Electrodeposited MOFs Membrane with In Situ Incorporation of Charged Molecules for Osmotic Energy Harvesting

Ion-selective membranes are considered as the promising candidates for osmotic energy harvesting. However, the fabrication of highly perm-selective membrane is the major challenge. Metal-organic frameworks (MOFs) with well-defined nanochannels along functional charged groups show great importance to tackle this problem. Here, a series of dense sodium polystyrene sulfonate (PSS) incorporated MOFs composite membranes (PSS@MOFs) on a porous anodic aluminum oxide (AAO) membrane via in situ anodic electrodeposition process are developed. Benefiting to the novel structural design of the confined Ag layer, PSS@MOFs dense composite membrane with less defects formed. The sulfonated nanochannels of the PSS@MOFs composite membrane provided rapid and selective transport of cations due to the enhanced electrostatic interaction between the permeating ions and MOFs. While osmotic energy conversion, 860 nm thick negatively charged PSS@MOFs composite membrane achieves an ultrahigh cation transfer number of 0.993 and energy conversion efficiency of 48.8% at a 100-fold salinity gradient. Moreover, a large output power of 2.90 µW has been achieved with an ultra-low internal resistance of 999 Ω, employing an effective area of 12.56 mm². This work presents a promising strategy to construct a high-performance MOFs-based osmotic energy harvesting system for practical applications.     

Dewetting behavior of Au films on porous substrates

Understanding the stability of thin films and their spontaneous pattern formation upon dewetting is essential to a host of physical phenomena. In this paper, we study the dewetting phenomena of Au thin films deposited on anodic aluminum oxide (AAO) membranes to analyze the stability of the metal film on porous substrates. AAO membranes, as-sputtered and dewetted Au films are all characterized by scanning electronic microscopy and X-ray diffraction. We found that both the roughness of AAO surface and modification of AAO pores exhibit remarkable influences on the dewetting behavior of Au films. The observed dewetting phenomena are explained from an energetic point of view since dewetting is a process of minimization of the system free energy.     

Photoluminescence properties of TiO2: Eu3 + thin films deposited on different substrates

Strong photoluminescence of Eu^3 + due to intra 4f transitions are obtained from amorphous xerogel TiO₂: Eu^3 + films prepared by sol–gel method and treated at a low temperature of 100 °C. The films are deposited on four different substrates: Si, Al, AAO (anodic alumina oxide) and porous silicon. We find that the luminescence intensity on AAO substrate increased 4 times comparing with that of Si or Al, and luminescence intensity decreases obviously on porous silicon substrate. Energy transfer mechanism from TiO₂ host to Eu^3 + is deduced through analysis of photoluminescence and photoluminescence excitation spectrum. Concentration quenching of Eu^3 + does not appear even at high atomic concentration of 7.69%.     

Confined Synthesis of Carbon Nitride in a Layered Host Matrix with Unprecedented Solid‐State Quantum Yield and Stability

Fluorescent carbon nanomaterials have drawn tremendous attention for their intriguing optical performances, but their employment in solid‐state luminescent devices is rather limited as a result of aggregation‐induced photoluminescence quenching. Herein, ultrathin carbon nitride (CN) is synthesized within the 2D confined region of layered double hydroxide (LDH) via triggering the interlayer condensation reaction of citric acid and urea. The resulting CN/LDH phosphor emits strong cyan light under UV‐light irradiation with an absolute solid‐state quantum yield (SSQY) of 95.9 ± 2.2%, which is, to the best of our knowledge, the highest value of carbon‐based fluorescent materials ever reported. Furthermore, it exhibits a strong luminescence stability toward temperature, environmental pH, and photocorrosion. Both experimental studies and theoretical calculations reveal that the host–guest interactions between the rigid LDH matrix and interlayer carbon nitride give the predominant contribution to the unprecedented SSQY and stability. In addition, prospective applications of the CN/LDH material are demonstrated in both white light‐emitting diodes and upconversion fluorescence imaging of cancer cells.     

A nanohybrid material of SWNTs covalently functionalized with porphyrin for light harvesting antenna: synthesis and photophysical properties

Novel covalently porphyrin functionalized single-walled carbon nanotubes (SWNTs) were synthesized using carboxylic group functionalized carbon nanotubes (o-SWNTs) with meso-aniline substituted porphyrin. The structure and morphology of this SWNT nanohybrid material were fully characterized with FTIR, Raman, UV-Vis-NIR spectra as well as TGA and TEM measurements. The energy transfer efficiency from porphyrin to SWNTs and porphyrin fluorescence quenching mechanism were studied by means of steady state fluorescence and time-resolved fluorescence measurement. The fast and efficient electron transfer occurring in this nanohybrid illustrates that they can be utilized as a good candidate for light harvesting materials in molecular photonic devices and solar energy utilization.     

Protein‐Directed Synthesis of NIR‐Emitting,Tunable HgS Quantum Dots and their Applications in Metal‐Ion Sensing

The development of luminescent mercury sulfide quantum dots (HgS QDs) through the bio‐mineralization process has remained unexplored. Herein, a simple, two‐step route for the synthesis of HgS quantum dots in bovine serum albumin (BSA) is reported. The QDs are characterized by UV–vis spectroscopy, Fourier transform infrared (FT‐IR) spectroscopy, luminescence, Raman spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), circular dichroism (CD), energy dispersive X‐ray analysis (EDX), and picosecond‐resolved optical spectroscopy. Formation of various sizes of QDs is observed by modifying the conditions suitably. The QDs also show tunable luminescence over the 680–800 nm spectral regions, with a quantum yield of 4–5%. The as‐prepared QDs can serve as selective sensor materials for Hg(II) and Cu(II), based on selective luminescence quenching. The quenching mechanism is found to be based on Dexter energy transfer and photoinduced electron transfer for Hg(II) and Cu(II), respectively. The simple synthesis route of protein‐capped HgS QDs would provide additional impetus to explore applications for these materials.     

Versatile and Switchable Responsive Properties of a Lanthanide‐Viologen Metal–Organic Framework

Metal–organic frameworks (MOFs) provide intriguing platforms for the design of responsive materials. It is challenging to mobilize as many components as possible of a MOF to collaboratively accomplish multiple responsive properties. Here, reversible photochromism, piezochromism, hydrochromism, ionochromism, and luminescence modulation of an ionic Eu(III) MOF is reported furnished by cationic electron‐deficient viologen units and exchangeable guest anions. Mechanistically, the extraordinarily versatile responsive properties are owed to electron transfer (ET), charge transfer (CT), and energy transfer, involving viologen as electron acceptor, anion as electron donor, luminescing Eu(III) as energy donor, and anion‐viologen CT complex or ET‐generated radical as energy acceptor (luminescence quencher). Moreover, guest anions and waters provide flexible handles to control the ET‐based responsive properties. Water release/reuptake or exchange with organic solvents can switch on/off the response to light, while reversible anion exchange can disenable or awaken the responses to pressure, light, and water release/reuptake. The impacts of water and anions on ET are justified by the high polarity and hydrogen‐bonding capability of water, the different electron donor strength of anions, and the strong I^?‐viologen CT interactions. The rich responsive behaviors have great implications for applications such as pressure sensors, iodide detection, and chemical logic gates.     

Gas detection by structural variations of fluorescent guest molecules in a flexible porous coordination polymer

The development of a new methodology for visualizing and detecting gases is imperative for various applications. Here, we report a novel strategy in which gas molecules are detected by signals from a reporter guest that can read out a host structural transformation. A composite between a flexible porous coordination polymer and fluorescent reporter distyrylbenzene (DSB) selectively adsorbed CO? over other atmospheric gases. This adsorption induced a host transformation, which was accompanied by conformational variations of the included DSB. This read-out process resulted in a critical change in DSB fluorescence at a specific threshold pressure. The composite shows different fluorescence responses to CO? and acetylene, compounds that have similar physicochemical properties. Our system showed, for the first time, that fluorescent molecules can detect gases without any chemical interaction or energy transfer. The host-guest coupled transformations play a pivotal role in converting the gas adsorption events into detectable output signals.     

Efficient Aggregation‐Induced Emission Manipulated by Polymer Host Materials

Linear copolymer hosts bearing a number of pillar[5]arene dangling side chains are synthesized for the facile construction of highly emissive supramolecular polymer networks (SPNs) upon noncovalently cross‐linking with a series of tetraphenyethylene (TPE)‐based tetratopic guests terminated with different functional groups through supramolecular host–guest interactions. An extremely high fluorescence quantum yield (98.22%) of the SPNs materials is obtained in tetrahydrofuran (THF) by fine‐tuning the parameters, and meanwhile supramolecular light‐harvesting systems based on spherical supramolecular nanoparticles are constructed by interweaving 9,10‐distyrylanthracene (DSA) and TPE‐based guest molecules of aggregation‐induced emission (AIE) with the copolymer hosts in the mixed solvent of THF/H₂O. The present study not only illustrates the restriction of the intramolecular rotations (RIR)‐ruled emission enhancement mechanism regulated particularly by macrocyclic arene‐containing copolymer hosts, but also suggests a new self‐assembly approach to construct high‐performance light‐harvesting materials.     

Morphological evolution of porous nanostructures grown from a single isolated anodic alumina nanochannel

Porous anodic aluminum oxide (AAO) membranes have been widely used as templates for growing nanomaterials because of their ordered nanochannel arrays with high aspect ratio and uniform pore diameter. However, the intrinsic growth behavior of an individual AAO nanochannel has never been carefully studied for the lack of a means to fabricate a single isolated anodic alumina nanochannel (SIAAN). In this study, we develop a lithographic method for fabricating a SIAAN, which grows into a porous hemispherical structure with its pores exhibiting fascinating morphological evolution during anodization. We also discover that the mechanical stress affects the growth rate and pore morphology of AAO porous structures. This study helps reveal the growth mechanism of arrayed AAO nanochannels grown on a flat aluminum surface and provides insights to help pave the way to altering the geometry of nanochannels on AAO templates for the fabrication of advanced nanocomposite materials.     

Fabrication and characterization of white polymer light emitting diodes using PFO:MDMO-PPV

White polymer light emitting diodes (WPLEDs) with a glass/ITO/PEDOT:PSS/PFO:MDMO-PPV/ TPBI/LIF/Al structure were fabricated in order to investigate the optimum doping concentration of the emission materials. PEDOT:PSS was introduced as the hole transport material. The PFO and MDMO-PPV were used as the light emitting host and the guest materials, respectively. The PFO:MDMO-PPV mixed solution was spin-coated onto the PEDOT:PSS/ITO substrate. TPBI, LiF and Al were deposited by thermal evaporation as the hole blocking, electron injection, and cathode materials, respectively. As a result, the current density and luminance of the WPLED with the 20.0 wt% MDMO-PPV concentration in the PFO host material were found to be about 365 mA/cm2 and 4315 cd/m2, respectively. The maximum external quantum efficiency (EQE) of the same sample was found to be 11.26%, which may be ascribed to the efficient energy transfer from the PFO host to the MDMO-PPV guest material.     

采用阳极氧化铝做掩膜生长氮化镓膜

采用均匀的多孔阳极氧化铝做掩膜在氢化物气相外延设备中生长出高质量的氮化镓膜.采用扫描电镜观察了氮化镓膜的界面性质并用阴极发光谱表征了截面上氮化镓层在不同位置的的发光性质,发现随着厚度的增加,其发光特性得到改善,而且由于掩膜结构的引入,外延膜中的压应力得到一定程度的释放.     

Eu3+掺杂硼酸盐玻璃的发光性质及其热稳定性研究

荧光玻璃具有发光中心分布均匀和热稳定好等优点, 成为LED领域研究的热点。本研究采用传统的高温熔融淬火法合成了一系列Eu³⁺掺杂的硼酸盐玻璃, 通过荧光光谱手段对其发光性质及热稳定性进行了表征; 利用Van Uitert模型对样品中Eu³⁺的浓度猝灭行为进行了研究。结果表明: 样品中Eu³⁺的浓度猝灭机理为Eu³⁺离子间的交换作用导致的无辐射能量传递; 利用Arrhenius公式对荧光玻璃样品的温度猝灭行为进行了分析。结果表明: 样品中Eu³⁺的发光温度猝灭属于Crossover过程; 最后分析了Eu³⁺与荧光玻璃基质之间的相互作用。     

Influence of copper on the microstructure of sol–gel titanium oxide nanotubes array

The effect of copper addition in the microstructure of sol–gel titanium oxide (TiO₂) supported on anodic aluminum oxide (AAO) membranes is reported. Two deposition methods based on immersion and flow techniques were used for the coating of the porous AAO membrane. Copper-free membranes were studied as a function of different ratios of H⁺/Ti, H₂O/Ti, selecting the most appropriate for the sensitization with copper. For copper-doped TiO₂ arrays, the presence of copper causes the reduction of grain size and enhances titania deposition inside the AAO pores, although no clear tendency with copper content was found. The formation of copper-doped titania nanotubes was validated after dissolving the AAO membranes, finding a deposition-dependent stability in the Cu-doped materials. Titania and Cu-doped titania nanotubes analyzed as colloidal solutions show band gaps substantially shifted to the red in comparison to the direct band gap of near-spherical colloidal materials. These arrays are important for photocatalysis and for the development of third generation photovoltaic devices.     

Metal–Organic Frameworks as a Versatile Platform for Proton Conductors

Metal–organic frameworks (MOFs) are an intriguing type of crystalline porous materials that can be readily built from metal ions or clusters and organic linkers. Recently, MOF materials, featuring high surface areas, rich structural tunability, and functional pore surfaces, which can accommodate a variety of guest molecules as proton carriers and to systemically regulate the proton concentration and mobility within the available space, have attracted tremendous attention for their roles as solid electrolytes in fuel cells. Recent advances in MOFs as a versatile platform for proton conduction in the field of humidity condition proton-conduction, anhydrous atmosphere proton-conduction, single-crystal proton-conduction, and including MOF-based membranes for fuel cells, are summarized and highlighted. Furthermore, the challenges, future trends, and prospects of MOF materials for solid electrolytes are also discussed.     

Recent Progress of Singlet‐Exciton‐Harvesting Fluorescent Organic Light‐Emitting Diodes by Energy Transfer Processes

The external quantum efficiency (EQE) of organic light‐emitting diodes (OLEDs) has been dramatically improved by developing highly efficient organic emitters such as phosphorescent emitters and thermally activated delayed fluorescent (TADF) emitters. However, high‐EQE OLED technologies suffer from relatively poor device lifetimes in spite of their high EQEs. In particular, the short lifetimes of blue phosphorescent and TADF OLEDs remain a big hurdle to overcome. Therefore, the high‐EQE approach harvesting singlet excitons of fluorescent emitters by energy transfer processes from the host or sensitizer has been explored as an alternative for high‐EQE OLED strategies. Recently, there has been a big jump in the EQE and device lifetime of singlet‐exciton‐harvesting fluorescent OLEDs. Recent progress on the materials and device structure is discussed herein.     

Porous Host–Guest MOF-Semiconductor Hybrid with Multisites Heterojunctions and Modulable Electronic Band for Selective Photocatalytic CO2 Conversion and H2 Evolution

Optimizing catalysts for competitive photocatalytic reactions demand individually tailored band structure as well as intertwined interactions of light absorption, reaction activity, mass, and charge transport.  Here, a nanoparticulate host–guest structure is rationally designed that can exclusively fulfil and ideally control the aforestated uncompromising requisites for catalytic reactions. The all-inclusive model catalyst consists of porous Co₃O₄ host and Zn_xCd_1-xS guest with controllable physicochemical properties enabled by self-assembled hybrid structure and continuously amenable band gap. The effective porous topology nanoassembly, both at the exterior and the interior pores of a porous metal–organic framework (MOF), maximizes spatially immobilized semiconductor nanoparticles toward high utilization of particulate heterojunctions for vital charge and reactant transfer. In conjunction, the zinc constituent band engineering is found to regulate the light/molecules absorption, band structure, and specific reaction intermediates energy to attain high photocatalytic CO₂ reduction selectivity. The optimal catalyst exhibits a H₂-generation rate up to 6720 µmol g⁻¹ h⁻¹ and a CO production rate of 19.3 µmol g⁻¹ h⁻¹. These findings provide insight into the design of discrete host–guest MOF-semiconductor hybrid system with readily modulated band structures and well-constructed heterojunctions for selective solar-to-chemical conversion.     

Molecularly Imprinted Porous Aromatic Frameworks Serving as Porous Artificial Enzymes

Artificially designed enzymes are in demand as ideal catalysts for industrial production but their dense structure conceals most of their functional fragments, thus detracting from performance. Here, molecularly imprinted porous aromatic frameworks (MIPAFs) which are exploited to incorporate full host–guest interactions of porous materials within the artificial enzymes are presented. By decorating a porous skeleton with molecularly imprinted complexes, it is demonstrated that MIPAFs are porous artificial enzymes possessing excellent kinetics for guest molecules. In addition, due to the abundance of accessible sites, MIPAFs can perform a wide range of sequential processes such as substrate hydrolysis and product transport. Through its two functional sites in tandem, the MIPAF subsequently manifests both hydrolysis and transport behaviors. Advantageously, the obtained catalytic rate is ≈58 times higher than that of all other conventional artificial enzymes and even surpasses by 14 times the rate for natural organophosphorus hydrolase (Flavobacterium sp. strain ATCC 27551).     

Optochemically Responsive 2D Nanosheets of a 3D Metal–Organic Framework Material

Outstanding functional tunability underpinning metal–organic framework (MOF) confers a versatile platform to contrive next‐generation chemical sensors, optoelectronics, energy harvesters, and converters. A rare exemplar of a porous 2D nanosheet material constructed from an extended 3D MOF structure is reported. A rapid supramolecular self‐assembly methodology at ambient conditions to synthesize readily exfoliatable MOF nanosheets, functionalized in situ by adopting the guest@MOF (host) strategy, is developed. Nanoscale confinement of light‐emitting molecules (as functional guest) inside the MOF pores generates unusual combination of optical, electronic, and chemical properties, arising from the strong host–guest coupling effects. Highly promising photonics‐based chemical sensing opened up by the new guest@MOF composite systems is shown. By harnessing host–guest optochemical interactions of functionalized MOF nanosheets, detection of an extensive range of volatile organic compounds and small molecules important for many practical applications has been accomplished.     

Transient characteristics of organic light-emitting diodes with efficient energy transfer in emitting material

We have investigated the combination effect of host–guest materials in an emitting layer on the transient property of an organic light-emitting diode (OLED). We found that an efficient energy transfer owing to the large overlap between the photoluminescence spectrum of host material and the absorption spectrum of guest material was an important factor to improve the response speed of the OLED. As a result, the rise time of optical response was mainly affected by the combination of host–guest materials, and it increased using the optimal guest material, 1,4-bis[2-[4-N,N-di(p-tolyl)amino]phenyl]vinyl]benzene (DSB). A maximum −3 dB cutoff frequency of 15.8 MHz was achieved for an OLED with DSB as a guest material.