Highly effective H2/D2 separation in a stable Cu-based metal-organic framework

A three-dimensional copper metal-organic framework with the rare chabazite(CHA)topology namely FJI-Y11 has been constructed with flexibly carboxylic ligand 5,5'-[(1,4-phenylenebis(methylene))bis(oxy)]diisophthalic acid(H₄L).FJI-Y11 exhibits high water stability with the pH range from 2 to 12 at temperature as high as 373 K.Importantly,FJI-Y11 also shows high efficiency of hydrogen isotope separation using dynamic column breakthrough experiments under atmospheric pressure at 77 K.Attributed to its excellent structural stability,FJI-Y11 possesses good regenerated performance and maintains high separation efficiency after three cycles of breakthrough experiments.     

Layer-by-layer assembled dual-ligand conductive MOF nano-films with modulated chemiresistive sensitivity and selectivity

In this paper,a dual-ligand design strategy is demonstrated to modulate the performance of the electronically conductive metalorganic frameworks(EC-MOFs)thin film with a spray layer-by-layer assembly method.The thin film not only can be precisely prepared in nanometer scale(20-70 nm),but also shows the pin-hole-free smooth surface.The high quality nano-film of 2,3,6,7,10,11-hexaiminotriphenylene(HITP)doped Cu-HHTP enables the precise modulation of the chemiresistive sensitivity and selectivity.Selectivity improvement over 220%were realized for benzene vs.NH3>as well as enhanced response and recovery properties.In addition,the selectivity of the EC-MOF thin film sensors toward other gases(e.g.triethylamine,methane,ethylbenzene,hydrogen,butanone,and acetone)vs.NH3 at room temperature is also discussed.     

Colloidal lead-free Cs2AgBiBr6 double perovskite nanocrystals: Synthesis,uniform thin-film fabrication,and application in solution-processed solar cells

Recently developed lead-free double perovskite nanocrystals(NCs)have been proposed for the possible application in solutionprocessed optoelectronic devices.However,the optoelectronic applications of double perovskite NCs have been hampered due to the structural and chemical instability in the presence of polar molecules.Here,we report a facile strategy for the synthesis and purification of Cs₂AgBiBr₆double perovskite NCs that remained stable even after washing with polar solvent.This is realized with our efficient colloidal route to synthesize Cs₂AgBiBr₆NCs that involve stable and strongly coordinated precursor such as silvertrioctyl phosphine complex together with bismuth neodecanoate,which leads to a significantly improved chemical and colloidal stability.Using layer-by-layer solid-state ligand exchange technique,a compact and crack-free thin film of Cs₂AgBiBr₆NCs were fabricated.Finally,perovskite solar cells consisting of Cs₂AgBiBr₆as an absorber layer were fabricated and tested.     

Recent advances in engineered nanomaterials for acute kidney injury theranostics

Acute kidney injury(AKI),has become the focus of increasing attention due to its high risk of death.The early diagnosis and treatment of AKI significantly reduce the risk of renal tissue damage and kidney dysfunction.However,the efficient early diagnosis and treatment approach for AKI remains a challenge.AKI screening via precise nanomaterial theranostics is a new alternative approach.This study summarizes the recent advances in functional nanomaterials in the early detection and treatment of AKI.The challenges and problems in the use of nanomaterials for AKI in clinical applications are also discussed.It is anticipated that highlighting these new advances will lay the foundation for further translational research on the promising application of nanomaterials for AKI.     

Corrosion formation and phase transformation of nickel-iron hydroxide nanosheets array for efficient water oxidation

Designing earth-abundant electrocatalysts with high performance towards water oxidation is highly decisive for the sustainable energy technologies. This study develops a facile natural corrosion approach to fabricate nickel-iron hydroxides for water oxidation. The resulted electrode demonstrates an outstanding activity and stability with an overpotential of 275 mV to deliver 10 mA·cm⁻². Experimental and theoretical results suggest the corrosion-induced formation of hydroxides and their transformation to oxyhydroxides would account for this excellent performance. This work not only provides an interesting corrosion approach for the fabrication of excellent water oxidation electrode, but also bridges traditional corrosion engineering and novel materials fabrication, which would offer some insights in the innovative principles for nanomaterials and energy technologies.

     

Nanovilli electrode boosts hydrogen evolution: A surface with superaerophobicity and superhydrophilicity

Although tremendous efforts have been paid on electrocatalysts toward efficient electrochemical hydrogen generation,breakthrough is still highly needed in the design and synthesis of wonderful non-precious-metal electrocatalyst.Herein,a nanovilli Ni2P electrode,which with superaerophobic and superhydropholic can significantly facilitate the mass and electron transfer was constructed via a facial morphology control strategy.Meanwhile,the substitution of sluggish oxygen evolution with urea oxidation,lowering the two-electrode cell voltage to only 1.48 volts to achieve a current density of 10 mA·cm^-2.Thus,the as-constructed electrode achieves the operation of hydrogen generation by an AA battery.This work sheds new light on the exploration of other high-efficient electrocatalysts for hydrogen generation by using intermittent clean energy.     

Coarse and fine-tuning of lasing transverse electromagnetic modes in coupled all-inorganic perovskite quantum dots

Inorganic perovskite lasers are of particular interest,with much recent work focusing on Fabry-P6rot cavity-forming nanowires.We demonstrate the direct observation of lasing from transverse electromagnetic(TEM)modes with a long coherence time-9.5ps in coupled CsPbBr₃ quantum dots,which dispense with an external cavity resonator and show how the wavelength of the modes can be controlled via two independent tuning-mechanisms.Controlling the pump power allowed us tofine-tune the TEM mode structure to the emission wavelength,thus providing a degree of control over the properties of the lasing signal.The temperature-tuning provided an additional degree of control over the wavelength of the lasing peak,importantly,maintained a constant full width at half maximum(FWHM)over the entire tuning range without mode-hopping.     

Broadband and sensitive two-dimensional halide perovskite photodetector for full-spectrum underwater optical communication

Full-spectrum underwater optical communication(UOC)is of great significance for major strategic needs including resource development,scientific exploration,and homeland security.As the core of the full-spectrum UOC system,photodetectors(PDs)are plagued by stringent requirements including a broadband response,intrinsic water resistance,and a high detectivity.In this work,two-dimensional(2D)halide perovskites(HPs)and corresponding PDs are constructed by stearamine(SA),representing the rarely explored long-chain aliphatic amine series,to own waterproofness,ultralow noise,and superior optoelectronic performance,which consequently enable a high suitability for UOC.By dimensionality and composition modulations to extend the absorption onset down to 1.5 eV,a broadband response covering the entire transmission window of water(>1.55 eV)for full-spectrum UOC can be obtained.Besides,featuring a high responsivity of 3.27 A·W^-1,a peak external quantum efficiency(EQE)of 630%,fast rise/decay times of 0.35 ms/0.54 ms,a superior detectivity up to 1.35×10¹²Jones and the capability to distinguish various waveforms and light intensities,the PDs present sensitive and persistent photoresponse underwater.As a result,proof-of-concept wireless transmission of ASCII codes in water is demonstrated.     

Rapid room-temperature synthesis of a porphyrinic MOF for encapsulating metal nanoparticles

While metal nanoparticles(NPs)have shown great promising applications as heterogeneous catalysts,their agglomeration caused by thermodynamic instability is detrimental to the catalytic performance.To tackle this hurdle,we successfully prepared a functional and stable porphyrinic metal-organic framework(MOF),PCN-224-RT,as a host for encapsulating metal nanoparticles by direct stirring at room temperature.As a result,Pt@PCN-224-RT composites with well-dispersed Pt NPs can be constructed by introducing pre-synthesized Pt NPs into the precursor solution of PCN-224-RT.Of note,the rapid and simple stirring method in this work is more in line with the requirements of environmental friendly and industrialization compared with traditional solvothermal methods.     

Two-dimensional polymer nanosheets for efficient energy storage and conversion

As a promising graphene analogue, two-dimensional (2D) polymer nanosheets with unique 2D features, diversified topological structures and as well as tunable electronic properties, have received extensive attention in recent years. Here in this review, we summarized the recent research progress in the preparation methods of 2D polymer nanosheets, mainly including interfacial polymerization and solution polymerization. We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications, such as batteries, supercapacitors, electrocatalysis and photocatalysis. Finally, on the basis of their current development, we put forward the existing challenges and some personal perspectives.

     

Structural revolution of atomically dispersed Mn sites dictates oxygen reduction performance

An efficient preparation and local coordination environment regulation of isolated single-atom sites catalysts (ISASC) for improved activity is still challenging. Herein, we develop a solid phase thermal diffusion strategy to synthesize Mn ISASC on highly uniform nitrogen-doped carbon nanotubes by employing MnO₂ nanowires@ZIF-8 core-shell structure. Under high-temperature, the Mn species break free from core-MnO₂ lattice, which will be trapped by carbon defects derived from shell-ZIF-8 carbonization, and immobilized within carbon substrate. Furthermore, the poly-dispersed Mn sites with two nitrogen-coordinated centers can be controllably renovated into four-nitrogen-coordinated Mn sites using NH₃ treatment technology. Both experimental and computational investigations indicate that the symmetric coordinated Mn sites manifest outstanding oxygen reduction activity and superior stability in alkaline and acidic solutions. This work not only provides efficient way to regulate the coordination structure of ISASC to improve catalytic performance but also paves the way to reveal its significant promise for commercial application.

     

Ambipolar two-dimensional bismuth nanostructures in junction with bismuth oxychloride

Despite the unique properties of bismuth(Bi),there is a lack of two-dimensional(2D)heterostructures between Bi and other functional 2D materials.Here,a coherent strategy is reported to simultaneously synthesize rhombohedral phase Bi nanoflakes and bismuth oxychloride(BiOCI)nanosheets.The delicate balance between several reactions is mediated mainly for the reduction and chlorination in the chemical vapor transport(CVT)process.The Bi-BiOCI lateral heterostructures have been constructed via the coalescence of the two different 2D nanostructures.The characteristics of ambipolar conducting Bi and insulator-like BiOCI are elaborated by scanning microwave impedance microscopy(sMIM).This work demonstrates a way to construct a 2D Bi nanostructure in junction with its oxyhalide.     

Surface active-site engineering in hierarchical PtNi nanocatalysts for efficient triiodide reduction reaction

Hierarchical Pt-alloys enriched with active sites are highly desirable for efficient catalysis, but their syntheses generally need time-consuming and elaborate annealing treatment at high temperature. We herein report a surface active-site engineering strategy for constructing the hierarchical PtNi nanocatalysts with an atomic Pt-skin layer (PtNi@Pt-SL) towards efficient triiodide reduction reaction (TRR) via an acid-dealloying approach. The facile acid-dealloying process promotes the formation of surface Pt active sites on the hierarchical Pt-alloys, and thus results in good catalytic performance towards TRR. Theoretical calculation reveals that the enhanced catalytic property stems from the moderate energy barriers for iodide atoms on the surface Pt active-sites. The surface active-site engineering strategy paves a new way for the design of active and durable electrocatalysts.

     

Two-dimensional oxide derived from high-temperature liquid metals via bubble templating

Two-dimensional (2D) oxide can be continuously produced by bubbling oxygen into liquid metals and the harvesting of these oxide relies on the proper choice of dispersion solvents. The mass-production of ligand-free 2D materials from high melting-point metals will not be possible if the limited stability of the traditional dispersion solvents is not circumvented. Herein, liquid tin was used for the first time in the bubbling protocol and 2D tin oxide was obtained in molten salts. The nanosheets were studied with combined microscopic and spectroscopic techniques, and high-density grain boundaries was identified between the sub-5-nm nano-crystallites in the nanosheets. It gives rise to the high performance in electrocatalytic CO₂ reduction reaction. Density-functional-theory based calculation was applied to achieve a deeper understanding of the relationship between the activity, selectivity, and the grain-boundary features. The molten-salt based protocol could be explored for the synthesis of a library of functional 2D oxides.

     

Synthesis of graphene quantum dots for their supramolecular polymorphic architectures

How to regulate the supramolecular structures in the assembly of graphene quantum dots(GQDs)is still a great challenge to be overcome.Herein,the GQDs of 1-3 layers with high quality are synthesized from the new precursor m-trihydroxybenzene in a green method.More importantly,a strategy for designing the supramolecular structures of GQDs is demonstrated,and the novel supramolecular morphologies of GQDs have been constructed for the first time.Moreover,the supramolecular morphologies of GQDs can be well controlled by regulating the preparation conditions,and the formation mechanism of the branch-like supramolecular structure has been explained by the the diffusion-limited aggregation(DLA)model.This work not only develops a new precoursor to synthesize GQDs,but also opens up an effective route toform the polymorphic supermolecules,thus greatly facilitating their potential applications.     

Basic science of water: Challenges and current status towards a molecular picture

Rapid developments in both fundamental science and modern technology that target water-related problems, including the physical nature of our planet and environment, the origin of life, energy production via water splitting, and water purification, all call for a molecular-level understanding of water. This invokes relentless efforts to further our understanding of the basic science of water. Current challenges to achieve a molecular picture of the peculiar properties and behavior of water are discussed herein, with a particular focus on the structure and dynamics of bulk and surface water, the molecular mechanisms of water wetting and splitting, application-oriented research on water decontamination and desalination, and the development of complementary techniques for probing water at the nanoscale.

     

Highly efficient multi-metal catalysts for carbon dioxide reduction prepared from atomically sequenced metal organic frameworks

The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed for achieving enhanced reactivity.The present work illustrates how through the transformation of MOFs with desired arrangements of metal cations,multi-metal spinel oxides with precise compositions can be obtained,and used as catalyst precursor for the reverse water-gas shift reaction.The differences in the spinel initial composition and structure,determined by neutron powder diffraction,influence the overall catalytic activity with changes in the process of in s itu formation of active,metal-oxide supported metal nanoparticles,which have been monitored and characterized with in situ X-ray diffraction and photoelectron spectroscopy studies.     

Pulsed laser reshaping and fragmentation of upconversion nanoparticles — from hexagonal prisms to 1D nanorods through “Medusa”-like structures

One dimensional (1D) nanostructures attract considerable attention, enabling a broad application owing to their unique properties. However, the precise mechanism of 1D morphology attainment remains a matter of debate. In this study, ultrafast picosecond (ps) laser-induced treatment on upconversion nanoparticles (UCNPs) is offered as a tool for 1D-nanostructures formation. Fragmentation, reshaping through recrystallization process and bioadaptation of initially hydrophobic (β-Na_1.5Y_1.5F₆: Yb³⁺, Tm³⁺/β-Na_1.5Y_1.5F₆) core/shell nanoparticles by means of one-step laser treatment in water are demonstrated. “True” 1D nanostructures through “Medusa”-like structures can be obtained, maintaining anti-Stokes luminescence functionalities. A matter of the one-dimensional UCNPs based on direction of energy migration processes is debated. The proposed laser treatment approach is suitable for fast UCNP surface modification and nano-to-nano transformation, that open unique opportunities to expand UCNP applications in industry and biomedicine.

     

Discovery of Zr-based metal-organic polygon: Unveiling new design opportunities in reticular chemistry

Metal-based secondary building unit and the shape of organic ligands are the two crucial factors for determining the final topology of metal-organic materials.A careful choice of organic and inorganic structural building units occasionally produces unexpected structures,facilitating deeper fundamental understanding of coordination-driven self-assembly behind metal-organic materials.Here,we have synthesized a triangular metal-organic polygon(MOT-1),assembled from bulky tetramethyl terephthalate and Zr-based secondary building unit.Surprisingly,the Zr-based secondary building unit serves as an unusual ditopic Zr-connector,toform metal-organic polygon MOT-1,proven to be a good candidate for water adsorption with recyclability.This study highlights the interplay of the geometrically frustrated ligand and secondary building unit in controlling the connectivity of metal-organic polygon.Such a strategy can be further used to unveil a new class of metal-organic materials.     

Oxygen-assisted direct growth of large-domain and high-quality graphene on glass targeting advanced optical filter applications

Growing high quality graphene films directly on glass by chemical vapor deposition(CVD)meets a growing demand for constructing high-performance electronic and optoelectronic devices.However,the graphene synthesized by prevailing methodologies is normally of polycrystalline nature with high nucleation density and limited domain size,which significantly handicaps its overall properties and device performances.Herein,we report an oxygen-assisted CVD strategy to allow the direct synthesis of 6-inch-scale graphene glass harvesting markedly increased graphene domain size(from 0.2 to 1.8μm).Significantly,as-produced graphene glass attains record high electrical conductivity(realizing a sheet resistance of 900Ω·sq^-1at a visible-light transmittance of 92%)amongst the state-of-the-art counterparts,readily serving as transparent electrodes for fabricating high-performance optical filter devices.This work might open a new avenue for the scalable production and application of emerging graphene glass materials with high quality and low cost.