Project description:In this present work, we synthesized a yolk-shell shaped CuCo₂S₄ by a simple anion exchange method. The morphological and structural properties of the as-synthesized sample were characterized using X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (UV-vis DRS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The SEM and TEM results confirmed that the uniform yolk-shell structure was formed during the solvothermal process. The band gap was about 1.41 eV, which have been confirmed by UV⁻vis DRS analysis. The photocatalytic property was evaluated by the photocatalytic degradation of methylene blue (MB) dye as a target pollutant under the visible-light irradiation. The experimental results confirmed the potential application of yolk-shell shape CuCo₂S₄ in visible-light photocatalytic applications.
Project description:Metal nanoparticles are potent reaction catalysts, but they tend to aggregate, thereby limiting their catalytic efficiency. Their coordination with specific functional groups within a porous structure prevents their aggregation and facilitates the mass flow of catalytic starting materials and products. Herein, we use a thiacalix[4]arene-based polymer as a porous support with abundant docking sites for Au nanoparticles. The sulfur atoms bridging the phenolic subunits of thiacalix[4]arene serve as Lewis basic sites that coordinate Au atoms. Therefore, this approach takes advantage of the functional groups inherent in the monomer and avoids laborious postsynthetic modifications of the polymer. The presented system was tested for visible-light-driven photocatalytic CO2 reduction, where it showed adequate ability to generate 6.74 μmol g-1 CO over the course of 4 h, while producing small amounts of the CH4 product. This study aims to stimulate interest in the design and development of synthetically simpler porous polymer supports for various metal nanoparticles in catalytic and other applications.
Project description:The incorporation of Cu(OAc)2 into ascorbic acid coated TiO2 nanoparticles easily provided a new heterogeneous visible-light active titania-based photocatalyst (TiO2-AA-Cu(ii)) which was characterized by different techniques such as FT-IR, XPS, ICP-AES, TGA and TEM. A red-shift of the band-edge and a reduction of the band-gap (2.8 eV vs. 3.08 for TiO2) were demonstrated by UV-DRS and Tauc plots. The combination of the as-prepared TiO2-AA-Cu(ii) nanoparticles with TEMPO and molecular oxygen (air) afforded an active catalytic system for the selective oxidation of diverse set of benzylic alcohols under solvent-free conditions. A photoassisted pathway was confirmed for oxidation reactions evidenced by good correlation between apparent quantum yield (AQY) and diffuse reflectance spectra (DRS) of the as-prepared nanohybrid. The spectral data and recycling experiments demonstrated the structural stability of the title copper photocatalyst during oxidation reactions.
Project description:In this work, monodisperse BiFeO3 nanoparticles with a particle diameter of 5.5 nm were synthesized by a nanocasting technique using mesoporous silica SBA-15 as a hard template and pre-fabricated metal carboxylates as metal precursors. To the best of our knowledge, the synthesized particles are the smallest BiFeO3 particles ever prepared by any method. The samples were characterized by X-ray powder diffraction, transmission electron microscopy and UV-vis diffuse reflectance spectroscopy. The phase purity of the product depends on the type of carboxylic acid used in the synthesis of the metal precursors, the type of solvent in the wet impregnation process, and the calcination procedure. By using tartaric acid in the synthesis of the metal precursors, acidified 2-methoxyethanol in the wet impregnation process and a calcination procedure with intermediate plateaus, monodisperse 5.5 nm BiFeO3 nanoparticles were successfully obtained. Furthermore, the nanoparticles were applied in photodegradation reactions of rhodamine B in aqueous solution under visible-light irradiation. Notably, the cast BiFeO3 nanoparticles demonstrated very high efficiencies and stability under visible-light irradiation, much higher than those of BiFeO3 nanoparticles synthesized by other synthetic methods. The possible mechanism in the photodegradation process has been deeply discussed on the basis of radical trapping experiments.
Project description:The BiVO4 photocatalyst plays a very important role in photocatalytic reactions attributed to its unique crystalline structure, size, morphology and surface area. Herein, we report a facet-dependent monoclinic scheelite BiVO4 (m-BiVO4) photocatalyst with uniform truncated square (18 sided) hexagonal bipyramidal shape synthesized by a template-free and surfactant-free solvothermal method using ethylene glycol solvent under cost-effective and mild reactions. The structural, morphological and optical properties of the m-BiVO4 photocatalyst are widely characterized. The photocatalytic activity of the m-BiVO4 photocatalyst is tested towards 20 ppm methylene blue (MB) dye aqueous solution as a pollutant model under visible light irradiation. Enhanced visible-light driven photoactivity with dye degradation efficiency of approx. 91% at a rate of 0.388 × 10-2 min-1 is obtained, presumably due to the presence of high-active (040) facets. Zebrafish embryo toxicity test of treated MB dye solution reveals the degradation and toxicity reduction of the MB dye. Moreover, the recycling experiment validates that the m-BiVO4 photocatalyst has a great structural stability with reliable performance. This work may provide a lucid and expedient strategy to synthesize highly crystalline (040) facet-dependent semiconductor photocatalyst toward dye degradation and obviously industrial wastewater remediation.
Project description:Metal nanoparticles are synthesized via various methods and have found many applications in areas such as sensing, electronics and catalysis. Light induced formation of noble metal nanoparticles, especially platinum, in solution or loaded on semiconductor surfaces, is an established practice in photocatalysis. Nevertheless, preparation of catalytically-active non-precious metal nanoparticles via photo-reduction still have room to be further explored. Here, we report a visible light driven system that can coordinate photo-reduction of CuSO4 to selectively prepare Cu2O or Cu nanoparticles, while at the same time, mediating efficient hydrogen production with in situ generating Cu catalyst without further need to add any components. The Cu2O and Cu nanoparticles in situ generated are crystalline in nature and can perform as pre-catalyst (Cu2O) or catalyst (Cu) to catalyze hydrogen production when reincorporated into the same photo-reduction system with organic photosensitizers. Our work offers an exploratory pathway to prepare target metal nanoparticles while provides some insight into harnessing solar energy for multi-functional purposes.
Project description:The visible-light responsive Cu(I)-complex photosensitizers were developed by introducing various aromatic substituents at the 4,7-positions of a 2,9-dimethyl-1,10-phenanthroline (dmp) ligand in a heteroleptic CuI(dmp)(DPEphos)+-type complexes (DPEphos = [2-(diphenylphosphino)phenyl]ether) for photocatalytic CO2 reduction. Introducing biphenyl groups (Bp-) on the dmp ligand enhanced the molar extinction coefficient (ε) of the metal-to-ligand charge transfer (MLCT) band in the visible region (ε = 7,500 M-1cm-1) compared to that of the phenyl (Ph-)-containing analog (ε = 5,700 M-1cm-1 at λmax = 388 nm). However, introducing 4-R-Ph- groups (R = the electron-withdrawing groups NC-, or NO2-) led to a red shift in the band to λmax = 390, 400, and 401 nm, respectively. Single-crystal X-ray analysis showed the Ph- groups were twisted because of the steric repulsion between the 2,6-protons of the Ph- groups and 5,6-protons of the dmp ligand. The result strongly indicated that the π-conjugation effect of the 4-R-Ph- groups is so weak that the lowering of the energy of the dmp π* orbitals is small. However, when 4-R-ph- was substituted by a 5-membered heterorings, there was a larger red shift, leading to an increase in the ε value of the MLCT absorption band. Thus, the substitution to 2-benzofuranyl- groups resulted in visible-light absorption up to 500 nm and a shoulder peak at around 420 nm (ε = 12,300 M-1cm-1) due to the expansion of π-conjugation over the substituted dmp ligand. The photocatalytic reaction for CO2 reduction was tested using the obtained CuI complexes as photosensitizers in the presence of a Fe(dmp)2(NCS)2 catalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as a sacrificial reductant, which showed improved CO generation.
Project description:ZnIn2S4 (ZIS) is widely used in the field of photocatalytic hydrogen production due to its unique photoelectric properties. Nonetheless, the photocatalytic performance of ZIS usually faces problems of poor conductivity and rapid recombination of charge carriers. Heteroatom doping is often regarded as one of the effective strategies for improving the catalytic activity of photocatalysts. Herein, phosphorus (P)-doped ZIS was prepared by hydrothermal method, whose photocatalytic hydrogen production performance and energy band structure were fully studied. The band gap of P-doped ZIS is about 2.51 eV, which is slightly smaller than that of pure ZIS. Moreover, due to the upward shift of its energy band, the reduction ability of P-doped ZIS is enhanced, and P-doped ZIS also exhibits stronger catalytic activity than pure ZIS. The optimized P-doped ZIS exhibits a hydrogen production rate of 1566.6 μmol g-1 h-1, which is 3.8 times that of the pristine ZIS (411.1 μmol g-1 h-1). This work provides a broad platform for the design and synthesis of phosphorus-doped sulfide-based photocatalysts for hydrogen evolution.
Project description:N-aryl imidazoles play an important role as structural and functional units in many natural products and biologically active compounds. Herein, we report a photocatalytic route for the C-N cross-coupling reactions over a Cu/graphene catalyst, which can effectively catalyze N-arylation of imidazole and phenylboronic acid, and achieve a turnover frequency of 25.4 h(-1) at 25°C and the irradiation of visible light. The enhanced catalytic activity of the Cu/graphene under the light irradiation results from the localized surface plasmon resonance of copper nanoparticles. The Cu/graphene photocatalyst has a general applicability for photocatalytic C-N, C-O and C-S cross-coupling of arylboronic acids with imidazoles, phenols and thiophenols. This study provides a green photocatalytic route for the production of N-aryl imidazoles.
Project description:Novel green bismuth oxybromide (BiOBr-G) nanoflowers were successfully synthesized via facile hydrolysis route using an Azadirachta indica (Neem plant) leaf extract and concurrently, without the leaf extract (BiOBr-C). The Azadirachta indica leaf extract was employed as a sensitizer and stabilizer for BiOBr-G, which significantly expanded the optical window and boosted the formation of photogenerated charge carriers and transfer over the BiOBr-G surface. The photocatalytic performance of both samples was investigated for the degradation of methyl orange (MO) and phenol (Ph) under the irradiation of visible light. The leaf extract mediated BiOBr-G photocatalyst displayed significantly higher photocatalytic activity when compared to BiOBr-C for the degradation of both pollutants. The degradation rate of MO and Ph by BiOBr-G was found to be nearly 23% and 16% more when compared to BiOBr-C under visible light irradiation, respectively. The substantial increase in the photocatalytic performance of BiOBr-G was ascribed to the multiple synergistic effects between the efficient solar energy harvesting, narrower band gap, high specific surface area, porosity, and effective charge separation. Furthermore, BiOBr-G displayed high stability for five cycles of photocatalytic activity, which endows its practical application as a green photocatalyst in the long run.