光功能杂化凝胶玻璃器件研究进展

光功能杂化凝胶玻璃是一类具有广泛应用潜力的新型杂化材料与器件,集成融合了凝胶玻璃和光功能材料的特性和优势。本文主要综述了多种玻璃基质为载体的光功能杂化玻璃器件,尤其是凝胶玻璃基质作为光学材料载体的杂化凝胶玻璃器件的最新研究进展,系统介绍了非线性光学激光防护/调制杂化玻璃器件和发光/转换杂化玻璃器件2大类。最后,结合当前研究进展,展望了光功能杂化凝胶玻璃未来发展过程中可能面临的问题和挑战。本综述将有望为光功能杂化材料与玻璃的设计制备、性能优化以及器件制备和应用提供一定的启示,推动光功能杂化凝胶玻璃器件的发展。

Evolution of microstructure and mechanical properties in multi-layer 316L-TiC composite fabricated by selective laser melting additive manufacturing

In this study,the microstructure and mechanical properties of a multi-layered 316L-TiC composite material produced by selective laser melting(SLM)additive manufacturing process are investigated.Three different layers,consisting of 316L stainless steel,316L-5 wt%TiC and 316L-10 wt%TiC,were additively manufactured.The microstructure of these layers was characterized by optical microscopy(OM)and scanning electron microscopy(SEM).X-ray diffraction(XRD)was used for phase analysis,and the mechanical properties were evaluated by tensile and nanoindentation tests.The microstructural observations show epitaxial grain growth within the composite layers,with the elongated grains growing predominantly in the build direction.XRD analysis confirms the successful incorporation of the TiC particles into the 316L matrix,with no unwanted phases present.Nanoindentation results indicate a significant increase in the hardness and modulus of elasticity of the composite layers compared to pure 316L stainless steel,suggesting improved mechanical properties.Tensile tests show remarkable strength values for the 316L-TiC composite samples,which can be attributed to the embedded TiC particles.These results highlight the potential of SLM in the production of multi-layer metal-ceramic composites for applications that require high strength and ductility of metallic components in addition to the exceptional hardness of the ceramic particles.

Strategies for engineering metal-organic frameworks as efficient photocatalysts

Environmental pollution and energy deficiency represent major problems for the sustainability of the modern world. Photocatalysis has recently emerged as an effective and environmentally friendly technique to address some of these sustainability issues,although the key to the success of this approach is dependent on the photocatalysts themselves. Based on their attractive physic chemical properties,including their ultrahigh surface areas,homogeneous active sites and tunable functionality,metal-organic frameworks（MOFs） have become interesting platforms for the development of solar energy conversion devices. Furthermore,MOFs have recently been used in a wide variety of applications,including heterogeneous photocatalysis for pollutant degradation,organic transformations,hydrogen production and CO2 reduction. In this review,we have highlighted recent progress towards the application of MOFs in all of these areas. We have collected numerous reported examples of the use of MOFs in these areas,as well as providing some analysis of the key factors influencing the efficiency of these systems. Moreover,we have provided a detailed discussion of new strategies that have been developed for enhancing the photocatalytic activity of MOFs. Finally,we have provided an outlook for this area in terms of the future challenges and potential prospects for MOFs in photocatalysis.

Intraclonal Resource Sharing and Functional Specialization of Ramets in Response to Resource Heterogeneity in Three Stoloniferous Herbs

Environments with reciprocal patchiness of resources, in which the availability of two resources such as light and soil nutrients are patchily distributed in horizontal space and negatively correlated in each patch, are common in many ecosystems. The strategies by which clonal plants adapt to this type of heterogeneous environment were examined in three stoloniferous herbs,Potentilla reptans L. var. sericophylla Franch., P. anserina L. and Halerpestes ruthenica (Jacq.) Qvcz., commonly inhabiting forest understories, grasslands and low saline meadows, respectively. As pairs of connected ramets were subjected to reciprocal patchiness of light and nutrients, stolon connection between the two ramets significantly enhanced biomass of both ramet growing in low light intensity but high soil nutrient condition (LH ramet) and ramet growing in high light intensity but low soil nutrient condition (HL ramet) as well as whole ramet pairs (consisting of LH ramets and HL ramets). Additionally, stolon connection greatly increased root/shoot ratio of LH ramet while significantly decreased that of HL ramet. The results indicate that a reciprocal transportation of resources between interconnected ramets and a functional specialization of ramets in uptake of abundant resources occurred. By resource sharing and functional specialization, clonal plants can efficiently acquire locally abundant resources and buffer the stress caused by reciprocal patchiness of resources.

Amorphous CoOx coupled carbon dots as a spongy porous bifunctional catalyst for efficient photocatalytic water oxidation and CO2 reduction

Cobalt-based oxides,with high abundance,good stability and excellent catalytic performance,are regarded as promising photocatalysts for artificial photosynthetic systems to alleviate foreseeable energy shortages and global warming.Herein,for the first time,a series of novel spongy porous CDs@CoOx materials were synthesized to act as an efficient and stable bifunctional photocatalyst for water oxidation and CO2 reduction.Notably,the preparation temperatures visibly influence the morphologies and photocatalytic performances of the CDs@CoOx.Under the optimal conditions,a maximum O2 yield of 40.4% and pretty apparent quantum efficiency(AQE)of 58.6% at 460 nm were obtained over CDs@CoOx-300 for water oxidation.Similarly,the optimized sample CDs@CoOx-300 manifests significant enhancement on the CO2-to-CO conversion with a high selectivity of 89.3% and CO generation rate of 8.1μmol/h,which is superior to most previous cobalt-based catalysts for CO2 reduction.The composite CDs@CoOx-300 not only exposes more active sites but also facilitates electron transport,which results in excellent photocatalytic activity.In addition,the boosted photocatalytic behavior is attributed to the synergistic effect between CoOx and CDs,which was verified by the photocatalytic activity control experiments and electrochemical characterization.The work offers a novel strategy to fabricate a high performance bifunctional photocatalyst for water oxidation and CO2 reduction.

Bifunctional TiO2 Catalysts for Efficient Cr（VI） Photoreduction Under Solar Light Irradiation Without Addition of Acids

Bifunctional TiO2 photocatalysts co-doped with nitrogen and sulfur were prepared by the controlled thermal decomposition of ammonium titanyl sulfate precursor. They have both photocatalytic activity and Brφnsted acidity, and thus are active in the photoreduction of Cr（VI） under solar light irradiation without the addition of acids. The activity is superior to that of Degussa P25 in the acidified suspension at the same pH adjusted by H2SO4.

Hidden Relaxation Channels in Aqueous Methylene Blue after Functionalization of Graphene Oxide Probed by Transient Absorption Spectroscopy

The mixture of graphene oxide （GO） and dye molecules may provide some new applications due to unique electronic, optical, and structural properties. Methylene blue （MB）, a typ- ical anionic dye, can attach on GO via π-π stacking and electrostatic interaction, and the molecule removal process on GO has been observed. However, it remains unclear about the ultrafast carrier dynamics and the internal energy transfer pathways of the system which is composed of GO and MB. We have employed ultrafast optical pump-probe spectroscopy to investigate the excited dynamics of the GO-MB system dispersed in water by exciting the samples at 400 nm pump pulse. The pristine MB and GO dynamics are also analyzed in tandem for a direct comparison. Utilizing the global analysis to fit the measured signal via a sequential model, five lifetimes are acquired：（0.61±0.01） ps, （3.52±0.04） ps, （14.1±0.3） ps, （84±2） ps, and （3.66±0.08） ns. The ultrafast dynamics corresponding to these lifetimes was analyzed and the new relaxation processes were found in the GO-MB system, compared with the pristine MB. The results reveal that the functionalization of GO can alter the known decay pathways of MB via the energy transfer from GO to MB in system, the increased intermediate state, and the promoted energy transfer from triplet state MB to ground state oxygen molecules dissolved in aqueous sample.

Precisely decorating CdS on Zr-MOFs through pore functionalization strategy: A highly efficient photocatalyst for H2 production

Different materials,such as metal sulphides,are often combined with metal‐organic frameworks(MOFs)to develop multi‐functional composites and improve their photocatalytic properties.However,the high interfacial energy barrier limits the formation and nano‐assembly of the heterogeneous junctions between MOFs and metal sulphides.Herein,the heterostructured Zr‐MOF‐S@CdS are successfully constructed through a sequential synthesis method,in which the mesoporous Zr‐MOF are firstly decorated with thioglycolic acid through pore functionalization,and followed by the S^(2-)anion exchange process resulting in the surface close attached growth of CdS onto Zr‐MOF‐S materials.Due to the presence of molecules linkers,the CdS can be precisely decorated onto Zr‐MOF‐S without aggregation,which can provide more active sites.Moreover,the intimate connections and the suitable band structures between two materials can also facilitate the photogenerated electron‐hole pairs separation.Therefore,the resulting Zr‐MOF‐S@CdS with appropriate ratio exhibits high photocatalytic activity for water reduction,in which the H_(2) evolution rate can reach up to 1861.7μmol·g^(‒1)·h^(‒1),4.5 times higher than pure CdS and 2.3 times higher than of Zr‐MOF/CdS,respectively.Considering the promising future of MOF‐based photocatalysts,this work may provide an avenue for the further design and synthesis MOF‐based composite photocatalysts for efficient H_(2) evolution.

Interface microstructure and mechanical properties of selective laser melted multilayer functionally graded materials

Functionally graded material(FGM)can tailor properties of components such as wear resistance,corrosion resistance,and functionality to enhance the overall performance.The selective laser melting(SLM)additive manufacturing highlights the capability in manufacturing FGMs with a high geometrical complexity and manufacture flexibility.In this work,the 316L/CuSn10/18Ni300/CoCr four-type materials FGMs were fabricated using SLM.The microstructure and properties of the FGMs were investigated to reveal the effects of SLM processing parameters on the defects.A large number of microcracks were found at the 316L/CuSn10 interface,which initiated from the fusion boundary of 316L region and extended along the building direction.The elastic modulus and nano-hardness in the 18Ni300/CoCr fusion zone decreased significantly,less than those in the 18Ni300 region or the CoCr region.The iron and copper elements were well diffused in the 316L/CuSn10 fusion zone,while elements in the CuSn10/18Ni300 and the 18Ni300/CoCr fusion zones showed significantly gradient transitions.Compared with other regions,the width of the CuSn10/18Ni300 interface and the CuSn10 region expand significantly.The mechanisms of materials fusion and crack generation at the 316L/CuSn10 interface were discussed.In addition,FGM structures without macro-crack were built by only altering the deposition subsequence of 316L and CuSn10,which provides a guide for the additive manufacturing of FGM structures.

A Multi-Condition Relighting with Optimal Feature Selection to Robust Face Recognition with Illumination Variation

In this paper, we proposed a new approach for face recognition with robust to illumination variation. The improved performance to various lights in recognition is obtained by a novel combination of multicondition relighting and optimal feature selection. Multi-condition relighting provides a "coarse" compensation for the variable illumination, and then the optimal feature selection further refines the compensation, and additionally offers the robustness to shadow and highlight, by deemphasizing the local mismatches caused by imprecise lighting compensation, shadow or highlight on recognition. For evaluation, two databases with various illumination mismatches have been used. The results have demonstrated the improved robustness of the new methods.

A thioether-functionalized pyrene-based covalent organic framework anchoring ultrafine Au nanoparticles for efficient photocatalytic hydrogen generation

Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.

Density Functional Theory Investigation of Structures and Electronic Spectra of N-protonated Corroles

The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density functional theory （DFT）. The results indicate that all these compounds have two conformers, one with C2 symmetry （denoted as Sl） is more stable than the other （denoted as $2, C1 symmetry） by 15.8-18.5 kJ/mol. The corrole macrocycles of these compounds show significant out-of-plane deformation. The enantiomerizations of the chiral S1 conformers were found to be a multi-step process with the $2 conformers as the intermediates. Electronic absorption spectra and electronic circular dichroism （ECD） of these compounds were calculated with time-dependent DFT. In comparison with H4Cor＋, the UV- Vis absorptions of meso-triaryl species are significantly red-shifted and their Q bands are enhanced due to the π-π conjugation between the aryl and corrole rings. Several neighboring electronic transitions were calculated with opposite signs in rotatory strengths, suggesting that ECD spectroscopy may be a useful tool in studying the electronic transitions of these compounds.

Effect of ultraviolet photofunctionalization of dental titanium implants on osseointegration

Objective： The aim of the current study was to evaluate the effect of ultraviolet（UV） photofunctionalization of dental titanium implants with exposure to the oral cavity on osseointegration in an animal model. Methods： Forty-eight titanium implants（Camlog~？ Conelog~？ 4.3 mmx9.0 mm） were placed epicrestally into the edentulous jaws of three minipigs and implant stability was assessed by measuring the implant stability quotient（ISQ）. Prior to implantation half of the implants were photofunctionalized with intense UV-light. After three months, the implants were exposed and ISQ was measured again. After six months of implant exposure, the minipigs were sacrificed and the harvested specimens were analyzed using histomorphometric, light, and fluorescence microscopy. Main results： Forty-two of 48 implants osseointegrated. The overall mean bone-implant contact area（BIC） was（64±22）%. No significant differences were found in BIC or ISQ value（multivariate analysis of variance（MANOVA）, P〉0.05） between implants with and without exposure to UV photofunctionalization. Conclusions： No significant effects were observed on osseointegration of dental titanium implants nine months after exposure of UV photofunctionalization.

Simultaneous N-intercalation and N-doping of epitaxial graphene on 6H-SiC（0001） through thermal reactions with ammonia

Surface functionalization of epitaxial graphene overlayers on 6H-SiC（0001） has been attempted through thermal reactions in NH3. X-ray photoelectron spectroscopy and micro-region low energy electron diffraction results show that a significant amount of N is present at the NHB-treated graphene surface, which results in strong band bending at the SiC surface as well as decoupling of the graphene overlayers from the substrate. The majority of the surface N species can be removed by annealing in vacuum up to 850 ~C, weakening the surface band bending and resuming the strong coupling of graphene with the SiC surface. The desorbed N atoms can be attributed to the intercalated species between graphene and SiC. Low temperature scanning tunneling spectroscopy and density functional theory simulations confirm the presence of N dopants in the graphene lattice, which are in the form of graphitic substitution and can be stable above 850 ~C. This is the first report of simultaneous N intercalation and N doping of epitaxial graphene overlayers on SiC, and it may be employed to alter the surface physical and chemical properties of epitaxial graphene overlayers.

A nano-functionalized real-time electrochemiluminescent biosensor for alanine transaminase assay

An electrochemiluminescent (ECL) biosensor was constructed for selective assay of alanine aminotransferase (ALT) based on the enzymatically catalyzed oxidation of pyruvate by pyruvate oxidase (PYOD). The composite of potassium ferricyanide and carbon nanotube was adopted to pre-functionalize the basal platinum electrode while the potassium ferricyanide acted as the activator of PYOD. The ALT catalyzed the reaction of L-alanine and-ketoglutarate to produce pyruvate which could be further enzymatically oxidized by PYOD to yield H2O2 to intensify the ECL of luminol. The biosensor showed rapid response for real-time measurement of ALT in the linear concentration range from 0.00475 to 350 U/L (r = 0.993) with a relatively standard deviation of 2.5% (CALT = 47.5 U/L,n = 6). The biosensor was applied to assay the ALT in rat serum with average recovery of 90.5%.

Post-functionalization of disubstituted polyacetylenes via click chemistry

We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes （PAs, P3） through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA （P2） was derived by desilylation of the pristine PA with trimethylethynylsilane side chains （P1）. P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane （M） under the promotion of WC16-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps （from P1 to P3 via precursor P2） and one-pot （from P1 to P3 without separation and purification of P2） were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.

Full-temperature covered switching material with triple optic-dielectric states in a lead-free hybrid perovskite

Optic-electric responsive materials have attracted much attention for their applications in temperaturesensing,actuators,and memory switches.However,it is a challenge to integrate various functions to form multifunctional responsive materials.As molecule-based hybrid materials usually consist of organic and inorganic components,the introduction of multiple functions can be achieved through structural construction.Thus far,even though fulltemperature cover is required for device applications,fulltemperature covered multi-switchable hybrid materials have rarely been successfully synthesized.Herein,the dynamic[(CH3)3NOH]+cation and luminous center Mn(II)were introduced to form a hybrid material[(CH3)3NOH][Mn Cl3],showing multiple temperature-responsive behaviors.Upon temperature change,it exhibits multi-state dielectric switching response and intensity or peak shift response of luminous in full-temperature range(low,room,and high temperatures).These responsive behaviors are triggered by the motion or reorientation of[(CH3)3NOH]+cations and inorganic framework.Overall,the switchable photoelectric material has potential applications in multiple encrypted storage and sensor devices.

High-efficiency room temperature phosphorescence from amorphous metal-free copolymers

Photofunctional materials with room-temperature phosphorescence（RTP）commonly appeared in expensive metal-coordination complexes and rare-earth-based compounds.Recently,the metal-free organic RTP materials have been paid growing attention from scientific community because of the ease of molecular design,low cost as well as potential applications in molecular switches,chemical sensors and biological imaging.To date,efficient RTP materials with high quantum yield are still very limited due to the T_1-S_0 spinforbidden process and weak spin-orbital coupling.Current mechanism based on crystallization-induced or aggregationinduced phosphorescence may serve as an effective way to enhance the RTP[1,2];

Bifunctional fluorescent probes for hydrogen peroxide and diols based on a 1,8-naphthalimide fluorophore

This report discloses a series of naphthalimide-based bifunctional fluorescent probes for hydrogen peroxide and diols.As a result,these molecules not only demonstrated high turn-on fluorescent response and good selectivity towards hydrogen peroxide over other relevant reactive oxygen species,but also displayed different responses to diols.Therefore,these fluorescent probes could be served as sensitive,selective and practical chemosensors for both hydrogen peroxide and diols under physiologicallike conditions.

Functionalized, carbon nanotube material for the catalytic degradation of organophosphate nerve agents

Recent world events have emphasized the need to develop innovative, functional materials that will safely neutralize chemical warfare （CW） agents in situ to protect military personnel and civilians from dermal exposure. Here, we demonstrate the efficacy of a novel, proof-of-concept design for a Cu-containing catalyst, chemically bonded to a single-wall carbon nanotube （SWCNT） structural support, to effectively degrade an organophosphate simulant. SWCNTs have high tensile strength and are flexible and light-weight, which make them a desirable structural component for unique, fabric-like materials. This study aims to develop a self-decontaminating, carbon nanotube-derived material that can ultimately be incorporated into a wearable fabric or protective material to minimize dermal exposure to organophosphate nerve agents and to prevent accidental exposure during decontamination procedures. Carboxylated SWCNTs were functionalized with a polymer, which contained Cu-chelating bipyridine groups, and their catalytic activity against an organophosphate simulant was measured over time. The catalytically active, functionalized nanomaterial was characterized using X-ray fluorescence and Raman spectroscopy. Assuming zeroth-order reaction kinetics, the hydrolysis rate of the organophosphate simulant, as monitored by UV-vis absorption in the presence of the catalytically active nanomaterial, was 63 times faster than the uncatalyzed hydrolysis rate for a sample containing only carboxylated SWCNTs or a control sample containing no added nanotube materials.