Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Ultrafast Synthesis of Metal-Layered Hydroxides in a Dozen Seconds for High-Performance Aqueous Zn(Micro-)Battery

Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly rely on traditional bottom-up method,which involves tedious steps,time-consuming treatments,or additional alkaline media,and is unfavorable for high-efficiency production.Herein,we present a facile,ultrafast and general avenue to synthesize transition metal hydroxides on carbon substrate within 13 s by Joule-heating method.With high reaction kinetics caused by the instantaneous high temperature,seven kinds of transition metal-layered hydroxides(TM-LDHs)are formed on carbon cloth.Therein,the fastest synthesis rate reaches~0.46 cm^(2)s^(-1).Density functional theory calculations further demonstrate the nucleation energy barriers and potential mechanism for the formation of metal-based hydroxides on carbon substrates.This efficient approach avoids the use of extra agents,multiple steps,and long production time and endows the LDHs@carbon cloth with outstanding flexibility and machinability,showing practical advantages in both common and micro-zinc ion-based energy storage devices.To prove its utility,as a cathode in rechargeable aqueous alkaline Zn(micro-)battery,the NiCo LDH@carbon cloth exhibits a high energy density,superior to most transition metal LDH materials reported so far.

Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia

Direct electrochemical nitrate reduction reaction(NITRR)is a promising strategy to alleviate the unbalanced nitrogen cycle while achieving the electrosynthesis of ammonia.However,the restructuration of the high-activity Cu-based electrocatalysts in the NITRR process has hindered the identification of dynamical active sites and in-depth investigation of the catalytic mechanism.Herein,Cu species(single-atom,clusters,and nanoparticles)with tunable loading supported on N-doped TiO_(2)/C are successfully manufactured with MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy.Restructuration behavior among Cu species is co-dependent on the Cu loading and reaction potential,as evidenced by the advanced operando X-ray absorption spectroscopy,and there exists an incompletely reversible transformation of the restructured structure to the initial state.Notably,restructured CuN_(4)&Cu_(4) deliver the high NH_(3) yield of 88.2 mmol h^(−1)g_(cata)^(−1) and FE(~94.3%)at−0.75 V,resulting from the optimal adsorption of NO_(3)^(−) as well as the rapid conversion of^(*)NH_(2)OH to^(*)NH_(2) intermediates originated from the modulation of charge distribution and d-band center for Cu site.This work not only uncovers CuN_(4)&Cu_(4) have the promising NITRR but also identifies the dynamic Cu species active sites that play a critical role in the efficient electrocatalytic reduction in nitrate to ammonia.

Dual-doping for enhancing chemical stability of functional anionic units in sulfide for high-performance all-solid-state lithium batteries

The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.

Ultraconformable Integrated Wireless Charging Micro-Supercapacitor Skin

Conformable and wire-less charging energy storage devices play important roles in enabling the fast development of wearable,non-contact soft electronics.However,current wire-less charging power sources are still restricted by limited flexural angles and fragile connection of components,resulting in the failure expression of performance and constraining their fur-ther applications in health monitoring wearables and moveable artificial limbs.Herein,we present an ultracompatible skin-like integrated wireless charging micro-supercapacitor,which building blocks(including electrolyte,electrode and substrate)are all evaporated by liquid precursor.Owing to the infiltration and permeation of the liquid,each part of the integrated device attached firmly with each other,forming a compact and all-in-one configuration.In addition,benefitting from the controllable volume of electrode solution precursor,the electrode thickness is easily regulated varying from 11.7 to 112.5μm.This prepared thin IWC-MSC skin can fit well with curving human body,and could be wireless charged to store electricity into high capacitive micro-supercapacitors(11.39 F cm-3)of the integrated device.We believe this work will shed light on the construction of skin-attachable electronics and irregular sensing microrobots.

Synergy enhancement of Co single atoms and asymmetric subnanoclusters for Fenton-like activation

As a new water treatment technology,Fenton-like reaction has great potential.In this study,we successfully prepared an excellent Fenton-like catalyst,which is composed of cobalt monoatoms and asymmetric subnanoclusters(labeled CoSA/Clu-C_(2)N),and exhibits excellent peroxymonosulfate(PMS)activation reactivity.By directly comparing the catalytic properties of CoSA-C_(2)N and CoSA/Clu-C_(2)N,the synergistic effects of coasymmetric Co subclusters and Co atoms on the activation of PMS and degradation of organic micropollutants were investigated.The results showed that CoSA/Clu-C_(2)N had higher degradation rates of carbamazepine(CBZ),antipyrine(AT)and chlorobenzoic acid(CA)when combined with active oxidant PMS.The cyclic frequency of CBZ was 5.4 min^(-1),which was twice as high as the catalytic constant of CoSA-C_(2)N(2.4 min^(-1)).The results show that CoSA/Clu-C_(2)N cobalt subnanoclusters and cobalt single atom can synergistically improve the catalytic performance of activated PMS oxidation of micropollutants in water.In addition,electron paramagnetic resonance(EPR)technology has proved that the introduction of Co subnano clusters in CoSA/Clu-C_(2)N is conducive to the production of singlet oxygen(1O_(2)),thereby improving the efficiency of pollutant oxidation.This work lays a solid foundation for the future design of advanced multifunctional catalysts by carefully regulating and combining monmetallic atoms and metal subnanoclusters.

Moisture‑Electric–Moisture‑Sensitive Heterostructure Triggered Proton Hopping for Quality‑Enhancing Moist‑Electric Generator

Moisture-enabled electricity(ME)is a method of converting the potential energy of water in the external environment into electrical energy through the interaction of functional materials with water molecules and can be directly applied to energy harvesting and signal expression.However,ME can be unreliable in numerous applications due to its sluggish response to moisture,thus sacrificing the value of fast energy harvesting and highly accurate information representation.Here,by constructing a moisture-electric-moisture-sensitive(ME-MS)heterostructure,we develop an efficient ME generator with ultra-fast electric response to moisture achieved by triggering Grotthuss protons hopping in the sensitized ZnO,which modulates the heterostructure built-in interfacial potential,enables quick response(0.435 s),an unprecedented ultra-fast response rate of 972.4 mV s^(−1),and a durable electrical signal output for 8 h without any attenuation.Our research provides an efficient way to generate electricity and important insight for a deeper understanding of the mechanisms of moisture-generated carrier migration in ME generator,which has a more comprehensive working scene and can serve as a typical model for human health monitoring and smart medical electronics design.

Copper(I)Cluster of Aggregation-Induced Emission and X-Ray Scintillator Characteristic

Due to their precise atomic structures,photoluminescent copper nanoclusters(Cu NCs)have promising applications in basic research and technical applications,such as bioimaging,cell labeling,phototherapy,and photoactivation catalysis.In this work,we report a simple strategy for synthesizing novel CuNCs co-protected by alkynyl and phosphine ligands with the molecular formula[Cu_(7)(PPh_(3))_(10)(PE)_(3)(CH_(3)O)](Cu_(4)@Cu_(3)).Single-crystal X-ray crystallography reveals that the NC core exhibits an open square structure and an overall pyramid shape.Two Cu_(4)@Cu_(3) units are connected through weak interactions to form dimers in crystals,creating a molecular cage that looks like two tightly closed bowls.Cu_(4)@Cu_(3)exhibits dual emission in the visible region.It is also an aggregation-induced emission(AIE)-active luminescent substance,which exhibits strong emission in the visible light region when aggregated.Besides,it has the properties of radioluminescent(RL)and could be a potential scintillator material.This study not only enriches the types of atomically accurate AIE clusters,but also holds significant importance for the development of a new generation of high-performance and environmentally friendly X-ray scintillators.

MWCNT Doped Reverse-Mode Polymer Network Liquid Crystals with Frequency Response Property

Polymer-liquid crystals(PLCs)are common materials for smart windows.However,PLC smart windows usually require high driving voltage to maintain transparency.We synthesized a novel PLC smart film by doping multi-wall carbon nanotubes(MWCNTs)into a reverse-mode polymer network liquid crystal(R-PNLC).

Construction and Properties of Structure-and Size-controlled Micro/Nano-energetic Materials

The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.

Research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts

With the increasing concerns to energy shortage and environmental problems in modern society,the development of cheap,clean,and sustainable energy alternatives has been attracting tremendous attention globally.Among various strategies of renewable energy exploration,solar-driven water splitting into its compositional elements H2 and O2 is an ideal approach to convert and store renewable solar energy into chemical bonds.In recent few decades,as an emerging new type of catalysts,polyoxometalates(POMs)have been widely utilized for water splitting due to their versatile synthetic methodology and highly tunable physicochemical and photochemical properties.This critical review addresses the research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts,including plenary POMs,transition-metal-substituted POMs,POM@MOF composites,and POM-semiconductor hybrids,under UV,near UV and visible light irradiation.In addition,the catalytic mechanism for each reaction system has been thoroughly discussed and summarized.Finally,a comprehensive outlook of this research area is also prospected.

Amorphous Ru nanoclusters onto Co‐doped 1D carbon nanocages enables efficient hydrogen evolution catalysis

The development of high-performance electrocatalysts for hydrogen evolution reaction(HER)is of great significance for green,sustainable,and renewable energy conversion.Herein,we report the synthesis of amorphous Ru clusters on Co-doped defect-rich hollow carbon nanocage(a-Ru@Co-DHC)as an efficient electrocatalyst for HER in the basic media.Due to the advantages such as high surface area,rich edge defect,atomic Co doping and amorphous Ru clusters,the as-made a-Ru@Co-DHC displays an efficient HER performance with a near-zero onset overpotential,a low Tafel slope(62 mV dec^(−1)),a low overpotential of 40 mV at 10 mA cm^(−2) and high stability,outperforming the commercial Ru nanocrystal/C,commercial Pt/C,and other reported Ru-based catalysts.This work provides a new insight into designing new metal doped carbon nanocages catalysts supported by amorphous nanoclusters for achieving the enhanced electrocatalysis.

Preferential oxidation of CO in excess H_2 over CeO_2/CuO catalyst:Effect of calcination temperature

Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.

Laser fabrication of functional micro-supercapacitors

Due to the rapid development of portable,wearable and implantable electronics in the fields of mobile communications,biomonitoring,and aerospace or defense,there is an increasing demand for miniaturized and lightweight energy storage devices.Micro-supercapacitors(MSCs)possessing long lifetime,high power density,environment friendliness and safety,have attracted great attention recently.Since the performance of the MSCs is mainly related to the structure of the active electrode,there is a great need to explore the efficient fabricating strategies to deterministically coordinate the structure and functionality of microdevices.Considering that laser technology possesses many superior features of facility,high-precision,low-cost,high-efficiency,shape-adaptability and maneuverability,herein we summarize the development of laser technologies in MSCs manufacturing,along with their strengths and weaknesses.The current achievements and challenges are also highlighted and discussed,aiming to provide a valuable reference for the rational design and manufacture of MSCs in the future.

Two-dimensional materials of group-IVA boosting the development of energy storage and conversion

Graphene,an emerging fabric of carbon atoms,has manifested its versatility in all kinds of fields encompassing electronics,optoelectronics,thermoelectrics,taking advantage of its excellent mechanical strength,exceptional electronic and thermal conductivities,high surface specific area,and so forth.The prosperity of graphene never seen before has led the attention to silicene,siloxene,germanene,stanene,and plumbene due to their promising applications in the quantum spin Hall effect,topological insulator,batteries,capacitors,catalysis,and topological superconductivity.Herein,we review the existing production methods,numerous applications of two-dimensional group-IVA materials,and critically discuss the challenges of these materials,providing potential implications to the exploration of uncharted material systems.

Synthesis of Hierarchically Porous FAU/γ-Al2O3 Composites with Different Morphologies via Directing Agent Induced Method

Zeolite FAU composites with a macro/meso-microporous hierarchical structure were hydrothermally synthesized using macro-mesoporous γ-Al_2O_3 monolith as the substrate by means of the liquid crystallization directing agent(LCDA) induced method. No template was needed throughout the synthesis processes. The structure and porosity of zeolite composites were analyzed by means of X-ray powder diffraction(XRD), scanning electron microscopy(SEM) and N_2adsorption-desorption isotherms. The results showed that the supported zeolite composites with varied zeolitic crystalline phases and different morphologies can be obtained by adjusting the crystallization parameters, such as the crystallization temperature, the composition and the alkalinity of the precursor solution. The presence of LCDA was defined as a determinant for synthesizing the zeolite composites. The mechanisms for formation of the hierarchically porous FAU zeolite composites in the LCDA induced synthesis process were discussed. The resulting monolithic zeolite with a trimodal-porous hierarchical structure shows potential applicability where facile diffusion is required.

A panoramic view of Li_(7)P_(3)S_(11) solid electrolytes synthesis, structural aspects and practical challenges for all-solid-state lithium batteries

The development of an inorganic electrochemical stable solid-state electrolyte is essentially responsible for future state-of-the-art all-solid-state lithium batteries(ASSLBs).Because of their advantages in safety,working temperature,high energy density,and packaging,ASSLBs can develop an ideal energy storage system for modern electric vehicles(EVs).A solid electrolyte(SE)model must have an economical synthesis approach,exhibit electrochemical and chemical stability,high ionic conductivity,and low interfacial resistance.Owing to its highest conductivity of 17 mS·cm^(-1),and deformability,the sulfide-based Li_(7)P_(3)S_(11) solid electrolyte is a promising contender for the high-performance bulk type of ASSLBs.Herein,we present a current glimpse of the progress of synthetic procedures,structural aspects,and ionic conductivity improvement strategies.Structural elucidation and mechanistic approaches have been extensively discussed by using various characterization techniques.The chemical stability of Li_(7)P_(3)S_(11) could be enhanced via oxide doping,and hard and soft acid/base(HSAB)concepts are also discussed.The issues to be undertaken for designing the ideal solid electrolytes,interfacial challenges,and high energy density have been discoursed.This review aims to provide a bird’s eye view of the recent development of Li_(7)P_(3)S_(11)-based solid-state electrolyte applications and explore the strategies for designing new solid electrolytes with a target-oriented approach to enhance the efficiency of high energy density allsolid-state lithium batteries.

Direct oxidation of methyl radicals in OCM process deduced from correlation of product selectivities

Selectivity of hydrogen in reaction of oxidative coupling of methane （OCM） was evaluated over the MxOy-BaCO3 （MzOy： La2O3, Sm2O3, MgO, CaO） catalysts. Correlation of product selectivities was thus discussed. From the correlation of product selectivities, it is revealed that the carbon oxides （CO and CO2） were most probably formed from the direct oxidation of methyl radicals under the conditions adopted in the present work. This is also in accordance with the OCM mechanism proposed in literature.

Fabrication of Hierarchically Porous FAU/α-Al_(2)O_(3) Monoliths via Gel Pre-aging Routes Using Seed Gel as Directing Agent

Hierarchically porous FAU monoliths were synthesized via the gel pre-aging route using seed gel as directing agent andα-Al2O3 as monolithic carrier.The as-synthesized samples were characterized by means of the Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and N2 adsorption techniques.The effects of seed gel,gel pre-treatment,and gel pre-aging step were determined,while the possible mechanism for formation of alumina composites via different synthesis processes were discussed.The results showed that the crystal size,the shape,and the loading of the supported FAU could be readily tuned by varying the composition of the crystallization gel without notably changing the structure ofα-Al2O3.The proposed seed gel pre-treating and gel pre-aging route are simple,reproducible,and practically easy to integrate triple porous structures into large-dimension monoliths,which are proved to be very effective in depositing pure FAU crystals on theα-Al2O3 skeleton surface and strengthening the interfacial interaction between them.Moreover,it may provide inspiration to the synthesis of other hierarchical zeolites.

Preparation and Analysis of Thermal and Mechanical Properties of HTPB-type Polyurethane Elastomer Containing Paraffin Microcapsules

Two microcapsules with different paraffin phase changes were prepared using styrene-divinylbenzene copolymer and melamine resin as the capsule wall and paraffin(with a melting point of 50°C)as the capsule core.The microcapsules were directly added to the hydroxyl terminated polybutadiene(HTPB)-polyurethane elastomer system to fabricate the polyurethane elastomer composites.The thermodynamic stability and mechanical properties of the material were then studied.The results show that the thermal stability of the polyurethane elastomer does not decrease after adding paraffin phase change microcapsules,and the thermal stability of the polyurethane elastomer with melamine resin as the wall increases.Tensile strength increased from 367 kPa to 797 kPa,and compression strength increased from 245.9 N to 344.7 N.In addition,capsule walls comprised different monomers/paraffin microcapsules of the copolymer of styrene and divinylbenzene.The optimal mechanical property was obtained at a monomer/paraffin ratio of 1:1.The compression strength increased and the tensile strength decreased.The tensile strength of the microcapsule with melamine resin capsule wall and the compression strength of the microcapsule with polystyrene capsule wall were considerably improved.