Tunable High-Performance Electromagnetic Interference Shielding of VO2 Nanowires-Based Composite.

The unique metal-insulator transition of VO2 is very suitable for dynamic electromagnetic (EM) regulation materials due to its sharp change in electrical conductivity. Here, we have developed an off/on switchable electromagnetic interference (EMI) shielding composite by interconnecting VO2 nanowires (NWs) in poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) to form conductive networks, resulting in outstanding performance at the X and Ku bands with maximum change values of 44.8 and 59.4 dB, respectively. The unique insulator-to-metal transition (IMT) of VO2 NWs has dominated the variation of polarization loss (εp″) and conductivity loss (εσ″) for the composites, which is the mechanism of EMI shielding switching between off and on states. Furthermore, the composite exhibits good cycling stability of the off/on switchable EMI shielding performance and has excellent mechanical properties, especially with 200 times abrasion resistance without obvious weight loss. This study provides a unique approach for dynamic switching of EM response with the potential to construct practical intelligent EM response systems for next-generation smart electromagnetic devices in various scenarios.

A Light/Pressure Bifunctional Electronic Skin Based on a Bilayer Structure of PEDOT:PSS-Coated Cellulose Paper/CsPbBr3 QDs Film.

With the continuous development of electronic skin (e-skin), multifunctional e-skin is approaching, and in some cases even surpassing, the capabilities of real human skin, which has garnered increasing attention. Especially, if e-skin processes eye's function, it will endow e-skins more powerful advantages, such as the vision reparation, enhanced security, improved adaptability and enhanced interactivity. Here, we first study the photodetector based on CsPbBr3 quantum dots film and the pressure sensor based on PEDOT: PSS-coated cellulose paper, respectively. On the base of these two kinds of sensors, a light/pressure bifunctional sensor was successfully fabricated. Finally, flexible bifunctional sensors were obtained by using a flexible interdigital electrode. They can simultaneously detect light and pressure stimulation. As e-skin, a high photosensitivity with a switching ratio of 168 under 405 nm light at a power of 40 mW/cm2 was obtained and they can also monitor human motions in the meantime. Our work showed that the strategy to introduce perovskite photodetectors into e-skins is feasible and may open a new way for the development of flexible multi-functional e-skin.

The Evolution of Classical Spiro-OMeTAD: Synthesis of Arylamine Endcapped Indenone Spirofluorene.

Spiro-OMeTAD is the well-known hole transporting material (HTM) in perovskite solar cells. In this work, its derivatives, namely four D-A shaped triphenylamine or biphenylamine endcapped indenone spirofluorene (SFD-TPA, SFD-OMeTPA, SFD-TAD, and SFD-OMeTAD), were designed and synthesized. With the introduction of electron-donating moieties and the extension of conjugation length, a series of changes in photophysical and electrochemical properties could be detected. Notably, in comparison with the optical gap (2.96 eV) of the reported spiro-OMeTAD, SFD-OMeTAD presents an optical gap as low as 1.87 eV. Moreover, density functional theory simulations were employed to further investigate their geometric and electronic structures. Finally, steady-state photoluminescence measurements proved the efficient charge separation and collection processes at the perovskite/HTM interface. It can be predicted that all four compounds with enhanced sunlight absorption capability and suitable frontier energy levels can be used as hole-transporting materials for perovskite solar cells.

Stimuli-Responsive Metal-Organic Framework on a Metal-Organic Framework Heterostructure for Efficient Antibiotic Detection and Anticounterfeiting.

Stimuli-responsiveness is an important characteristic that show promising potential in various applications. Herein, a novel ZIF-8-on-Tb-dpn (H3dpn = 5-(2',4'-dicarboxylphenyl)nicotic acid) heterostructure is constructed using a heteroepitaxial strategy combining the chemical-responsive (antibiotics) and light-responsive behaviors. The pyridine nitrogen of Tb-dpn acts as an anchor site for Zn2+, which helps to overcome the limit of lattice mismatch between two metal-organic frameworks (MOFs) and promotes the growth of ZIF-8 nanocrystals. Based on the synergy effect of two MOFs, ZIF-8-on-Tb-dpn exhibits an efficient turn-off response toward tetracycline and chloramphenicol via competitive absorption, Förster resonance energy transfer, and photoinduced electron transfer processes with limit of detection values of 5.6 and 37.6 nM, respectively, which are three- to -fivefold lower than those of Tb-dpn. Moreover, the nanocage of ZIF-8 is utilized to encapsulate photochromic spiropyran (SP) molecules and realize the reversible conversion between SP and merocyanine (MC) under visible light and ultraviolet light. The MC form is accompanied with strong adsorption at 555 nm, which can erase the emission of Tb3+. Therefore, a reversible invisible anticounterfeiting pattern is designed with SP ⊂ ZIF-8-on-Tb-dpn for information anticounterfeiting. The excellent stimuli-responsive ability makes the luminescent platform a potential candidate in luminescence applications.

In situ self-assembled cationic lanthanide metal organic framework membrane sensor for effective MnO4- and ascorbic acid detection.

Developing portable membrane sensors to accurately detect the biomolecule ascorbic acid (AA) is extremely important for food safety and human health. Herein, we successfully design and synthesize a novel cationic metal organic framework (Eu-pbmc, Hpbmc = 2-(pyridine-2-yl)-1H-benzimidazole-5-carboxylic acid) and assemble polyacrylonitrile/Eu-pbmc membrane (PEM) by an in-situ growth strategy. Benefiting from the appreciable loading of Eu-pbmc nanoparticles and high water permeation flux, PEM possesses effective detection for MnO4- with a limit of detection (LOD) of 17 nM. Utilizing the cationic porous framework, we load MnO4- into PEM and construct a "on-off-on" system for effective AA detection. The oxidative MnO4- can be reduced by AA and the resulting turn-on luminescence can reflect the concentration of AA. Compared with pure Eu-pbmc crystals, PEM exhibits improved AA detection performance with LOD of 48 nM and detection time of 1 min via a concise detection operation. The stable membrane sensor realizes an accurate detection in real biological samples, meeting the practical requirement. Moreover, an IMP logic gate is helpful to analyze MnO4- and AA in water. The proposed novel luminescence platform as well as reasonable "on-off-on" luminescence mode provide a promising method for AA detection.

Hydrophobicity-Adjustable MOF Constructs Superhydrophobic MOF-rGO Aerogel for Efficient Oil-Water Separation.

Accurate hydrophobicity adjustment of single-phase material is quite challenging and meaningful for water treatment. Here, a strategy combining crystal morphology regulation and post-synthetic modification is reported based on a novel metal-organic framework (MOF, Eu-bdo-COOH, H4bdo = 2,5-bis(3,5-dicarboxylphenyl)-1,3,4-oxadiazole). The hydrophobicity is regulated by crystal size and morphology regulation, and a rough microspherical MOF is successfully synthesized. Meanwhile, the obtained MOF microspheres exhibit high water, chemical, and thermal stability. The post-synthetic modification of alkyl chains achieves fine-tuning of hydrophobicity of MOF microspheres. The static water contact angles can controllably range from 43 to 142°, and the amylamine-modified MOF (AM) obtains the strongest hydrophobicity. In addition, a superhydrophobic aerogel is constructed with AM microspheres and reduced graphene oxide (rGO) for efficient oil-water separation. The AM-rGO aerogel (AM-rGA) exhibits fast and efficient absorption of various oily substances from water, and the adsorption capacity of dibromoethane reaches up to 14,728 wt %. This outstanding oil adsorption capacity can maintain even beyond 50 cycles by the support of the stable aerogel. The strategy of morphology regulation and post-synthetic modification provides a broad approach for the hydrophobic adjustment of numerous MOF materials.

Ce-Doped Ordered Mesoporous Cobalt Ferrite Phosphides as Robust Catalysts for Water Oxidation.

Controllable synthesis and rational design of ordered nanostructures are crucial for their renewable energy applications. In this work, a mesoporous CoP/Fe2 P doped with 5 % Ce by a simple nanocasting method is designed as a superior electrocatalyst for the oxygen evolution reaction (OER). The well-designed composite delivers an efficient electrocatalytic activity with a low overpotential of 250 mV at 10 mA cm-2 and excellent long-term stability with no degradation after 10 h of electrochemical OER test, superior to that of the state-of-the-art RuO2 electrocatalyst in alkaline electrolyte. A comprehensive analysis demonstrates that the outstanding OER performance is due to the desirable combination of the highly exposed active centers in the Ce-doped bimetallic phosphides, efficient mass transfer, and effective electron conduction owing to the hierarchically mesoporous hybridization. Furthermore, the synergistic effect between Ce and CoP/Fe2 P accelerates the migration rate of electrons/ions and increases the electrochemical active area. This excellent OER performance observed by Ce doping of CoP/Fe2 P makes them possible candidates toward OER in alkaline electrolytes.

Heterojunction Incorporating Perovskite and Microporous Metal-Organic Framework Nanocrystals for Efficient and Stable Solar Cells.

In this paper, we present a facile approach to enhance the efficiency and stability of perovskite solar cells (PSCs) by incorporating perovskite with microporous indium-based metal-organic framework [In12O(OH)16(H2O)5(btc)6]n (In-BTC) nanocrystals and forming heterojunction light-harvesting layer. The interconnected micropores and terminal oxygen sites of In-BTC allow the preferential crystallization of perovskite inside the regular cavities, endowing the derived films with improved morphology/crystallinity and reduced grain boundaries/defects. Consequently, the In-BTC-modified PSC yields enhanced fill factor of 0.79 and power conversion efficiency (PCE) of 20.87%, surpassing the pristine device (0.76 and 19.52%, respectively). More importantly, over 80% of the original PCE is retained after 12 days of exposure to ambient environment (25 °C and relative humidity of ~ 65%) without encapsulation, while only about 35% is left to the pristine device.

Micromesoporous Nitrogen-Doped Carbon Materials Derived from Direct Carbonization of Metal-Organic Complexes for Efficient CO2 Adsorption and Separation.

Metal-organic complexes (MOCs) are considered as excellent precursors to prepare carbon materials, due to the fact that heteroatoms and functional groups can be naturally reserved in the resulting carbon materials through the carbonization. Herein, micromesoporous nitrogen-doped carbons MPNC-1 and MPNC-2 are successfully obtained by direct carbonization (800 °C, KOH activation) of metal-organic complexes DQA-1 and DQA-2. MPNC-1 and MPNC-2 exhibit high BET surface area (2368.9 and 2327.6 m2 g-1), pore volume (1.95 and 1.89 cm3 g-1), and N contents (17.2% and 12.3%). At 25 °C and 1 bar, MPNC-1 and MPNC-2 show high CO2 adsorption of 7.53 and 6.58 mmol g-1, the estimated CO2/N2 selectivity are 20.5 and 22.6, indicating excellent promise for practical CO2 adsorption and separation applications. Theoretical calculation indicates carbon surfaces with pyridinic-N, pyrrolic-N, and graphitic-N coexistence could strongly change the local electronic distribution and electrostatic surface potential, enhancing the CO2 adsorption with adsorption energy of -58.96 kJ mol g-1. Theoretical calculation also highlights that CO2 adsorption mechanism is electrostatic interaction with a large green isosurface between CO2 molecules and the carbon surface.

Carbon-Coated and Interfacial-Functionalized Mixed-Phase Mox Ti1-x O2-δ Nanotubes as Highly Active and Durable PtRu Catalyst Support for Methanol Electrooxidation.

A synchronous carbon-coating and interfacial-functionalizing approach is proposed for the fabrication of Mo-doped Mox Ti1-x O2-δ nanotubes (C@IF-MTNTs) under mild hydrothermal reaction with subsequent annealing as advanced catalyst supports for PtRu nanoparticles (NPs) towards methanol electrooxidation. The carbonation of glucose and Mo-doping takes place simultaneously at the interface of pristine anatase TiO2 nanotubes (TNTs), generating a unique concentric multilayered one-dimensional (1D) structure with crystalline an anatase/rutile mixed-phase TiO2 core and Mo-functionalized interface and subsequently a carbon shell. The obtained PtRu/C@IF-MTNTs catalyst exhibits an over 2 times higher mass activity with comparable durability than that of the unmodified PtRu/C@TNTs catalyst and over 1.7 times higher mass activity with over 20 % higher stability than that of PtRu/C catalyst. Such superior catalytic performance towards methanol electrooxidation is ascribed to the Mo-functionalized interface, concentric multilayered 1D architecture, and anatase/rutile mixed-phase core, which facilitates the charge transport through 1D structural support and electronic interaction between C@IF-MTNTs and ultrafine PtRu NPs. This work reveals the critical application of a 1D interfacial functionalized architecture for advanced energy storage and conversion.

Enhanced Efficiency of Planar Heterojunction Perovskite Solar Cells by a Light Soaking Treatment on Tris(pentafluorophenyl)borane-Doped Poly(triarylamine) Solution.

This research used Lewis acid tris(pentafluorophenyl)borane (BCF) as a p-type dopant and a light soaking (LS) treatment to improve the conductivity of poly(triarylamine) (PTAA). Specifically, the conductivity of PTAA films was improved by two orders of magnitude using BCF as a p-type dopant, and the conductivity of BCF-doped PTAA films could be further improved by using the LS treatment on its solution. The working mechanism of the formation of frustrated Lewis pairs between BCF and PTAA was proposed to explain the BCF doping and LS treatment effects on the hole transport property of PTAA. When 5 min LS-PTAA films with 8 wt % BCF were used as the hole transport layer in p-i-n planar heterojunction perovskite solar cells, a maximum power conversion efficiency of 17.12% was achieved. This work provides a deep understanding of the enhancement of the conductivity of PTAA by the BCF doping and LS treatment. In addition, a convenient and quick LS method was explored to improve the conductivity of the PTAA hole transport material. Our findings may help in improving the hole transport properties of other organic photoelectric materials and devices.

A Dual Associated-Functional Fluorescent Switch: From Alternate Detection Cycle for Fe(III) and pH to Molecular Logic Operations.

With the expansion and deepening of scientific research, dual-functional or multifunctional materials are urgently needed to replace those for single application. Herein, a fluorescence sensing system based on an In(III)-organic complex with in situ Lewis acid sites has been constructed, exhibiting high sensitivity for the detection of Fe(III) ions with a low detection limit of 3.95 µM and a short response time of within 10 s. It is noteworthy that the quenched fluorescence of the Fe(III)-incorporated sample could be reopened linearly with an increase of alkalinity, followed by the reactivation of its functionality to identify Fe(III) ions, forming an alternate detection cycle for Fe(III) and pH with off-on-off fluorescent switch characteristics. Considering its unique molecular recognition capability, an advanced three-input (Fe(III), EDTA, and OH-) and two-output (B440 and G489) Boolean logic operation comprising BUFF, NOT, OR, and AND logic gates was integrated, possessing potential applications in intelligent multianalyte sensing systems.

Hot-Pressing Method To Prepare Imidazole-Based Zn(II) Metal-Organic Complexes Coatings for Highly Efficient Air Filtration.

Particulate matters (PMs) air pollution has become a serious environmental issue due to its great threat to human health. Herein, metal-organic complexes PBM-Zn1 and PBM-Zn2 coatings (noted as PBM-Zn-Filter) have been produced by the hot-pressing method on various substrates for the first time. Layer-by-layer PBM-Zn-Filters were also obtained through varying hot-pressing cycles. The obtained PBM-Zn-Filters with high robustness show excellent performance in PMs removal. In particular, benefiting from thelarger conjugation system, micropore structure, lower pressure drop, higher electrostatic potential ζ, and electron cloud exposed metal center of PBM-Zn2 (DFT calculations), PBM-Zn2@melamine foam-4 gives the highest removal rates, PM2.5:99.5% ± 1.2% and PM10:99.3% ± 1.1%, and the removal efficiency for capture PM2.5 and PM10 particles in cigarette smoke were both retained at high levels (>95.5%) after 24 h tests. More importantly, a homemade mask is made up by imbedding the PBM-Zn2@melamine foam-4 into a commercial breathing mask, which shows higher removal efficiency, lower pressure drop, smaller thickness, and higher quality factor than two commercial breathing masks, the PMs removal efficiencies for both PM2.5 and PM10 are 99.6% ± 0.5% and 99.4% ± 0.8%, and acceptable air resistance are demonstrated.

Research on the Mechanism of Aggregation-Induced Emission through Supramolecular Metal-Organic Frameworks with Mechanoluminescent Properties and Application in Press-Jet Printing.

This study investigates the mechanism of AIE in the solid state through supramolecular metal-organic frameworks and mechanoluminescent materials for the first time. Herein, four novel differently substituted Schiff base building blocks, SB1-SB4, exhibit typical AIE properties with various fluorescence emissions from yellow to green. SB1-SB4 are linked through C-H···O hydrogen bonding interactions to construct supramolecular metal-organic frameworks (SMOFs): namely, SMOFSB1-SMOFSB4. Particularly, among these SMOFs, SMOFSB3 is observed to have micropores in the 3D supramolecular structure and exhibits mechanoluminescent properties (grinding). An emission turn-on mechanism occurs with destruction of micropores by grinding and blockage of intramolecular rotations of the methyl and acetonitrile in the micropores, resulting in emission turn-on in SMOFSB3. Single-crystal X-ray structures, powder X-ray diffraction, emission spectra at room temperature, temperature-dependent emission spectra, DFT calculations, and a charge separation hypothesis well demonstrate the emission turn-on mechanism, which is consistent with the mechanism of AIE. More importantly, the molecules demonstrated potential application for press-jet printing.

A Mini-Electrochemical System with Integrated Micropipet Tip and Pencil Graphite Electrode for Measuring Cytotoxicity.

A novel mini-electrochemical system has been developed for evaluating cytotoxicity of anticancer drugs based on trace cell samples. The mini-electrochemical system was integrated by using pencil graphite modified with threonine as working electrode, an Ag/AgCl reference electrode and a micropipet tip as electrochemical cell. The mini-electrochemical system dramatically reduces sample volumes from 500 µL in a traditional electrochemical system to 10 µL, and exhibits excellent electrocatalytic activity toward oxidation of purine from MCF-7 cells due to increased sensitivity provided by threonine. Moreover, the relationship between peak current and the cell concentration in the range from 3.0 × l03 to 7.0 × l06 cells/mL was studied, and a nonlinear exponential relationship between them was established over a wide concentration range. In evaluating the effect of anticancer drugs on cell viability, the results of drug cytotoxicity test based on cyclophosphamide were in close agreement with classical 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium (MTT) assays. The proposed device is so simple, cheap, and easy to operate that it could be applied to single-use applications. The mini-electrochemical system proved to be a useful tool and can be applied to electrochemical studies of cancer cells as well as other biological samples such as proteins and DNA.

(E)-4-Methyl-N-((quinolin-2-yl)ethylidene)aniline as ligand for IIB supramolecular complexes: synthesis, structure, aggregation-induced emission enhancement and application in PMMA-doped hybrid material.

Judicious structural design employing 2-quinolinecarboxaldehyde and 4-methylaniline was used to generate the Schiff base ligand (E)-4-methyl-N-((quinolin-2-yl)ethylidene)aniline (L). Five IIB complexes, namely, [ZnLCl2] (1), [ZnL(NO3)2] (2), [ZnL(OAc)2]3 (3), [CdL(OAc)2]3 (4), and [HgLCl2] (5) have been synthesized based on L. Single-crystal X-ray diffraction analysis indicates that complexes 1, 3 and 4 exhibit 3D networks, whereas 2 and 5 form 2D layers and 1D chains, respectively. TD-DFT calculations show a good correlation with the UV-vis absorption assigned to π → π* intraligand transitions. Furthermore, complexes 1-5 displayed strong greenish luminescent emissions (518-524 nm) in the aggregate state but weak emissions in solution (aggregation-induced emission enhancement), which may be due to the existence of C-HCl/O hydrogen bonding and ππ stacking interactions, resulting in restriction of intramolecular rotation (RIR). Variable-concentration 1H NMR studies suggested that the aggregates undergo intramolecular changes in conformation due to intermolecular interactions. Moreover, the emission intensity and lifetime exhibited obvious increases induced by mechanical grinding and temperature reduction, which were also attributed to AIEE properties. Subsequently, complex 1 was incorporated into poly(methyl methacrylate) (PMMA), whereby 1-PMMA exhibited enhanced emission intensity (20-fold increase in comparison with that of 1), which offers opportunities for use in plastic greenhouses to increase leaf photosynthesis.

The facile synthesis of mesoporous g-C3N4 with highly enhanced photocatalytic H2 evolution performance.

Mesoporous g-C3N4 has been obtained by a facile sucrose-mediated approach via thermal condensation of sucrose and melamine for the first time. The mesoporous g-C3N4 presents a much higher BET surface area and displays highly enhanced photocatalytic H2 evolution performance.

The synthesis of condensed C-PDA-g-C3N4 composites with superior photocatalytic performance.

Carbonized polydopamine-graphitic carbon nitride (C-PDA-g-C3N4) composites have been synthesised via in situ polymerization of dopamine (DA) on the surface of melamine followed by carbonization and condensation for the first time. The obtained C-PDA-g-C3N4 composites display enhanced crystallinity and superior photocatalytic performance.

A mini-electrochemical system integrated micropipet tip and pencil graphite electrode for detection of anticancer drug sensitivity in vitro.

Developing a reliable and cost-effective miniaturized electroanalysis tool is of vital importance for cell electrochemical analysis. In this work, a novel mini-electrochemical system has been constructed for trace detection of cell samples. The mini-electrochemical system was constructed by integrating a pencil graphite modified by threonine (PT/PGE) as working electrode, an Ag/AgCl (Sat'd) as reference electrode, platinum wire as counter electrode and a micropipet tip as electrochemical cell. The mini-electrochemical system not only saved dramatically usage of samples from 500 µL in traditional electrochemical system to 10 µL, but also possessed an adjustable active surface area by changing the length of PT/PGE immersed into the cell suspension from 3mm to 15 mm, and the linear equation was ipa = 2.25 l-2.64 (R(2) = 0.990). The system was successfully used in detection of MCF-7 cells, and a nonlinear exponent relationship between peak current and the cell number range from 3.0 × l0(3) to 7.0 × l0(6) cells mL(-1) was established firstly with the index equation ipa = 59.557 e (-C/1.709)-71.486 (R(2) = 0.954). Finally, the system was used for evaluating the sensitivity of cyclophosphamide on MCF-7 cell, and the result was corresponded well with that of MTT assay. The proposed system is sufficiently simple, cheap and easy operated, and could be applied in electrochemical detection of other biological samples.

The sulfur-bubble template-mediated synthesis of uniform porous g-C3N4 with superior photocatalytic performance.

A facile sulfur-bubble template-mediated synthesis of uniform porous g-C3N4 has been developed for the first time. The obtained sulfur-mediated g-C3N4 presents a uniform porous structure with higher BET surface area and displays superior photocatalytic performance compared with pure g-C3N4.