Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications.

Transition metal dichalcogenides (TMDs) are a promising class of layered materials in the post-graphene era, with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior. Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties, providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs. The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable (opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts (0-100%). Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase, band alignment/structure, carrier density, and surface reactive activity, enabling novel and promising applications. This review comprehensively elaborates on atomically substitutional engineering in TMD layers, including theoretical foundations, synthetic strategies, tailored properties, and superior applications. The emerging type of ternary TMDs, Janus TMDs, is presented specifically to highlight their typical compounds, fabrication methods, and potential applications. Finally, opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Intrinsic Optical Properties and Emerging Applications of Gold Nanostructures.

The collective oscillation of free electrons at the nanoscale surface of gold nanostructures is closely modulated by tuning the size, shape/morphology, phase, composition, hybridization, assembly, and nanopatterning, along with the surroundings of the plasmonic surface located at a dielectric interface with air, liquid, and solid. This review first introduces the physical origin of the intrinsic optical properties of gold nanostructures and further summarizes stimuli-responsive changes in optical properties, metal-field-enhanced optical signals, luminescence spectral shaping, chiroptical response, and photogenerated hot carriers. The current success in the landscape of nanoscience and nanotechnology mainly originates from the abundant optical properties of gold nanostructures in the thermodynamically stable face-centered cubic (fcc) phase. It has been further extended by crystal phase engineering to prepare thermodynamically unfavorable phases (e.g., kinetically stable) and heterophases to modulate their intriguing phase-dependent optical properties. A broad range of promising applications, including but not limited to full-color displays, solar energy harvesting, photochemical reactions, optical sensing, and microscopic/biomedical imaging, have fostered parallel research on the multitude of physical effects occurring in gold nanostructures.

Thermoelectric Silver-Based Chalcogenides.

Heat is abundantly available from various sources including solar irradiation, geothermal energy, industrial processes, automobile exhausts, and from the human body and other living beings. However, these heat sources are often overlooked despite their abundance, and their potential applications remain underdeveloped. In recent years, important progress has been made in the development of high-performance thermoelectric materials, which have been extensively studied at medium and high temperatures, but less so at near room temperature. Silver-based chalcogenides have gained much attention as near room temperature thermoelectric materials, and they are anticipated to catalyze tremendous growth in energy harvesting for advancing internet of things appliances, self-powered wearable medical systems, and self-powered wearable intelligent devices. This review encompasses the recent advancements of thermoelectric silver-based chalcogenides including binary and multinary compounds, as well as their hybrids and composites. Emphasis is placed on strategic approaches which improve the value of the figure of merit for better thermoelectric performance at near room temperature via engineering material size, shape, composition, bandgap, etc. This review also describes the potential of thermoelectric materials for applications including self-powering wearable devices created by different approaches. Lastly, the underlying challenges and perspectives on the future development of thermoelectric materials are discussed.

BSA-assisted hydrothermal conversion of MoS2 nanosheets into quantum dots with high yield and bright fluorescence for constructing a sensing platform via dual quenching effects.

With large surface-responsive and excitation-dependent fluorescence, two-dimensional fluorescent quantum dots (QDs) have been receiving tremendous attention to develop their facile synthetic approaches and/or expand their promising applications. Here, a two-step strategy is demonstrated for high-yield production of MoS2 QDs from MoS2 powder through first sonication-driven exfoliation and subsequent hydrothermal splitting with the assistance of bovine serum albumin (BSA). Experimentally, ∼100 nm-sized MoS2 nanosheets are ultrasonically exfoliated from MoS2 powder in a BSA solution, and further hydrothermally split into âˆ¼ 8.2 nm-sized QDs (NQDs) at 200 °C. In addition to their excellent stability/dispersibility in aqueous solution, the resultant MoS2 NQDs also exhibit much brighter blue fluorescence than those synthesized by other methods. The strong fluorescence is significantly quenched by p-nitrophenol for constructing a sensitive sensor with high selectivity, which is attributed to dual quenching effects from inner filter effect (IFE) and fluorescence resonance energy transfer (FRET). Interestingly, with the increment of pH from 5 to 10, the ratio of IFE in fluorescence quenching gradually decreases accompanied by an increment of FRET ratio, resulting in the high sensitivity and responsivity for detecting p-nitrophenol at a wide range of pH. Clearly, the MoS2 NQD-based sensing approach demonstrates a promising potential for selective detection and fast analysis of pollutants in environment monitoring and security screening.

Highly Transparent, Dual-Color Emission, Heterophase Cs3Cu2I5/CsCu2I3 Nanolayer for Transparent Luminescent Solar Concentrators.

Transparent luminescent solar concentrators (TLSCs) have been attracting wide attentions for their applications in transparent photovoltaic (PV) windows, smart greenhouses, and mobile electronics on account of the simple architecture and low-cost preparation. We report a novel strategy to fabricate TLSCs using the heterophase lead-free perovskites. The heterophase nanolayered films which combined CsCu2I3 and Cs3Cu2I5 were prepared in one step using a dual-source coevaporation technique. The CsCu2I3/Cs3Cu2I5 films exhibited UV light absorption, a high average visible transmission (AVT) of 86.70%, and dual-color white emission between 350 and 760 nm. Importantly, the TLSCs incorporated with the CsCu2I3/Cs3Cu2I5 films exhibited an impressive optical conversion efficiency of 1.15% under keeping a high AVT of 86.70%. Meanwhile, the TLSCs incorporated with the heterophase films showed considerable stability under ambient conditions. The CIE 1960 color coordinates (0.2082, 0.4680) of the TLSCs incorporated with the CsCu2I3/Cs3Cu2I5 films showed excellent aesthetic quality as compared with those of the TLSCs incorporated with lead-based perovskites. Our finding offers a strategy to prepare lead-free metal halides toward high-performance TLSCs and future transparent PV windows.

Metal-facilitated Photocatalytic Nanohybrids: Rational Design and Promising Environmental Applications.

As a promising technique to potentially address the energy crisis and environmental issues, photocatalysis has been reported widely to exhibit various outstanding behaviors in production of new fuels/chemicals and treatment of contaminants. The photocatalytic performance is extremely dependent on the used photocatalysts, so that the design and preparation of efficient photocatalysts are critically important for significantly improving the photocatalytic activity. Among various strategies, the hybridization of metal with semiconductors has recently been attracting more and more research interest owing to their expended spectral absorption, promoted transferring rate of charge carriers and Plasmon-enhanced effect. In this minireview, the metal-facilitated hybrid photocatalysts are overviewed comprehensively to first reveal unique functions of metals in improvement of photoactivity and summarize the emerging metal-involved hybrid systems. Subsequently, the synthetic methods towards hybrid photocatalysts are introduced and their practical applications are emphasized in environmental remediation including degradation of organic pollutants, conversion of harmful gases, treatment of heavy metal ions and sterilization of bacteria. At the end, the challenges for industrializing these hybrid photocatalysts are discussed carefully and future development is suggested rationally.

Plasmonically Modulated Gold Nanostructures for Photothermal Ablation of Bacteria.

With the wide utilization of antibiotics, antibiotic-resistant bacteria have been often developed more frequently to cause potential global catastrophic consequences. Emerging photothermal ablation has been attracting extensive research interest for quick/effective eradication of pathogenic bacteria from contaminated surroundings and infected body. In this field, anisotropic gold nanostructures with tunable size/morphologies have been demonstrated to exhibit their outstanding photothermal performance through strong plasmonic absorption of near-infrared (NIR) light, efficient light to heat conversion, and easy surface modification for targeting bacteria. To this end, this review first introduces thermal treatment of infectious diseases followed by photothermal therapy via heat generation on NIR-absorbing gold nanostructures. Then, the usual synthesis and spectral features of diversified gold nanostructures and composites are systematically overviewed with the emphasis on the importance of size, shape, and composition to achieve strong plasmonic absorption in NIR region. Further, the innovated photothermal applications of gold nanostructures are comprehensively demonstrated to combat against bacterial infections, and some constructive suggestions are also discussed to improve photothermal technologies for practical applications.

Innovative utilization of molecular imprinting technology for selective adsorption and (photo)catalytic eradication of organic pollutants.

The rapid development of industrialization and urbanization results in a numerous production of various organic chemicals to meet the increasing demand in high-quality life. During the synthesis and utilization of these chemical products, their residues unavoidably emerged in environments to severely threaten human's health. It is thus urgent to exploit effective technology for readily removing the organic pollutants with high selectivity and good reusability. As one of the most promising approaches, molecular imprinting technology (MIT) employs a chemically synthetic route to construct artificial recognition sites in highly-crosslinked matrix with complementary cavity and functional groups to target species, which have been attracting more and more interest for environmental remediation, such as the selective adsorption/separation and improved catalytic degradation of pollutants. In this review, MIT is first introduced briefly to understand their preparing process, recognition mechanism and common imprinted systems. Then, their specific binding affinities are demonstrated for selectively adsorbing and removing target molecules with a large capacity. Furthermore, the innovative utilization of MIT in catalytic eradication of pollutants is comprehensively overviewed to emphasize their enhanced efficiency and improved performances, which are classified by the used catalytically-active nanocrystals and imprinted systems. After summarizing recent advances in these fields, some limitations are discussed and possible suggestions are given to guide the future exploitation on MIT for environmental protection.

Hybridized 2D Nanomaterials Toward Highly Efficient Photocatalysis for Degrading Pollutants: Current Status and Future Perspectives.

Organic pollutants including industrial dyes and chemicals and agricultural waste have become a major environmental issue in recent years. As an alternative to simple adsorption, photocatalytic decontamination is an efficient and energy-saving technology to eliminate these pollutants from water environment, utilizing the energy of external light, and unique function of photocatalysts. Having a large specific surface area, numerous active sites, and varied band structures, 2D nanosheets have exhibited promising applications as an efficient photocatalyst for degrading organic pollutants, particularly hybridization with other functional components. The novel hybridization of 2D nanomaterials with various functional species is summarized systematically with emphasis on their enhanced photocatalytic activities and outstanding performances in environmental remediation. First, the mechanism of photocatalytic degradation is given for discussing the advantages/shortcomings of regular 2D materials and identifying the importance of constructing hybrid 2D photocatalysts. An overview of several types of intensively investigated 2D nanomaterials (i.e., graphene, g-C3 N4 , MoS2 , WO3 , Bi2 O3 , and BiOX) is then given to indicate their hybridized methodologies, synergistic effect, and improved applications in decontamination of organic dyes and other pollutants. Finally, future research directions are rationally suggested based on the current challenges.

Functionalized Hybridization of 2D Nanomaterials.

The discovery of graphene and subsequent verification of its unique properties have aroused great research interest to exploit diversified graphene-analogous 2D nanomaterials with fascinating physicochemical properties. Through either physical or chemical doping, linkage, adsorption, and hybridization with other functional species into or onto them, more novel/improved properties are readily created to extend/expand their functionalities and further achieve great performance. Here, various functionalized hybridizations by using different types of 2D nanomaterials are overviewed systematically with emphasis on their interaction formats (e.g., in-plane or inter plane), synergistic properties, and enhanced applications. As the most intensely investigated 2D materials in the post-graphene era, transition metal dichalcogenide nanosheets are comprehensively investigated through their element doping, physical/chemical functionalization, and nanohybridization. Meanwhile, representative hybrids with more types of nanosheets are also presented to understand their unique surface structures and address the special requirements for better applications. More excitingly, the van der Waals heterostructures of diverse 2D materials are specifically summarized to add more functionality or flexibility into 2D material systems. Finally, the current research status and faced challenges are discussed properly and several perspectives are elaborately given to accelerate the rational fabrication of varied and talented 2D hybrids.

Morphological Growth and Theoretical Understanding of Gold and Other Noble Metal Nanoplates.

For the last decades, the chemical reduction of Au3+ to Au0 has been widely employed to produce various gold nanostructures. In comparison with the fast reduction, the slow reduction is systematically investigated in this research to provide more insights to reveal intermediary process and further disclose the underlying mechanism for growing gold nanostructures by using a series of simple ligands with aldehyde groups as weak reducing agents. The different binding energies of ligands to Aun+ (n=3, 1 and 0) exhibit variable binding affinities in starting, intermediate, and final gold species. For example, formic acid has much stronger binding affinity to Au+ than Au3+ , and thus Au+ intermediate is able to be stabilized/captured during slow reduction of Au3+ . Upon the disproportionation of Au+ to Au0 and Au3+ , formic acid has much stronger binding affinity to the newly formed Au0 than other ligands for the controlled formation of gold nanostructures. Meanwhile, the adsorption of ligands causes substantially decreased surface energies on different gold planes. There are much higher energies on {110} planes compared to the other two {111} and {100} planes with certain ratios in these energies, leading to morphological growth of gold nanosheets. In this paper, we experimentally demonstrate anisotropic growth of gold nanosheets by using various ligands with weak reducing and appropriate coordination capabilities, and further provide insights to understand their morphological growth mechanism behind. This synthetic strategy is successfully extended to prepare silver, palladium, and platinum nanoplates.

Hydrophobic-Force-Driven Removal of Organic Compounds from Water by Reduced Graphene Oxides Generated in Agarose Hydrogels.

Hydrophobic reduced graphene oxides (rGOs) were generated in agarose hydrogel beads (AgarBs) by NaBH4 reduction of graphene oxides (GOs) initially loaded in the AgarBs. The resulting rGO-loaded AgarBs were able to effectively adsorb organic compounds in water as a result of the attractive hydrophobic force between the rGOs in the AgarBs and the organic compounds dissolved in aqueous media. The adsorption capacity of the rGOs was fairly high even toward reasonably water-soluble organic compounds such as rhodamine B (321.7 mg g-1 ) and aspirin (196.4 mg g-1 ). Yet they exhibited salinity-enhanced adsorption capacity and preferential adsorption of organic compounds with lower solubility in water. Such peculiar adsorption behavior highlights the exciting possibility for adopting an adsorption strategy, driven by hydrophobic forces, in practical wastewater treatment processes.

BSA-caged metal clusters to exfoliate MoS2 nanosheets towards their hybridized functionalization.

Herein, we develop a facile exfoliation and in situ functionalization strategy to produce hybridized Au/MoS2 nanostructures comprised of size-controlled gold nanoparticles (Au NPs) and ultrathin MoS2 nanosheets by using bovine serum albumin (BSA)-caged Au25 clusters as both exfoliating and functionalizing agents. As revealed, BSA molecules are strongly adsorbed on MoS2via their hydrophobic interaction, and this drives the expansion of the BSA molecules that initially protect Au25 cores at pH 4, leading to the effective exfoliation of MoS2 nanosheets together with the epitaxial growth of Au25 cores into 5 nm-sized Au NPs on MoS2 nanosheets due to their reduced surface protection. Upon the addition of H2O2, the resulting Au NPs can further grow to achieve a controlled size from 5 to 30 nm with an increase of the reaction time. It is demonstrated that the hybridized Au/MoS2 nanosheets exhibit a better performance in the photocatalytic degradation of substrates compared to the individual components or their mixture. Moreover, the hybridized Ag/MoS2, Au/WO3 and Au/graphene nanosheets are further produced by the usage of BSA-caged Ag and Au clusters, respectively. Overall, this work reports the first utilization of protein-caged metal clusters for the exfoliation and hybridized functionalization of 2D materials, and this brings more opportunities to exploit unusual properties of hybridized 2D materials for novel applications.

Electrostatic-Driven Exfoliation and Hybridization of 2D Nanomaterials.

Here, direct and effective electrostatic-driven exfoliation of tungsten trioxide (WO3 ) powder into atomically thin WO3 nanosheets is demonstrated for the first time. Experimental evidence together with theoretical simulations clearly reveal that the strong binding of bovine serum albumin (BSA) on the surface of WO3 via the protonation of NH2 groups in acidic conditions leads to the effective exfoliation of WO3 nanosheets under sonication. The exfoliated WO3 nanosheets have a greatly improved dispersity and stability due to surface-protective function of BSA, and exhibit a better performance and unique advantages in applications such as visible-light-driven photocatalysis, high-capacity adsorption, and fast electrochromics. Further, simultaneous exfoliation and hybridization of WO3 and MoS2 nanosheets are demonstrated to form hybrid WO3 /MoS2 nanosheets through respective electrostatic and hydrophobic interaction processes. In addition, this electrostatic-driven exfoliation strategy is applied to exfoliate ultrathin black-phosphorus nanosheets from its bulk to exhibit a greatly improved stability due to the surface protection by BSA. Overall, the work presented not only presents a facile and effective route to fabricate 2D materials but also brings more opportunities to exploit unusual exotic and synergistic properties in resulting hybrid 2D materials for novel applications.

Carbon nanoscroll-silk crystallite hybrid structures with controllable hydration and mechanical properties.

Hybrid structures of nanomaterials (e.g. tubes, scrolls, threads, cages) and biomaterials (e.g. proteins) hold tremendous potential for applications as drug carriers, biosensors, tissue scaffolds, cancer therapeutic agents, etc. However, in many cases, the interacting forces at the nano-bio interfaces and their roles in controlling the structures and dynamics of nano-bio-hybrid systems are very complicated but poorly understood. In this study, we investigate the structure and mechanical behavior of a protein-based hybrid structure, i.e., a carbon nanoscroll (CNS)-silk crystallite with a hydration level controllable by an interlayer interaction in CNS. Our findings demonstrate that CNS with a reduced core size not only shields the crystallite from a weakening effect of water, but also markedly strengthens the crystallite. Besides water shielding, the enhanced strength arises from an enhanced interaction between the crystallite and CNS due to the enhanced interlayer interaction in CNS. In addition, the interfacial strength for pulling the crystallite out of the CNS-silk structure is found to be dependent on both the interlayer interaction energy in CNS as well as the sequence of protein at the CNS-silk interface. The present study is of significant value in designing drugs or protein delivery vehicles for biomedical applications, and serves as a general guide in designing novel devices based on rolled-up configurations of two-dimensional (2D) materials.

Preparation, Functionality, and Application of Metal Oxide-coated Noble Metal Nanoparticles.

With their remarkable properties and wide-ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal-oxide components. In this review, particular attention is given to core-shell type metal oxide-coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard.

Visualization of exhaled hydrogen sulphide on test paper with an ultrasensitive and time-gated luminescent probe.

Luminescent chemosensors for hydrogen sulphide (H2S) are of great interest because of the close association of H2S with our health. However, current probes for H2S detection have problems such as low sensitivity/selectivity, poor aqueous-solubility or interference from background fluorescence. This study reports an ultrasensitive and time-gated "switch on" probe for detection of H2S, and its application in test paper for visualization of exhaled H2S. The complex probe is synthesized with a luminescent Tb(3+) centre and three ligands of azido (-N3) substituted pyridine-2,6-dicarboxylic acid, giving the probe high hydrophilicity and relatively fast reaction dynamics with H2S because there are three -N3 groups in each molecule. The introduced -N3 group as a strong electron-withdrawing moiety effectively changes the energy level of ligand via intramolecular charge transfer (ICT), and thus breaks the energy transferring from ligand to lanthanide ion, resulting in quenching of Tb(3+) luminescence. On addition of H2S, the -N3 group can be reduced to an amine group to break the process of ICT, and the luminescence of Tb(3+) is recovered at a nanomolar sensitivity level. With a long lifetime of luminescence of Tb(3+) centre (1.9 ms), use of a time-gated technique effectively eliminates the background fluorescence by delaying fluorescence collection for 0.1 ms. The test paper imprinted by the complex probe ink can visualize clearly the trace H2S gas exhaled by mice.

Color-Multiplexing-Based Fluorescent Test Paper: Dosage-Sensitive Visualization of Arsenic(III) with Discernable Scale as Low as 5 ppb.

Fluorescent colorimetry test papers are promising for the assays of environments, medicines, and foods by the observation of the naked eye on the variations of fluorescence brightness and color. Unlike dye-absorption-based pH test paper, however, the fluorescent test papers with wide color-emissive variations with target dosages for accurate quantification remain unsuccessful even if the multicolorful fluorescent probes are used. Here, we report the dosage-sensitive fluorescent colorimetry test paper with a very wide/consecutive "from red to cyan" response to the presence and amount of arsenic ions, As(III). Red quantum dots (QDs) were modified with glutathione and dithiothreitol to obtain the supersensitivity to As(III) by the quenching of red fluorescence through the formation of dispersive QDs aggregates. A small amount of cyan carbon dots (CDs) with spectral blue-green components as the photostable internal standard were mixed into the QDs solution to produce a composited red fluorescence. Upon the addition of As(III) into the sensory solution, the fluorescence color could gradually be reversed from red to cyan with a detection limit of 1.7 ppb As(III). When the sensory solution was printed onto a piece of filter paper, surprisingly a serial of color evolution from peach to pink to orange to khaki to yellowish to yellow-green to final cyan with the addition of As(III) was displayed and clearly discerned the dosage scale as low as 5 ppb. The methodology reported here opens a novel pathway toward the real applications of fluorescent test papers.

High-Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide.

High-level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag(+) in the synthesis of bovine serum albumin (BSA)-protected Au NCs, and the resulting structure is determined to be bimetallic Ag28 Au10-BSA NCs through a series of characterizations including energy-dispersive X-ray spectroscopy, mass spectroscopy, and X-ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag28 Au10 NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag28 Au10 NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low-level incorporation of Ag or by using the individual metal NCs.

Peptide-Graphene Interactions Enhance the Mechanical Properties of Silk Fibroin.

Studies reveal that biomolecules can form intriguing molecular structures with fascinating functionalities upon interaction with graphene. Then, interesting questions arise. How does silk fibroin interact with graphene? Does such interaction lead to an enhancement in its mechanical properties? In this study, using large-scale molecular dynamics simulations, we first examine the interaction of graphene with several typical peptide structures of silk fibroin extracted from different domains of silk fibroin, including pure amorphous (P1), pure crystalline (P2), a segment from N-terminal (P3), and a combined amorphous and crystalline segment (P4), aiming to reveal their structural modifications. Our study shows that graphene can have intriguing influences on the structures formed by the peptides with sequences representing different domains of silk fibroin. In general, for protein domains with stable structure and strong intramolecular interaction (e.g., ß-sheets), graphene tends to compete with the intramolecular interactions and thus weaken the interchain interaction and reduce the contents of ß-sheets. For the silk domains with random or less ordered secondary structures and weak intramolecular interactions, graphene tends to enhance the stability of peptide structures; in particular, it increases the contents of helical structures. Thereafter, tensile simulations were further performed on the representative peptides to investigate how such structure modifications affect their mechanical properties. It was found that the strength and resilience of the peptides are enhanced through their interaction with graphene. The present work reveals interesting insights into the interactions between silk peptides and graphene, and contributes in the efforts to enhance the mechanical properties of silk fibroin.