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Metallacages with suitable cavities and specific functions are promising delivery vectors in biological systems. Herein, we report a morpholine-functionalized metallacage for lysosome-targeted cell imaging. The efficient host-guest interactions between the metallacage and dyes prevent them from aggregation, so their emission in aqueous solutions is well maintained. The fluorescence quantum yield of these host-guest complexes reaches 74.40%. Therefore, the metallacage is further employed as a vector to deliver dyes with different emission colors (blue, green, and red) into lysosomes for targeted imaging. This research affords a type of vector for the delivery of various cargos toward biological applications, which will enrich the usage of metallacages in biomedical engineering.

Membrane technology is attractive for natural gas separation (removing CO2, H2O, and hydrocarbons from CH4) because of membranes' low energy consumption and small environmental footprint. Compared to polymeric membranes, microporous inorganic membranes such as silicoaluminophosphate-34 (SAPO-34) membrane can retain their separation performance under conditions close to industrial requirements. However, moisture and hydrocarbons in natural gas can be strongly adsorbed in the pores of those membranes, thereby reducing the membrane separation performance. Herein, we report the fabrication of a polycrystalline MIL-160 membrane on an Al2O3 substrate by in situ hydrothermal synthesis. The MIL-160 membrane with a thickness of ca. 3 μm shows a remarkable molecular sieving effect in gas separation. Besides, the pore size and environment of the MIL-160 membrane can be precisely controlled using reticular chemistry by regulating the size and functionality of the ligand. Interestingly, the more polar fluorine-functionalized multivariate MIL-160/CAU-10-F membrane exhibits a 10.7% increase in selectivity for CO2/CH4 separation and a 31.2% increase in CO2 permeance compared to those of the MIL-160 membrane. In addition, hydrophobic MIL-160 membranes and MIL-160/CAU-10-F membranes are more resistant to water vapor and hydrocarbons than the hydrophilic SAPO-34 membranes.

Isoreticular functionalization is a well-elucidated strategy for pore environment tuning and the basis of gas separation performance in extended frameworks. The extension of this approach to discrete porous molecules such as metal-organic cages (MOCs) is conceptually straightforward but hindered by synthetic complications, especially stability concerns. We report the successful isoreticular functionalization of a zirconium MOC with tetrazole moiety by bottom-up synthesis. The title compound (ZrT-1-tetrazol) shows promising C2 H2 /CO2 and C2 H2 /C2 H4 separation performance, as demonstrated by adsorption isotherms, breakthrough experiments, and density functional theory calculations. The design analogy between MOFs and highly stable MOCs may guide the synthesis of novel porous materials for challenging separation applications.

The realization of metal-organic framework (MOF) layers onto solid surfaces is a prerequisite for their integration into devices. This work reports the direct growth of Fe

We herein report the preparation of a series of hexaphenylbenzene (HPB)-based deep blue-emissive metallacages via multicomponent coordination-driven self-assembly. These metallacages feature prismatic structures with HPB derivatives as the faces and tetracarboxylic ligands as the pillars, as evidenced by NMR, mass spectrometry and X-ray diffraction analysis. Light-harvesting systems were further constructed by employing the metallacages as the donor and a naphthalimide derivative (NAP) as the acceptor, owing to their good spectral overlap. The judiciously chosen metallacage serves as the antenna, providing the suitable energy to excite the non-emissive NAP, and thus resulting in bright emission for NAP in the solid state. This study provides a type of HPB-based multicomponent emissive metallacage and explores their applications as energy donors to light up non-emissive fluorophores in the solid state, which will advance the development of emissive metallacages as useful luminescent materials.

The introduction of porous nanofillers into the polyamide selective layer of thin-film composite membranes is a promising strategy towards improved water flux and salt rejection for reverse osmosis...

Lithium (Li) metal, with its high energy density, is auspicious for use in Li-ion batteries. However, the ubiquitous problem of Li dendrite formation on Li metal anodes during cycling remains unresolved and impedes their practical utilization in multitudinous scenarios. Herein, we propose an alternative strategy to address the challenge above via the fabrication of Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2-modified Cu-foil (Ni3(HITP)2@Cu-foil) current collectors to provide “honeycomb”-like architectures without sacrificing Li-ion transport. The large specific surface area and layered crystallographic nature of Ni3(HITP)2 afford fast and homogeneous transport channels of Li ions and a lower local current density. Meanwhile, the lithiophilic nitrogen (N)-containing functional groups (pyridinic and pyrrolic N) in Ni3(HITP)2 exhibit good lithium affinity and therefore endow uniform nucleation and growth of the metallic Li on the current collectors. These claims were verified by microscopic imaging and density functional theory (DFT) calculations. Hence, the formation of Li dendrites during Li plating/stripping processes can be circumvented. Concomitantly, the Ni3(HITP)2 modified Cu-foil anodes show high coulombic efficiency of 99.7% after nearly 1000 cycles compared with Li/graphite@Cu-foil, Li/Ni-NDC@Cu-foil, and Li/Cu-foil in half-cell systems. This study sheds light on the rational design of current collectors via a combination of novel conductive metal–organic frameworks for stabilizing Li metal anodes.

Although many studies on luminescent metal–organic frameworks (MOFs) have been reported for chemical sensing applications, it has yet to be realized in MOFs the precise linearity control over photo...

State-of-the-art chemical sensors based on covalent organic frameworks (COFs) are restricted to the transduction mechanism relying on luminescence quenching and/or enhancement. Herein, we present an alternative methodology via a combination of in situ-grown COF films with interdigitated electrodes utilized for capacitive benzene detection. The resultant COF-based sensors exhibit highly sensitive and selective detection at room temperature toward benzene vapor over carbon dioxide, methane, and propane. Their benzene detection limit can reach 340 ppb, slightly inferior to those of the metal oxide semiconductor-based sensors, but with reduced power consumption and increased selectivity. Such a sensing behavior can be attributed to the large dielectric constant of the benzene molecule, distinctive adsorptivity of the chosen COF toward benzene, and structural distortion induced by the custom-made interaction pair, which is corroborated by sorption measurements and density functional theory (DFT) calculations. This study provides new perspectives for fabricating COF-based sensors with specific functionality targeted for selective gas detection.

We report an in situ polymerization strategy to incorporate a thermo-responsive polymer, poly(N-isopropylacrylamide) (PNIPAM), with controlled loadings into the cavity of a mesoporous metal-organic framework (MOF), MIL-101(Cr). The resulting MOF/polymer composites exhibit an unprecedented temperature-triggered water capture and release behavior originating from the thermo-responsive phase transition of the PNIPAM component. This result sheds light on the development of stimuli-responsive porous adsorbent materials for water capture and heat transfer applications under relatively mild operating conditions.

Membrane technology is attractive for natural gas separation (removing CO

Gas sensing technologies for smart cities require miniaturization, cost-effectiveness, low power consumption, and outstanding sensitivity and selectivity. On-chip, tailorable capacitive sensors integrated with metal-organic framework (MOF) films are presented, in which abundant coordinatively unsaturated metal sites are available for gas detection. The in situ growth of homogeneous Mg-MOF-74 films is realized with an appropriate metal-to-ligand ratio. The resultant sensors exhibit selective detection for benzene vapor and carbon dioxide (CO2 ) at room temperature. Postsynthetic modification of Mg-MOF-74 films with ethylenediamine decreases sensitivity toward benzene but increases selectivity to CO2 . The reduced porosity and blocked open metal sites caused by amine coordination account for a deterioration in the sensing performance for benzene (by ca. 60 %). The enhanced sensitivity for CO2 (by ca. 25 %) stems from a tailored amine-CO2 interaction. This study demonstrates the feasibility of tuning gas sensing properties by adjusting MOF-analyte interactions, thereby offering new perspectives for the development of MOF-based sensors.

Isoreticular functionalization is a well-elucidated strategy for pore environment tuning and the basis of gas separation performance in extended frameworks. The extension of this approach to discrete porous molecules such as metal-organic cages (MOCs) is conceptually straightforward but hindered by synthetic complications, especially stability concerns. We report the successful isoreticular functionalization of a zirconium MOC with tetrazole moiety by bottom-up synthesis. The title compound (ZrT-1-tetrazol) shows promising C

Infrared gas sensors hold great promise in the internet of things and artificial intelligence. Making infrared light sources with miniaturized size, reliable and tunable emission is essential but remains challenging. Herein, we present the tailorability of radiant power and the emergence of new emission wavelength of microelectromechanical system (MEMS)-based thermal emitters with nickel oxide (NiO) films. The coating of NiO on emitters increases top surface emissivity and induces the appearance of new wavelengths between 15 and 19 µm, all of which have been justified by spectroscopic methods. Furthermore, a sensor array is assembled for simultaneous monitoring of concentrations of carbon dioxide (CO2), methane (CH4), humidity, and temperature. The platform shows selective and sensitive detection at room temperature toward CO2 and CH4 with detection limits of around 50 and 1750 ppm, respectively, and also shows fast response/recovery and good recyclability. The demonstrated emission tailorability of MEMS emitters and their usage in sensor array provide novel insights for designing and fabricating optical sensors with good performance, which is promising for mass production and commercialization. Agency for Science, Technology and Research (A*STAR) National Research Foundation (NRF) Published version Agency for Science, Technology and Research (IAF-PP A1789a0024); National Research Foundation Singapore (NRF-CRP18-2017-02).

There is an urgent demand for separation membranes based on metal-organic frameworks (MOFs) with high efficiency, low waste generation, and low energy consumption. Herein, we report the fabrication of high-quality, continuous iron(III)-based PCN-250 polycrystalline MOF membranes for organic solvent nanofiltration. Due to the usage of rub seeding, the PCN-250 membrane has a small thickness of 3.7 μm and exhibits pure solvent permeance as high as 337.9 L m−2 h−1 bar−1 for methanol, 69.2 L m−2 h−1 bar−1 for ethanol, and 17.2 L m−2 h−1 bar−1 for N-methyl-2-pyrrolidone (NMP). The membrane has pore sizes ranging from 0.6 to 1.0 nm, with a molecular weight cut-off of ca. 1300 g/mol. In addition, it exhibits excellent molecular separation performance (methyl blue rejection of 93.7%) alongside a high NMP permeance of 2.6 L m−2 h−1 bar−1. Moreover, our study confirms that the PCN-250 MOF membrane has good water, acid, and organic solvent resistance. This remarkable separation performance, combined with the outstanding stability in water, acid, and organic solvents, makes the PCN-250 membrane a promising candidate for organic solvent nanofiltration.

Interfacial compatibility between metal-organic framework (MOF) films and the underlying substrates determines the integrity of MOF films and their associated functions, and thus it has been gaining growing attention. Herein, we present a comparison of adhesion properties at the chip level of two disparate nickel (Ni)-MOF films, respectively, obtained by direct hydro/solvothermal growth and template-directed conversion approaches. We demonstrate that the on-chip delamination/corrugation of the films obtained by the direct growth approach can be circumvented by adopting the template-directed approach, which enables delicate dissolution of primarily grown nanoflaked nickel hydroxide (Ni(OH)2) films and thus triggers the controllable formation of Ni-MOF films. Successful on-chip conversions of Ni(OH)2 layers to different Ni-MOF thin films with good homogeneity, compactness, and appreciable affinity to the substrates are verified by multiple microscopic and spectroscopic techniques. Notably, the resultant Ni-MOF films do not show delamination even after activation with additional treatments, such as solvent soaking, nitrogen (N2) blowing for 1 h, and scotch-tape tests. As a demonstration of the application of MOF films, a Ni-NDC (NDC stands for 2,6-naphthalenedicarboxylate) MOF-coated sensor exhibits selective detection toward benzene vapor. This study highlights the importance of interfaces between MOF films and substrates and provides new perspectives for integrating MOF films onto microelectronic devices with robust adhesion for practical applications.

The ever-increasing concerns over indoor/outdoor air quality, industrial gas leakage, food freshness, and medical diagnosis require miniaturized gas sensors with excellent sensitivity, selectivity, stability, low power consumption, cost-effectiveness, and long lifetime. Metal-organic frameworks (MOFs), featuring structural diversity, large specific surface area, controllable pore size/geometry, and host-guest interactions, hold great promises for fabricating various MOF-based devices for diverse applications including gas sensing. Tremendous progress has been made in the past decade on the fabrication of MOF-based sensors with elevated sensitivity and selectivity toward various analytes due to their preconcentrating and molecule-sieving effects. Although several reviews have recently summarized different aspects of this field, a comprehensive review focusing on MOF-based gas sensors is absent. In this review, the latest advance of MOF-based gas sensors relying on different transduction mechanisms, for example, chemiresistive, capacitive/impedimetric, field-effect transistor or Kelvin probe-based, mass-sensitive, and optical ones are comprehensively summarized. The latest progress for making large-area MOF films essential to the mass-production of relevant gas sensors is also included. The structural and compositional features of MOFs are intentionally correlated with the sensing performance. Challenges and opportunities for the further development and practical applications of MOF-based gas sensors are also given.

Metal-organic frameworks (MOFs) intrinsically lack fluidity and thus solution processability. Direct synthesis of MOFs exhibiting solution processability like polymers remains challenging but highly sought-after for multitudinous applications. Herein, a one-pot, surfactant-free, and scalable synthesis of highly stable MOF suspensions composed of exceptionally large (average area > 15 000 µm2 ) NUS-8 nanosheets with variable functionalities and excellent solution processability is presented. This is achieved by adding capping molecules during the synthesis, and by judicious controls of precursor concentration and MOF nanosheet-solvent interactions. The resulting 2D NUS-8 nanosheets with variable functionalities exhibit excellent solution processability. As such, relevant monoliths, aero- and xerogels, and large-area textured films with a great homogeneity, controllable thickness, and appreciable mechanical properties can be facilely fabricated. Additionally, from both the molecular- and chip-level it is demonstrated that capacitive sensors integrated with NUS-8 films functionalized with different terminal groups exhibit distinguishable sensing behaviors toward acetone due to their disparate host-guest interactions. It is envisioned that this simple approach will greatly facilitate the integration of MOFs in miniaturized electronic devices and benefit their mass production.

Infrared gas sensors have been proven promising for broad applications in Internet of Things and Industrial Internet of Things. However, the lack of miniaturized light sources with good compatibility and tunable spectral features hinders their widespread utilization. Herein, a strategy is proposed to increase the radiated power from microelectromechanical-based thermal emitters by coating with graphene oxide (GO). The radiation can be substantially enhanced, which partially stems from the high emissivity of GO coating demonstrated by spectroscopic methods. Moreover, the sp2 structure within GO may induce plasmons and thus couple with photons to produce blackbody radiation and/or new thermal emission sources. As a proof-of-concept demonstration, the GO-coated emitter is integrated into a multifunctional monitoring platform and evaluated for gas detection. The platform exhibits sensitive and highly selective detection toward CO2 at room temperature with a detection limit of 50 ppm and short response/recovery time, outperforming the state-of-the-art gas sensors. This study demonstrates the emission tailorability of thermal emitters and the feasibility of improving the associated gas sensing property, offering perspectives for designing and fabricating high-end optical sensors with cost-effectiveness and superior performance. NRF (Natl Research Foundation, S’pore) ASTAR (Agency for Sci., Tech. and Research, S’pore) Accepted version

Phosphate film is generally not compact, left with microscopic cracks or pores during the phosphating process. Silica sol is incorporated into the phosphating solution to fabricate phosphate films on stainless steel 316L by electrochemical method. It is found that at appropriate amount of silica sol (8 vol.-%), the cracks on the hopeite film are effectively filled, while they appear again when much more silica sol is added as observed by SEM images. Moreover, zinc is found simultaneously formed as detected by the energy dispersive spectroscopy and X-ray diffraction measurements. In order to improve the performances of the hopeite film, we use titania sol by dip coating to cover the hopeite film. The titania sol can improve the anticorrosion ability of the films with limited extent since its crack formation during curing. By adding polyvinyl butyral (2 wt-%) in this sol, the composite film exhibits great improvement in corrosion resistance resulting from the cracks remedy and synergy effect of zinc...

Surmounting the inhomogeniety issue of gas sensors and realizing their reproducible ppb-level gas sensing are highly desirable for widespread deployments of sensors to build networks in applications of industrial safety and indoor/outdoor air quality monitoring. Herein, a strategy is proposed to substantially improve the surface homogeneity of sensing materials and gas sensing performance via chip-level pyrolysis of as-grown ZIF-L (ZIF stands for zeolitic imidazolate framework) films to porous and hierarchical zinc oxide (ZnO) nanosheets. A novel approach to generate adjustable oxygen vacancies is demonstrated, through which the electronic structure of sensing materials can be fine-tuned. Their presence is thoroughly verified by various techniques. The sensing results demonstrate that the resultant oxygen vacancy-abundant ZnO nanosheets exhibit significantly enhanced sensitivity and shortened response time toward ppb-level carbon monoxide (CO) and volatile organic compounds encompassing 1,3-butadiene, toluene, and tetrachloroethylene, which can be ascribed to several reasons including unpaired electrons, consequent bandgap narrowing, increased specific surface area, and hierarchical micro-mesoporous structures. This facile approach sheds light on the rational design of sensing materials via defect engineering, and can facilitate the mass production, commercialization, and large-scale deployments of sensors with controllable morphology and superior sensing performance targeted for ultratrace gas detection.

Oxide films on Ti6Al4V alloy are prepared using sodium hydroxide–sodium silicate as the base electrolyte with addition of aminopropyl trimethoxysilane (APS) as additive by potentiostatic anodizing under 10 V. APS is incorporated into the films during anodizing and the surface morphology of the oxide films is changed from particle stacked to honeycomb-like porous surfaces as shown by scanning electron microscopy (SEM) with Energy Disperse Spectroscopy (EDX). The surface roughness and aminopropyl existence on the oxide films result in their differences in wettability as tested by the surface profile topography and contact angle measurements. The anti-abrasive ability of the anodic films is improved with the addition of APS due to its toughening effects and serving as lubricants in the ceramic oxide films as measured by ball-on-disk friction test. Also, potentiodynamic corrosion test proves that their anticorrosive ability in 3.5 wt.% NaCl is greatly improved as reflected by their much lower corrosion current ( I corr ) and higher corrosion potential ( E corr ) than those of the substrate.

Terrestrial carbon sequestration involves a series of processes, including photosynthesis, plant autotrophic respiration and soil microbial heterotrophic respiration. Field measurements of carbon dioxide (CO2) using either eddy covariance or chamber methods usually provide bulk CO2 fluxes from more than one sink or source. For the purpose of estimating the C budget in ecosystems, it is inherently important to determine the individual sinks or sources. This report describes how we tested the Forest-DNDC model using a dataset collected at a subtropical forest site in Sichuan Province, China. One-year field measurements were conducted using a chamber method at four plots with different treatments that were specifically designed to distinguish the CO2 fluxes produced from three sources: root respiration, forest floor respiration and mineral soil respiration. The obtained datasets were utilized to verify the modeled CO2 fluxes from the corresponding sources for the tested forest ecosystem. Results from the tests indicated that Forest-DNDC was capable not only of quantifying the total CO2 emissions but also of distinguishing their sources related to plant autotrophic and soil microbial heterotrophic respiration. Because measuring root respiration is always difficult in field investigations, adopting Forest-DNDC for quantifying root respiration represents an appropriate complement to most field measurements. (C) 2010 Elsevier B.V. All rights reserved.