Ultrahigh Energy Storage in 2D High-κ Perovskites.

Dielectric capacitors have greater power densities than batteries, and, unlike batteries, they do not utilize chemical reactions during cycling. Thus, they can become ideal, safe energy storage devices. However, dielectric capacitors yield rather low energy densities compared with other energy storage devices such as batteries and supercapacitors. Here, we present a rational approach for designing ultrahigh energy storage capacitors using two-dimensional (2D) high-κ dielectric perovskites (Ca2Nam-3NbmO3m+1; m = 3-6). Individual Ca2Nam-3NbmO3m+1 nanosheets exhibit an ultrahigh dielectric strength (638-1195 MV m-1) even in the monolayer form, which exceeds those of conventional dielectric materials. Multilayer stacked nanosheet capacitors exhibit ultrahigh energy densities (174-272 J cm-3), high efficiencies (>90%), excellent reliability (>107 cycles), and temperature stability (-50-300 °C); the maximum energy density is much higher than those of conventional dielectric materials and even comparable to those of lithium-ion batteries. Enhancing the energy density may make dielectric capacitors more competitive with batteries.

Solution-Processed Two-Dimensional Metal Oxide Anticorrosion Nanocoating.

Molecularly thin two-dimensional (2D) nanomaterials are attractive building blocks for constructing anticorrosion nanocoatings as an ultimate pursuit in the metal-related industry. However, the nanocoating of prefocused graphene is far from industrial demands due to its high cost, low scalability, and insufficient quality. We propose all requirements to realize rational anticorrosion nanocoating of metal oxide nanosheets. The proof-of-concept study with Ti0.87O2 and Ca2Nb3O10 nanosheets demonstrates that the 10 and 20 nm thick coatings fabricated by a facile layer-by-layer (LbL) self-assembly on stainless steel (SUS) give perfect inhibition efficiency (IE) values of 99.92% and 99.89%, respectively. A driving test with a nanosheet-coated car-baffle demonstrated suitable corrosion resistance and mechanical and thermal robustness for industrial applications. The revealed and controlled thermal oxidation mechanisms are critical toward high-temperature application of the 2D oxide anticorrosion nanocoating. The advantages of nanosheet coating and extensible materials design will open a solid but exciting route to anticorrosion nanotechnology.

Acetate-dependent tRNA acetylation required for decoding fidelity in protein synthesis.

Modification of tRNA anticodons plays a critical role in ensuring accurate translation. N4-acetylcytidine (ac4C) is present at the anticodon first position (position 34) of bacterial elongator tRNAMet. Herein, we identified Bacillus subtilis ylbM (renamed tmcAL) as a novel gene responsible for ac4C34 formation. Unlike general acetyltransferases that use acetyl-CoA, TmcAL activates an acetate ion to form acetyladenylate and then catalyzes ac4C34 formation through a mechanism similar to tRNA aminoacylation. The crystal structure of TmcAL with an ATP analog reveals the molecular basis of ac4C34 formation. The ΔtmcAL strain displayed a cold-sensitive phenotype and a strong genetic interaction with tilS that encodes the enzyme responsible for synthesizing lysidine (L) at position 34 of tRNAIle to facilitate AUA decoding. Mistranslation of the AUA codon as Met in the ΔtmcAL strain upon tilS repression suggests that ac4C34 modification of tRNAMet and L34 modification of tRNAIle act cooperatively to prevent misdecoding of the AUA codon.

Vapour-liquid-solid growth of monolayer MoS2 nanoribbons.

Chemical vapour deposition of two-dimensional materials typically involves the conversion of vapour precursors to solid products in a vapour-solid-solid mode. Here, we report the vapour-liquid-solid growth of monolayer MoS2, yielding highly crystalline ribbons with a width of few tens to thousands of nanometres. This vapour-liquid-solid growth is triggered by the reaction between MoO3 and NaCl, which results in the formation of molten Na-Mo-O droplets. These droplets mediate the growth of MoS2 ribbons in the 'crawling mode' when saturated with sulfur. The locally well-defined orientations of the ribbons reveal the regular horizontal motion of the droplets during growth. Using atomic-resolution scanning transmission electron microscopy and second harmonic generation microscopy, we show that the ribbons are grown homoepitaxially on monolayer MoS2 with predominantly 2H- or 3R-type stacking. Our findings highlight the prospects for the controlled growth of atomically thin nanostructure arrays for nanoelectronic devices and the development of unique mixed-dimensional structures.

Decoding system for the AUA codon by tRNAIle with the UAU anticodon in Mycoplasma mobile.

Deciphering the genetic code is a fundamental process in all living organisms. In many bacteria, AUA codons are deciphered by tRNA(Ile2) bearing lysidine (L) at the wobble position. L is a modified cytidine introduced post-transcriptionally by tRNA(Ile)-lysidine synthetase (TilS). Some bacteria, including Mycoplasma mobile, do not carry the tilS gene, indicating that they have established a different system to decode AUA codons. In this study, tRNA(Ile2) has been isolated from M. mobile and was found to contain a UAU anticodon without any modification. Mycoplasma mobile isoleucyl-tRNA synthetase (IleRS) recognized the UAU anticodon, whereas Escherichia coli IleRS did not efficiently aminoacylate tRNA(Ile2)(UAU). In M. mobile IleRS, a single Arg residue at position 865 was critical for specificity for the UAU anticodon and, when the corresponding site (W905) in E. coli IleRS was substituted with Arg, the W905R mutant efficiently aminoacylated tRNA with UAU anticodon. Mycoplasma mobile tRNA(Ile2) cannot distinguish between AUA and AUG codon on E. coli ribosome. However, on M. mobile ribosome, M. mobile tRNA(Ile2)(UAU) specifically recognized AUA codon, and not AUG codon, suggesting M. mobile ribosome has a property that prevents misreading of AUG codon. These findings provide an insight into the evolutionary reorganization of the AUA decoding system.

Structural dynamics of a mitochondrial tRNA possessing weak thermodynamic stability.

Folding dynamics are ubiquitously involved in controlling the multivariate functions of RNAs. While the high thermodynamic stabilities of some RNAs favor purely native states at equilibrium, it is unclear whether weakly stable RNAs exist in random, partially folded states or sample well-defined, globally folded conformations. Using a folding assay that precisely tracks the formation of native aminoacylable tRNA, we show that the folding of a weakly stable human mitochondrial (hmt) leucine tRNA is hierarchical with a distinct kinetic folding intermediate. The stabilities of the native and intermediate conformers are separated by only about 1.2 kcal/mol, and the species are readily interconvertible. Comparison of folding dynamics between unmodified and fully modified tRNAs reveals that post-transcriptional modifications produce a more constrained native structure that does not sample intermediate conformations. These structural dynamics may thus be crucial for recognition by some modifying enzymes in vivo, especially those targeting the globular core region, by allowing access to pretransition state conformers. Reduced conformational sampling of the native, modified tRNAs could then permit improved performance in downstream processes of translation. More generally, weak stabilities of small RNAs that fold in the absence of chaperone proteins may facilitate conformational switching that is central to biological function.

Reversibly tunable upconversion luminescence by host-guest chemistry.

Tuning upconversion (UPC) luminescence using external stimuli and fields, as well as chemical reactions, is expected to lead to novel and efficient optical sensors. Herein, highly tunable UPC luminescence was achieved through a host-guest chemistry approach. Specifically, interlayer ion exchange reactions reversibly tuned the emission intensity and green-red color of Er/Yb-codoped A2La2Ti3O10 layered perovskite, where A corresponds to proton and alkali metal ions, enabling the visualization of host-guest interactions and reactions.

Proton conductivities of graphene oxide nanosheets: single, multilayer, and modified nanosheets.

Proton conductivities of layered solid electrolytes can be improved by minimizing strain along the conduction path. It is shown that the conductivities (σ) of multilayer graphene oxide (GO) films (assembled by the drop-cast method) are larger than those of single-layer GO (prepared by either the drop-cast or the Langmuir-Blodgett (LB) method). At 60% relative humidity (RH), the σ value increases from 1×10(-6) S cm(-1) in single-layer GO to 1×10(-4) and 4×10(-4) S cm(-1) for 60 and 200 nm thick multilayer films, respectively. A sudden decrease in conductivity was observed for with ethylenediamine (EDA) modified GO (enGO), which is due to the blocking of epoxy groups. This experiment confirmed that the epoxide groups are the major contributor to the efficient proton transport. Because of a gradual improvement of the conduction path and an increase in the water content, σ values increase with the thickness of the multilayer films. The reported methods might be applicable to the optimization of the proton conductivity in other layered solid electrolytes.

Facet-controlled growth and soft-chemical exfoliation of two-dimensional titanium dioxide nanosheets.

TiO2 remains one of the most popular materials used in catalysts, photovoltaics, coatings, and electronics due to its abundance, chemical stability, and excellent catalytic properties. The tailoring of the TiO2 structure into two-dimensional nanosheets prompted the successful isolation of graphene and MXenes. In this review, facet-controlled TiO2 and monolayer titanate are outlined, covering their synthesis route and formation mechanism. The reactive facet of TiO2 is usually controlled by a capping agent. In contrast, the monolayer titanate is achieved by ion-exchange and delamination of layered titanates. Each route leads to 2D structures with unique physical and chemical properties, which expands its utilisation into several niche applications. We elaborate the detailed outlook for the future use and research studies of facet-controlled TiO2 and monolayer titanates. Advantages and disadvantages of both structures are provided, along with suggested applications for each type of 2D TiO2 nanosheets.

Graphene oxide nanosheet with high proton conductivity.

We measured the proton conductivity of bulk graphite oxide (GO'), a graphene oxide/proton hybrid (GO-H), and a graphene oxide (GO) nanosheet for the first time. GO is a well-known electronic insulator, but for proton conduction we observed the reverse trend, as it exhibited superionic conductivity. The hydrophilic sites present in GO as -O-, -OH, and -COOH functional groups attract the protons, which propagate through hydrogen-bonding networks along the adsorbed water film. The proton conductivities of GO' and GO-H at 100% humidity were ∼10(-4) and ∼10(-5) S cm(-1), respectively, whereas that for GO was amazingly high, nearly 10(-2) S cm(-1). This finding indicates the possibility of GO-based perfect two-dimensional proton-conductive materials for applications in fuel cells, sensors, and so on.

Thermal and Chemical Phase Engineering of Two-Dimensional Ruthenate.

Monolayer ruthenate nanosheets obtained by exfoliating layered ruthenium oxide exhibit excellent electrical conductivity, redox activity, and catalytic activity, which render them suitable for advanced electronic and energy devices. However, to fully exploit the benefits, we require further structural insights into a complex polymorphic nature and diversity in relevant electronic states of two-dimensional (2D) ruthenate systems. In this study, the 2D structures, stability, and electronic states of 2D ruthenate are investigated on the basis of thermal and chemical phase engineering approaches. We reveal that contrary to a previous report, exfoliation of an oblique 1T phase precursor leads to nanosheets having an identical phase without exfoliation-induced phase transition to a 1H phase. The oblique 1T phase in the nanosheets is found to be metastable and, thus, transforms successively to a rectangular 1T phase upon heating. A phase-controllable synthesis via Co doping affords nanosheets with metastable rectangular and thermally stable hexagonal 1T phases at a Co content of 5-10 and 20 at%, respectively. The 1T phases show metallic electronic states, where the d-d optical transitions between the Ru 4d (t2g) orbital depend on the symmetry of the Ru framework. The Co doping in ruthenate nanosheets unexpectedly suppresses the redox and catalytic activities under acidic conditions. In contrast, the Co2+/3+ redox pair is activated and produces conductive nanosheets with high electrochemical capacitance in an alkaline condition.

Damage-free LED lithography for atomically thin 2D material devices.

Desired electrode patterning on two-dimensional (2D) materials is a foremost step for realizing the full potentials of 2D materials in electronic devices. Here, we introduce an approach for damage-free, on-demand manufacturing of 2D material devices using light-emitting diode (LED) lithography. The advantage of this method lies in mild photolithography by simply combining an ordinary optical microscope with a commercially available LED projector; the low-energy red component is utilized for optical characterization and alignment of devices, whereas the high-energy blue component is utilized for photoresist exposure and development of personal computer designed electrode patterns. This method offers maskless, damage-free photolithography, which is particularly suitable for 2D materials that are sensitive to conventional lithography. We applied this LED lithography to device fabrication of selected nanosheets (MoS2, graphene oxides and RuO2), and achieved damage-free lithography of various patterned electrodes with feature sizes as small as 1-2 µm. The LED lithography offers a useful approach for cost-effective mild lithography without any costly instruments, high vacuum, or complex operation.

Accelerated Ionic and Charge Transfer through Atomic Interfacial Electric Fields for Superior Sodium Storage.

Atomic interfacial electric fields hold great potential for boosting ionic and charge transfer and accelerating electrochemical reaction kinetics. Here, built-in electric fields within the heterostructure are created by electrostatic assembly of unilamellar titano-niobate/graphene (reduced graphene oxide) nanosheets as building blocks. Scanning Kelvin probe microscopy confirms the existence of built-in electric fields by detecting the unbalanced surface potential of disparate nanosheets in the heterostructure, which facilitates ion and electron transfer, thus enabling an excellent reversible sodium storage capacity of 245 mAh g-1 at 0.05 A g-1. Theoretical analysis also confirms that the electric field can enhance the electric conductivity and facilitate electron transfer at the atomic interface. Moreover, in situ TEM observations confirm the homogeneous intercalation of sodium ions and very small volume expansion of the hybrid materials. As a result, a highly stable lifetime of 3000 cycles is achieved with capacity retention of 98.8%. This work attests the importance of accelerating ionic and charge transfer through atomic interfacial electric field for superior sodium storage.

Tailoring the CO2-selectivity of interfacial polymerized thin film nanocomposite membrane via the barrier effect of functionalized boron nitride.

Membrane-based separation is an appealing solution to mitigate CO2 emission sustainably due to its energy efficiency and environmental friendliness. Attributed to its excellent separation endowed by nanomaterial incorporation, nanocomposite membrane is rigorously developed. This study explored the feasibility of boron nitride (BN) embedment and changes to formation mechanism of ultrathin selective layer of thin film nanocomposite (TFN) are investigated. The effects of amine-functionalization on nanosheet-polymer interaction and CO2 separation performance are also identified. Participation of nanosheets during interfacial polymerization reduced the crosslinking of selective layer, hence, improved TFN permeance while the formation of contorted diffusion paths by the nanosheets favors transport of small gases. Amine-functionalization enhanced the nanosheet-polymer interaction and elevated the membrane affinity towards CO2 which led to enhanced CO2 selectivity. The best TFN prepared in this study exhibited 37% and 20% increment in permeability and selectivity, respectively with respect to neat thin film composite (TFC). It is found that the CO2 separation performance of BN incorporated TFN is on par with many non-porous nanosheet-incorporated TFNs reported in literatures. The transport and barrier effects of BN and functionalized BN are discussed in detail to provide further insights into the development of commercially attractive CO2 selective TFN membranes.

Tunable Doping of Rhenium and Vanadium into Transition Metal Dichalcogenides for Two-Dimensional Electronics.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) with unique electrical properties are fascinating materials used for future electronics. However, the strong Fermi level pinning effect at the interface of TMDCs and metal electrodes always leads to high contact resistance, which seriously hinders their application in 2D electronics. One effective way to overcome this is to use metallic TMDCs or transferred metal electrodes as van der Waals (vdW) contacts. Alternatively, using highly conductive doped TMDCs will have a profound impact on the contact engineering of 2D electronics. Here, a novel chemical vapor deposition (CVD) using mixed molten salts is established for vapor-liquid-solid growth of high-quality rhenium (Re) and vanadium (V) doped TMDC monolayers with high controllability and reproducibility. A tunable semiconductor to metal transition is observed in the Re- and V-doped TMDCs. Electrical conductivity increases up to a factor of 108 in the degenerate V-doped WS2 and WSe2 . Using V-doped WSe2 as vdW contact, the on-state current and on/off ratio of WSe2 -based field-effect transistors have been substantially improved (from ≈10-8 to 10-5 A; ≈104 to 108 ), compared to metal contacts. Future studies on lateral contacts and interconnects using doped TMDCs will pave the way for 2D integrated circuits and flexible electronics.

A RuO2 Nanosheet as a Novel Quencher-free Platform for the Detection of Nucleic Acids in a Homogeneous Solution.

A fluorescent dye-labeled DNA probe was adsorbed and quenched on the monolayer of RuO2 nanosheets. Significant fluorescent recovery was observed upon the addition of complementary DNA due to desorption of the probe from the surface of the RuO2 nanosheet through duplex formation. The efficiency of fluorescence recovery was higher than that for graphene oxide, which was known as a quencher-free platform for the detection of nucleic acids in a homogeneous solution.

CoNiFe Layered Double Hydroxide/RuO2.1 Nanosheet Superlattice as Carbon-Free Electrocatalysts for Water Splitting and Li-O2 Batteries.

Efficient electrocatalysts are highly demanded for oxygen evolution reaction (OER) in water splitting and metal-air batteries. Here, superlattice structured materials composed of CoNiFe layered double hydroxide (LDH)/ruthenium oxide nanosheets are synthesized as carbon-free electrocatalysts for OER. The positively charged CoNiFe LDH and negatively charged RuO2.1 are alternately stacked at the molecular level into superlattice-like hybrids by electrostatic interaction upon mixing their dispersions under suitable conditions. Such heterostructured composites are found to act as effective catalysts toward OER of water splitting with a small overpotential of 281 mV and Tafel plot of 48.9 mV/decade. Such composites also serve as efficient carbon-free cathode catalysts for aprotic Li-O2 batteries with remarkable higher specific capacities and lower overvoltages than RuO2 nanoparticles. The superior performance may be attributed to the peculiar superlattice structure, resulting in strong interfacial electronic coupling, better electrical conductivity, and the suppression of side reactions caused by traditional carbon-based materials. Furthermore, potential difference between RuO2.1 and CoNiFe LDH nanosheets is observed directly by scanning Kelvin probe microscopy, indicating that electrostatic fields might be induced in the superlattice structures to benefit the transport of electrons and charged ions as well as the catalytic process.

On/Off Boundary of Photocatalytic Activity between Single- and Bilayer MoS2.

Molecularly thin two-dimensional (2D) semiconductors are emerging as photocatalysts owing to their layer-number-dependent quantum effects and high charge separation efficiency. However, the correlation among the dimensionality, crystallinity, and photocatalytic activity of such 2D nanomaterials remains unclear. Herein, a Ag photoreduction technique coupled with microscopic analyses is employed to spatially resolve the photocatalytic activity of MoS2 as a model catalyst. Interestingly, we find that only monolayer (1L)-MoS2 is active for a Ag photoreduction reaction. The photocatalytic activity of 1L-MoS2 is enhanced by a built-in electrical field originated from the MoS2/SiO2 interface, instead of by the specific surface structure and quantum electronic state of 1L-MoS2. Furthermore, we observe photocatalytic active sites to be geometrically distributed on triangular 1L-MoS2 crystals, wherein the Ag particles are preferentially deposited on the outermost zigzag edges and defective inner parts of the triangular grains. The degradation of photocatalytic activity and electron mobility with the formation of Mo(VI) species indicates that the species inhibit the in-plane diffusion of the photogenerated electrons to the reductive sites. The monolayer-selectivity, activation, and inactivation mechanisms, unveiled in this work, will offer future directions in designing 2D nanophotocatalysts.

Photoelectrochemical properties of a well-structured 1.3 nm-thick pn junction crystal.

A 1.3 nm-thick nickel hydroxide (p-type, 0.5 nm)/titania (n-type, 0.8 nm) pn junction prepared by lamination of nanosheets improved the onset potential for photoelectrochemical oxidation and increased the photooxidation current, indicating that ultrathin pn junctions suppress the recombination of photo-generated carriers.

Tunable Chemical Coupling in Two-Dimensional van der Waals Electrostatic Heterostructures.

Heterostructures of two-dimensional (2D) atomic crystals provide fascinating molecular-scale design elements for emergent physical phenomena and functional materials, as integrating distinct monolayers into vertical heterostructures can afford coupling between disparate properties. However, the available examples have been limited to either van der Waals (vdW) or electrostatic (ES) heterostructures that are solely composed of noncharged and charged monolayers, respectively. Here, we propose a "vdW-ES heterostructure" chemical design in which charge-neutral and charged monolayer-building blocks with highly disparate chemical and physical properties are conjugated vertically through asymmetrically charged interfaces. We demonstrate vdW-ES heteroassembly of semiconducting MoS2 and dielectric Ca2Nb3O10- (CNO) monolayers using an amphipathic molecular starch, resulting in the emergence of trion luminescence observed at the lowest energy among MoS2-related materials, probably due to interfacial confinement effects given by vdW-ES dual interactions. In addition, interface engineering leads to tailored exciton of the vdW/ES heterostructures owing to the pronounced dielectric proximity effects, bringing an intriguing interlayer chemistry to modify 2D materials. Furthermore, the current approach was successfully extended to create a graphene/CNO heterostructure, which verifies the versatility of the preparative method.