectives for them.

Design strategies for MOF-derived porous functional materials: Preserving surfaces and nurturing pores

MOFs are among the most popular precursors and templates for deriving various porous materials,where the derivatives can inherit a large surface area,abundant active sites for targeted functionalities and a high degree of porosity inherited from their parent MOFs.Those unique structural features make them promising candidates in multiple applications.More interestingly,the structure and properties of these MOF derivatives can be modulated by the choice of the parent MOFs and the design in the conversion process.In this overview,the transformation pathways from MOFs into their porous derivatives,the principles underlying these transformations,and the behavior of the MOF components in the transition process are discussed.Recently,there has been tremendous progress in preserving and enhancing the surface area,the amount of active sites and the level of porosity of the MOF-derived materials for targeted applications,from the perspectives of both customizing the parent MOFs and tailoring the transformation process.To develop the rationally designed MOF-derived materials and thus to elucidate the precursor-process-product correlations,some typical examples of the MOF derivatives applied in electrochemical energy storage and conversion,water treatment,gas sensing,and biomedicine are discussed to demonstrate the effectiveness of the key design strategies.