Two-dimensional nanomaterials confined single atoms: New opportunities for environmental remediation

Two-dimensional(2D)supports confined single-atom catalysts(2D SACs)with unique geometric and electronic structures have been attractive candidates in different catalytic applications,such as energy conversion and storage,value-added chemical synthesis and environmental remediation.However,their environmental appli-cations lack of a comprehensive summary and in-depth discussion.In this review,recent progresses in synthesis routes and advanced characterization techniques for 2D SACs are introduced,and a comprehensive discussion on their applications in environmental remediation is presented.Generally,2D SACs can be effective in catalytic elimination of aqueous and gaseous pollutants via radical or non-radical routes and transformation of toxic pollutants into less poisonous species or highly value-added products,opening a new horizon for the contami-nant treatment.In addition,in-depth reaction mechanisms and potential pathways are systematically discussed,and the relationship between the structure-performance is highlighted.Finally,several critical challenges within this field are presented,and possible directions for further explorations of 2D SACs in environmental remediation are suggested.Although the research of 2D SACs in the environmental application is still in its infancy,this review will provide a timely summary on the emerging field,and would stimulate tremendous interest for designing more attractive 2D SACs and promoting their wide applications.

Phonon Confinement Effect in Two-dimensional Nanocrystallites of Monolayer MoS_2 to Probe Phonon Dispersion Trends Away from Brillouin-Zone Center

The fundamental momentum conservation requirement q - 0 for the Raman process is relaxed in the nanocrystal- lites （NCs）, and phonons away from the Brillouin-zone center will be involved in the Raman scattering, which is well-known as the phonon confinement effect in NCs. This usually gives a downshift and asymmetric broadening of the Raman peak in various NCs. Recently, the A1 mode of 1L MoS2 NCs is found to exhibit a blue shift and asymmetric broadening toward the high-frequency side [Chem. Soc. Rev. 44 （2015） 2757 and Phys. Rev. B 91 （2015） 195411]. In this work, we carefully check this issue by studying Raman spectra of lL MoS2 NCs prepared by the ion implantation technique in a wide range of ion-implanted dosage. The same confinement coefficient is used for both E＇ and A＇1 modes in 1L MoS2 NCs since the phonon uncertainty in an NC is mainly determined by its domain size. The asymmetrical broadening near the A＇1 and E＇ modes is attributed to the appearance of defect-activated phonons at the zone edge and the intrinsic asymmetrical broadening of the two modes, where the anisotropy of phonon dispersion curves along Г-K and Г- M is also considered. The photoluminescence spectra confirm the formation of small domain size of 1L MoS2 nanocrystallites in the ion-implanted 1L MoS2. This study provides not only an approach to quickly probe phonon dispersion trends of 2D materials away from Г by the Raman scattering of the corresponding NCs, but also a reference to completely understand the confinement effect of different modes in various nanomaterials.

A Novel Synthesis of Two-dimensional Nanopatterned TiO_(2)Thin Film

A novel two-dimensional nanopattemed TiO2 thin film has been synthesized through the interaction between cationic Gemini surfactant molecules and the prepared TiO2 colloid nanoparticles with average diameters of 8 nm by controlling the surface pressure of the monolayer. TEM photographs from the formed Gemini-TiO2 composite monolayer confirm that the prepared TiO2 film is of a branch nanopattern.

Tortuosity regulation of two-dimensional nanofluidic films for water evaporation-induced electricity generation

Water evaporation-induced electricity generation is a promising technology for renewable energy harvesting.However,the output power of some reported two-dimensional(2D)nanofluidic films is still restricted by the relatively weak water–solid interactions within the tortuous nanochannels.To further enhance the comprehension and utilization of water–solid interactions,it is of utmost importance to conduct an in-depth investigation and propose a regulatory concept encompassing ion transport.Herein,we propose tortuosity regulation of 2D nanofluidic titanium oxide(Ti_(0.87)O_(2))films to optimize the ion transport within the interlayer nanochannel for enhanced efficiency in water evaporation-induced electricity generation for the first time.The significance of tortuosity in ion transport is elucidated by designing three 2D nanofluidic films with different tortuosity.Tortuosity analysis and in situ Raman measurement demonstrate that low tortuosity can facilitate the formation of efficient pathways for hydrated proton transport and promote water–solid interactions.Consequently,devices fabricated with the optimized 2D nanofluidic films exhibited a significantly enhanced output power density of approximately 204.01μW·cm^(−2),far exceeding those prepared by the high-tortuosity 2D nanofluidic films.This work highlights the significance of the construction of low tortuosity channels for 2D nanofluidic films with excellent performance.

Photocatalytic applications and modification methods of two-dimensional nanomaterials:a review

Due to its unique electronic structure and special size effect,two-dimensional(2D)nanomaterials have shown great potential far beyond bulk materials in the field of photocatalysis.How to deeply explore the photocatalytic mechanism of 2D nanomaterials and design more efficient 2D semiconductor photocatalysts are research hotspots.This review provides a comprehensive introduction to typical 2D nanomaterials and discusses their current application status in the field of photocatalysis.The effects of material properties such as band structure,morphology,crystal face structure,crystal structure and surface defects on the photocatalytic process are discussed.The main modification methods are highlighted,including doping,noble metal deposition,heterojunction,thickness adjustment,defect engineering,and dye sensitization in 2D material systems.Finally,the future development of 2D nanomaterials is prospected.It is hoped that this paper can provide systematic and useful information for researchers engaged in the field of photocatalysis.

Selective and asymmetric ion transport in covalent organic framework-based two-dimensional nanofluidic devices

Two-dimensional(2D)covalent organic framework(COF)mem-branes featuring well-aligned and programmable vertical nano-channels have emerged as a promising candidate for advanced nanofluidic devices and showcased vast potential in the fields of smart-gating,ion-separation,and energy-harvesting.However,the transverse interlayer nanochannels with a height of sub-nanometer-scale in 2D-COF membranes have scarcely been studied in com-parison.Here,we report the ion transport characteristics in 2D interlayer nanochannels of protonated CoF membranes.The dis-tinct surface-charge-governed ionic conductance in domination of electrolyte concentration below 1o-3 M as well as the exceptional anion/cation(Cl^(-)/K^(+))selectivity is revealed due to the pronounced charge and nano-confinement effects.Additionally,evident ion current rectification is witnessed when incorporating asymmetric geometry into the system,which is attributed to the dynamic process of ion enrichment and dissipation within the protonated nanochannels.This work offers immense prospects for 2D-COF membranes in the fields of biomimetic nanofluidic devices and cutting-edge electronic devices.

Control of light-matter interactions in two-dimensional materials with nanoparticle-on-mirror structures

Light–matter interactions in two-dimensional(2D)materials have been the focus of research since the discovery of graphene.The light–matter interaction length in 2D materials is,however,much shorter than that in bulk materials owing to the atomic nature of 2D materials.Plasmonic nanostructures are usually integrated with 2D materials to enhance the light–matter interactions,offering great opportunities for both fundamental research and technological applications.Nanoparticle-on-mirror(NPo M)structures with extremely confined optical fields are highly desired in this aspect.In addition,2D materials provide a good platform for the study of plasmonic fields with subnanometer resolution and quantum plasmonics down to the characteristic length scale of a single atom.A focused and up-to-date review article is highly desired for a timely summary of the progress in this rapidly growing field and to encourage more research efforts in this direction.In this review,we will first introduce the basic concepts of plasmonic modes in NPo M structures.Interactions between plasmons and quasi-particles in 2D materials,e.g.,excitons and phonons,from weak to strong coupling and potential applications will then be described in detail.Related phenomena in subnanometer metallic gaps separated by 2D materials,such as quantum tunneling,will also be touched.We will finally discuss phenomena and physical processes that have not been understood clearly and provide an outlook for future research.We believe that the hybrid systems of2D materials and NPo M structures will be a promising research field in the future.

Effective Qubit Emerging from the Nanoheterointerface Two-Dimensional Electron Gas Photodynamics

An “Eigenstate Adjustment Autonomy” Model, permeated by the Nanosystem’s Fermi Level Pinning along with its rigid Conduction Band Discontinuity, compatible with pertinent Experimental Measurements, is being employed for studying how the Functional Eigenstate of the Two-Dimensional Electron Gas (2DEG) dwelling within the Quantum Well of a typical Semiconductor Nanoheterointerface evolves versus (cryptographically) selectable consecutive Cumulative Photon Dose values. Thus, it is ultimately discussed that the experimentally observed (after a Critical Cumulative Photon Dose) Phenomenon of 2DEG Negative Differential Mobility allows for the Nanosystem to exhibit an Effective Qubit Specific Functionality potentially conducive to (Telecommunication) Quantum Information Registering.

A novel two-dimensional nanoheterojunction via facilitating electron–hole pairs separation for synergistic tumor phototherapy and immunotherapy

Nanomaterial-mediated phototherapy in tumor treatment has been developed rapidly in the past few years due to its noninvasive character.However,the low energy conversion efficiency and high recombination rate of the photo-triggered electron–hole pairs of single nano-agent limit the phototherapy efficiency.Herein,we constructed a novel two-dimensional nanoheterojunction MoS_(2)-Ti_(3)C_(2)(MT),which allowed a high photothermal conversion efficiency(59.1%)as well as an effective separation of photo-triggered electron–hole pairs for reactive oxygen species(ROS)generation under single 808 nm laser irradiation.Upon the modification of the mitochondrial targeted molecule(3-proxycarboxylic)triphenyl phosphine bromide(TPP)and 4T1 cell membrane,m@MoS_(2)-Ti_(3)C_(2)/TPP(m@MTT)could effectively target to the tumor cell and further locate to the mitochondria to amplify tumor-specific oxidative stress,which not merely effectively inhibits the local tumor growth but also induces tumor immunogenic cell death(ICD)for activating antitumor immune response.Additionally,cytosine guanine dinucleotide(CPG),as a Toll-like receptor 9(TLR9)agonist,was further introduced to the system to boost adaptive immune responses,resulting in improved level of cytotoxic T cells as well as a decrease in the number of regulatory T cells.In vivo antitumor mechanism studies demonstrated that not only the primary and distant tumors in 4T1 bearing-tumor mice model were significantly inhibited,but also the lung metastasis of tumor was effectively suppressed.Therefore,this work revealed the ROS generation mechanism of MT nanoheterojunction and provided a novel strategy to fabricate a biomedically applicable MT nanoheterojunction for tumor treatment.

Phase engineering two-dimensional nanostructures for electrocatalytic hydrogen evolution reaction

Hydrogen(H2)is considered to be a promising substitute for fossil fuels.Two-dimensional(2D)nanomaterials have exhibited an efficient electrocatalytic capacity to catalyze hydrogen evolution reaction(HER).Particularly,phase engineering of 2D nanomaterials is opening a novel research direction to endow 2D nanostructures with fascinating properties for deep applications in catalyzing HER.In this review,we briefly summarize the research progress and present the current challenges on phase engineering of 2D nanomaterials for their applications in electrocatalytic HER.Our summary will be of significance to provide fundamental understanding for designing novel 2D nanomaterials with unconventional phases to electrochemically catalyze HER.

Bifunctional Two-Dimensional Nanocomposite with Electromagnetic Wave Absorption and Anti-bacterial Performance

In current electronic information era,the complex application circumstance of 5G devices pursues the exploration of multi-functional electromagnetic wave(EMW)absorbent materials and it has become the crucial focus in industrial development.A two-dimensional(2D)graphite nanosheet decorated by nickel nanocapsules(2D graphite/Ni@C nanocomposite)was fabricated to possess the EMW absorption and the Escherichia coli(E.coli)anti-bacterial performance simultaneously.By adjusting the filling ratio and injecting nitrogen doping,the value of minimum reflection loss is−36.08 dB and the effective absorption bandwidth reaches to 5.12 GHz(from 11.4 to 16.52 GHz)with the mass ratio of 30 wt%and the absorber thickness of 2 mm.This 2D nanocomposite simultaneously gets an excellent anti-bacterial function expressing an E.coli anti-bacterial rate of 92%during 24 h which is significantly correlated to the interaction between the nanostructure of the 2D nanographite and the nickel ion released from Ni@C nanocapsules.This work provides a new approach to develop a promising 2D anti-bacterial EMW absorber.

Progress on two-dimensional ferrovalley materials

The electron's charge and spin degrees of freedom are at the core of modern electronic devices. With the in-depth investigation of two-dimensional materials, another degree of freedom, valley, has also attracted tremendous research interest. The intrinsic spontaneous valley polarization in two-dimensional magnetic systems, ferrovalley material, provides convenience for detecting and modulating the valley. In this review, we first introduce the development of valleytronics.Then, the valley polarization forms by the p-, d-, and f-orbit that are discussed. Following, we discuss the investigation progress of modulating the valley polarization of two-dimensional ferrovalley materials by multiple physical fields, such as electric, stacking mode, strain, and interface. Finally, we look forward to the future developments of valleytronics.

Recent advances in two-dimensional photovoltaic devices

Two-dimensional(2D)materials have attracted tremendous interest in view of the outstanding optoelectronic properties,showing new possibilities for future photovoltaic devices toward high performance,high specific power and flexibility.In recent years,substantial works have focused on 2D photovoltaic devices,and great progress has been achieved.Here,we present the review of recent advances in 2D photovoltaic devices,focusing on 2D-material-based Schottky junctions,homojunctions,2D−2D heterojunctions,2D−3D heterojunctions,and bulk photovoltaic effect devices.Furthermore,advanced strategies for improving the photovoltaic performances are demonstrated in detail.Finally,conclusions and outlooks are delivered,providing a guideline for the further development of 2D photovoltaic devices.

Unlocking the potential of ultra-thin two-dimensional antimony materials:Selective growth and carbon coating for efficient potassium-ion storage

Antimony-based anodes have attracted wide attention in potassium-ion batteries due to their high theoretical specific capacities(∼660 mA h g^(-1))and suitable voltage platforms.However,severe capacity fading caused by huge volume change and limited ion transportation hinders their practical applications.Recently,strategies for controlling the morphologies of Sb-based materials to improve the electrochemical performances have been proposed.Among these,the two-dimensional Sb(2D-Sb)materials present excellent properties due to shorted ion immigration paths and enhanced ion diffusion.Nevertheless,the synthetic methods are usually tedious,and even the mechanism of these strategies remains elusive,especially how to obtain large-scale 2D-Sb materials.Herein,a novel strategy to synthesize 2D-Sb material using a straightforward solvothermal method without the requirement of a complex nanostructure design is provided.This method leverages the selective adsorption of aldehyde groups in furfural to induce crystal growth,while concurrently reducing and coating a nitrogen-doped carbon layer.Compared to the reported methods,it is simpler,more efficient,and conducive to the production of composite nanosheets with uniform thickness(3–4 nm).The 2D-Sb@NC nanosheet anode delivers an extremely high capacity of 504.5 mA h g^(-1) at current densities of 100 mA g^(-1) and remains stable for more than 200 cycles.Through characterizations and molecular dynamic simulations,how potassium storage kinetics between 2D Sb-based materials and bulk Sb-based materials are explored,and detailed explanations are provided.These findings offer novel insights into the development of durable 2D alloy-based anodes for next-generation potassium-ion batteries.

Recent progress on valley polarization and valley-polarized topological states in two-dimensional materials

Valleytronics, using valley degree of freedom to encode, process, and store information, may find practical applications in low-power-consumption devices. Recent theoretical and experimental studies have demonstrated that twodimensional(2D) honeycomb lattice systems with inversion symmetry breaking, such as transition-metal dichalcogenides(TMDs), are ideal candidates for realizing valley polarization. In addition to the optical field, lifting the valley degeneracy of TMDs by introducing magnetism is an efficient way to manipulate the valley degree of freedom. In this paper, we first review the recent progress on valley polarization in various TMD-based systems, including magnetically doped TMDs,intrinsic TMDs with both inversion and time-reversal symmetry broken, and magnetic TMD heterostructures. When topologically nontrivial bands are empowered into valley-polarized systems, valley-polarized topological states, namely valleypolarized quantum anomalous Hall effect can be realized. Therefore, we have also reviewed the theoretical proposals for realizing valley-polarized topological states in 2D honeycomb lattices. Our paper can help readers quickly grasp the latest research developments in this field.

Global dust density in two-dimensional complex plasma

The driven-dissipative Langevin dynamics simulation is used to produce a two-dimensional(2D) dense cloud, which is composed of charged dust particles trapped in a quadratic potential. A 2D mesh grid is built to analyze the center-to-wall dust density. It is found that the local dust density in the outer region relative to that of the inner region is more nonuniform,being consistent with the feature of quadratic potential. The dependences of the global dust density on equilibrium temperature, particle size, confinement strength, and confinement shape are investigated. It is found that the particle size, the confinement strength, and the confinement shape strongly affect the global dust density, while the equilibrium temperature plays a minor effect on it. In the direction where there is a stronger confinement, the dust density gradient is bigger.

Boosting MA-based two-dimensional Ruddlesden-Popper perovskite solar cells by incorporating a binary spacer

Two-dimensional Ruddlesden-Popper(2DRP)perovskite exhibits excellent stability in perovskite solar cells(PSCs)due to introducing hydrophobic long-chain organic spacers.However,the poor charge transporting property of bulky organic cation spacers limits the performance of 2DRP PSCs.Inspired by the Asite cation alloying strategy in 3D perovskites,2DRP perovskites with a binary spacer can promote charge transporting compared to the unary spacer counterparts.Herein,the superior MA-based 2DRP perovskite films with a binary spacer,including 3-guanidinopropanoic acid(GPA)and 4-fluorophenethylamine(FPEA)are realized.These films(GPA_(0.85)FPEA_(0.15))_(2)MA_(4)Pb_5I_(16)show good morphology,large grain size,decreased trap state density,and preferential orientation of the as-prepared film.Accordingly,the present 2DRP-based PSC with the binary spacer achieves a remarkable efficiency of 18.37%with a V_(OC)of1.15 V,a J_(SC)of 20.13 mA cm^(-2),and an FF of 79.23%.To our knowledge,the PCE value should be the highest for binary spacer MA-based 2DRP(n≤5)PSCs to date.Importantly,owing to the hydrophobic fluorine group of FPEA and the enhanced interlayer interaction by FPEA,the unencapsulated 2DRP PSCs based on binary spacers exhibit much excellent humidity stability and thermal stability than the unary spacer counterparts.

Anomalous valley Hall effect in two-dimensional valleytronic materials

The anomalous valley Hall effect(AVHE)can be used to explore and utilize valley degrees of freedom in materials,which has potential applications in fields such as information storage,quantum computing and optoelectronics.AVHE exists in two-dimensional(2D)materials possessing valley polarization(VP),and such 2D materials usually belong to the hexagonal honeycomb lattice.Therefore,it is necessary to achieve valleytronic materials with VP that are more readily to be synthesized and applicated experimentally.In this topical review,we introduce recent developments on realizing VP as well as AVHE through different methods,i.e.,doping transition metal atoms,building ferrovalley heterostructures and searching for ferrovalley materials.Moreover,2D ferrovalley systems under external modulation are also discussed.2D valleytronic materials with AVHE demonstrate excellent performance and potential applications,which offer the possibility of realizing novel low-energy-consuming devices,facilitating further development of device technology,realizing miniaturization and enhancing functionality of them.

Low-frequency hybridized excess vibrations of two-dimensional glasses

One hallmark of glasses is the existence of excess vibrational modes at low frequenciesωbeyond Debye’s prediction.Numerous studies suggest that understanding low-frequency excess vibrations could help gain insight into the anomalous mechanical and thermodynamic properties of glasses.However,there is still intensive debate as to the frequency dependence of the population of low-frequency excess vibrations.In particular,excess modes could hybridize with phonon-like modes and the density of hybridized excess modes has been reported to follow D_(exc)(ω)~ω^(2)in 2D glasses with an inverse power law potential.Yet,the universality of the quadratic scaling remains unknown,since recent work suggested that interaction potentials could influence the scaling of the vibrational spectrum.Here,we extend the universality of the quadratic scaling for hybridized excess modes in 2D to glasses with potentials ranging from the purely repulsive soft-core interaction to the hard-core one with both repulsion and attraction as well as to glasses with significant differences in density or interparticle repulsion.Moreover,we observe that the number of hybridized excess modes exhibits a decrease in glasses with higher density or steeper interparticle repulsion,which is accompanied by a suppression of the strength of the sound attenuation.Our results indicate that the density bears some resemblance to the repulsive steepness of the interaction in influencing low-frequency properties.

Emerging two-dimensional Mo-based materials for rechargeable metal-ion batteries:Advances and perspectives

With the rapid development of rechargeable metal-ion batteries(MIBs)with safety,stability and high energy density,significant efforts have been devoted to exploring high-performance electrode materials.In recent years,two-dimensional(2D)molybdenum-based(Mo-based)materials have drawn considerable attention due to their exceptional characteristics,including low cost,unique crystal structure,high theoretical capacity and controllable chemical compositions.However,like other transition metal compounds,Mo-based materials are facing thorny challenges to overcome,such as slow electron/ion transfer kinetics and substantial volume changes during the charge and discharge processes.In this review,we summarize the recent progress in developing emerging 2D Mo-based electrode materials for MIBs,encompassing oxides,sulfides,selenides,carbides.After introducing the crystal structure and common synthesis methods,this review sheds light on the charge storage mechanism of several 2D Mo-based materials by various advanced characterization techniques.The latest achievements in utilizing 2D Mo-based materials as electrode materials for various MIBs(including lithium-ion batteries(LIBs),sodium-ion batteries(SIBs)and zinc-ion batteries(ZIBs))are discussed in detail.Afterwards,the modulation strategies for enhancing the electrochemical performance of 2D Mo-based materials are highlighted,focusing on heteroatom doping,vacancies creation,composite coupling engineering and nanostructure design.Finally,we present the existing challenges and future research directions for 2D Mo-based materials to realize high-performance energy storage systems.