Regulating Catalytic Oxidation Enantiomers Behavior by Imparting Chiral Microenvironment in Zr-Based Metal-Organic Frameworks.

Chiral inversions of enantiomers have significantly different biological activities, so it is important to develop simple and effective methods to efficiently identify optically pure compounds. Inspired by enzyme catalysis, the construction of chiral microenvironments resembling enzyme pockets in the pore space structure of metal-organic frameworks (MOFs) to achieve asymmetric enantioselective recognition and catalysis has become a new research hotspot. Here, a super-stable porphyrin-containing material PCN-224 is constructed by solvothermal method and a chiral microenvironment around the existing catalytic site of the material is created by post-synthesis modifications of the histidine (His) enantiomers. Experimental and theoretical calculations results show that the modulation of chiral ligands around Zr oxide clusters produces different spatial site resistances, which can greatly affect the adsorption and catalytic level of the enantiomeric molecules of tryptophan guests, resulting in a good enantioselective property of the material. It provides new ideas and possibilities for future chiral recognition and asymmetric catalysis.

Facile Fabrication of Hollow Nanoporous Carbon Architectures by Controlling MOF Crystalline Inhomogeneity for Ultra-Stable Na-Ion Storage.

Hollow nanoporous carbon architectures (HNCs) present significant utilitarian value for a wide variety of applications. Facile and efficient preparation of HNCs has long been pursued but still remains challenging. Herein, we for the first time demonstrate that single-component metal-organic frameworks (MOFs) crystals, rather than the widely reported hybrid ones which necessitate tedious operations for preparation, could enable the facile and versatile syntheses of functional HNCs. By controlling the growth kinetics, the MOFs crystals (STU-1) are readily engineered into different shapes with designated styles of crystalline inhomogeneity. A subsequent one-step pyrolysis of these MOFs with intraparticle difference can induce a simultaneous self-hollowing and carbonization process, thereby producing various functional HNCs including yolk-shell polyhedrons, hollow microspheres, mesoporous architectures, and superstructures. Superior to the existing methods, this synthetic strategy relies only on the complex nature of single-component MOFs crystals without involving tedious operations like coating, etching, or ligand exchange, making it convenient, efficient, and easy to scale up. An ultra-stable Na-ion battery anode is demonstrated by the HNCs with extraordinary cyclability (93 % capacity retention over 8000 cycles), highlighting a high level of functionality of the HNCs.

An Ultra-stable Supramolecular Framework Based on Consecutive Side-by-side Hydrogen Bonds for One-step C2H4/C2H6 Separation.

The one-step efficient separation of high-purity C2H4 from C2H4/C2H6 mixtures by hydrogen-bonded organic frameworks (HOFs) faces two problems: lack of strategies for constructing stable pores in HOFs and how to obtain high C2H6 selectivity. Herein, we have developed a microporous Mortise-Tenon-type HOF (MTHOF-1, MT is short for Mortise-Tenon structure) with a new self-assembly mode for C2H4/C2H6 separation. Unlike previous HOFs which usually possess discrete head-to-head hydrogen bonds, MTHOF-1 is assembled by unique consecutive side-by-side hydrogen bonds, which result in mortise-and-tenon pores decorated with orderly arranged amide groups and benzene rings. As expected, MTHOF-1 exhibits excellent stability under various conditions and shows clear separation trends for C2H6/C2H4. The IAST selectivity is as high as 2.15 at 298 K. More importantly, dynamic breakthrough experiments have demonstrated that MTHOF-1 can effectively separate the C2H6/C2H4 feed gas to obtain polymer-grade C2H4 in one step even under high-humidity conditions.

Over One Million DNA and Protein Events Through Ultra-Stable Chemically-Tuned Solid-State Nanopores.

Stability, long lifetime, resilience against clogging, low noise, and low cost are five critical cornerstones of solid-state nanopore technology. Here, a fabrication protocol is described wherein >1 million events are obtained from a single solid-state nanopore with both DNA and protein at the highest available lowpass filter (LPF, 100 kHz) of the Axopatch 200B-the highest event count mentioned in literature. Moreover, a total of ≈8.1 million events are reported in this work encompassing the two analyte classes. With the 100 kHz LPF, the temporally attenuated population is negligible while with the more ubiquitous 10 kHz, ≈91% of the events are attenuated. With DNA experiments, the pores are operational for hours (typically >7 h) while the average pore growth is merely ≈0.16 ± 0.1 nm h-1 . The current noise is exceptionally stable with traces typically showing <10 pA h-1 increase in noise. Furthermore, a real-time method to clean and revive pores clogged with analyte with the added benefit of minimal pore growth during cleaning (< 5% of the original diameter) is showcased. The enormity of the data collected herein presents a significant advancement to solid-state pore performance and will be useful for future ventures such as machine learning where large amounts of pristine data are a prerequisite.

Fluorinated Interface Engineering toward Controllable Zinc Deposition and Rapid Cation Migration of Aqueous Zn-Ion Batteries.

Metallic zinc (Zn) is a highly promising anode material for aqueous energy storage systems due to its low redox potential, high theoretical capacity, and low cost. However, rampant dendrites/by-products and torpid Zn2+ transfer kinetics at electrode/electrolyte interface severely threaten the cycling stability, which deteriorate the electrochemical performance of Zn-ion batteries. Herein, an interfacial engineering strategy to construct alkaline earth fluoride modified metal Zn electrodes with long lifespan and high capacity retention is reported. The compact fluoride layer is revealed to guide uniform Zn stripping/plating and accelerate the transfer/diffusion of Zn2+ via Maxwell-Wagner polarization. A series of in situ and ex situ spectroscopic studies verified that the fluoride layer can guide uniform Zn stripping/plating. Electrochemical kinetics analyses reveal that positive effect on the removal of Zn2+ solvation sheath provided by fluoride layer. Meanwhile, this fluoride coating layer can act as a barrier between the Zn electrode and electrolyte, providing a high electrode overpotential toward hydrogen evolution reaction to hold back H2 evolution. Consequently, the fluoride-modified Zn anode exhibited a capacity retention of 88.2% after 4000 cycles under10 A g-1 . This work opens up a new path to interface engineering for propelling the exploration of advanced rechargeable aqueous Zn-ion batteries.

A GPS-Referenced Wavelength Standard for High-Precision Displacement Interferometry at λ = 633 nm.

Since the turn of the millennium, the development and commercial availability of optical frequency combs has led to a steadily increase of worldwide installed frequency combs and a growing interest in using them for industrial-related metrology applications. Especially, GPS-referenced frequency combs often serve as a "self-calibrating" length standard for laser wavelength calibration in many national metrology institutes with uncertainties better than u = 1 × 10-11. In this contribution, the application of a He-Ne laser source permanently disciplined to a GPS-referenced frequency comb for the interferometric measurements in a nanopositioning machine with a measuring volume of 200 mm × 200 mm × 25 mm (NPMM-200) is discussed. For this purpose, the frequency stability of the GPS-referenced comb is characterized by heterodyning with a diode laser referenced to an ultrastable cavity. Based on this comparison, an uncertainty of u = 9.2 × 10-12 (τ = 8 s, k = 2) for the GPS-referenced comb has been obtained. By stabilizing a tunable He-Ne source to a single comb line, the long-term frequency stability of the comb is transferred onto our gas lasers increasing their long-term stability by three orders of magnitude. Second, short-term fluctuations-related length measurement errors were reduced to a value that falls below the nominal resolving capabilities of our interferometers (ΔL/L = 2.9 × 10-11). Both measures make the influence of frequency distortions on the interferometric length measurement within the NPMM-200 negligible. Furthermore, this approach establishes a permanent link of interferometric length measurements to an atomic clock.

Bulk Mn2+ Doped 1D Hybrid Lead Halide Perovskite with Highly Efficient, Tunable and Stable Broadband Light Emissions.

Mn2+ doped colloidal three-dimensional (3D) lead halide perovskite nanocrystal (PNC) has attracted intensive research attention; however, the low exciton binding energy and fatal optical instability of 3D PNC seriously hinder the optoelectronic application. Therefore, it remains significant to explore new stable host perovskite with strongly bound exciton to realize more desirable luminescent property. In this work, we utilized bulk one-dimensional (1D) hybrid perovskite of [AEP]PbBr5 ⋅ H2 O (AEP=N-aminoethylpiperazine) as structural platform to rationally optimize the luminescent property by a controllable Mn2+ doping strategy. Significantly, the series of Mn2+ -doped 1D [AEP]PbBr5 ⋅ H2 O show enhanced energy transfer efficiency from the strongly bound excitons of host material to 3d electrons of Mn2+ ions, resulting in tunable broadband light emissions from weak yellow to strong red spectral range with highest photoluminescence quantum yield up to 28.41 %. More importantly, these Mn2+ -doped 1D perovskites display ultrahigh structural and optical stabilities in humid atmosphere, water and high temperature exceeding the conventional 3D PNC. Combined highly efficient, tunable and stable broadband light emissions enable Mn2+ -doped 1D perovskite as excellent down-converting phosphor showcasing the potential application in white light emitting diode. This work not only provides a profound understanding of low-dimensional perovskites but also opens a new way to rationally design high-performance broadband light emitting perovskites for solid-state lighting and displaying devices.

Design of a Ultra-Stable Low-Noise Space Camera Based on a Large Target CMOS Detector and Image Data Analysis.

To detect faint target stars of 22nd magnitude and above, an astronomical exploration project requires its space camera's readout noise to be less than 5e- with long-time working stability. Due to the limitation of satellite, the traditional CCD detector-based camera does not meet the requirements, including volume, weight, and power consumption. Thereby, a low-noise ultra-stable camera based on 9 K × 9 K large target surface CMOS is designed to meet the needs. For the first time, the low-noise ultra-stable camera based on CMOS detector will be applied to space astronomy projects, remote sensing imaging, resource survey, atmospheric and oceanic observation and other fields. In this paper, the design of the camera is introduced in detail, and the camera is tested for several rounds at -40 °C; it also undergoes further testing and data analysis. Tests proved super stability and that the readout noise is lower than 4.5e-. Dark current, nonlinearity and PTC indicators meet the requirements of the astronomical exploration project.

Dynamic Intelligent Cu Current Collectors for Ultrastable Lithium Metal Anodes.

Three-dimensional (3D) current collectors have shown great potential in realizing dendrite-free lithium (Li) metal anodes. However, the rigid 3D current collectors could not simultaneously suppress Li dendrite growth and allow Li plating/stripping under high capacities and large current densities. Here, we report a dynamic intelligent Cu (DICu) current collector that dynamically accommodates the volume change by changing the packing density of the assembled particles. The Li/DICu electrode achieves a high Coulombic efficiency of 99.6% after 800 cycles. The symmetrical cell shows exceptional cycling stability under the high current density of 10 mA cm-2. Notably, when assembled in full-cell batteries, the Li/DICu|LiFePO4 battery maintains a specific capacity of 139.5 mAh g-1 at 1 C for 500 cycles, and the Li/DICu|S battery delivers a specific capacity of 804 mAh g-1 after 500 cycles at 0.5 C, corresponding to the best performance among Li metal batteries with Cu-based current collectors to date.

Tin Nanodots Derived From Sn2+ /Graphene Quantum Dot Complex as Pillars into Graphene Blocks for Ultrafast and Ultrastable Sodium-Ion Storage.

Tin (Sn) is considered to be an ideal candidate for the anode of sodium ion batteries. However, the design of Sn-based electrodes with maintained long-term stability still remains challenging due to their huge volume expansion (≈420%) and easy pulverization during cycling. Herein, a facile and versatile strategy for the synthesis of nitrogen-doped graphene quantum dot (GQD) edge-anchored Sn nanodots as the pillars into reduced graphene oxide blocks (NGQD/Sn-NG) for ultrafast and ultrastable sodium-ion storage is reported. Sn nanodots (2-5 nm) anchored at the edges of "octopus-like" GQDs via covalent SnOC/SnNC bonds function as the pillars that ensure fast Na-ion/electron transport across the graphene blocks. Moreover, the chemical and spatial (layered structure) confinements not only suppress Sn aggregation, but also function as physical barriers for buffering volume change upon sodiation/desodiation. Consequently, the NGQD/Sn-NG with high structural stability exhibits excellent rate performance (555 mAh g-1 at 0.1 A g-1 and 198 mAh g-1 at 10 A g-1 ) and ultra-long cycling stability (184 mAh g-1 remaining even after 2000 cycles at 5 A g-1 ). The confinement-induced synthesis together with remarkable electrochemical performances should shed light on the practical application of highly attractive tin-based anodes for next generation rechargeable sodium batteries.

Swelling-Deswelling Microencapsulation-Enabled Ultrastable Perovskite-Polymer Composites for Photonic Applications.

Metal halide perovskite nanocrystals are emerging as novel optoelectronic materials. Owing to their excellent optical and electronic properties such as tunable band gap, narrow-band emission and high charge mobility, they are quite promising in various fields including liquid-crystal display backlighting, solid-state lighting and other energy conversion applications. However, the intrinsic low formation energy makes them vulnerable to external stimulus, e. g. water, oxygen, heat, etc. Among many methods, swelling-deswelling microencapsulation emerges as one of the most promising strategies to improve their stability. Herein, recent developments and future research directions in swelling-deswelling microencapsulation-enabled ultrastable perovskite-polymer composites are summarized. We believe this strategy has great potential to deliver successful perovskite-based commercial products for many photonics applications.

Ultrastable Surface-Dominated Pseudocapacitive Potassium Storage Enabled by Edge-Enriched N-Doped Porous Carbon Nanosheets.

The development of ultrastable carbon materials for potassium storage poses key limitations caused by the huge volume variation and sluggish kinetics. Nitrogen-enriched porous carbons have recently emerged as promising candidates for this application; however, rational control over nitrogen doping is needed to further suppress the long-term capacity fading. Here we propose a strategy based on pyrolysis-etching of a pyridine-coordinated polymer for deliberate manipulation of edge-nitrogen doping and specific spatial distribution in amorphous high-surface-area carbons; the obtained material shows an edge-nitrogen content of up to 9.34 at %, richer N distribution inside the material, and high surface area of 616 m2 g-1 under a cost-effective low-temperature carbonization. The optimized carbon delivers unprecedented K-storage stability over 6000 cycles with negligible capacity decay (252 mA h g-1 after 4 months at 1 A g-1 ), rarely reported for potassium storage.

Calorimetric glass transition in a mean-field theory approach.

The study of the properties of glass-forming liquids is difficult for many reasons. Analytic solutions of mean-field models are usually available only for systems embedded in a space with an unphysically high number of spatial dimensions; on the experimental and numerical side, the study of the properties of metastable glassy states requires thermalizing the system in the supercooled liquid phase, where the thermalization time may be extremely large. We consider here a hard-sphere mean-field model that is solvable in any number of spatial dimensions; moreover, we easily obtain thermalized configurations even in the glass phase. We study the 3D version of this model and we perform Monte Carlo simulations that mimic heating and cooling experiments performed on ultrastable glasses. The numerical findings are in good agreement with the analytical results and qualitatively capture the features of ultrastable glasses observed in experiments.

Phosphorus Enhanced Intermolecular Interactions of SnO2 and Graphene as an Ultrastable Lithium Battery Anode.

SnO2 suffers from fast capacity fading in lithium-ion batteries due to large volume expansion as well as unstable solid electrolyte interphase. Herein, the design and synthesis of phosphorus bridging SnO2 and graphene through covalent bonding are demonstrated to achieve a robust structure. In this unique structure, the phosphorus is able to covalently "bridge" graphene and tin oxide nanocrystal through PC and SnOP bonding, respectively, and act as a buffer layer to keep the structure stable during charging-discharging. As a result, when applied as a lithium battery anode, SnO2 @P@GO shows very stable performance and retains 95% of 2nd capacity onward after 700 cycles. Such unique structural design opens up new avenues for the rational design of other high-capacity materials for lithium battery, and as a proof-of-concept, creates new opportunities in the synthesis of advanced functional materials for high-performance energy storage devices.

Ultrastable Liquid-Liquid Interface as Viable Route for Controlled Deposition of Biodegradable Polymer Nanocapsules.

Liquid-liquid interfaces are highly dynamic and characterized by an elevated interfacial tension as compared to solid-liquid interfaces. Therefore, they are gaining an increasing interest as viable templates for ordered assembly of molecules and nanoparticles. However, liquid-liquid interfaces are more difficult to handle compared to solid-liquid interfaces; their intrinsic instability may affect the assembly process, especially in the case of multiple deposition. Indeed, some attempts have been made in the deposition of polymer multilayers at liquid-liquid interfaces, but with limited control over size and stability. This study reports on the preparation of an ultrastable liquid-liquid interface based on an O/W secondary miniemulsion and its possible use as a template for the self-assembly of polymeric multilayer nanocapsules. Such polymer nanocapsules are made of entirely biodegradable materials, with highly controlled size-well under 200 nm-and multi-compartment and multifunctional features enriching their field of application in drug delivery, as well as in other bionanotechnology fields.

Synthesis of Ultrastable Ag Nanoplates/Polyethylenimine-Reduced Graphene Oxide and Its Application as a Versatile Electrochemical Sensor.

Investigations on Ag nanostructures/reduced graphene oxide composites have been frequently reported, yet the morphology control of those loaded Ag nanocrystals is still challenging. We herein develop a facile method to grow triangular Ag nanoplates (AgP) on polyethylenimine-modified reduced graphene oxide (AgP/PEI-rGO). The AgP/PEI-rGO hybrids show unexpected high stability against chloride ions (Cl(-) ) and hydrogen peroxide (H2 O2 ), which is possibly due to the strong interaction between surface Ag atoms with the amine groups of PEI. In the chronoamperometry measurements for detecting H2 O2 , N2 H4 , and NaNO2 , the AgP/PEI-rGO hybrid shows very wide linear ranges (usually 10(-6) -10(-2)  mol L(-1) for H2 O2 , N2 H4 , and NaNO2 ) and low detection limits (down to ≈1×10(-7)  mol L(-1) ), which demonstrate the promising electrochemical sensor applications of these metal/graphene hybrids with well-defined morphologies and facets. In addition, this strategy could be extended to the deposition of other noble metals on rGO with controlled morphologies.

Self-assembled C-Ag hybrid nanoparticle on nanoporous GaN enabled ultra-high enhancement factor SERS sensor for sensitive thiram detection.

Considering pesticide residues cause significant harm to public health and the environment, developing a simple, sensitive, and reliable approach to pesticide residue detection to address this issue is necessary. In this study, an ultrasensitive and reliable surface-enhanced Raman scattering (SERS) sensor was developed using cetylpyridinium chloride as a protecting and reducing agent for the in situ synthesis and self-assembly of C-Ag nanoparticles on nanoporous GaN for the quantitative detection of thiram. A systematic investigation of the performance of the SERS sensor revealed that the SERS sensor delivered a limit of detection (LOD) of 10-14 M and an enhancement factor of up to 1.80 × 1011 with reasonable uniformity and reproducibility, with the stability of the SERS sensor demonstrated via long-term storage for up to 22 weeks in air. The enhancement mechanism of the SERS sensor was verified using a finite-difference time-domain simulation. The SERS sensor successfully detected thiram in real samples with an LOD of 10-10 M. Hence, this study provides an effective platform for monitoring food safety and the environment.

Selenium-induced anion vacancy and active site migration stimulating remarkable sulfide Na-Ion storage.

Heterojunctions and controllable anionic vacancies are perceived to be powerful means of ameliorating the performance of sodium-ion batteries assignable to their unique physical and chemical properties. However, the mechanism by which heterojunction and vacancy structures affect sodium-ion battery storage remains to be systemically explored. In this study, the Se doped CoS2@CoS1.035@Carbon (Se-CoS2@CoS1.035@C) heterostructure with anion vacancy was synthesized by a one-step calcination. These heterostructures with lower metal oxidation states and anionic vacancies exhibit exceptional Na+ storage performance (554.3 mA h g-1 after 1500 cycles at 5.0 A g-1). Both electrochemical tests and theoretical calculations demonstrate excellent pseudocapacitive behavior and enhanced Na+ adsorption during discharge because of anionic vacancies and Se doping. Additionally, introducing weaker Co-Se bonds and extending Co-S and Co-Se bonds reduce binding energies, which effectively accelerates the conversion reaction. Our findings provide a feasible way to rationally design and facilely prepare heterostructured anode materials with rich anionic vacancies for sodium-ion batteries.

Synergetic Sn Incorporation-Zn Substitution in Copper-Based Sulfides Enabling Superior Na-Ion Storage.

Transition-metal sulfides have been regarded as perspective anode candidates for high-energy Na-ion batteries. Their application, however, is precluded severely by either low charge storage or huge volumetric change along with sluggish reaction kinetics. Herein, an effective synergetic Sn incorporation-Zn substitution strategy is proposed based on copper-based sulfides. First, Na-ion storage capability of copper sulfide is significantly improved via incorporating an alloy-based Sn element. However, this process is accompanied by sacrifice of structural stability due to the high Na-ion uptake. Subsequently, to maintain the high Na-ion storage capacity, and concurrently improve cycling and rate capabilities, a Zn substitution strategy (taking partial Sn sites) is carried out, which could significantly promote Na-ion diffusion/reaction kinetics and relieve mechanical strain-stress within the crystal framework. The synergetic Sn incorporation and Zn substitution endow copper-based sulfides with high specific capacity (≈560 mAh g-1 at 0.5 A g-1 ), ultrastable cyclability (80 k cycles with ≈100% capacity retention), superior rate capability up to 200 A g-1 , and ultrafast charging feature (≈4 s per charging with ≈190 mAh g-1 input). This work provides in-depth insights for developing superior anode materials via synergetic multi-cation incorporation/substitution, aiming at solving their intrinsic issues of either low specific capacity or poor cyclability.

Liquid Gallium-Assisted Pyrolysis of MOF Affording CNT Non-Hollow Frameworks in High Yields for High-Performance Sodium-Ion Battery Anode.

Carbon materials have great potential for applications in energy, biology, and environment due to their excellent chemical and physical properties. Their preparation by carbonization methods encounters limitations and the carbon loss during pyrolysis in the form of gaseous molecules results in low yield of carbon materials. Herein a low-energy (600 °C) and high-yield (82 wt.%) carbonization strategy is developed using liquid gallium-assisted pyrolysis of metal-organic frameworks (MOFs) affording the N-doped carbon nanotube (CNT) non-hollow frameworks encapsulating Co nanoparticles. The liquid gallium layer offers protection against air, promotes heat transfer, and limits the escape of small carbonaceous gaseous molecules, which greatly improve the yields of the pyrolysis reaction. Experimental and theoretical results reveal that the synergistic interaction between CNTs and N/O-containing groups gives a non-hollow framework composed of N/O-enriched and open CNTs (NOCNTF-15, 15 denotes the 15 mm thickness of the liquid gallium layer during the pyrolysis) with high specific capacity (185 mAh g-1 at 10 A g-1) and ultra-stable cyclability (stable operation at 10 A g-1 and 50 °C for 20 000 cycles). This study provides a unique approach to carbonization that facilitates the practical application of low-cost CNTs and other MOFs-derived carbon materials in high-performance sodium-ion batteries (SIBs).