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1.
A straightforward aqueous synthesis of MoO3?x nanoparticles at room temperature was developed by using (NH4)6Mo7O24?4 H2O and MoCl5 as precursors in the absence of reductants, inert gas, and organic solvents. SEM and TEM images indicate the as‐prepared products are nanoparticles with diameters of 90–180 nm. The diffuse reflectance UV‐visible‐near‐IR spectra of the samples indicate localized surface plasmon resonance (LSPR) properties generated by the introduction of oxygen vacancies. Owing to its strong plasmonic absorption in the visible‐light and near‐infrared region, such nanostructures exhibit an enhancement of activity toward visible‐light catalytic hydrogen generation. MoO3?x nanoparticles synthesized with a molar ratio of MoVI/MoV 1:1 show the highest yield of H2 evolution. The cycling catalytic performance has been investigated to indicate the structural and chemical stability of the as‐prepared plasmonic MoO3?x nanoparticles, which reveals its potential application in visible‐light catalytic hydrogen production.  相似文献   

2.
A novel single‐source precursor NaGd(TFA)4(diglyme) (TFA=trifluoroacetate) was synthesized, characterized thoroughly, and used to obtain the hexagonal phase of NaGdF4 nanoparticles as an efficient matrix for lanthanide‐doped upconverting nanocrystals (NCs) that convert near‐infrared radiation into shorter‐wavelength UV/visible light. These NCs were then used to prepare well‐characterized TiO2@NaGdF4:Yb3+,Tm3+ nanocomposites to extend the absorption range of the TiO2 photocatalyst from the UV to the IR region. While the visible/near IR part of the photoluminescent spectra remains almost unaffected by the presence of TiO2, the UV part is strongly quenched due to the absorption of TiO2 above its gap at approximately 380 nm by energy transfer or FRET. Preliminary results on the photocatalytic activity of the above obtained nanocomposites are presented.  相似文献   

3.
Vacancy‐rich layered materials with good electron‐transfer property are of great interest. Herein, a full‐spectrum responsive vacancy‐rich monolayer BiO2−x has been synthesized. The increased density of states at the conduction band (CB) minimum in the monolayer BiO2−x is responsible for the enhanced photon response and photo‐absorption, which were confirmed by UV/Vis‐NIR diffuse reflectance spectra (DRS) and photocurrent measurements. Compared to bulk BiO2−x, monolayer BiO2−x has exhibited enhanced photocatalytic performance for rhodamine B and phenol removal under UV, visible, and near‐infrared light (NIR) irradiation, which can be attributed to the vacancy VBi‐O′′′ as confirmed by the positron annihilation spectra. The presence of VBi‐O′′′ defects in monolayer BiO2−x promoted the separation of electrons and holes. This finding provides an atomic level understanding for developing highly efficient UV, visible, and NIR light responsive photocatalysts.  相似文献   

4.
《化学:亚洲杂志》2017,12(18):2486-2493
A new class of phenanthrene‐fused BF2 azadipyrromethene (azaBODIPY) dyes have been synthesized through a tandem Suzuki reaction and oxidative ring‐fusion reaction, or a palladium‐catalyzed intramolecular C−H activation reaction. These phenanthrene‐fused azaBODIPY dyes are highly photostable and display markedly redshifted absorption (up to λ =771 nm) and emission bands (λ ≈800 nm) in the near‐infrared region. DFT calculations and cyclic voltammetry studies indicate that, upon annulation, more pronounced stabilization of the LUMO is the origin of the bathochromic shift of the absorption and high photostability.  相似文献   

5.
《化学:亚洲杂志》2017,12(23):2980-2984
Two‐dimensional (2D) semiconductors have recently emerged as a remarkable class of plasmonic alternative to conventional noble metals. However, tuning of their plasmonic resonances towards different wavelengths in the visible‐light region with physical or chemical methods still remains challenging. In this work, we design a simple room‐temperature chemical reaction route to synthesize amorphous molybdenum oxide (MoO3−x ) nanodots that exhibit strong localized surface plasmon resonances (LSPR) in the visible and near‐infrared region. Moreover, tunable plasmon resonances can be achieved in a wide range with the changing surrounding solvent, and accordingly the photoelectrocatalytic activity can be optimized with the varying LSPR peaks. This work boosts the light–matter interaction at the nanoscale and could enable photodetectors, sensors, and photovoltaic devices in the future.  相似文献   

6.
Visible‐light‐responsive reversible color‐switching systems are attractive to many applications because visible light has superior penetration and causes far less damage to organic molecules than UV. Herein, we report that self‐doping of SnO2−x nanocrystals with Sn2+ red‐shifts their absorption to the visible region and simultaneously produces oxygen vacancies, which can effectively scavenge photogenerated holes and thus enable the color switching of redox dyes using visible light. Wavelength‐selective switching can also be achieved by coupling the photocatalytic activity of the SnO2−x NCs with the color‐switching kinetics of different redox dyes. The fast light response enables the further fabrication of a solid film that can be repeatedly written on using a visible laser pen or projection printing through a photomask. This discovery represents a big step forward towards practical applications, especially in areas in which safety issues and photodamage by UV light are of concern.  相似文献   

7.
《化学:亚洲杂志》2017,12(19):2597-2603
In this paper, an Ag‐doped WO3 (and MoO3) composite has been prepared by following a simple micelle‐directed method and high‐temperature sintering route. The as‐prepared samples were characterized by X‐ray diffraction, inductively coupled plasma, transmission electron microscopy, X‐ray photoelectron spectroscopy, UV/Vis diffuse reflectance spectroscopy, Brunauer–Emmett–Teller, photoluminescence spectroscopy, and electrochemical impedance spectroscopy techniques. The photocatalytic experiments reveal that their oxygen‐production rates are up to 95.43 μmol (75.45 μmol) for Ag‐doped WO3 (MoO3), which is 9.5 (7.3) times higher than that of pure WO3: 9.012 μmol (MoO3: 9.00 μmol) under visible‐light illumination (λ ≥420 nm), respectively. The improvement of their photocatalytic activity is attributed to the enhancement of their visible‐light absorption and the separation efficiency of photogenerated carriers by Ag doping. Moreover, Ag‐doped WO3 (MoO3) also shows excellent adsorption of rhodamine B (RhB) and methylene blue (MB) in aqueous solution, with maximum adsorption capacities towards RhB and MB of 822 and 820 mg g−1 for Ag‐doped WO3, and 642 and 805 mg g−1 for Ag‐doped MoO3, respectively.  相似文献   

8.
A platinum complex with the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl ligand ( 1 ) was synthesized and the crystal structure was determined. UV/Vis absorption, emission, and transient difference absorption of 1 were systematically investigated. DFT calculations were carried out on 1 to characterize the electronic ground state and aid in the understanding of the nature of low‐lying excited electronic states. Complex 1 exhibits intense structured 1π–π* absorption at λabs<440 nm, and a broad, moderate 1M LCT/1LLCT transition at 440–520 nm in CH2Cl2 solution. A structured 3ππ*/3M LCT emission at about 590 nm was observed at room temperature and at 77 K. Complex 1 exhibits both singlet and triplet excited‐state absorption from 450 nm to 750 nm, which are tentatively attributed to the 1π–π* and 3π–π* excited states of the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridine ligand, respectively. Z‐scan experiments were conducted by using ns and ps pulses at 532 nm, and ps pulses at a variety of visible and near‐IR wavelengths. The experimental data were fitted by a five‐level model by using the excited‐state parameters obtained from the photophysical study to deduce the effective singlet and triplet excited‐state absorption cross sections in the visible spectral region and the effective two‐photon absorption cross sections in the near‐IR region. Our results demonstrate that 1 possesses large ratios of excited‐state absorption cross sections relative to that of the ground‐state in the visible spectral region; this results in a remarkable degree of reverse saturable absorption from 1 in CH2Cl2 solution illuminated by ns laser pulses at 532 nm. The two‐photon absorption cross sections in the near‐IR region for 1 are among the largest values reported for platinum complexes. Therefore, 1 is an excellent, broadband, nonlinear absorbing material that exhibits strong reverse saturable absorption in the visible spectral region and large two‐photon‐assisted excited‐state absorption in the near‐IR region.  相似文献   

9.
A new polymeric dyad of oligo‐anthracene‐block‐poly(3‐hexylthiophene) (Oligo‐ANT‐b‐P3HT) has been synthesized as a donor–donor dyad building block for organic photovoltaics. The polymer dyad and oligomer of anthracene‐9,10‐diyl (Oligo‐ANT) are prepared by Grignard Metathesis. The higher order of crystallinity and molecular chains ordering at solid phase reveal the intrinsic optical and electrical properties of polymeric dyad resulting in relatively higher light harvesting ability compared to the oligo(anthracene‐9,10‐diyl). The UV‐visible spectrum of (Oligo‐ANT‐b‐P3HT) in solution shows broad absorption with two sets of absorption from both anthracene and thiophene core units, covering a wide range of the visible spectrum. The test devices of the blends of polymeric dyad with fullerene C61 (PCBM) show improved photovoltaic performance with a power conversion efficiency of 3.26% upon subjecting to pre‐fabrication thermal treatments. With optimized morphology of the interpenetrating network and the shorter fluorescence lifetime of the annealed dyad/PCBM blends, the effective charge transfer from the donor dyad to PCBM has evidenced. Thus, these studies will allow further synthetic advances to make potential high crystalline polymeric dyads with significantly improved light harvesting capability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3032–3045  相似文献   

10.
We exploit the utilization of two‐dimensional (2D) molybdenum oxide nanoflakes as a co‐catalyst for ZnO nanorods (NRs) to enhance their photocatalytic performance. The 2D nanoflakes of orthorhombic α‐MoO3 were synthesized through a sonication‐aided exfoliation technique. The 2D MoO3 nanoflakes can be further converted to substoichiometric quasi‐metallic MoO3?x by using UV irradiation. Subsequently, 1D–2D MoO3/ZnO NR and MoO3?x/ZnO NR composite photocatalysts have been successfully synthesized. The photocatalytic performances of the novel nanosystems in the decomposition of methylene blue are studied by using UV‐ and visible‐illumination setup. The incorporated 2D nanoflakes show a positive influence on the photocatalytic activity of the ZnO. The obtained rate constant values follow the order of pristine ZnO NR<MoO3/ZnO NR<MoO3?x/ZnO NR composites. The enhancement of the photocatalytic efficiency can be ascribed to a fast charge carrier separation and transport within the heterojunctions of the MoO3/ZnO NRs. In particular, the best photocatalytic performance of the MoO3?x/ZnO NR composite can be additionally attributed to a quasi‐metallic conductivity and substoichiometry‐induced mid‐gap states, which extend the light absorption range. A tentative photocatalytic degradation mechanism was proposed. The strategy presented in this work not only demonstrates that coupling with nanoscale molybdenum oxide nanoflakes is a promising approach to significantly enhance the photocatalytic activity of ZnO but also hints at new type of composite catalyst with extended applications in energy conversion and environmental purification.  相似文献   

11.
A new conjugated polymer (PBAIIDTT) based on bay‐annulated indigo and indacenodithieno[3,2‐b]thiophene was designed, synthesized, and characterized. PBAIIDTT shows strong absorption in 400–500 and 600–800 nm, and its HOMO and LUMO energy levels are −5.45 eV and −3.65 eV, respectively. In organic field‐effect transistors, the polymer exhibits a relatively high hole mobility of 0.39 cm2 V−1 s−1. PBAIIDTT was added to poly(3‐hexylthiophene) (P3HT) and phenyl‐C61‐butyric acid methyl ester (PC61BM) based organic solar cells. Ternary blend solar cells with 10% PBAIIDTT show an increased short circuit current density due to the broadened photocurrent generated in the near‐infrared region, and a power conversion efficiency of 3.78%, which is higher than that of the P3HT:PC61BM binary control devices (3.33%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 213–220  相似文献   

12.
Photocatalytic degradation of methyl orange (MO) as a model of an organic pollution was accomplished with magnetic and porous TiO2/ZnO/Fe3O4/PANI and ZnO/Fe3O4/PANI nanocomposites under visible light irradiation. The structures of nanocomposites were characterized by various techniques including UV–Vis absorption spectroscopy, XRD, SEM, EDS, BET and TGA. Optical absorption investigations show two λmax at 450 and 590 nm for TiO2/ZnO/Fe3O4/PANI nanocomposites respectively possessing optical band gaps about 2.75 and 2.1 eV smaller than that of the neat TiO2 and ZnO nanoparticles. Due to these optical absorptions, the nanocomposites can be considered promising candidates as visible light photocatalysts to produce more electron‐hole pairs. The degradation of MO, extremely increased using polymeric photocatalysts and decolorization in the presence of visible light achieved up to 90% in less than 20 min in comparison with the neat nanoparticles (about 10%). All these advantages promise a bright future for these composites as useful photocatalysts. The degradation efficiency of MO using stable nanocomposites was still over 70% after ten times reusing. The highest decolorizing efficiencies were achieved with 0.75 g L?1 of catalyst and 10 mg L?1 of MO at natural pH under visible light irradiation in less than 20 min.  相似文献   

13.
Pure phase ZnTiO3 was prepared through a sol–gel process, then graphene-ZnTiO3 nanocomposites were synthesized by a hydrothermal method using the prepared ZnTiO3 nanoparticles and graphene oxide as precursors. X-ray diffraction results revealed the production of pure cubic ZnTiO3 at 600 °C. ZnTiO3 was anchored on the graphene nanosheets, demonstrating a spherical morphology in transmission electron microscope images. The existence of chemical bond Ti–O–C in the nanocomposites was proved by Fourier-transforming infrared spectroscopy. UV–Vis diffusive reflection spectra indicated that the absorption edge of the nanocomposites shifted towards the visible region. The photocatalytic activity of the composites was tested through the photocatalytic degradation of methyl blue under simulated solar irradiation. The results showed that the photocatalytic activity of the nanocomposites was obviously increased in contrast to pure ZnTiO3, which was strongly affected by the crystalline structure of ZnTiO3 and the concentration of graphene. The enhanced photocatalytic activity was mainly attributed to the conglomeration inhibition of ZnTiO3 nanoparticles, the electron transfer between ZnTiO3 and graphene and the extended absorption range. Furthermore, other contaminants such as tetracycline, Rhodamine B and methyl orange were tested under the same conditions to investigate the photocatalytic performance of the photocatalysts. The reusability tests indicated that the prepared composites exhibited good stability.  相似文献   

14.
Although two‐dimensional (2D) metal oxide/sulfide hybrid nanostructures have been synthesized, the facile preparation of ultrathin 2D nanosheets in high yield still remains a challenge. Herein, we report the first high‐yield preparation of solution‐processed ultrathin 2D metal oxide/sulfide hybrid nanosheets, that is, Tix Ta1−x Sy Oz (x =0.71, 0.49, and 0.30), from Tix Ta1−x S2 precursors. The nanosheet exhibits strong absorbance in the near‐infrared region, giving a large extinction coefficient of 54.1 L g−1 cm−1 at 808 nm, and a high photothermal conversion efficiency of 39.2 %. After modification with lipoic acid‐conjugated polyethylene glycol, the nanosheet is a suitable photothermal agent for treatment of cancer cells under 808 nm laser irradiation. This work provides a facile and general method for the preparation of 2D metal oxide/sulfide hybrid nanosheets.  相似文献   

15.
The coupling of metal oxide semiconductors has become an effective method to improve the separation of photon‐generated carriers and light absorption efficiency. In this study, we explored electronic and optical properties of monolayer and bilayer α‐MoO3 on TiO2 (001) surface. It is observed that α‐MoO3/TiO2 heterostructures can form a stable Mo‐O‐Ti bonding mode at the interface. Electrons transfer from TiO2 (001) surface to the α‐MoO3, leading to the enhancement of the valence band and the optical absorption spectrum in visible light region. In addition, this proper charge transfer generates a built‐in electric field between the interface regions of bilayer α‐MoO3/TiO2 heterostructure and forms a favorable type‐II band alignment between the two α‐MoO3 layers. The α‐MoO3/TiO2 heterostructure can prevent the recombination of the electron‐hole pairs; thus, excite electrons can easily move from TiO2 to the inner layer, and then to the outer layer of α‐MoO3. These results demonstrate that the bilayer α‐MoO3/TiO2 heterostructure, especially the outer layer α‐MoO3, has efficient photoelectric performance.  相似文献   

16.
Plasmonic materials have drawn emerging interest, especially in nontraditional semiconductor nanostructures with earth‐abundant elements and low resistive loss. However, the actualization of highly efficient catalysis in plasmonic semiconductor nanostructures is still a challenge, owing to the presence of surface‐capping agents in their synthetic procedures. To fulfill this, a facile non‐aqueous procedure was employed to prepare well‐defined molybdenum oxide nanosheets in the absence of surfactants. The obtained MoO3‐x nanosheets display intense absorption in a wide range attributed to the localized surface plasmon resonances, which can be tuned from the visible to the near‐infrared region. Herein, we demonstrate that such plasmonic semiconductor nanostructures could be used as highly efficient catalysts that dramatically enhance the hydrogen‐generation activity of ammonia borane under visible light irradiation.  相似文献   

17.
As a remarkable class of plasmonic materials, two dimensional (2D) semiconductor compounds have attracted attention owing to their controlled manipulation of plasmon resonances in the visible light spectrum, which outperforms conventional noble metals. However, tuning of plasmonic resonances for 2D semiconductors remains challenging. Herein, we design a novel method to obtain amorphous molybdenum oxide (MoO3) nanosheets, in which it combines the oxidation of MoS2 and subsequent supercritical CO2‐treatment, which is a crucial step for the achievement of amorphous structure of MoO3. Upon illumination, hydrogen‐doped MoO3 exhibits tuned surface plasmon resonances in the visible and near‐IR regions. Moreover, a unique behavior of the amorphous MoO3 nanosheets has been found in an optical biosensing system; there is an optimum plasmon resonance after incubation with different BSA concentrations, suggesting a tunable plasmonic device in the near future.  相似文献   

18.
The Pb‐V oxyhalide apatite compounds Pb5(VO4)3X (X=F, Cl, Br, I) were successfully synthesized using a facile solution method and studied with respect to their structural/optical characteristics and electronic band structures. UV‐visible diffuse reflectance spectroscopy, electrochemical analysis and first‐principles calculations showed that the synthesized apatites behaved as n‐type semiconductors, with absorption bands in the UV‐visible region that could be assigned to electron transitions from the valence band to a conduction band formed by hybridized V 3d and Pb 6p orbitals. Among the apatites examined, Pb5(VO4)3I had the smallest band gap of 2.7 eV, due to an obvious contribution of I 5p orbitals to the valence band maximum. Based on its visible light absorption capability, Pb5(VO4)3I generated a continuous anodic photocurrent under visible light (λ>420 nm) in a solution of 0.1 m NaI in acetonitrile.  相似文献   

19.
Two phenothiazine‐based conjugated polymers, poly(3, 7‐divinylene‐N‐octyl‐phenothiazine‐alt‐benzo‐2,1,3‐ thiadiazole) (PQS) and poly(3,7‐divinylene‐N‐octyl‐phenothiazine‐alt‐benzo‐2,1,3‐selenodiazole) (PQSe) were synthesized by Heck coupling reaction. The chemical structures of the two polymers were confirmed by 1H‐NMR and Ft‐IR. They showed good solubility in some common organic solvents such as tetrahydrofuran (THF), chloroform. The weight‐average molecular weight (Mw) of the polymers determined by GPC in THF against polystyrene standards was 3.7 × 103 for PQS and 1.9 × 103 for PQSe, respectively. The temperatures of 5% weight loss (T5) were 385.0°C for PQS and 324.0°C for PQSe, respectively, determined by TGA measurements under nitrogen ambience. UV–vis absorption spectra of the polymer films showed the absorption maxima at 537 nm for PQS and 539 nm for PQSe, with the full width at half maximum (FWHM) of 190 and 230 nm, respectively. The optical band gaps ( ) of the polymer films are 1.86 eV for PQS and 1.80 eV for PQSe, respectively. As the polymers have low‐band‐gap and broad absorption in the visible region, they may be used as potential light‐harvesting materials for photovoltaic devices (PVDs). Furthermore, photoluminescence (PL) spectra of the polymer solutions showed the emission maxima at 698 nm for PQS and 709 nm for PQSe, with FWHM of 152 nm and 167 nm, respectively, which revealed that these two polymers may be used as red and near infrared light‐emitting materials for polymeric light‐emitting diodes (PLEDs). Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

20.
《先进技术聚合物》2018,29(3):1107-1116
Carbopol‐silver nanocomposites, CP‐Ag‐NCs, were prepared by a chemical reducing method by using formaldehyde as a reducing agent (nanocomposite F), and formaldehyde in the presence of an alkaline medium resulting from the addition of Na2CO3 (nanocomposite FC), or NaOH (nanocomposite FO) to enhance the rate of reduction of the silver ions. The UV‐visible spectra showed the appearance of bands centered around 275, 286, and 274 nm for the nanocomposites F, FC, and FO, respectively, attributed to small silver nanoparticles (Ag‐NPs) with an average size less than 10 nm. Other bands centered around 405 and 470 nm for the nanocomposites F and FC, respectively, were attributed to large Ag‐NPs with an average size greater than 50 nm. The absence of large Ag‐NPs in the nanocomposites FO makes them as the materials of choice for the preparation of selective ultrasmall Ag‐NPs with an average size less than 3 nm. Furthermore, photoluminescence was observed upon blue excitation of the ultrasmall colloidal Ag‐NPs. Scanning electron microscopy images showed a good dispersion of the metallic Ag‐NPs in the polymer matrix. Moreover, X‐ray diffraction patterns showed peaks corresponding to the face‐centered‐cubic of the Ag‐NPs. The nature of the interaction between carbopol and Ag‐NPs was further studied by attenuated total reflectance‐Fourier transform infrared spectroscopy, and the mechanism of reduction of the silver ions was proposed. The antimicrobial activities of the CP‐Ag‐NCs were examined against Escherichia coli and Candida albicans microorganisms. The results demonstrate that the CP‐Ag‐NCs can provide new applications of these nanocomposites as efficient sensors and antimicrobial materials.  相似文献   

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