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The exponential rise in the use of LIBs raises concerns over the supply chain of critical metals, e.g., Li, Co, and Ni, used in their cathodes. Deep Eutectic Solvents (DES) are considered as green lixiviants for hydrometallurgical recycling of cathodes to recover these metals, although their efficiencies are still not at par with conventionally used harsh inorganic solvents. Here it is demonstrated that when assisted by microwave, a choline chloride (ChCl): ethylene glycol (EG) based DES shows ultrafast selective extraction of Li from different commercially used cathode compositions, with a leaching efficiency of >50% in just 30 s and nearly 100% in ≈ 30 min. The ultrafast selective Li leaching can be attributed to microwave irradiation‐induced preferential non‐thermal activation of the polar ChCl in the DES. The rapid microwave approach allows time and energy‐efficient recovery of Li and also prevents the degradation of DES, as is seen in conventional prolonged high‐temperature procedures, and is able to extract Li from high solid/liquid concentrations of LIB cathodes in DES. [ABSTRACT FROM AUTHOR]

Ternary metal sulfides (TMSs) have garnered significant attention as alternative electrode materials for rechargeable metal‐ion battery anodes and electrodes for electrochemical supercapacitors (SCs). With the escalating costs of lithium, research has shifted toward alternative sources like sodium‐ion batteries (NIBs) and potassium‐ion batteries (KIBs), offering cost‐effectiveness and greater natural abundance globally. However, pursuing suitable electrode materials beyond lithium‐ion batteries (LIBs), such as NIBs, KIBs, and SCs with enhanced energy and power density, remains a formidable challenge. In this context, TMSs demonstrate remarkable reversibility as NIB, KIB, and SC electrode materials, showcasing multi‐electron redox reactions, improved electronic conductivity, and higher theoretical capacities. Numerous research articles have highlighted the promising future of TMSs as electrodes for electrochemical energy conversion and storage (EECS). Nonetheless, practical applications are hindered by limitations, including structural stability during long‐standing cyclability, electronic conductivity, and scalability. This review systematically demonstrates how varying synthesis routes can tailor nanostructures and their influence on electrochemical activity. Additionally, an in‐depth literature survey is provided on the electrochemical performances of TMSs in NIBs, KIBs, and SCs and summarize recent advancements with the best available literature. Moreover, promising prospects and challenges are highlighted, expressing optimism that TMSs will emerge as pivotal electrodes for EECS. [ABSTRACT FROM AUTHOR]

Egg waste is a major contributor to global food waste, accounting for 15% of discarded food in the United States. Typically, eggs have a shorter shelf life at room temperature and are preserved in refrigeration from production to consumption. However, maintaining constant refrigeration is energy‐intensive and expensive. Here, a bionanocomposite coating has been developed that incorporates each element of eggs – egg white, yolk, and eggshell – to increase the shelf life of fresh eggs without requiring further refrigeration. The quality of eggs has been successfully preserved for up to three weeks at room temperature. The coated eggs maintain the highest grade (AA) and exhibit improved Haugh Unit (HU), Yolk Index (YI), and pH compared to uncoated eggs. The coating reduces weight loss by ≈37% with an increase in HU (≈12.5%) and YI (≈13.9%). Morphological analysis reveals strong adhesion of the coating to the eggshell surface, showcasing promising barrier properties. The coating demonstrates an optimal combination of oxygen permeability (≈12.2 cm3 µm m−2 d−1 kPa−1) and water vapor transmission (≈31.5 g mm m−2 per day) with excellent antimicrobial properties. Overall, this approach of repurposing eggs into a high‐performance coating shows a promising viable alternative to refrigeration and a solution to combat egg waste. [ABSTRACT FROM AUTHOR]

Many industrial processes such transesterification of fatty acid for biodiesel production, soap manufacturing and biosynthesis of ethanol generate glycerol as a major by‐product that can be used to produce commodity chemicals. Photocatalytic transformation of glycerol is an enticing approach that can exclude the need of harsh oxidants and extraneous thermal energy. However, the product yield and selectivity remain poor due to low absorption and unsymmetrical site distribution on the catalyst surface. Herein, tellurium (Te) nanorods/nanosheets (TeNRs/NSs) wrapped potassium‐doped carbon nitride (KCN) van der Waal (vdW) heterojunction (TeKCN) is designed to enhance charge separation and visible‐NIR absorption. The iridium (Ir) single atom sites decoration on the TeKCN core‐shell structure (TeKCNIr) promotes selective oxidation of glycerol to glyceraldehyde with a conversion of 45.6% and selectivity of 61.6% under AM1.5G irradiation. The catalytic selectivity can reach up to 88% under 450 nm monochromatic light. X‐ray absorption spectroscopy (XAS) demonstrates the presence of undercoordinated IrN2O2 sites which improved catalytic selectivity for glycol oxidation. Band energies and computational calculations reveal faile charge transfer in the TeKCNIr heterostructure. EPR and scavenger tests discern that superoxide (O2•−) and hydroxyl (•OH) radicals are prime components driving glycerol oxidation. [ABSTRACT FROM AUTHOR]

Covalent Organic Frameworks (COFs) are crystalline, porous organic materials. Recent studies have demonstrated novel processing strategies for COFs to form adaptable architectures, but these have focused primarily on imine‐linked COFs. This work presents a new synthesis and processing route to produce crystalline hydrazone‐linked COF gels and aerogels with hierarchical porosity. The method was implemented to produce a series of hydrazone‐linked COFs with different alkyl side‐chain substituents, achieving control of the hydrophilicity of the final aerogel. Variation in the length of the alkyl substituents yielded materials with controllable form factors that can preferentially adsorb water or nonpolar organic solvents. Additionally, a method for additive manufacturing of hydrazone‐linked COFs using hydroxymethylcellulose as a sacrificial additive is presented. This work demonstrates an effective and simple approach to the fabrication of hydrazone COF aerogels and additive manufacturing to produce hydrazone COFs of desired shape. [ABSTRACT FROM AUTHOR]

Review: 182 refs. [ABSTRACT FROM AUTHOR]

Efficient electrocatalysts are highly desirable for promising electrochemical reactions that are likely to mitigate the long‐standing energy and environment problems mainly resulting from human activities. However, most of them are partly composed by scarce and precious metals, thus hampering their large‐scale utilization. In this regard, developing efficient electrocatalysts with reduced noble metals loading or without noble metals is highly desirable. In the past decade, carbon nanotubes (CNTs)‐based electrocatalysts have proven to be efficient in many typical electrocatalytic reactions, and its strong structure operability and easy accessibility enable the utilization of related electrocatalysts to be sustainable. This review is aimed to summarize the research progress in CNTs‐based electrocatalysts, which are widely used in various electrochemical reactions. The major structure regulation approaches toward CNTs‐based electrocatalysts are highlighted. The primary functions of CNTs‐based electrocatalysts in electrochemical reactions are also highlighted here, together with the discussions on the support effect related to CNTs. Synchrotron‐based spectroscopies which can explore the intrinsic structure details that contribute to the performance enhancement and the electrochemical structure evolution of electrocatalysts under working conditions are also discussed. Finally, the challenges for shedding light on the very essence of the activity and the research perspectives are suggested. [ABSTRACT FROM AUTHOR]

Functionalized fullerene nanostructures are a distinct class of materials that exhibit the combined properties of both fullerene and nanostructures including excellent optoelectronic features, modified band edges, high electron affinity, fast charge transfer capabilities, and tunable structural and textural properties. These fascinating properties allow for their utilization in many applications such as polymer solar cells, photovoltaics, photocatalysis, photodynamic therapy, electrocatalysis, environmental remediation, and drug and gene delivery. Numerous synthesis methods and anchoring groups are employed for functionalized fullerenes with nanostructures by using convergent bottom‐up and top‐down strategies. The supramolecular self‐assembly and functionalization of fullerenes through robust chemistry approaches such as surface oxidation, grafting, polymer coating, doping of metals/nonmetal heteroatoms, noncovalent modification with 2D materials and nanoparticle attachment result in achieving fine control over its surface and bulk properties, including increased solubility, wettability, electron transport, acid–base properties, adsorption, electronic conductivity, and light absorption. This review analyzes the salient developments in the fabrication of nanostructured fullerenes and their functionalized derivatives for many applications including adsorption, catalysis, sensors, energy storage, solar cells, drug delivery, magnetic and superconducting devices. The contents of this review will allow the readers to cherish exciting possibilities and opportunities in field of functionalized nanofullerenes. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) have emerged as an exciting new class of porous materials constructed by organic building blocks via dynamic covalent bonds. They have been extensively explored as potentially superior candidates for electrode materials, electrolytes, and separators, due to their tunable chemistry, tailorable structures, and well‐defined pores. These features enable rational design of targeted functionalities, facilitate the penetration of electrolytes, and enhance ion transport. This review provides an in‐depth summary of the recent progress in the development of COFs for diverse battery applications, including lithium‐ion, lithium–sulfur, sodium‐ion, potassium‐ion, lithium–CO2, zinc‐ion, zinc–air batteries, etc. This comprehensive synopsis pays particular attention to the structure and chemistry of COFs and novel strategies that have been implemented to improve battery performance. Additionally, current challenges, possible solutions, and potential future research directions on COFs for batteries are discussed, laying the groundwork for future advances for this exciting class of material. [ABSTRACT FROM AUTHOR]

Spontaneous emission can be altered by external electromagnetic environment with the bridge of local density of optical states. Microcavities have been widely integrated to accelerate the irreversible spontaneous decay, known as the Purcell effect. However, the Purcell effect breaks down in the strong coupling regime, where the light‐matter interaction is not a perturbation to Fermi's golden rule. Here, it is found that the emission intensity of plasmon–exciton polaritons is asymmetrically dependent on the spectral detuning, confirming the collapse of Purcell effect in strongly coupled systems. Ultrafast nonradiative decays of polaritons play a significant role in revealing the polariton emission intensity. The nonradiative effect is not affected by the coherent energy exchange since final states of nonradiative decays are optically dark and decoupled from Rabi oscillations. Moreover, the nonradiative effect is still valid under intermediate coupling and agrees with the Purcell effect, which suggests its universality at a variety of coupling regimes. This study opens up a successful approach to investigate spontaneous emission in cavity quantum electrodynamics, which is insightful to photonic and opto‐electronic applications based on exciton‐polaritons. [ABSTRACT FROM AUTHOR]

Exploring highly active and inexpensive bifunctional electrocatalysts for water‐splitting is considered to be one of the prerequisites for developing hydrogen energy technology. Here, an efficient simultaneous etching‐doping sedimentation equilibrium (EDSE) strategy is proposed to design and prepare hollow Rh‐doped CoFe‐layered double hydroxides for overall water splitting. The elaborate electrocatalyst with optimized composition and typical hollow structure accelerates the electrochemical reactions, which can achieve a current density of 10 mA cm−2 at an overpotential of 28 mV (600 mA cm−2 at 188 mV) for hydrogen evolution reaction (HER) and 100 mA cm−2 at 245 mV for oxygen evolution reaction (OER). The cell voltage for overall water splitting of the electrolyzer assembled by this electrocatalyst is only 1.46 V, a value far lower than that of commercial electrolyzer constructed by Pt/C and RuO2 and most reported bifunctional electrocatalysts. Furthermore, the existence of Fe vacancies introduced by Rh doping and the typical hollow structure are demonstrated to optimize the entire HER and OER processes. EDSE associates doping with template‐directed hollow structures and paves a new avenue for developing bifunctional electrocatalysts for overall water splitting. It is also believed to be practical in other catalysis fields as well. [ABSTRACT FROM AUTHOR]

Ongoing interest is focused on aqueous zinc ion batteries (ZIBs) for mass‐production energy storage systems as a result of their affordability, safety, and high energy density. Ensuring the stability of the electrode/electrolyte interface is of particular importance for prolonging the cycling ability to meet the practical requirements of rechargeable batteries. Zinc anodes exhibit poor cycle life and low coulombic efficiency, stemming from the severe dendrite growth, and irreversible byproducts such as H2 and inactive ZnO. Great efforts have recently been devoted to zinc anode protection for designing high‐performance ZIBs. However, the intrinsic origins of zinc plating/striping are poorly understood, which greatly delay its potential applications. Rather than focusing on battery metrics, this review delves deeply into the underlying science that triggers the deposition/dissolution of zinc ions. Furthermore, recent advances in modulating the zinc coordination environment, uniforming interfacial electric fields, and inducing zinc deposition are highlighted and summarized. Finally, perspectives and suggestions are provided for designing highly stable zinc anodes for the industrialization of the aqueous rechargeable ZIBs in the near future. [ABSTRACT FROM AUTHOR]

Charge and mass transfer at the interface between electrode and electrolyte are of vital significance for energy conversion and storage in aqueous rechargeable zinc ion batteries (ZIBs). Approaching rational design and preparation of unique nanostructures with enhanced mass transfer is still facing great challenges in response to these problems. Herein, the highly uniform and round new‐state nsutite‐type vanadium dioxide (VO2) nanoplates with novel ancient Chinese coin structure (with thickness of ≈50 nm and diameter of ≈500 nm, with a hole in the middle) are prepared successfully. During the hydrothermal process, the VO2 nanoplate undergoes an interesting Ostwald ripening guided dissolution‐regrowth process, resulting in the formation of the unusual ancient Chinese coin structure. Impressively, based on structural merits of the abundant electrolyte‐accessible sites and transfer pathways, the mass transfer can be enhanced at the surface of as‐prepared VO2 nanoplates‐based electrode. The VO2 nanoplates further deliver high reversible specific capacity and rate ability for rechargeable ZIBs. Hence, this work presents a new avenue for designing unique nanostructure vanadium oxides to boost the electrochemical properties of aqueous ZIBs. [ABSTRACT FROM AUTHOR]

Hybridizing faradaic and non‐faradaic charge storage mechanisms permits hybrid supercapacitors to achieve desirable high energy‐power characteristics. Although the hybridization approach increases the energy density, discrepancies in the reaction kinetics, especially sluggish charge‐transfer reactions in Faradaic battery‐type electrodes, curtails the power density. To increase the power density of battery‐type electrodes, an orthorhombic phase of niobium pentoxide (Nb2O5) is one of the most prominent contenders because the orthorhombic crystal structure provides two‐dimensional transport channels for fast Li‐ion diffusion. However, such ultrafast Li‐ion diffusion cannot be realized due to its electrical‐insulating nature. Herein, we synthesized a composite of the orthorhombic phase of niobium pentoxide (Nb2O5) interconnected with reduced graphene oxide nanosheets via facile microwave assisted methods. Such a dual‐conductive composite anode exhibits excellent rate performance to match that of the cathode which operates conventional adsorption‐desorption charge storage mechanism. By combining the composite anode with a nitrogen doped reduced graphene oxide (N‐rGO) cathode, the device delivers maximum energy density of 89 Wh kg−1 (at 125 W kg−1), and the energy density of 20 Wh kg−1 is retained even at 3500 W kg−1, which is one of the highest energy density reported for Nb2O5 based HSC to the best of our knowledge. Niobium pentaoxide bridging the gap between Li‐ion batteries and Supercapacitors: A high power hybrid supercapacitor comprising of reduced graphene oxide/Nb2O5 nanocomposite cathode and nitrogen doped reduced graphene oxide cathode delivers high energy and power densities. [ABSTRACT FROM AUTHOR]

For the first time, a 3D Prussian blue analogue (PBA) with well-defined spatial organization is fabricated by using a nickel hydroxide array as a precursor. The nickel hydroxide arrays are synthesized in titanium foil and reacted with K3[Fe(CN)6]. The plate-like morphology of the nickel hydroxide is perfectly preserved and combined with abundant PBA nanocubes. After phosphidation at 350 °C, the obtained sample demonstrated excellent hydrogen evolution reaction (HER) activity in both acid and alkaline solutions to reach a current density of 10 mA cm-2 with an overpotential of only 70 and 121 mV, respectively. With an overpotential of 266 mV, it can reach a larger current density of 500 mA cm-2 in acid. The efficient HER activity of the obtained sample is mainly ascribed to its structural advantage with various active metal sites derived from the nickel hydroxide and PBA precursor. In addition, long-term stability measurements have verified the good performance of the obtained sample in acid and alkaline solutions. An increment of overpotential of only 8 and 9 mV is observed, in the acid and alkaline solutions respectively. Beyond these assets, it is supposed that the strategy to synthesize 3D PBA arrays from nickel hydroxide can be extended to other metal-organic frameworks arrays for more electrochemical applications. [ABSTRACT FROM AUTHOR]

Abstract: Developing facile preparation routes and atomic‐level characterization methods for single‐atom catalysts is highly desirable but still challenging. Herein, a general strategy is proposed to construct transition metal single atoms within 1D and 2D carbon supports. The carbon supports, typically graphene and carbon nanotubes, are coated with various transition metal‐containing bimetal hydroxides, followed by polydopamine coating and high‐temperature pyrolysis. X‐ray absorption fine structure spectroscopy measurements and simulations efficiently indicate that single atoms (Co, Fe, or Cu) are captured within the applied carbon supports, distinctively forming exclusive molecule‐type sites. As a proof‐of‐concept application, the obtained catalysts exhibit remarkable performance for electrochemical oxygen reduction reaction, even surpassing commercial Pt/C catalyst. The developed versatile route opens up new avenues for the design of carbon‐based catalysts with definite molecular active sites. The atomic‐level structural identifications provide significant guidance for mechanistic studies toward single‐atom catalysts. [ABSTRACT FROM AUTHOR]

Abstract: Electrochemical reduction of CO2 provides an opportunity to reach a carbon‐neutral energy recycling regime, in which CO2 emissions from fuel use are collected and converted back to fuels. The reduction of CO2 to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for CO2 conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO2 reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The CO2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N4) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene. [ABSTRACT FROM AUTHOR]

Abstract: For the first time, a 3D Prussian blue analogue (PBA) with well‐defined spatial organization is fabricated by using a nickel hydroxide array as a precursor. The nickel hydroxide arrays are synthesized in titanium foil and reacted with K3[Fe(CN)6]. The plate‐like morphology of the nickel hydroxide is perfectly preserved and combined with abundant PBA nanocubes. After phosphidation at 350 °C, the obtained sample demonstrated excellent hydrogen evolution reaction (HER) activity in both acid and alkaline solutions to reach a current density of 10 mA cm−2 with an overpotential of only 70 and 121 mV, respectively. With an overpotential of 266 mV, it can reach a larger current density of 500 mA cm−2 in acid. The efficient HER activity of the obtained sample is mainly ascribed to its structural advantage with various active metal sites derived from the nickel hydroxide and PBA precursor. In addition, long‐term stability measurements have verified the good performance of the obtained sample in acid and alkaline solutions. An increment of overpotential of only 8 and 9 mV is observed, in the acid and alkaline solutions respectively. Beyond these assets, it is supposed that the strategy to synthesize 3D PBA arrays from nickel hydroxide can be extended to other metal–organic frameworks arrays for more electrochemical applications. [ABSTRACT FROM AUTHOR]

Abstract: The realization of quasicrystals has attracted a considerable attention due to their unusual structures and properties. The concept of quasicrystals in the atomically thin materials is even more appealing due to the in‐plane covalent bonds and weak interlayer interactions. Here, it is demonstrated that 2D quasicrystals can be created/isolated from bulk phases because of long‐range interlayer ordered aperiodic arrangements. An ultrasonication‐assisted exfoliation of polygrained icosahedral Al–Pd–Mn quasicrystals at room temperature shows the formation of a large area of mono‐ and few layers in threefold quasicrystalline plane. The formation of these layers from random grain orientation consistently indicates that the threefold plane is most stable in comparison to the twofold and fivefold planes in icosahedral clusters. The above experimental observations are further supported with help of theoretical simulations. The mono‐ and few‐layered aperiodic planes render plentiful active sites for the catalysis of hydrogen evolution reaction. The threefold 2D quasicrystalline plane exhibits a hydrogen evolution reaction overpotential of ≈100 mV (160 times less than bulk counterpart) and long‐term durability. These systems constitute the first demonstration of quasicrystalline monolayer ordering in a free‐standing thin layer without requiring the support of periodic or aperiodic substrate. [ABSTRACT FROM AUTHOR]

Abstract: Anisotropic 2D materials exhibit unique optical, electrical, and thermoelectric properties that open up possibilities for diverse angle‐dependent devices. However, the explored anisotropic 2D materials are very limited and the methods to identify the crystal orientations and to study the in‐plane anisotropy are in the initial stage. Here azimuth‐dependent reflectance difference microscopy (ADRDM), angle‐resolved Raman spectra, and electrical transport measurements are used to systematically characterize the influence of the anisotropic structure on in‐plane optical and electrical anisotropy of 2D GeAs, a novel group IV–V semiconductor. It is proved that ADRDM offers a way to quickly identify the crystal orientations and also to directly characterize the in‐plane optical anisotropy of layered GeAs. The anisotropic electrical transport behavior of few‐layer GeAs field‐effect transistors is further measured and the anisotropic ratio of the mobility is as high as 4.6, which is higher than the other 2D anisotropic materials such as black phosphorus. The dependence of the Raman intensity anisotropy on the sample thickness, excitation wavelength, and polarization configuration is investigated both experimentally and theoretically. These data will be useful for designing new high‐performance devices and the results suggest a general methodology for characterizing the in‐plane anisotropy of low‐symmetry 2D materials. [ABSTRACT FROM AUTHOR]

Abstract: The advancement in high power lasers has urged the requisite of efficient optical limiting materials for both eye and sensor protection. The discovery of atomically thin 2D transition metal dichacogenides with distinctive properties has paved the way for a variety of applications including optical limiting. Until recently, the optical limiting effect exhibited by 2D materials is inferior to the benchmark materials fullerene (C60) and graphene. This article reports the optical limiting activity of the 2D transition metal dichalcogenide, titanium disulfide (TiS2) nanosheets, using optical and photoacoustic z‐scan techniques. The 77% nonlinear optical limiting exhibited by the TiS2 sheets with 73% linear‐transmittance is superior to that of any other existing 2D dichalcogenide sheets, graphene, and the benchmark optical limiting material, C60. The enhanced nonlinear response is attributed to the concerted effect of 2‐photon and the induced excited state absorptions. By using photoacoustic z‐scan, a unique tool developed to determine the nonlinear optical limiting mechanism in materials, it is found that the optical limiting exhibited by TiS2 2D sheets and graphene are mainly due to nonlinear absorption rather than scattering effects. These results have opened the door for 2D‐dichalcogenide‐materials‐based highly efficient optical limiters, especially at low fluences. [ABSTRACT FROM AUTHOR]

Carbon-based nanomaterials have garnered a lot of attention in the research of yesteryear. Here this study reports a composite based on fluorinated graphene oxide-a multifunctional subsidiary of graphene; and iron oxide nanoparticles as a contrast agent for magnetic resonance imaging (MRI). Extensive structural and functional characterization is carried out to understand composite behavior toward biotoxicity and its performance as a contrast agent. The electron withdrawing fluorine group decreases the charge transfer to iron oxide increasing the magnetic saturation of the composite thus enhancing the contrast. The interaction of paramagnetic and superparamagnetic systems yields a superior contrast agent for MRI and fluorescent imaging. [ABSTRACT FROM AUTHOR]

Photocatalysis is the most promising method for achieving artificial photosynthesis, but a bottleneck is encountered in finding materials that could efficiently promote the water splitting reaction. The nontoxicity, low cost, and versatility of photocatalysts make them especially attractive for this application. This study demonstrates that small amounts of α-Fe2O3 nanosheets can actively promote exfoliation of g-C3N4, producing 2D hybrid that exhibits tight interfaces and an all-solid-state Z-scheme junction. These nanostructured hybrids present a high H2 evolution rate >3 × 104 µmol g-1 h-1 and external quantum efficiency of 44.35% at λ = 420 nm, the highest value so far reported among the family of g-C3N4 photocatalysts. Besides effectively suppressing the recombination of electron-hole pairs, this Z-scheme junction also exhibits activity toward overall water splitting without any sacrificial donor. The proposed synthetic route for controlled production of 2D g-C3N4-based structures provides a scalable alternative toward the development of highly efficient and active photocatalysts. [ABSTRACT FROM AUTHOR]

Graphene/hexagonal boron nitride (h‐BN) monolayer in‐plane heterostructure offers a novel material platform for both fundamental research and device applications. To obtain such a heterostructure in high quality via controllable synthetic approaches is still challenging. In this work, in‐plane epitaxy of graphene/h‐BN heterostructure is demonstrated on Cu–Ni substrates. The introduction of nickel to copper substrate not only enhances the capability of decomposing polyaminoborane residues but also promotes graphene growth via isothermal segregation. On the alloy surface partially covered by h‐BN, graphene is found to nucleate at the corners of the as‐formed h‐BN grains, and the high growth rate for graphene minimizes the damage of graphene‐growth process on h‐BN lattice. As a result, high‐quality graphene/h‐BN in‐plane heterostructure with epitaxial relationship can be formed, which is supported by extensive characterizations. Photodetector device applications are demonstrated based on the in‐plane heterostructure. The success will have important impact on future research and applications based on this unique material platform. [ABSTRACT FROM AUTHOR]

Toxic organic pollutants in the aquatic environment cause severe threats to both humans and the global environment. Thus, the development of robust strategies for detection and removal of these organic pollutants is essential. For this purpose, a multifunctional and recyclable membrane by intercalating gold nanoparticles and graphitic carbon nitride into graphene oxide (GNPs/g-C3N4/GO) is fabricated. The membranes exhibit not only superior surface enhanced Raman scattering (SERS) activity attributed to high preconcentration ability to analytes through π-π and electrostatic interactions, but also excellent catalytic activity due to the enhanced electron-hole separation efficiency. These outstanding properties allow the membrane to be used for highly sensitive detection of rhodamine 6G with a limit of detection of 5.0 × 10−14 m and self-cleaning by photocatalytic degradation of the adsorbed analytes into inorganic small molecules, thus achieving recyclable SERS application. Furthermore, the excellent SERS activity of the membrane is demonstrated by detection of 4-chlorophenol at less than nanomolar level and no significant SERS or catalytic activity loss was observed when reusability is tested. These results suggest that the GNPs/g-C3N4/GO membrane provides a new strategy for eliminating traditional, single-use SERS substrates, and expands practical SERS application to simultaneous detection and removal of environmental pollutants. [ABSTRACT FROM AUTHOR]

Many unique properties arise when the 3D stacking of layered materials is disrupted, originating nanostructures. Stabilization, and further reorganization of these individual layers into complex 3D structures, can be essential to allow these properties to persist in macroscopic systems. It is demonstrated that a simple hydrothermal process, assisted by ionic liquids (ILs), can convert bulk g-C3N4 into a stable hydrogel. The gelation occurs through delamination of the layered structure, driven by particular interactions between the IL and the carbon nitride sheets, forming an amphiphilic foam-like network. This study employs spectroscopic and computational tools to unravel the gelation mechanism, and provides a rational approach toward the stabilization of 2D materials in hydrogels. The solution-processable hydrogels can also be used as building blocks of complex devices. Chemiresistive gas sensors employing g-C3N4 3D hydrogels exhibit superior response at room temperature, enabling effective gas sensing under low power conditions. [ABSTRACT FROM AUTHOR]

Perovskite materials due to their exceptional photophysical properties are beginning to dominate the field of thin-film optoelectronic devices. However, one of the primary challenges is the processing-dependent variability in the properties, thus making it imperative to understand the origin of such variations. Here, it is discovered that the precursor solution aging time before it is cast into a thin film, is a subtle but a very important factor that dramatically affects the overall thin-film formation and crystallinity and therein factors such as grain growth, phase purity, surface uniformity, trap state density, and overall solar cell performance. It is shown that progressive aging of the precursor promotes efficient formation of larger seeds after the fast nucleation of a large density of small seeds. The hot-casting method then leads to the growth of large grains in uniform thin-films with excellent crystallinity validated using scanning microscopy images and X-ray diffraction patterns. The high-quality films cast from aged solution is ideal for thin-film photovoltaic device fabrication with reduced shunt current and good charge transport. This observation is a significant step toward achieving highly crystalline thin-films with reliability in device performance and establishes the subtle but dramatic effect of solution aging before fabricating perovskite thin-films. [ABSTRACT FROM AUTHOR]

2D atomic crystals such as single layer graphene (SLG) and hexagonal boron nitride (hBN) have been shown to be 'unexpectedly permeable' to hydrogen ions under ambient conditions with the proton conductivity rising exponentially with temperature. Here, the first successful addition of SLG made by a chemical vapor deposition (CVD) method is shown to an operational direct methanol fuel cell significantly enhancing the performance of the cell once the temperature is raised above 60 °C, the temperature at which the proton conductivity of SLG is higher than the Nafion membrane on which it is mounted. Above this temperature, the resistance to proton transport of the system is not affected by the graphene but the barrier properties of graphene inhibit methanol crossover. The performance of the fuel cell is shown to increase linearly with coverage of SLG above this temperature. Results show that the maximum power density is increased at 70 °C by 45% in comparison to the standard membrane electrode assembly without graphene. In addition, a membrane with CVD hBN shows enhanced performance across the entire temperature range due to better proton conductivity at lower temperatures. [ABSTRACT FROM AUTHOR]

Nonfunctionalized and functionalized fluorographene systems are studied of which acid functionalized system shows greater magnetic moment. This is experimentally verified and the hysteresis and low temperature studies reveal paramagnetic behaviour. The inherent paramagnetism along with the fluorine content is utilized in its development as a dual modal agent for proton and 19F MRI. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) layered semiconducting transition-metal dichalcogenides (TMDCs) are promising candidates for next-generation ultrathin, flexible, and transparent electronics. Chemical vapor deposition (CVD) is a promising method for their controllable, scalable synthesis but the growth mechanism is poorly understood. Herein, we present systematic studies to understand the CVD growth mechanism of monolayer MoSe2, showing reaction pathways for growth from solid and vapor precursors. Examination of metastable nanoparticles deposited on the substrate during growth shows intermediate growth stages and conversion of non-stoichiometric nanoparticles into stoichiometric 2D MoSe2 monolayers. The growth steps involve the evaporation and reduction of MoO3 solid precursors to sub-oxides and stepwise reactions with Se vapor to finally form MoSe2. The experimental results and proposed model were corroborated by ab initio Car-Parrinello molecular dynamics studies. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) layered semiconducting transition-metal dichalcogenides (TMDCs) are promising candidates for next-generation ultrathin, flexible, and transparent electronics. Chemical vapor deposition (CVD) is a promising method for their controllable, scalable synthesis but the growth mechanism is poorly understood. Herein, we present systematic studies to understand the CVD growth mechanism of monolayer MoSe2, showing reaction pathways for growth from solid and vapor precursors. Examination of metastable nanoparticles deposited on the substrate during growth shows intermediate growth stages and conversion of non-stoichiometric nanoparticles into stoichiometric 2D MoSe2 monolayers. The growth steps involve the evaporation and reduction of MoO3 solid precursors to sub-oxides and stepwise reactions with Se vapor to finally form MoSe2. The experimental results and proposed model were corroborated by ab initio Car-Parrinello molecular dynamics studies. [ABSTRACT FROM AUTHOR]

Here, pyridinic nitrogen dominated graphene aerogels with/without iron incorporation (Fe-NG and NG) are prepared via a facile and effective process including freeze-drying of chemically reduced graphene oxide with/without iron precursor and thermal treatment in NH3. A high doping level of nitrogen has been achieved (up to 12.2 at% for NG and 11.3 at% for Fe-NG) with striking enrichment of pyridinic nitrogen (up to 90.4% of the total nitrogen content for NG, and 82.4% for Fe-NG). It is found that the Fe-NG catalysts display a more positive onset potential, higher current density, and better four-electron selectivity for ORR than their counterpart without iron incorporation. The most active Fe-NG exhibits outstanding ORR catalytic activity, high durability, and methanol tolerance ability that are comparable to or even superior to those of the commercial Pt/C catalyst at the same catalyst loading in alkaline environment. The excellent ORR performance can be ascribed to the synergistic effect of pyridinic N and Fe-N x sites (where iron probably coordinates with pyridinic N) that serve as active centers for ORR. Our Fe-NG can be developed into cost-effective and durable catalysts as viable replacements of the expensive Pt-based catalysts in practical fuel cell applications. [ABSTRACT FROM AUTHOR]

3D CoNi2S4-graphene-2D-MoSe2 (CoNi2S4-G-MoSe2) nanocomposite is designed and prepared using a facile ultrasonication and hydrothermal method for supercapacitor (SC) applications. Because of the novel nanocomposite structures and resultant maximized synergistic effect among ultrathin MoSe2 nanosheets, highly conductive graphene and CoNi2S4 nanoparticles, the electrode exhibits rapid electron and ion transport rate and large electroactive surface area, resulting in its amazing electrochemical properties. The CoNi2S4-G-MoSe2 electrode demonstrates a maximum specific capacitance of 1141 F g-1, with capacitance retention of ≈108% after 2000 cycles at a high charge-discharge current density of 20 A g-1. As to its symmetric device, 109 F g-1 at a scan rate of 5 mV s-1 is exhibited. This pioneering work should be helpful in enhancing the capacitive performance of SC materials by designing nanostructures with efficient synergetic effects. [ABSTRACT FROM AUTHOR]

Batteries for high temperature applications capable of withstanding over 60 °C are still dominated by primary cells. Conventional rechargeable energy storage technologies which have exceptional performance at ambient temperatures employ volatile electrolytes and soft separators, resulting in catastrophic failure under heat. A composite electrolyte/separator is reported that holds the key to extend the capability of Li-ion batteries to high temperatures. A stoichiometric mixture of hexagonal boron nitride, piperidinium-based ionic liquid, and a lithium salt is formulated, with ionic conductivity reaching 3 mS cm−1, electrochemical stability up to 5 V and extended thermal stability. The composite is used in combination with conventional electrodes and demonstrates to be stable for over 600 cycles at 120 °C, with a total capacity fade of less than 3%. The ease of formulation along with superior thermal and electrochemical stability of this system extends the use of Li-ion chemistries to applications beyond consumer electronics and electric vehicles. [ABSTRACT FROM AUTHOR]

Two-dimensional hexagonal boron carbon nitride (BCN) nanosheets (NSs) were synthesized by new approach in which a mixture of glucose and an adduct of boric acid (H3BO3) and urea (NH2CONH2) is heated at 900 °C. The method is green, scalable and gives a high yield of BCN NSs with average size of about 1 μm and thickness of about 13 nm. Structural characterization of the as-synthesized material was carried out by several techniques, and its energy-storage properties were evaluated electrochemically. The material showed excellent capacitive behaviour with a specific capacitance as high as 244 F g−1 at a current density of 1 A g−1. The material retains up to 96 % of its initial capacity after 3000 cycles at a current density of 5 A g−1. [ABSTRACT FROM AUTHOR]

The emergence of semiconducting transition metal dichalcogenide (TMD) atomic layers has opened up unprecedented opportunities in atomically thin electronics. Yet the scalable growth of TMD layers with large grain sizes and uniformity has remained very challenging. Here is reported a simple, scalable chemical vapor deposition approach for the growth of MoSe2 layers is reported, in which the nucleation density can be reduced from 105 to 25 nuclei cm−2, leading to millimeter-scale MoSe2 single crystals as well as continuous macrocrystalline films with millimeter size grains. The selective growth of monolayers and multilayered MoSe2 films with well-defined stacking orientation can also be controlled via tuning the growth temperature. In addition, periodic defects, such as nanoscale triangular holes, can be engineered into these layers by controlling the growth conditions. The low density of grain boundaries in the films results in high average mobilities, around ≈42 cm2 V−1 s−1, for back-gated MoSe2 transistors. This generic synthesis approach is also demonstrated for other TMD layers such as millimeter-scale WSe2 single crystals. [ABSTRACT FROM AUTHOR]

Due to the novel optical and optoelectronic properties, 2D materials have received increasing interests for optoelectronics applications. Discovering new properties and functionalities of 2D materials is challenging yet promising. Here broadband polarization sensitive photodetectors based on few layer ReS2 are demonstrated. The transistor based on few layer ReS2 shows an n-type behavior with the mobility of about 40 cm2 V−1 s−1 and on/off ratio of 105. The polarization dependence of photoresponse is ascribed to the unique anisotropic in-plane crystal structure, consistent with the optical absorption anisotropy. The linear dichroic photodetection with a high photoresponsivity reported here demonstrates a route to exploit the intrinsic anisotropy of 2D materials and the possibility to open up new ways for the applications of 2D materials for light polarization detection. [ABSTRACT FROM AUTHOR]

Nitrogen-doped carbon nanotubes (NCNTs) have been considered as a promising electrocatalyst for carbon-dioxide-reduction reactions, but two fundamental chemistry questions remain obscure: 1) What are the active centers with respect to various defect species and 2) what is the role of defect density on the selectivity of NCNTs? The aim of this work is to address these questions. The catalytic activity of NCNTs depends on the structural nature of nitrogen in CNTs and defect density. Comparing with pristine CNTs, the presence of graphitic and pyridinic nitrogen significantly decreases the overpotential (ca. −0.18 V) and increases the selectivity (ca. 80 %) towards the formation of CO. The experimental results are in congruent with DFT calculations, which show that pyridinic defects retain a lone pair of electrons that are capable of binding CO2. However, for graphitic-like nitrogen, electrons are located in the π* antibonding orbital, making them less accessible for CO2 binding. [ABSTRACT FROM AUTHOR]

Nitrogen-doped carbon nanotubes (NCNTs) have been considered as a promising electrocatalyst for carbon-dioxide-reduction reactions, but two fundamental chemistry questions remain obscure: 1) What are the active centers with respect to various defect species and 2) what is the role of defect density on the selectivity of NCNTs? The aim of this work is to address these questions. The catalytic activity of NCNTs depends on the structural nature of nitrogen in CNTs and defect density. Comparing with pristine CNTs, the presence of graphitic and pyridinic nitrogen significantly decreases the overpotential (ca. −0.18 V) and increases the selectivity (ca. 80 %) towards the formation of CO. The experimental results are in congruent with DFT calculations, which show that pyridinic defects retain a lone pair of electrons that are capable of binding CO2. However, for graphitic-like nitrogen, electrons are located in the π* antibonding orbital, making them less accessible for CO2 binding. [ABSTRACT FROM AUTHOR]

Batteries have become fundamental building blocks for the mobility of modern society. Continuous development of novel battery chemistries and electrode materials has nourished progress in building better batteries. Simultaneously, novel device form factors and designs with multi-functional components have been proposed, requiring batteries to not only integrate seamlessly to these devices, but to also be a multi-functional component for a multitude of applications. Thus, in the past decade, along with developments in the component materials, the focus has been shifting more and more towards novel fabrication processes, unconventional configurations, and additional functionalities. This work attempts to critically review the developments with respect to emerging electrochemical energy storage configurations, including, amongst others, paintable, transparent, flexible, wire or cable shaped, ultra-thin and ultra-thick configurations, as well as hybrid energy storage-conversion, or graphene-incorporated batteries and supercapacitors. The performance requirements are elaborated together with the advantages, but also the limitations, with respect to established electrochemical energy storage technologies. Finally, challenges in developing novel materials with tailored properties that would allow such configurations, and in designing easier manufacturing techniques that can be widely adopted are considered. [ABSTRACT FROM AUTHOR]

3D architecture V2O5 nanoribbon/reduced graphene oxide is successfully fabricated as an electrode material for supercapacitors. In combination with the advantages from the good rate performance of carbon‐based materials and the high specific capacitance of metal oxides, as well as its 3D architecture, this material shows high specific capacitance, superior rate performance, and stability. [ABSTRACT FROM AUTHOR]

Recently, a lot of interest has been centred on the optical properties of hexagonal boron nitride (h‐BN), which has a similar lattice structure to graphene. Interestingly, h‐BN has a wide bandgap and is biocompatible, so it has potential applications in multiphoton bioimaging, if it can exhibit large nonlinear optical (NLO) properties. However, extensive investigation into the NLO properties of h‐BN have not been done so far. Here, NLO properties of 2D h‐BN nanosheets (BNNS) are reported for the first time, using 1064‐nm NIR laser radiation with a pulse duration of 10 ns using the Z‐scan technique. The reverse saturable absorption occurs in aqueous colloidal solutions of BNNS with a very large two‐photon absorption cross section (σ 2PA) of ≈57 × 10−46 cm4 s−1 photon−1. Also, by using UV–Vis absorption spectroscopy, the temperature coefficient of the bandgap (dE g/dT) of BNNS is determined to be 5.9 meV K−1. Further defect‐induced photoluminescence emission in the UV region is obtained in the 283–303 K temperature range, under excitations of different wavelengths. The present report of large σ 2PA combined with stability and biocompatibility could open up new possibilities for the application of BNNS as a potential optical material for multiphoton bioimaging and advanced photonic devices. [ABSTRACT FROM AUTHOR]

The exceptional solution processing potential of graphene oxide (GO) is always one of its main advantages over graphene in terms of its industrial relevance in coatings, electronics, and energy storage. However, the presence of a variety of functional groups on the basal plane and edges of GO makes understanding suspension behavior in aqueous and organic solvents, a major challenge. Acoustic spectroscopy can also measure zeta potential to provide unique insight into flocculating, meta-stable, and stable suspensions of GO in deionized water and a variety of organic solvents (including ethanol, ethylene glycol, and mineral oil). As expected, a match between solvent polarity and the polar functional groups on the GO surface favors stable colloidal suspensions accompanied by a smaller aggregate size tending toward disperse individual flakes of GO. This work is significant since it describes the characteristics of GO in solution and its ability to act as a precursor for graphene-based materials. [ABSTRACT FROM AUTHOR]

Although Li-oxygen batteries offer extremely high theoretical specific energy, their practical application still faces critical challenges. One of the main obstacles is the high charge overpotential caused by sluggish kinetics of charge transfer that is closely related to the morphology of discharge products and their distribution on the cathode. Here, a series of noble metal nanoparticles (Pd, Pt, Ru and Au) are encapsulated inside end-opened carbon nanotubes (CNTs) by wet impregnation followed by thermal annealing. The resultant cathode materials exhibit a dramatic reduction of charge overpotentials compared to their counterparts with nanoparticles supported on CNT surface. Notably, the charge overpotential can be as low as 0.3 V when CNT-encapsulated Pd nanoparticles are used on the cathode. The cathode also shows good stability during discharge-charge cycling. Density functional theory (DFT) calculations reveal that encapsulation of 'guest' noble metal nanoparticles in 'host' CNTs is able to strengthen the electron density on CNT surfaces, and to avoid the regional enrichment of electron density caused by the direct exposure of nanoparticles on CNT surface. These unique properties ensure the uniform coverage of Li2O2 nanocrystals on CNT surfaces instead of localized distribution of Li2O2 aggregation, thus providing efficient charge transfer for the decomposition of Li2O2. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of multifunctional cement and concrete composites filled with hexagonal boron nitride (h-BN) and graphite oxide (GO), is reported and their superior mechanical strength and oil adsorption properties compared to composites devoid of fillers are illustrated. GO is utilized to bridge the cement surfaces while h-BN is used to mechanically reinforce the composites and adsorb the oil. Introduction of these fillers even at low filler weight fractions increases the compressive strength and toughness properties of pristine cement and of porous concrete significantly, while the porous composite concrete illustrates excellent ability for water separation and crude oil adsorption. Experimental results along with theoretical calculations show that such nanoengineered forms of cement based composites would enable the development of novel forms of multifunctional structural materials with a range of environmental applications. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) contains several chemical functional groups that are attached to the graphite basal plane and can be manipulated to tailor GO for specific applications. It is now revealed that the reaction of GO with ozone results in a high level of oxidation, which leads to significantly improved ionic (protonic) conductivity of the GO. Freestanding ozonated GO films were synthesized and used as efficient polymer electrolyte fuel cell membranes. The increase in protonic conductivity of the ozonated GO originates from enhanced proton hopping, which is due to the higher content of oxygenated functional groups in the basal planes and edges of ozonated GO as well as the morphology changes in GO that are caused by ozonation. The results of this study demonstrate that the modification of dispersed GO presents a powerful opportunity for optimizing a nanoscale material for proton-exchange membranes. [ABSTRACT FROM AUTHOR]

Graphene oxide (GO) contains several chemical functional groups that are attached to the graphite basal plane and can be manipulated to tailor GO for specific applications. It is now revealed that the reaction of GO with ozone results in a high level of oxidation, which leads to significantly improved ionic (protonic) conductivity of the GO. Freestanding ozonated GO films were synthesized and used as efficient polymer electrolyte fuel cell membranes. The increase in protonic conductivity of the ozonated GO originates from enhanced proton hopping, which is due to the higher content of oxygenated functional groups in the basal planes and edges of ozonated GO as well as the morphology changes in GO that are caused by ozonation. The results of this study demonstrate that the modification of dispersed GO presents a powerful opportunity for optimizing a nanoscale material for proton-exchange membranes. [ABSTRACT FROM AUTHOR]

Aligned carbon nanotube (CNT) forests filled with a dehydrated polymer electrolyte are used to fabricate flexible solid state supercapacitors (SSCs) for multifunctional structural-electronic applications. Local stiffness measurements on the composite electrodes determined through nano­indentation showed an 80% increase over the neat solid polymer electrolyte matrix. Electrochemical properties are monitored as a function of average tensile strain in the SSCs. Galvanostatic charge-discharge tests with in situ microtensile testing on SSCs are used to show a 10% increase in the specific capacitance through the elastic region of the composite. The increase in capacitance is partly attributed to the enhanced double layer interaction that results from the partial alignment of the polymer electrolyte chains at the electrode-electrolyte interface. When soaked in 1 m sulfuric acid, the specific capacitance of the CNT-polymer electrolyte reached approximately 72 F g-1 at 60 °C. [ABSTRACT FROM AUTHOR]