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A Specific Nucleophilic Ring-Opening Reaction of Aziridines as a Unique Platform for the Construction of Hydrogen Polysulfides Sensors
Hydrogen polysulfides (H 2 S n , n>1) have been recently suggested to be the actual signalling molecules that involved in sulfur-related redox biology. However the exact mechanisms of H 2 S n are still poorly understood and a major hurdle in this field is the lack of reliable and convenient methods for H 2 S n detection. In this work we report a unique ring-opening reaction of N-sulfonylaziridine by Na 2 S 2 under mild conditions. Based on this reaction a novel H 2 S n -specific fluorescent probe (AP) was developed. The probe showed high sensitivity and selectivity for H 2 S n . Notably, the fluorescent turn-on product, i.e. compound 1, exhibited excellent two-photon photophysical properties and a large Stokes shift. Moreover, the high solid state luminescent efficiency of compound 1 makes it a potential candidate for organic emitters and solid-state lighting devices.
Stepwise Bay Annulation of Indigo for the Synthesis of Desymmetrized Electron Acceptors and Donor–Acceptor Constructs
In this work, a selective stepwise annulation of indigo has been demonstrated as a means of providing both monoannulated and differentially double-annulated indigo derivatives. Disparate substitution of the electron accepting bay-annulated indigo system allows for fine control over both the electronic properties as well as donor-acceptor structural architectures. Optical and electronic properties were characterized computationally as well as through UV-vis absorption spectroscopy and cyclic voltammetry. Finally, this straightforward method provides a modular approach for the design of indigo-based materials with tailored optoelectronic properties.
Direct Construction of Mesoporous Metal Sulfides via Reactive Spray Deposition Technology
In this work, a rapid one-step flame combustion deposition method was developed to fabricate the mesoporous metal sulfides directly on nickel foam without binder and template. The first-row transition metal sulfides, Co 9 S 8 , Ni 3 S 4 , NiCo 2 S 4 , and FeS, were successfully synthesized with three-dimensional architecture, large specific surface area (around 110 m 2 g –1 ), and interconnected pore networks. The binary meso-NiCo 2 S 4 exhibited a high specific capacitance (1350 F g –1 at 10 A g –1 ), excellent rate capability, and robust cycling stability in both three-electrode half-cells and asymmetric supercapacitor. This study demonstrated a new scalable strategy to obtain mesoporous metal sulfides with high electrochemical performance.
Rational Construction of Porous Metal–Organic Frameworks for Uranium(VI) Extraction: The Strong Periodic Tendency with a Metal Node
Although metal-organic frameworks (MOFs) have been reported as important porous materials for the potential utility in metal ion separation, coordinating the functionality, structure, and component of MOFs remains a great challenge. Herein, a series of anionic rare earth MOFs (RE-MOFs) were synthesized via a solvothermal template reaction and for the first time explored for uranium(VI) capture from an acidic medium. The unusually high extraction capacity of UO2 2 + (e.g., 538 mg U per g of Y-MOF) was achieved through ion-exchange with the concomitant release of Me 2 NH 2 + , during which the uranium(VI) extraction in the series of isostructural RE-MOFs was found to be highly sensitive to the ionic radii of the metal nodes. That is, the uranium(VI) adsorption capacities continuously increased as the ionic radii decreased. Finally, in-depth mechanism insight was obtained from molecular dynamics simulations, suggesting that both the accessible pore volume of the MOFs and hydrogen-bonding interactions contribute to the strong periodic tendency of uranium(VI) extraction.
Stabilizing Aqueous Three-Dimensional Printed Constructs Using Chitosan-Cellulose Nanocrystal Assemblies
The assembly and binding of nanoparticles at the interfaces of aqueous two-phase systems enable the three-dimensional (3D) printing of all-aqueous naturally occurring materials. When a dispersion of cellulose nanocrystals (CNCs) in an aqueous solution of polyethylene glycol (PEG) is brought into contact with chitosan dissolved in an aqueous solution of dextran, the CNCs and chitosan diffuse to the interface between the two immiscible aqueous solutions, electrostatically interact, and form a solid, membranous layer sufficiently rapidly to 3D print tubules of one liquid in the other. Additionally, the diameter, length, spatial arrangement, and stability of the printed tubules can be broadly controlled. Adsorption and directional diffusion of ionic species across the membranous layer make heavy metal ion removal possible. The results present a platform for fabricating and developing all-aqueous compartmentalized systems where function can be independently coupled to the inherent functionality of the nanoparticles or ligands.
Construction of an Anion-Pillared MOF Database and the Screening of MOFs Suitable for Xe/Kr Separation
The separation of xenon/krypton (Xe/Kr) mixtures is a challenging process. Many porous materials allow the adsorption of both Xe and Kr but only with low selectivity. Anion-pillared metal–organic frameworks (MOFs), featuring the anion groups as structural pillars, show potential in gas separations, but only a limited number of them have been synthesized. Here, we describe a collection of 936 anion-pillared MOFs based on 22 experimentally available structures. We performed density functional theory (DFT) optimization and then assigned density-derived electrostatic and chemical (DDEC) charges for each MOF to make them well suited to molecular simulations. The structural properties of the MOFs vary more strongly with the choice of the organic ligand than with other aspects like fluorine groups and metal centers. We then screened the entire collection of MOFs in the context of Xe/Kr separation at room temperature. Compared with previously reported MOFs, the interpenetrated MOF SIFSIX-6-Cd-i is predicted to perform better for Xe/Kr separations, with a good balance between working capacity (1.62 mmol/g) and separation selectivity (16.4) at 298 K and 100 kPa. Here, we also found that the heterogeneity of fluorine groups within a MOF can help to enhance Xe working capacity without reducing the Xe/Kr selectivity, suggesting that synthesis of anion-pillared MOFs with mixed fluorine groups may lead to improved Xe/Kr separation performance.
Constructing Ultrathin W-Doped NiFe Nanosheets via Facile Electrosynthesis as Bifunctional Electrocatalysts for Efficient Water Splitting
Exploring cost-effective and efficient bifunctional electrocatalysts via simple fabrication strategies is strongly desired for practical water splitting. Herein, an easy and fast one-step electrodeposition process is developed to fabricate W-doped NiFe (NiFeW)-layered double hydroxides with ultrathin nanosheet features at room temperature and ambient pressure as bifunctional catalysts for water splitting. Notably, the NiFeW nanosheets require overpotentials of only 239 and 115 mV for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, to reach a current density of 10 mA/cm 2 in alkaline media. Their exceptional performance is further demonstrated in a full electrolyzer configuration with the NiFeW as both anode and cathode catalysts, which achieves a low cell voltage of 1.59 V at 10 mA/cm 2 , 110 mV lower than that of the commercial IrO 2 (anode) and Pt (cathode) catalysts. Moreover, the NiFeW nanosheets are superior to various recently reported bifunctional electrocatalysts. Such remarkable performances mainly ascribe to W doping, which not only effectively modulates the electrocatalyst morphology but also engineers the electronic structure of NiFe hydroxides to boost charge-transfer kinetics for both the OER and HER. Hence, the ultrathin NiFeW nanosheets with an efficient fabrication strategy are promising as bifunctional electrodes for alkaline water electrolyzers.
Effects of Ink Formulation on Construction of Catalyst Layers for High-Performance Polymer Electrolyte Membrane Fuel Cells
Rational design of catalyst layers in a membrane electrode assembly (MEA) is crucial for achieving high-performance polymer electrolyte membrane fuel cells. Establishing a clear understanding of the property (catalyst ink)–structure (catalyst layer)–performance (MEA) relationship lays the foundation for this rational design. Here, a synergistic approach was taken to correlate the ink formulation, the microstructure of catalyst layers, and the resulting MEA performance to establish such a property–structure–performance relationship. The solvent composition (n-PA/H 2 O mixtures) demonstrated a strong influence on the performance of the MEA fabricated with an 830-EW (Aquivion) ionomer, especially polarization losses of cell activation and mass transport. The performance differences were studied in terms of how the solvent composition affects the catalyst/ionomer interface, ionomer network, and pore structure of the resulting catalyst layers. The ionomer aggregates mainly covered the surface of catalyst aggregates acting as oxygen reduction reaction active sites, and the aggregate sizes of the ionomer and catalyst (revealed by ultrasmall angle X-ray scattering and cryo-transmission electron microscopy) were dictated by tuning the solvent composition, which in turn determined the catalyst/ionomer interface (available active sites). In n-PA/H 2 O mixtures with 50~90 wt % H 2 O, the catalyst agglomerates could be effectively broken up into small aggregates, leading to enhanced kinetic activities. The boiling point of the mixed solvents determined the pore structure of ultimate catalyst layers, as evidenced by mercury porosimetry and scanning electron microscopy. For mixed solvents with a higher boiling point, the catalyst–ionomer aggregates in the ink tend to agglomerate during the solvent evaporation process and finally form larger catalyst–ionomer aggregates in the ultimate catalyst layer, resulting in more secondary pores and thus lower mass transport resistance. Both the enlarged catalyst/ionomer interface and appropriate pore structure were achieved with the catalyst layer fabricated from an n-PA/H 2 O mixture with 90 wt % H 2 O, leading to the best MEA performance.
Implementation of a Core–Shell Design Approach for Constructing MOFs for CO 2 Capture
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Constructing Robust Electrode/Electrolyte Interphases to Enable Wide Temperature Applications of Lithium-Ion Batteries
The electrolyte generally dictates the working temperature range of lithium ion batteries (LIBs), thus developing new class of electrolytes (primarily functional additives) in LIBs for wide temperature applications will be quite essential for further development of LIBs for electric vehicle market. In this study, we develop new functional electrolytes containing multiple additives to enable the LIBs to perform well in a wide temperature range from -40°C to 60°C. Importantly, those cells based on the above optimized electrolytes have been proven to behave significantly enhanced discharging performance at -40°C, the long-term cycling stability at 25°C (more than 85% of capacity retention after 1000 cycles at 1C/1C rates in 1 Ah pouch cells), as well as the obviously improved cycling stability at 60°C. These remarkable cell performances originate from the highly conductive, uniform and compact passivating films formed on both anode and cathode surfaces by the synergistic effects of the multiple additives. Our finding on the synergistic benefits originating from certain additive combination in the optimized electrolytes would favorably widen the working temperature range of future high-performance LIBs.
Modularly Constructed Polyhedral Oligomeric Silsesquioxane-Based Giant Molecules for Unconventional Nanostructure Fabrication
Controlled assembly of nanoscale building blocks is a promising approach to obtain functional materials with unique properties. In this paper, we report a way to manipulate the supramolecular structures of giant molecules based on discotic triangle cores and isobutyl polyhedral oligomeric silsesquioxanes (BPOSS) nanoparticles (NPs). It is found that depending upon the number of BPOSS at the periphery of the discotic cores, the packing of these nanoscale components (discotic core and POSS) could be manipulated into either cylindrical or Frank–Kasper (F–K) A15 ($Pm\overline 3n$) phases. The formation of these supramolecular nanostructures is mandated by the balance between the stacking of the discotic cores and the steric hindrance effect of the BPOSS NPs. This strategy to manipulate the packing of nanoscale building blocks for different supramolecular nanostructures including the fabrication of cylindrical structures and A15 ($Pm\overline 3n$) phases may be extended to other nanoscale building blocks for future development of materials with complex structures as well as tailored functionalities and properties.
Construction of Single-Atom Platinum Catalysts Enabled by CsPbBr[subscript 3] Nanocrystals
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Stationary Oxygen Vacancy Construction toward a Superior-Performance Ultrahigh Nickel Single-Crystal Cathode
Oxygen vacancies exert a complex and profound influence on the layered cathodes, especially those with ultrahigh nickel content. They can facilitate lithium-ion transport and enhance electronic conductivity, while aggressive oxygen vacancy formation causes structural degradation and electrolyte decomposition. Herein, taking ultrahigh nickel single-crystal LiNi 0.92 Co 0.06 Mn 0.02 O 2 (SC-Ni92) as a model material, we propose a pinning strategy to harness the benefits of oxygen vacancies while mitigating their detrimental effects. Through a carefully controlled thermal process, both oxygen vacancies and pinning atoms are successfully introduced into the surface region. The resulting anchored oxygen vacancies, capitalizing on their inherent advantages, improve conductivity and lithium-ion diffusion. Simultaneously, the neighboring pinning atoms effectively increase the migration barrier and suppress the adverse effects of these vacancies, including electrolyte decomposition and structural degradation during long-term electrochemical cycling. Consequently, oxygen vacancy-anchored single-crystal LiNi 0.92 Co 0.06 Mn 0.02 O 2 (SC-Ni92-OV) demonstrates significantly improved high-voltage electrochemical performance, with 86.16% capacity retention after 200 cycles at 4.6 V and 1 C in a half-cell and 90.71% after 300 cycles at 4.5 V and 1 C in a full cell. Furthermore, this study not only provides valuable insights into the chemistry of oxygen vacancy but also introduces a viable strategy for leveraging oxygen vacancies to achieve stable high-voltage performance in ultrahigh nickel single-crystal cathodes.
Constructing “Designer Atoms” via Resonant Graphene-Induced Lamb Shifts
The properties of an electron in an atom or molecule are not fixed; rather they are a function of the optical environment of the emitter. Not only is the spontaneous emission a function of the optical environment, but also the underlying wave functions and energy levels, which are modified by the potential induced by quantum fluctuations of the electromagnetic field. In free space, this modification of atomic levels and wave functions is very weak and generally hard to observe due to the prevalence of other perturbations like fine structure. Here in this paper, we explore the possibility of highly tailorable electronic structure by exploiting large Lamb shifts in tunable electromagnetic environments such as graphene, whose optical properties are dynamically controlled via doping. The Fermi energy can be chosen so that the Lamb shift is very weak, but it can also be chosen so that the shifts become more prominent than the fine structure of the atom and even potentially the Coulomb interaction with the nucleus. Potential implications of this idea include being able to electronically shift an unfavorable emitter structure into a favorable one, a new approach to probe near-field physics in fluorescence, and a way to access regimes of physics where vacuum fluctuations are not a weak perturbation but rather the dominant physics.
Improved Combinatorial Assembly and Barcode Sequencing for Gene-Sized DNA Constructs
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