Ultrafine Pt Nanoparticles Anchored on 2D Metal-Organic Frameworks as Multifunctional Electrocatalysts for Water Electrolysis and Zinc-Air Batteries.

Multifunctional electrocatalysts are crucial to cost-effective electrochemical energy conversion and storage systems requiring mutual enhancement of disparate reactions. Embedding noble metal nanoparticles in 2D metal-organic frameworks (MOFs) are proposed as an effective strategy, however, the hybrids usually suffer from poor electrochemical performance and electrical conductivity in operating conditions. Herein, ultrafine Pt nanoparticles strongly anchored on thiophenedicarboxylate acid based 2D Fe-MOF nanobelt arrays (Pt@Fe-MOF) are fabricated, allowing sufficient exposure of active sites with superior trifunctional electrocatalytic activity for hydrogen evolution, oxygen evolution, and oxygen reduction reactions. The interfacial Fe─O─Pt bonds can induce the charge redistribution of metal centers, leading to the optimization of adsorption energy for reaction intermediates, while the dispersibility of ultrafine Pt nanoparticles contributes to the high mass activity. When Pt@Fe-MOF is used as bifunctional catalysts for water-splitting, a low voltage of 1.65 V is required at 100 mA cm-2 with long-term stability for 20 h at temperatures (65 °C) relevant for industrial applications, outperforming commercial benchmarks. Furthermore, liquid Zn-air batteries with Pt@Fe-MOF in cathodes deliver high open-circuit voltages (1.397 V) and decent cycling stability, which motivates the fabrication of flexible quasisolid-state rechargeable Zn-air batteries with remarkable performance.

Area-Selective Chemical Doping on Solution-Processed MoS2 Thin-Film for Multi-Valued Logic Gates.

Multi-valued logic gates are demonstrated on solution-processed molybdenum disulfide (MoS2) thin films. A simple chemical doping process is added to the conventional transistor fabrication procedure to locally increase the work function of MoS2 by decreasing sulfur vacancies. The resulting device exhibits pseudo-heterojunctions comprising as-processed MoS2 and chemically treated MoS2 (c-MoS2). The energy-band misalignment of MoS2 and c-MoS2 results in a sequential activation of the MoS2 and c-MoS2 channel areas under a gate voltage sweep, which generates a stable intermediate state for ternary operation. Current levels and turn-on voltages for each state can be tuned by modulating the device geometries, including the channel thickness and length. The optimized ternary transistors are incorporated to demonstrate various ternary logic gates, including the inverter, NMIN, and NMAX gates.

Pressure-induced semiconductor-to-metal phase transition of a charge-ordered indium halide perovskite.

Phase transitions in halide perovskites triggered by external stimuli generate significantly different material properties, providing a great opportunity for broad applications. Here, we demonstrate an In-based, charge-ordered (In+/In3+) inorganic halide perovskite with the composition of Cs2In(I)In(III)Cl6 in which a pressure-driven semiconductor-to-metal phase transition exists. The single crystals, synthesized via a solid-state reaction method, crystallize in a distorted perovskite structure with space group I4/m with a = 17.2604(12) Å, c = 11.0113(16) Å if both the strong reflections and superstructures are considered. The supercell was further confirmed by rotation electron diffraction measurement. The pressure-induced semiconductor-to-metal phase transition was demonstrated by high-pressure Raman and absorbance spectroscopies and was consistent with theoretical modeling. This type of charge-ordered inorganic halide perovskite with a pressure-induced semiconductor-to-metal phase transition may inspire a range of potential applications.

In Situ, Atomic-Resolution Observation of Lithiation and Sodiation of WS2 Nanoflakes: Implications for Lithium-Ion and Sodium-Ion Batteries.

WS2 nanoflakes have great potential as electrode materials of lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of their unique 2D structure, which facilitates the reversible intercalation and extraction of alkali metal ions. However, a fundamental understanding of the electrochemical lithiation/sodiation dynamics of WS2 nanoflakes especially at the nanoscale level, remains elusive. Here, by combining battery electrochemical measurements, density functional theory calculations, and in situ transmission electron microscopy, the electrochemical-reaction kinetics and mechanism for both lithiation and sodiation of WS2 nanoflakes are investigated at the atomic scale. It is found that compared to LIBs, SIBs exhibit a higher reversible sodium (Na) storage capacity and superior cyclability. For sodiation, the volume change due to ion intercalation is smaller than that in lithiation. Also, sodiated WS2 maintains its layered structure after the intercalation process, and the reduced metal nanoparticles after conversion in sodiation are well-dispersed and aligned forming a pattern similar to the layered structure. Overall, this work shows a direct interconnection between the reaction dynamics of lithiated/sodiated WS2 nanoflakes and their electrochemical performance, which sheds light on the rational optimization and development of advanced WS2 -based electrodes.

Nanowires for Photonics.

All-photonic integrated circuits are promising platforms for future systems beyond the limitation of Moore's law. Over the last several decades, one-dimensional (1D) nanowires have demonstrated great potential in photonic circuitry because of their unique 1D structure to effectively generate and tightly confine optical signals as well as easily tunable optical properties. In this Review, we categorize nanowires based on the optical properties (i.e., semiconducting, metallic, and dielectric nanowires) for their potential photonic applications (as light emitters or plasmonic and photonic waveguides). We further discuss the recent efforts in integration of nanowire-based photonic elements toward next-generation optical information processors. However, there are still several challenges remaining before the nanowires are fully utilized as photonic building blocks. The scientific and technical challenges and outlooks are provided to indicate the future directions.

High-performance flexible transparent micro-supercapacitors from nanocomposite electrodes encapsulated with solution processed MoS2 nanosheets.

Two-dimensional molybdenum disulfide (MoS2) nanosheets have emerged as a promising material for transparent, flexible micro-supercapacitors, but their use in electrodes is hindered by their poor electrical conductivity and cycling stability because of restacking. In this paper, we report a novel electrode architecture to exploit electrochemical activity of MoS2 nanosheets. Electrochemically exfoliated MoS2 dispersion was spin coated on mesh-like silver networks encapsulated with a flexible conducting film exhibiting a pseudocapacitive behavior. MoS2 nanosheets were electrochemically active over the whole electrode surface and the conductive layer provided a pathway to transport electrons between the MoS2 and the electrolyte. As the result, the composite electrode achieved a large areal capacitance (89.44 mF cm-2 at 6 mA cm-2) and high energy and power densities (12.42 µWh cm-2 and P = 6043 µW cm-2 at 6 mA cm-2) in a symmetric cell configuration with 3 M KOH solution while exhibiting a high optical transmittance of ~80%. Because the system was stable against mechanical bending and charge/discharge cycles, a flexible micro-supercapacitor that can power electronics at different bending states was realized.

Organic-inorganic hybrid perovskite electronics.

Organic-inorganic hybrid perovskite is a leading successor for the next generation of electronic and optoelectronic applications, owing to its unique optical and electrical properties. In this perspective, tunable optical and electrical properties are discussed, based on the nanostructured morphologies of hybrid perovskites. The current methodologies used in creating semiconducting channels are highlighted, followed by a detailed discussion of the recent advances in unique electronics and optoelectronic applications such as light-emitting transistors, phototransistors, and perovskite-2D hybrid devices. Finally, the current technological challenges and their possible solutions are addressed to identify future research directions.

Three-Dimensional Phthalocyanine Metal-Catecholates for High Electrochemical Carbon Dioxide Reduction.

The synthesis of a new anionic 3D metal-catecholate framework, termed MOF-1992, is achieved by linking tetratopic cobalt phthalocyanin-2,3,9,10,16,17,23,24-octaol linkers with Fe3(-C2O2-)6(OH2)2 trimers into an extended framework of roc topology. MOF-1992 exhibits sterically accessible Co active sites together with charge transfer properties. Cathodes based on MOF-1992 and carbon black (CB) display a high coverage of electroactive sites (270 nmol cm-2) and a high current density (-16.5 mA cm-2; overpotential, -0.52 V) for the CO2 to CO reduction reaction in water (faradaic efficiency, 80%). Over the 6 h experiment, MOF-1992/CB cathodes reach turnover numbers of 5800 with turnover frequencies of 0.20 s-1 per active site.

Self-Assembly of Two-Dimensional Perovskite Nanosheet Building Blocks into Ordered Ruddlesden-Popper Perovskite Phase.

The self-assembly of nanoparticles, a process whereby nanocrystal building blocks organize into even more ordered superstructures, is of great interest to nanoscience. Here we report the layer-by-layer assembly of 2D perovskite nanosheet building blocks. Structural analysis reveals that the assembled superlattice nanocrystals match with the layered Ruddlesden-Popper perovskite phase. This assembly proves reversible, as these superlattice nanocrystals can be reversibly exfoliated back into their building blocks via sonication. This study demonstrates the opportunity to further understand and exploit thermodynamics to increase order in a system of nanoparticles and to study emergent optical properties of a superlattice from 2D, weakly attracted, perovskite building blocks.

Stable aqueous dispersions of optically and electronically active phosphorene.

Understanding and exploiting the remarkable optical and electronic properties of phosphorene require mass production methods that avoid chemical degradation. Although solution-based strategies have been developed for scalable exfoliation of black phosphorus, these techniques have thus far used anhydrous organic solvents in an effort to minimize exposure to known oxidants, but at the cost of limited exfoliation yield and flake size distribution. Here, we present an alternative phosphorene production method based on surfactant-assisted exfoliation and postprocessing of black phosphorus in deoxygenated water. From comprehensive microscopic and spectroscopic analysis, this approach is shown to yield phosphorene dispersions that are stable, highly concentrated, and comparable to micromechanically exfoliated phosphorene in structure and chemistry. Due to the high exfoliation efficiency of this process, the resulting phosphorene flakes are thinner than anhydrous organic solvent dispersions, thus allowing the observation of layer-dependent photoluminescence down to the monolayer limit. Furthermore, to demonstrate preservation of electronic properties following solution processing, the aqueous-exfoliated phosphorene flakes are used in field-effect transistors with high drive currents and current modulation ratios. Overall, this method enables the isolation and mass production of few-layer phosphorene, which will accelerate ongoing efforts to realize a diverse range of phosphorene-based applications.

Functional inks and printing of two-dimensional materials.

Graphene and related two-dimensional materials provide an ideal platform for next generation disruptive technologies and applications. Exploiting these solution-processed two-dimensional materials in printing can accelerate this development by allowing additive patterning on both rigid and conformable substrates for flexible device design and large-scale, high-speed, cost-effective manufacturing. In this review, we summarise the current progress on ink formulation of two-dimensional materials and the printable applications enabled by them. We also present our perspectives on their research and technological future prospects.

Silicon-Phosphorene Nanocavity-Enhanced Optical Emission at Telecommunications Wavelengths.

Generating and amplifying light in silicon (Si) continues to attract significant attention due to the possibility of integrating optical and electronic components in a single material platform. Unfortunately, silicon is an indirect band gap material and therefore an inefficient emitter of light. With the rise of integrated photonics, the search for silicon-based light sources has evolved from a scientific quest to a major technological bottleneck for scalable, CMOS-compatible, light sources. Recently, emerging two-dimensional materials have opened the prospect of tailoring material properties based on atomic layers. Few-layer phosphorene, which is isolated through exfoliation from black phosphorus (BP), is a great candidate to partner with silicon due to its layer-tunable direct band gap in the near-infrared where silicon is transparent. Here we demonstrate a hybrid silicon optical emitter composed of few-layer phosphorene nanomaterial flakes coupled to silicon photonic crystal resonators. We show single-mode emission in the telecommunications band of 1.55 µm ( Eg = 0.8 eV) under continuous wave optical excitation at room temperature. The solution-processed few-layer BP flakes enable tunable emission across a broad range of wavelengths and the simultaneous creation of multiple devices. Our work highlights the versatility of the Si-BP material platform for creating optically active devices in integrated silicon chips.

Toxicological Profiling of Highly Purified Single-Walled Carbon Nanotubes with Different Lengths in the Rodent Lung and Escherichia Coli.

Carbon nanotubes (CNTs) exhibit a number of physicochemical properties that contribute to adverse biological outcomes. However, it is difficult to define the independent contribution of individual properties without purified materials. A library of highly purified single-walled carbon nanotubes (SWCNTs) of different lengths is prepared from the same base material by density gradient ultracentrifugation, designated as short (318 nm), medium (789 nm), and long (1215 nm) SWCNTs. In vitro screening shows length-dependent interleukin-1ß (IL-1ß) production, in order of long > medium > short. However, there are no differences in transforming growth factor-ß1 production in BEAS-2B cells. Oropharyngeal aspiration shows that all the SWCNTs induce profibrogenic effects in mouse lung at 21 d postexposure, but there are no differences between tube lengths. In contrast, these SWCNTs demonstrate length-dependent antibacterial effects on Escherichia coli, with the long SWCNT exerting stronger effects than the medium or short tubes. These effects are reduced by Pluronic F108 coating or supplementing with glucose. The data show length-dependent effects on proinflammatory response in macrophage cell line and antibacterial effects, but not on collagen deposition in the lung. These data demonstrate that over the length scale tested, the biological response to highly purified SWCNTs is dependent on the complexity of the nano/bio interface.

Solution-Based Processing of Monodisperse Two-Dimensional Nanomaterials.

Exfoliation of single-layer graphene from bulk graphite and the subsequent discovery of exotic physics and emergent phenomena in the atomically thin limit has motivated the isolation of other two-dimensional (2D) layered nanomaterials. Early work on isolated 2D nanomaterial flakes has revealed a broad range of unique physical and chemical properties with potential utility in diverse applications. For example, the electronic and optical properties of 2D nanomaterials depend strongly on atomic-scale variations in thickness, enabling enhanced performance in optoelectronic technologies such as light emitters, photodetectors, and photovoltaics. Much of the initial research on 2D nanomaterials has relied on micromechanical exfoliation, which yields high-quality 2D nanomaterial flakes that are suitable for fundamental studies but possesses limited scalability for real-world applications. In an effort to overcome this limitation, solution-processing methods for isolating large quantities of 2D nanomaterials have emerged. Importantly, solution processing results in 2D nanomaterial dispersions that are amenable to roll-to-roll fabrication methods that underlie lost-cost manufacturing of thin-film transistors, transparent conductors, energy storage devices, and solar cells. Despite these advantages, solution-based exfoliation methods typically lack control over the lateral size and thickness of the resulting 2D nanomaterial flakes, resulting in polydisperse dispersions with heterogeneous properties. Therefore, post-exfoliation separation techniques are needed to achieve 2D nanomaterial dispersions with monodispersity in lateral size, thickness, and properties. In this Account, we survey the latest developments in solution-based separation methods that aim to produce monodisperse dispersions and thin films of emerging 2D nanomaterials such as graphene, boron nitride, transition metal dichalcogenides, and black phosphorus. First, we motivate the need for precise thickness control in 2D nanomaterials by reviewing thickness-dependent physical properties. Then we present a succinct survey of solution-based exfoliation methods that yield 2D nanomaterial dispersions in organic solvents and aqueous media. The Account subsequently focuses on separation methods, including a critical analysis of their relative strengths and weaknesses for 2D nanomaterials with different buoyant densities, van der Waals interactions, and chemical reactivities. Specifically, we evaluate sedimentation-based density gradient ultracentrifugation (sDGU) and isopycnic DGU (iDGU) for post-exfoliation 2D nanomaterial dispersion separation. The comparative advantages of sedimentation and isopycnic methods are presented in both aqueous and nonaqueous media for 2D nanomaterials with varying degrees of chemical reactivity. Finally, we survey methods for forming homogeneous thin films from 2D nanomaterial dispersions and emerging technologies that are likely to benefit from these structures. Overall, this Account provides not only an overview of the present state-of-the-art but also a forward-looking vision for the field of solution-processed monodisperse 2D nanomaterials.

Layer-by-Layer Sorting of Rhenium Disulfide via High-Density Isopycnic Density Gradient Ultracentrifugation.

Isopycnic density gradient ultracentrifugation (iDGU) has been widely applied to sort nanomaterials by their physical and electronic structure. However, the commonly used density-gradient medium iodixanol has a finite maximum buoyant density that prevents the use of iDGU for high-density nanomaterials. Here, we overcome this limit by adding cesium chloride (CsCl) to iodixanol, thus increasing its maximum buoyant density to the point where the high-density two-dimensional nanomaterial rhenium disulfide (ReS2) can be sorted in a layer-by-layer manner with iDGU. The resulting aqueous ReS2 dispersions show photoluminescence at ∼1.5 eV, which is consistent with its direct bandgap semiconductor electronic structure. Furthermore, photocurrent measurements on thin films formed from solution-processed ReS2 show a spectral response that is consistent with optical absorbance and photoluminescence data. In addition to providing a pathway for effective solution processing of ReS2, this work establishes a general methodology for sorting high-density nanomaterials via iDGU.

Metal-Free Carbon-Based Nanomaterial Coatings Protect Silicon Photoanodes in Solar Water-Splitting.

The decreasing cost of silicon-based photovoltaics has enabled significant increases in solar electricity generation worldwide. Silicon photoanodes could also play an important role in the cost-effective generation of solar fuels, but the most successful methods of photoelectrode passivation and performance enhancement rely on a combination of precious metals and sophisticated processing methods that offset the economic arguments for silicon. Here we show that metal-free carbon-based nanomaterial coatings deposited from solution can protect silicon photoanodes carrying out the oxygen evolution reaction in a range of working environments. Purified semiconducting carbon nanotubes (CNTs) act as a hole extraction layer, and a graphene (Gr) capping layer both protects the CNT film and acts as a hole exchange layer with the electrolyte. The performance of semiconducting CNTs is found to be superior to that of metallic or unsorted CNTs in this context. Furthermore, the insertion of graphene oxide (GO) between the n-Si and CNTs reduces the overpotential relative to photoanodes with CNTs deposited on hydrogen-passivated silicon. The composite photoanode structure of n-Si/GO/CNT/Gr shows promising performance for oxygen evolution and excellent potential for improvement by optimizing the catalytic properties and stability of the graphene protective layer.

Solution-Processed Dielectrics Based on Thickness-Sorted Two-Dimensional Hexagonal Boron Nitride Nanosheets.

Gate dielectrics directly affect the mobility, hysteresis, power consumption, and other critical device metrics in high-performance nanoelectronics. With atomically flat and dangling bond-free surfaces, hexagonal boron nitride (h-BN) has emerged as an ideal dielectric for graphene and related two-dimensional semiconductors. While high-quality, atomically thin h-BN has been realized via micromechanical cleavage and chemical vapor deposition, existing liquid exfoliation methods lack sufficient control over h-BN thickness and large-area film quality, thus limiting its use in solution-processed electronics. Here, we employ isopycnic density gradient ultracentrifugation for the preparation of monodisperse, thickness-sorted h-BN inks, which are subsequently layer-by-layer assembled into ultrathin dielectrics with low leakage currents of 3 × 10(-9) A/cm(2) at 2 MV/cm and high capacitances of 245 nF/cm(2). The resulting solution-processed h-BN dielectric films enable the fabrication of graphene field-effect transistors with negligible hysteresis and high mobilities up to 7100 cm(2) V(-1) s(-1) at room temperature. These h-BN inks can also be used as coatings on conventional dielectrics to minimize the effects of underlying traps, resulting in improvements in overall device performance. Overall, this approach for producing and assembling h-BN dielectric inks holds significant promise for translating the superlative performance of two-dimensional heterostructure devices to large-area, solution-processed nanoelectronics.

Two-dimensional materials as catalysts, interfaces, and electrodes for an efficient hydrogen evolution reaction.

Two-dimensional (2D) materials have been significantly investigated as electrocatalysts for the hydrogen evolution reaction (HER) over the past few decades due to their excellent electrocatalytic properties and their structural uniqueness including the atomically thin structure and abundant active sites. Recently, 2D materials with various electronic properties have not only been used as active catalytic materials, but also employed in other components of the HER electrodes including a conductive electrode layer and an interfacial layer to maximize the HER efficiency or utilized as templates for catalytic nanostructure growth. This review provides the recent progress and future perspectives of 2D materials as key components in electrocatalytic systems with an emphasis on the HER applications. We categorized the use of 2D materials into three types: a catalytic layer, an electrode for catalyst support, and an interlayer for enhancing charge transfer between the catalytic layer and the electrode. We first introduce various scalable synthesis methods of electrocatalytic-grade 2D materials, and we discuss the role of 2D materials as HER catalysts, an interface for efficient charge transfer, and an electrode and/or a growth template of nanostructured noble metals.

Dopant Control of Solution-Processed CuI:S for Highly Conductive p-Type Transparent Electrode.

Copper iodide (CuI) has garnered considerable attention as a promising alternative to p-type transparent conducting oxides owing to its low cation vacancy formation energy, shallow acceptor level, and readily modifiable conductivity via doping. Although sulfur (S) doping through liquid iodination has exhibited high efficacy in enhancing the conductivity with record high figure of merit (FOM) of 630 00 MΩ-1, solution-processed S-doped CuI (CuI:S) for low-cost large area fabrication has yet to be explored. Here, a highly conducting CuI:S thin-film for p-type transparent conducting electrode (TCE) is reported using low temperature solution-processing with thiourea derivatives. The optimization of thiourea dopant is determined through a comprehensive acid-base study, considering the effects of steric hindrance. The modification of active groups of thioureas facilitated a varying carrier concentration range of 9 × 1018-2.52 × 1020 cm-3 and conductivities of 4.4-390.7 S cm-1. Consequently, N-ethylthiourea-doped CuI:S exhibited a FOM value of 7 600 MΩ-1, which is the highest value among solution-processed p-type TCEs to date. Moreover, the formulation of CuI:S solution for highly conductive p-type TCEs can be extended to CuI:S inks, facilitating high-throughput solution-processes such as inkjet printing and spray coating.

Aramid Nanodielectrics for Ultraconformal Transparent Electronic Skins.

On-skin electronics require minimal thicknesses and decent transparency for conformal contact, imperceptible wearing, and visual aesthetics. It is challenging to search for advanced ultrathin dielectrics capable of supporting the active components while maintaining bending softness, easy handling, and wafer-scale processability. Here, self-delaminated aramid nanodielectrics (ANDs) are demonstrated, enabling any skin-like electronics easily exfoliated from the processing substrates after complicated nanofabrication. In addition, ANDs are mechanically strong, chemically and thermally stable, transparent and breathable, therefore are ideal substrates for soft electronics. As demonstrated, compliant epidermal electrodes comprising silver nanowires and ANDs can successfully record high-quality electromyogram signals with low motion artifacts and satisfying sweat and water resistance. Furthermore, ANDs can serve as both substrates and dielectrics in single-walled carbon nanotube field-effect transistors (FETs) with a merely 160-nm thickness, which can be operated within 4 V with on/off ratios of 1.4 ± 0.5 × 105 , mobilities of 39.9 ± 2.2 cm2 V-1 s-1 , and negligible hysteresis. The ultraconformal FETs can function properly when wrapped around human hair without any degradation in performance.