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1.
V5+‐doped Ag/AgCl photocatalysts were prepared via the ion exchange method. The catalysts were characterized using X‐ray diffractometry, transmission electron microscopy, and energy‐dispersive X‐ray, X‐ray photoelectron, Fourier transform infrared and ultraviolet–visible spectroscopies. The V5+‐doped Ag/AgCl photocatalysts show much higher photocatalytic activities than Ag/AgCl under visible light irradiation for methyl orange (MO) decomposition. Especially, the 2.0 wt% V5+‐doped Ag/AgCl photocatalyst shows the highest photocatalytic activity and also high stability after five cycles. The MO degradation rate during each cycle is almost maintained at 97%. Electron spin resonance spectroscopy and radical trapping experiments reveal that holes play an important role in the photocatalytic process.  相似文献   

2.
Although TiO2 is an efficient photocatalyst, its large band gap limits its photocatalytic activity only to the ultraviolet region. An experimentally synthesized ternary Fe/C/S‐doped TiO2 anatase showed improved visible light photocatalytic activity. However, a theoretical study of the underlying mechanism of the enhanced photocatalytic activity and the interaction of ternary Fe/C/S‐doped TiO2 has not yet been investigated. In this study, the defect formation energy, electronic structure and optical property of TiO2 doped with Fe, C, and S are investigated in detail using the density functional theory + U method. The calculated band gap (3.21 eV) of TiO2 anatase agree well with the experimental band gap (3.20 eV). The defect formation energy shows that the co‐ and ternary‐doped systems are thermodynamically favorable under oxygen‐rich condition. Compared to the undoped TiO2, the absorption edge of the mono‐, co‐, and ternary‐doped TiO2 is significantly enhanced in the visible light region. We have shown that ternary doping with C, S, and Fe induces a clean band structure without any impurity states. Moreover, the ternary Fe/C/S‐doped TiO2 exhibit an enhanced photocatalytic activity, a smaller band gap and negative formation energy compared to the mono‐ and co‐doped systems. Moreover, the band edges of Fe/C/S‐doped TiO2 align well with the redox potentials of water, which shows that the ternary Fe/C/S‐doped TiO2 is promising photocatalysts to split water into hydrogen and oxygen. These findings rationalize the available experimental results and can assist the design of TiO2‐based photocatalyst materials.  相似文献   

3.
Exploring noble‐metal‐free, highly active and durable catalysts is vital to get to grips with the energy and environmental issues. Herein, we first dexterously design and synthesize a class of ternary Nb6/CZS/g‐CN photocatalysts for the removal of hexavalent chromium Cr (VI) and organic dye pollutant (MO) from wastewater under visible‐light irradiation. A heterojunction Nb6–1/CZS/g‐CN loaded with 0.01 g K7HNb6O19 showed excellent photocatalytic performance, with the MO photodegradation efficiency of 94% in 1 h and the Cr (VI) (150 mg/l) photoreduction efficiency as high as 91% in 2 hr. The main active species were deemed to be O2.‐. Additionally, the as‐prepared ternary heterojunction exhibits superior hydrogen evolution reaction (HER) rate. A heterojunction Nb6–4/CZS/g‐CN loaded with 0.5 g K7HNb6O19 exhibited the highest H2 evolution rate as high as 1777.86 μmol h?1 g?1 under visible‐light illumination, which is increased to 5.7 and 2.7 times that of bare CZS and biphase heterojunction CZS/g‐CN. These findings afford a new class of promising low‐cost photocatalyst bodying for its huge potential value in sustainable energy development and wastewater treatment.  相似文献   

4.
Nanoscale anatase TiO2 single crystals were successfully synthesized using three kinds of activated carbon (AC) templates through a simple sol–gel method. The optimal photocatalyst (T‐WOAC) was obtained using wood‐based AC template. X‐ray diffraction, transmission electron microscopy and Brunauer–Emmett–Teller analyses revealed that T‐WOAC possessed a small crystallite size of 8.7 nm and a clear mesoporous structure. The photocatalytic properties of samples were then evaluated through photodegradation of crystal violet (CV). Results implied that the photocatalysts prepared using the AC templates exhibited superior photocatalytic activity to that of the original TiO2. This enhancement may be due to the small crystallite size, large specific surface area and pore volume of the catalysts prepared with ACs. T‐WOAC showed high photocatalytic activity, CV degradation of 99.01% after 120 min of irradiation and k = 0.03914 min?1, which is 3.9 times higher than that of the original TiO2 (k = 0.00994 min?1). This result can be mainly attributed to the application of WOAC with moderate specific surface area and pore volume to produce T‐WOAC. Alkaline conditions benefitted the photodegradation of CV over photocatalysts. This work proposes a possible degradation mechanism of CV and indicates that the fabricated photocatalysts can be used to effectively remove CV from aqueous solutions.  相似文献   

5.
《Comptes Rendus Chimie》2014,17(7-8):818-823
A series of W-modified TiO2 (W–TiO2) photocatalysts were synthesized by a simple sol–gel method. The new photocatalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis-diffuse reflectance spectroscopy (DRS), and Brunauer, Emmett and Teller (BET) surface area analyzer. The photoactivity of the W–TiO2 photocatalysts was evaluated by the photocatalytic oxidation of Congo red (CR) dye. It was found that the average size of the prepared photocatalysts is 10 nm. Moreover, they have high surface areas (∼ 216 m2 g−1) and their light-absorption extends to the visible region compared to pure TiO2. The effects of W-loading and of the calcination temperature of the prepared photocatalysts on their photocatalytic activity were also studied. The obtained results show that the W0.5–TiO2 photocatalyst calcined at 350 °C is much highly photoactive than non-doped or highly doped TiO2. The enhanced photocatalytic activity of the weakly doped TiO2 may be attributed to the increase in the charge separation efficiency and the presence of surface acidity on the W0.5–TiO2 photocatalyst.  相似文献   

6.
Fabrication of an efficient, stable, and versatile photocatalysts for the energy and environment remediation applications is an urgent task for the current researchers. In this work, we have successfully synthesized a versatile hybrid photocatalysts, i.e.; CdMoO4/g-C3N4 (CMO/CN) by a facile and simple one-pot in-situ hydrothermal method. Here CdMoO4 (CMO) microspheres were deposited on the g-C3N4 (CN) sheets. Fabricated CN, CMO, and CMO/CN composite photocatalysts were analyzed with various characterization techniques like UV–visible diffuse reflectance spectra (UV–Vis DRS), photoluminescence spectroscopy (PL), time-resolved fluorescence lifetime (TRFL), electrochemical impedance spectroscopy (EIS), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy–energy-dispersive X-ray analysis (SEM-EDX), transmission electron microscope (TEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller (BET). The results reveal that the formation of a strong heterojunction between two semiconductors leads to the formation of active photocatalyst. Furthermore, as-synthesized materials were tested for the photoelectrocatalytic (PEC) oxygen evolution reactions (OERs) in acidic medium, and photocatalytic (PC) degradation of methylene blue (MB) under light irradiation. Among all tested samples, CMO/CN-10 has shown the highest current density 52.74 mA cm?2 at 1.95 V with lowest over potential of 0.70 mV on glassy carbon electrode for OER in acidic medium under the light irradiation. The PC degradation rate constant of CMO/CN-10 composite in MB solution is k = 2.0 × 10?2 min?1, whereas for the pure CMO and CN degradation rate constant is k = 5.7 × 10?3 min?1 and k = 1.2 × 10?2 min?1, respectively. This enhancement in PEC and PC properties is due to the fast migration of photo-induced electrons in the case of CMO/CN-10 nanocomposite. Trapping experiment results reveal the major reactive species for PC degradation of MB is ?OH (hydroxyl radicals) and h+ (holes), respectively, and suitable PC reaction mechanism also proposed for CMO/CN-10 composites. Based on the above remarkable results, it would be a potential nanocomposite for the PEC oxygen evolution and PC degradation of MB under light illumination.  相似文献   

7.
The reduced graphene oxide‐Bi2WO6 (rGO‐BWO) photocatalysts with the different RF/O values (molar ratio of the F molar mass and the O's molar mass of Bi2WO6) had been successfully synthesized via one‐step hydrothermal method. The F‐doped rGO‐BWO samples were characterized by X‐ray diffraction patterns (XRD), field‐emission scanning electron microscopy (FE‐ESEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area (BET), X‐ray photoelectron spectroscopy (XPS) and UV–vis diffuse reflectance spectra (DRS). The results indicate that F? ions had been successfully doped into rGO‐BWO samples. With the increasing of the RF/O values from 0 to 2%, the evident change of the morphology and the absorption edges of F‐doped rGO‐BWO samples and the photocatalytic activities had been enhanced. Moreover, the photocatalytic activity of F‐doped rGO‐BWO with RF/O = 0.05 were better than rGO‐BWO and the other F‐doped rGO‐BWO under 500 W Xe lamp light irradiation. The enhanced photocatalytic activity can be attributed to the morphology of the intact microsphere that signify the bigger specific surface area for providing more possible reaction sites for the adsorption–desorption equilibrium of photocatalytic reaction, the introduction of F? ions that may cause the enhancement of surface acidity and creation of oxygen vacancies under visible light irradiation, the narrower band gap which means needing less energy for the electron hole pair transition.  相似文献   

8.
Photocatalytic hydrogenation of biomass‐derived organic molecules transforms solar energy into high‐energy‐density chemical bonds. Reported herein is the preparation of a thiophene‐containing covalent triazine polymer as a photocatalyst, with unique donor‐acceptor units, for the metal‐free photocatalytic hydrogenation of unsaturated organic molecules. Under visible‐light illumination, the polymeric photocatalyst enables the transformation of maleic acid into succinic acid with a production rate of about 2 mmol g?1 h?1, and furfural into furfuryl alcohol with a production rate of about 0.5 mmol g?1 h?1. Great catalyst stability and recyclability are also measured. Given the structural diversity of polymeric photocatalysts and their readily tunable optical and electronic properties, metal‐free photocatalytic hydrogenation represents a highly promising approach for solar energy conversion.  相似文献   

9.
Polyazine‐bridged RuIIRhIIIRuII complexes with two halide ligands, Cl? or Br?, bound to the catalytically active Rh center are efficient single‐component photocatalysts for H2O reduction to H2 fuel, with the coordination environment on Rh impacting photocatalysis. Herein reported is a new, halide‐free RuIIRhIIIRuII photocatalyst with OH? ligands bound to Rh, further enhancing the photocatalytic reactivity of the structural motif. H2 production experiments using the photocatalyst bearing OH? ligands at Rh relative to the analogues bearing halides at Rh in solvents of varying polarity (DMF, CH3CN, and H2O) suggest that ion pairing with halides deactivates photocatalyst function, representing an exciting phenomenon to exploit in the development of catalysts for solar H2 production schemes.  相似文献   

10.
Graphitic carbon nitride (g‐C3N4)‐based photocatalysts have received considerable attention in the field of photocatalysis, especially for photocatalytic H2 evolution. However, the intrinsic disadvantages of g‐C3N4 seriously limit its practical application. Herein, CdS nanospheres with an average diameter of 135 nm prepared using a solvothermal method were used as co‐catalysts to form CdS/g‐C3N4 composites (CSCN) to enhance the photocatalytic activity. Various techniques were employed to characterize the structure, composition and optical properties of the as‐prepared samples. It was found that the CdS nanospheres were relatively uniformly dispersed on the surface of g‐C3N4. Moreover, the photocatalytic H2 generation activity of the samples was evaluated using lactic acid as sacrificial reagent in water under visible light irradiation. When the amount of CdS nanospheres loaded in the hybridized composites was 5 wt%, the optimal H2 evolution rate reached 924 μmol g?1 h?1, which was approximately 1.4 times higher than that (680 μmol g?1 h?1) of Pt/g‐C3N4 (3 wt%). Based on the results of analysis, a possible mechanism for the photocatalytic activity of CSCN is proposed tentatively.  相似文献   

11.
The mesoporous titanium dioxide (MTiO2) photocatalysts co‐doped with Fe and H3PW12O40 were synthesized by template method using tetrabutyl titanate (Ti(OC4H9)4), Fe(NO3)k39H2Oand H3PW12O40 as precursors and Pluronic P123 as template. The as‐prepared photocatalyst was characterized by N2 adsorption‐desorption measurements, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and UV‐vis adsorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl blue (MB) (50 mg/L) in an aqueous solution. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m2/g. The results of MB photodecomposition showed that co‐doped mesoporous TiO2 exhibited higher photocatalytic activities than un‐doped, single‐doped mesoporous TiO2 under UV and visible light irradiation. It was shown that the co‐doped MTiO2 could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The synergistic effect of Fe and H3PW12O40 co‐doping played an important role in improving the photocatalytic activity.  相似文献   

12.
Sulfur doped ZnO/TiO2 nanocomposite photocatalysts were synthesized by a facile sol‐gel method. The structure and properties of catalysts were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV‐vis diffusive reflectance spectroscopy (DRS) and N2 desorption‐adsorption isotherm. The XRD study showed that TiO2 was anatase phase and there was no obvious difference in crystal composition of various S‐ZnO/TiO2. The XPS study showed that the Zn element exists as ZnO and S atoms form SO2?4. The prepared samples had mesoporosity revealed by N2 desorption‐adsorption isotherm result. The degradation of Rhodamine B dye under visible light irradiation was chosen as probe reaction to evaluate the photocatalytic activity of the ZnO/TiO2 nanocomposite. The commercial TiO2 photocatalyst (Degussa P25) was taken as standard photocatalyst to contrast the prepared different photocatalyst in current work. The improvement of the photocatalytic activity of S‐ZnO/TiO2 composite photocatalyst can be attributed to the suitable energetic positions between ZnO and TiO2, the acidity site caused by sulfur doping and the enlargement of the specific area. S‐3.0ZnO/TiO2 exhibited the highest photocatalytic activity under visible light irradiation after Zn amount was optimized, which was 2.6 times higher than P25.  相似文献   

13.
Novel F‐doped Ag/AgBr photocatalysts containing various amounts of F? were synthesized by an ion exchange method. The photocatalysts were characterized using X‐ray diffraction (XRD), scanning and transmission electron microscopies, X‐ray photoelectron, ultraviolet–visible absorption and photoluminescence spectroscopies and electron spin resonance (ESR). Powder XRD revealed that F? was inserted into the crystal lattices of AgBr and partially replaced Br?, resulting in the contraction of the AgBr lattices. Methyl orange photodegradation experiments showed that the photocatalytic activity of F‐doped Ag/AgBr was significantly dependent on the amount of F?. Ag/AgBr doped with 0.02 M F? achieved the highest activity of 91% after 8 min. ESR showed the main active species in methyl orange degradation was ?OH. The main enhancement mechanism is that F? inhibits the recombination of electron–hole pairs.  相似文献   

14.
In this study, we have introduced iodine into Bi4Ti3O12 (BTO) crystals with the aim of improving their photocatalytic activities in decomposing organic pollutants. The as-prepared Idoped-BTO photocatalysts were systematically analyzed by various techniques (e.g. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy and Fourier transform infrared spectroscopy), as well as density functional theory calculation. It is confirmed that I element is successfully doped, as an I? oxidation state, in the BTO crystals by substituting the O in the perovskite-like (Bi2Ti3O10)2? blocks. The photocatalytic activities between the Ix-BTO (x = 0, 0.2, 0.4, 0.6, and 0.8) samples were compared by the photodegradation of methylene blue (MB) under simulated-sunlight irradiation, revealing that I0.4-BTO is the optimal photocatalyst having a photocatalytic activity about 3.0 times higher than that of parent BTO. Based on the experimental data and density functional theory calculation, the enhanced photocatalytic mechanism for the Idoped-BTO photocatalysts was proposed and discussed. To promote the potential application of the optimal I0.4-BTO photocatalyst, its photocatalytic performances were further investigated by the photodegradation of ciprofloxacin, tetrabromobisphenol A, tetracycline hydrochloride and methyl orange/rhodamine B (RhB)/MB mixture dyes; moreover, the effect of inorganic anions and pH values on the MB photodegradation was also investigated.  相似文献   

15.
Photocatalytic water splitting for hydrogen production using sustainable sunlight is a promising alternative to industrial hydrogen production. However, the scarcity of highly active, recyclable, inexpensive photocatalysts impedes the development of photocatalytic hydrogen evolution reaction (HER) schemes. Herein, a metal–organic framework (MOF)‐template strategy was developed to prepare non‐noble metal co‐catalyst/solid solution heterojunction NiS/ZnxCd1?xS with superior photocatalytic HER activity. By adjusting the doping metal concentration in MOFs, the chemical compositions and band gaps of the heterojunctions can be fine‐tuned, and the light absorption capacity and photocatalytic activity were further optimized. NiS/Zn0.5Cd0.5S exhibits an optimal HER rate of 16.78 mmol g?1 h?1 and high stability and recyclability under visible‐light irradiation (λ>420 nm). Detailed characterizations and in‐depth DFT calculations reveal the relationship between the heterojunction and photocatalytic activity and confirm the importance of NiS in accelerating the water dissociation kinetics, which is a crucial factor for photocatalytic HER.  相似文献   

16.
《中国化学》2018,36(6):538-544
Bi‐ and Y‐codoped TiO2 photocatalysts were synthesized through a sol‐gel method, and they were applied in the photocatalytic reduction of CO2 to formic acid under visible light irradiation. The results revealed that, after doping Bi and Y, the surface area of TiO2 was increased from 5.4 to 93.1 m2/g when the mole fractions of doping Bi and Y were 1.0% and 0.5%, respectively, and the lattice structures of the photocatalysts changed and the oxygen vacancies on the surface of the photocatalysts formed, which would act as the electron capture centers and slow down the recombination of photo‐induced electron and hole. The photocurrent spectra also proved that the photocatalysts had better electronic transmission capacities. The HCOOH yield in CO2 photocatalytic reduction was 747.82 μmol/gcat by using 1% Bi‐0.5% Y‐TiO2 as a photocatalyst. The HCOOH yield was 1.17 times higher than that by using 1% Bi‐TiO2, and 2.23 times higher than that by using pure TiO2. Furthermore, the 1% Bi‐0.5% Y‐TiO2 showed the highest apparent quantum efficiency (AQE) of 4.45%.  相似文献   

17.
Photodeposition has been widely used as a mild and efficient synthetic method to deposit co‐catalysts. It is also worth studying how to synthesize non‐noble metal photocatalysts with uniform dispersion. Different synthetic conditions in photodeposition have a certain influence on particle size distribution and photocatalytic activity. Therefore, we designed experiments to prepare the inexpensive composite photocatalyst Ni(OH)2/g‐C3N4 by photodeposition. The Ni(OH)2 co‐catalysts disperse uniformly with particle sizes of about 10 nm. The photocatalytic hydrogen production rate of Ni(OH)2/g‐C3N4 reached about 19 mmol g?1 h?1, with the Ni(OH)2 deposition amount about 1.57 %. During 16 h stability testing, the rate of hydrogen production did not decrease significantly. The composite catalyst also revealed a good hydrogen production performance under sunlight. The Ni(OH)2 co‐catalyst enhanced the separation ability of photogenerated carriers, which was proved by surface photovoltage and fluorescence analysis.  相似文献   

18.
We optimized photocatalytic hydrogen production over TiO2-based photocatalyst by varying the dopant (nickel and copper oxide), thin film active area, nature and concentration of sacrificial agents, and light intensity in a photoelectrochemical (PEC) cell/dye-sensitized solar cell (DSSC). Various characterization techniques have been used to investigate the structural, morphological, optical, and PEC behavior of single and codoped TiO2. The TiO2 decorated with both Cu and Ni oxides with active area of 1 cm2 in a mixture of 5 vol % glycerol and 1 M KOH under light intensity of 100 mWcm?2 produced the maximum hydrogen of 338.4 μmol cm?2 for 2 h. The superior photocatalyst performance of this photocatalyst is attributed to its small crystallite size and large pore size, as confirmed by X-ray diffractometer, Transmission electron microscopy (TEM), and surface area of Brunauer-Emmet-Teller (SBET). The absorption edges of this photocatalyst had the highest red shift compared with single doped and pure TiO2 because of more indirect transitions of the photoexcited electrons, greater charge carrier separation, and lower recombination rate. The photoanode active area of 1 cm2 with better photocatalytic performance correlated with the number of defects and grain boundaries. Glycerol shifted the conduction band of the photocatalyst to more negative flat potential compared with others. Increasing the concentration of glycerol further than 5 vol% saturated the photocatalyst active sites, increased photooxidation intermediates of glycerol, and reduced the hydrogen production. The light intensity had the maximum impact on the hydrogen production and could strongly control the number of charge carriers in both the PEC cell and the DSSC.  相似文献   

19.
《中国化学快报》2022,33(8):3705-3708
A kind of CdS/Cd-BiOCl immobilized films photocatalyst was prepared. The optical and physicochemical properties of the CdS/Cd-BiOCl photocatalysts were analysed, and the detailed characterization revealed CdS/Cd-BiOCl films photocatalyst with good charge carrier separation effect. The reusabilities and photocatalytic properties of the samples were studied. The 15%CdS/Cd-BiOCl photocatalyst exhibited superior performance in photocatalytic degradation of tetracycline (TC) and favorable stability under visible light irradiation. As for the photodegradation rate of TC, 15%CdS/Cd-BiOCl exhibited an excellent photodegradation activity, which is 4.06 and 9.53 times higher than that of CdS/Cd and BiOCl, respectively. The results showed that dominant active species are ?O2? and ?OH radicals during photodegradation. The charge transfer in Z-scheme CdS/Cd-BiOCl films photocatalyst could synchronously generate conduct band (CB) electrons in BiOCl and valence band (VB) holes in CdS, and metal Cd served as electron mediator. This work can be a reference for the design of film photocatalysts and new insight for photodegradating towards contaminants.  相似文献   

20.
As a metal‐free nitrogen reduction reaction (NRR) photocatalyst, g‐C3N4 is available from a scalable synthesis at low cost. Importantly, it can be readily functionalized to enhance photocatalytic activities. However, the use of g‐C3N4‐based photocatalysts for the NRR has been questioned because of the elusive mechanism and the involvement of N defects. This work reports the synthesis of a g‐C3N4 photocatalyst modified with cyano groups and intercalated K+ (mCNN), possessing extended visible‐light harvesting capacity and superior photocatalytic NRR activity (NH3 yield: 3.42 mmol g?1 h?1). Experimental and theoretical studies suggest that the ‐C≡N in mCNN can be regenerated through a pathway analogous to Mars van Krevelen process with the aid of the intercalated K+. The results confirm that the regeneration of the cyano group not only enhances photocatalytic activity and sustains the catalytic cycle, but also stabilizes the photocatalyst.  相似文献   

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