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1.
Pt、N共掺杂TiO2在可见光下对三氯乙酸的催化降解作用   总被引:19,自引:0,他引:19  
采用溶胶-凝胶法制备了氮掺杂纳米TiO2(N-TiO2), 并用光分解沉积法在N-TiO2表面负载微量金属Pt(0.5%(w)), 形成铂-氮共掺杂纳米TiO2(Pt/N-TiO2). 实验结果表明, Pt 、N共掺杂纳米TiO2紫外可见光吸收边带较纳米TiO2红移约20 nm, 并在400~500 nm处有弱的吸收. Pt/N-TiO2电极在可见光区的光电流约为纳米TiO2电极的6倍. 以Pt/N-TiO2为催化剂, 催化三氯乙酸(TCA)光降解反应, 室温下经可见光照射2 h后TCA降解率约为8%. N掺杂减小了TiO2的禁带能隙, 使它在可见光区具有光催化活性, 适量Pt掺杂抑制了光生载流子的复合, 加速了电子界面传递速度, Pt、N共掺杂使两种效应相结合, 进一步提高了光催化反应性能.  相似文献   

2.
In order to make clear the roles of dissolved O2 in the photocatalytic decomposition of organic pollutants and to discriminate different degradation pathways (N-deethylation, chromophore cleavage, and mineralization) during the degradation of dye, the photodegradation of rhodamine B (RhB) has been investigated using vanadate and/or platinum species as electron acceptors in the presence or absence of O2 under visible light irradiation. It was found that with VO2+ as electron acceptor, RhB underwent efficient N-deethylation under visible light irradiation and O2 was found to slow down this process significantly. Little mineralization has been observed in the presence and absence of O2 in VO2+ systems. By contrast, Pt(IV) resulted in the cleavage of conjugated chromophore structure (bleaching) of RhB dye under the otherwise identical conditions. In this case, the presence of O2 did not affect the bleaching rate of the dye, but enhanced greatly the mineralization. Both cleavage of conjugated chromophore structure and N-deethylation occurred simultaneously upon the coaction of VO2+ and Pt(IV) under visible light irradiation. The mineralization yield of the combined system was evidently higher than the expected summation of separate ones. TOC, XPS, and ESR results indicate that in the VO2+ and Pt(IV) combined system VO2+ not only oxidized RhB leading to deethylation but also oxidized the reduced Pt(II) to regenerate Pt(IV) leading to the further cleavage of chromophore structure of RhB, which behaved quite different from the separate ones. A mechanism was also proposed to interpret the different pathways for the oxidative photodecomposition of RhB under visible irradiation.  相似文献   

3.
Visible light active platinum-ion-doped TiO2 photocatalyst   总被引:6,自引:0,他引:6  
Platinum-ion-doped TiO2 (Pt(ion)-TiO2) was synthesized by a sol-gel method, and its visible light photocatalytic activities were successfully demonstrated for the oxidative and reductive degradation of chlorinated organic compounds. Pt(ion)-TiO2 exhibited a yellow-brown color, and its band gap was lower than that of undoped TiO2 by about 0.2 eV. The flat band potential of Pt(ion)-TiO2 was positively shifted by 50 mV compared with that of undoped TiO2. X-ray absorption spectroscopy and X-ray photoelectron spectroscopy analyses showed that the Pt ions substituted in the TiO2 lattice were present mainly in the Pt(IV) state with some Pt(II) on the sample surface. Pt(ion)-TiO2 exhibited higher photocatalytic activities than undoped TiO2 under UV irradiation as well. The visible light activity of Pt(ion)-TiO2 was strongly affected by the calcination temperature and the concentration of Pt ion dopant, which were optimal at 673 K and 0.5 atom %, respectively. Under visible irradiation, Pt(ion)-TiO2 degraded dichloroacetate and 4-chlorophenol through an oxidative path and trichloroacetate via a reductive path. The activity of Pt(ion)-TiO2 was not reduced when used repeatedly under visible light. However, visible-light-illuminated Pt(ion)-TiO2 could not degrade substrates such as tetramethylammonium and trichloroethylene, which are degraded with UV-illuminated TiO2. The characteristics and reactivities of Pt(ion)-TiO2 as a new visible light photocatalyst were investigated in various ways and discussed in detail.  相似文献   

4.
Cu2+/TiO2对甲基橙的光催化降解机理   总被引:11,自引:1,他引:10  
以自制的掺铜离子的混晶型二氧化钛为光催化剂,考察了甲基橙光催化降解过程中pH值和光源的影响,提出了两种不同的光催化降解机理:在高压汞灯照射下,TiO2的价带电子被激发到导带,光生电子和空穴主要通过Cu2+ 的短路循环而复合,光催化剂的活性降低;在太阳光照射下,甲基橙发生自身光敏化氧化反应,受激电子从单线态或三线态的甲基橙分子跃迁到TiO2的导带,Cu2+起到电荷传递中继站的作用,加速了注入电子向H2O2的转移,从而促进了甲基橙的光催化降解。  相似文献   

5.
A new dye sensitization system incorporating Pt(dcbpy)Cl2 on Degussa P-25 TiO2 for the photomineralization of aqueous organic pollutants under visible light irradiation is described. The representative wastewater pollutant, 4-chlorophenol (4-CP), is readily oxidized (ultimately to CO2) when the PtII dye sensitized TiO2 is exposed to visible light in the presence of dissolved O2, and the reaction is accelerated when the solution is purged with O2 gas at 1 atm. The sensitizer is regenerated during the photocatalysis; therefore, 4-CP effectively reduces the oxidized form of the surface bound dye. The experimental data are consistent with parallel oxidative decomposition pathways for 4-CP, one which operates using conduction band electrons to produce hydroxyl radicals and another where the oxidized sensitizer irreversibly oxidizes 4-CP.  相似文献   

6.
Cerium-doped Titanium dioxide (TiO(2)) nanoparticles are prepared by sol-gel method. Doping shifts the UV absorption edge of TiO(2) to the visible region, making it efficient for visible light photocatalysis. Incorporation of cerium decreases the effective band gap of TiO(2) and increases the Urbach energy levels. At the dopant concentrations of 0.015 and 0.025 mol the luminescence intensity increases compared to undoped TiO(2); however, the luminescence is quenched at 0.035 mol. Quenching of luminescence indicates efficient separation of charge carriers. Undoped TiO(2) is showing poor performance in the photocatalytic degradation of methyl orange under visible light. However, on cerium doping its photoactivity is increased, and is drastically enhanced at 0.035 mol of cerium. Further increase in Ce(3+) doping level to 0.045 mol results in the reduction of the photodegradation of the dye. On UV irradiation, entire samples show good photocatalytic activity up to 30 min, but their efficiency decreases when irradiation time is increased to 45 min. Irradiation for longer time results in negative charging of the TiO(2) surface with migrating electrons. The negatively charged surface repels the OH(-) ion and O(2) molecule from adsorbing on its surface thus decreasing the availability of hydroxyl and superoxide radical for dye degradation.  相似文献   

7.
Surface-fluorinated TiO2 (F-TiO2) particles were prepared via the HF etching method. The surface characteristics of fluorinated TiO2, the adsorption modes of dyes, and the reaction pathways for the photocatalytic degradation of dye pollutants under visible light irradiation were investigated. It was found that, in the treatment of TiO2 by HF etching, F(-) not only displaces surface HO(-) but also substitutes some surface lattice oxygen. Using zwitterionic Rhodamine B (RhB) dye as a model, the change of the adsorption mode of RhB on F-TiO2 relative to that on pure TiO2 was validated by adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and IR techniques for the first time. RhB preferentially anchors on pure TiO2 through the carboxylic (-COOH) group, while its adsorption group is switched to the cationic moiety (-NEt 2 group) on F-TiO2. Both the photocatalytic degradation kinetics and mechanisms were drastically changed after surface fluorination. Dyes with positively charged nitrogen-alkyl groups such as methylene blue (MB), malachite green (MG), Rhodamine 6G (Rh6G), and RhB all underwent a rapid N-dealkylation process on F-TiO2, while on pure TiO2 direct cleavage of dye chromophore ring structures predominated. The relationship between surface fluorination and the degradation rate/pathway of dyes under visible irradiation was also discussed in terms of the effect of fluorination on the surface adsorption of dyes and on the energy band structure of TiO2.  相似文献   

8.
SiO2负载的TiO2光催化剂可见光催化降解染料污染物   总被引:19,自引:0,他引:19  
王侃  陈英旭  叶芬霞 《催化学报》2004,25(12):931-936
 采用酸催化溶胶-凝胶法制备了SiO2负载的TiO2光催化剂,考察了制备条件对负载型TiO2光催化剂的晶相、结构、比表面积和可见光催化活性的影响. 结果表明,采用SiO2为载体时,TiO2以纳米颗粒的形态分散在载体表面,负载型TiO2/SiO2催化剂的比表面积大、等电点低而且热稳定性能良好. 偶氮染料酸性橙7的可见光催化降解实验结果表明,染料污染物在催化剂表面的吸附是影响催化剂可见光催化活性的重要因素. 与试剂TiO2样品相比,负载型TiO2/SiO2光催化剂具有更好的光催化活性和沉降性能.  相似文献   

9.
In this work, a ternary composite, Pt/TiO(2)/RGO (reduced graphite oxide), was prepared via immobilizing Pt particles onto the TiO(2)/RGO composite that was obtained via redox reaction of TiCl(3) and GO. The composite was characterized by different techniques including X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The TiO(2) particles with size less than 10 nm were uniformly distributed throughout the RGO, and almost each Pt particle with size around 3 nm adhered to TiO(2) particles, resulting in high dispersion of all Pt particles on the support. The Pt particles were in the electron-deficient state due to the strong interactions with the TiO(2) particles and the RGO support. The catalytic performance of the composite for nitrobenzene hydrogenation was investigated under solvent-free condition. It was indicated that the Pt/TiO(2)/RGO catalyst exhibited high activity with a turnover frequency (e.g., 59,000 h(-1)) as well as superior selectivity to aniline (e.g., >99%). Moreover, the catalyst can be reused for six times without any activity loss, which resulted from the stable structure of the catalyst.  相似文献   

10.
UV-light irradiation to TiO(2) in an aqueous ethanol solution of (NH(4))(2)MoS(4) under deaerated conditions has yielded molybdenum(IV) sulfide nanoparticles on a TiO(2) surface (MoS(2)/TiO(2)) to be transformed into molybdenum(VI) oxide species highly dispersed at a molecular level by a subsequent heating at 773K in air (m-MoO(3)/TiO(2)). In HCOOH aqueous solutions, the MoS(2)/TiO(2) system exhibits a high level of photocatalytic activity for H(2) generation, while the m-MoO(3)/TiO(2) system shows unique photochromism.  相似文献   

11.
A novel method is reported for generation of the difficult-to-obtain (imine)Pt(II) compounds that involves reduction of the corresponding readily available Pt(IV)-based imines by carbonyl-stabilized phosphorus ylides, Ph3P=CHCO2R, in nonaqueous media. The reaction between neutral (imino)Pt(IV) compounds [PtCl4[NH=C(Me)ON=CR1R2]2] [R1R2 = Me2, (CH2)4, (CH2)5, (Me)C(Me)=NOH], [PtCl4[NH=C(Me)ONR2]2] (R = Me, Et, CH2Ph), (R1 = H; R2 = Ph or C6H4Me; R3 = Me) as well as anionic-type platinum(IV) complexes (Ph3PCH2Ph)[PtCl5[NH=C(Me)ON=CR2]] [R2 = Me2, (CH2)4, (CH2)5] and 1 equiv of Ph3P=CHCO2R (R = Me, Et) proceeds under mild conditions (ca. 4 h, room temperature) to give selectively the platinum(II) products (in good to excellent isolated yields) without further reduction of the platinum center. All thus prepared compounds (excluding previously described Delta4-1,2,4-oxadiazoline complexes) were characterized by elemental analyses, FAB mass spectrometry, IR and 1H, 13C[1H], 31P[1H] and 195Pt NMR spectroscopies, and X-ray single-crystal diffractometry, the latter for [PtCl2[NH=C(Me)ON=CMe2]2] [crystal system tetragonal, space group P4(2)/n (No. 86), a = b = 10.5050(10) A, c = 15.916(3) A] and (Ph3PCH2CO2Me)[PtCl3(NCMe)] [crystal system orthorhombic, space group Pna2(1) (No. 33), a = 19.661(7) A, b = 12.486(4) A, c = 10.149(3) A]. The reaction is also extended to a variety of other Pt(II)/Pt(IV) couples, and the ylides Ph3P=CHCO2R are introduced as mild and selective reducing agents of wide applicability for the conversion of Pt(IV) to Pt(II) species in nonaqueous media, a route that is especially useful in the case of compounds that cannot be prepared directly from Pt(II) precursors, and for the generation of systematic series of Pt(II)/Pt(IV) complexes for biological studies.  相似文献   

12.
Herein, we have demonstrated that the electrospun nanofibers of TiO(2)/CdS heteroarchitectures could be fabricated through combining electrospinning technique with hydrothermal process. The configuration, crystal structure, and element composition of the as-prepared TiO(2)/CdS heteroarchitectures were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), resonant Raman spectrometer, X-ray photoelectron spectroscopy (XPS). The results indicated that the high-density hexagonal wurtzite CdS crystalline particles of ca. 6-40 nm in diameter were uniformly and closely grown on anatase TiO(2) nanofibers. Especially, the light-absorption properties as well as photocatalytic characteristics of pure TiO(2) nanofibers and TiO(2)/CdS heteroarchitectures with different amount loading of CdS were also investigated. The absorption of TiO(2)/CdS heteroarchitectures was extended to the visible due to effective immobilization of sensitizing agent CdS on TiO(2). In contrast with the pure TiO(2) nanofibers, the TiO(2)/CdS heteroarchitectures showed excellent photocatalytic activity by using rhodamine B dye as a model organic substrate under visible-light irradiation. It was worth noting that the cooperative photocatalytic mechanism of the TiO(2)/CdS heteroarchitectures was also discussed.  相似文献   

13.
乙烯在Pt/Pt4+-TiO2上的可见光降解   总被引:5,自引:0,他引:5  
以TiO2为主的光催化氧化技术存在太阳能利用率低(~5%)和光量子转化效率低(~4%)等缺点,使其工业应用受到制约,人们尝试用过渡金属离子掺杂和贵金属表面修饰等技术来提高催化剂对太阳能的利用率和光量子的转化效率,但目前将铂离子掺杂和铂金属表面修饰技术结合用于光催化  相似文献   

14.
The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively.  相似文献   

15.
Phototoxicity of titanium dioxide modified with platinum(IV)-chloride complexes, [TiO2/PtCl4], irradiated with visible light was tested on murine macrophage cell line (RAW 264.7) in vitro. Presence of antioxidants such as alpha-tocopherol or beta-carotene during photodynamic treatment significantly increased cells viability. Our results indicate that observed cell death induced by [TiO2/PtCl4] was due to photogeneration of reactive species.  相似文献   

16.
紫外光辐射对TiO2溶胶的影响研究   总被引:5,自引:0,他引:5  
用紫外-可见吸收光谱、动态光散射与透射电镜研究紫外光辐射对T2溶胶的影响,结果表明,光辐射使T2溶胶在可见光区的吸收减少,紫外区吸收增加,吸收带隙增大.与非光辐射的T2溶胶粒子相比,光辐射使T2溶胶粒子分布均匀且平均粒径减小,提高了T2纳米粒子在室温下的晶化程度.  相似文献   

17.
The photoreduction process of PtCl(6)2- to Pt nanoparticles in poly(N-vinyl-2-pyrrolidone) solutions upon UV light irradiation was investigated by monitoring the change in the diffusion coefficient (D). The D values of chemical species during UV irradiation was measured by the laser-induced transient grating (TG) method. The TG signal of the PtCl(6)2- solution before UV irradiation was composed of three kinds of contributions, the thermal grating, the species grating due to the creation of PtCl4(2-), and the species grating due to the depletions of PtCl6(2-). Upon UV irradiation of the solution, the species grating signal due to PtCl6(2-) diminished and then the TG signal of Pt nanoparticles gradually appeared. This result indicates that the gradual clustering of Pt0 atoms into Pt nanoparticles occurs after all PtCl(6)2- ions are photochemically reduced to PtCl(4)2- and subsequently transformed to Pt0 atoms with a short delay. With increasing time of the UV irradiation, the TG signal intensity increased, while D of the Pt nanoparticles did not change. This suggests that the number of Pt nanoparticles increases, but the size of the Pt nanoparticles with the polymer layer is unchanged, in the course of the UV irradiation.  相似文献   

18.
Photoelectrocatalytic degradation of various dyes under visible light irradiation with a TiO(2) nanoparticles electrode has been investigated to reveal the mechanism for TiO(2)-assisted photocatalytic degradation of dyes. The degradation of both cationic and anionic dyes at different biases, including the change in the degradation rate of the dyes and the photocurrent change with the bias potential, the degraded intermediates, the voltage-induced adsorption of dyes, the accumulation of electrons in the TiO(2) electrode, the effect of various additives such as benzoquinone (BQ) and N,N-dimethyl aniline (DMA), and the formation of active oxygen species such as O(2)(*-) and H(2)O(2) were examined by UV-visible spectroscopy, HPLC, TOC, and spin-trap ESR spectrometry. It was found that the dyes could controllably interact with the TiO(2) surface by external bias changes and charging of dyes. The cationic dyes such as RhB and MG underwent efficient mineralization at negative bias, but the N-dealkylation process predominated at positive bias under visible light irradiation. The discolorations of the anionic dyes SRB and AR could not be accelerated significantly at either negative or positive bias. At a negative bias of -0.6 V vs SCE, O(2)(*-) and dye(*+) were formed simultaneously at the electrode/electrolyte interface during degradation of cationic RhB. In the case of anionic dyes, however, it is impossible for the O(2)(*-) and dye cationic radical to coexist at the electrode/electrolyte surface. Experimental results imply both the superoxide anionic radical and the dye cationic radical are essential to the mineralization of the dyes under visible light-induced photocatalytic conditions.  相似文献   

19.
Pt/gamma-Al2O3 catalysts were prepared using hydroxyl-terminated generation four (G4OH) PAMAM dendrimers as the templating agents and the various steps of the preparation process were monitored by extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS results indicate that, upon hydrolysis, chlorine ligands in the H(2)PtCl(6) and K(2)PtCl(4) precursors were partially replaced by aquo ligands to form [PtCl3(H2O)3]+ and [PtCl2(H2O)2] species, respectively. The results further suggest that, after interaction of such species with the dendrimer molecules, chlorine ligands from the first coordination shell of Pt were replaced by nitrogen atoms from the dendrimer interior, indicating that complexation took place. This process was accompanied by a substantial transfer of electron density from the dendrimer to platinum, indicating that the dendrimer plays the role of a ligand. Following treatment of the H(2)PtCl(6)/G4OH and K(2)PtCl(4)/G4OH complexes with NaBH4, no substantial changes were observed in the electronic or coordination environment of platinum, indicating that metal nanoparticles were not formed during this step under our experimental conditions. However, when the reduction treatment was performed with H2, the formation of extremely small platinum clusters, incorporating no more than four Pt atoms was observed. The nuclearity of these clusters depends on the length of the hydrogen treatment. These Pt species remained strongly bonded to the dendrimer. Formation of larger platinum nanoparticles, with an average diameter of approximately 10 A, was finally observed after the deposition and drying of the H(2)PtCl(6)/G4OH nanocomposites on a gamma-Al(2)O(3) surface, suggesting that the formation of such nanoparticles may be related to the collapse of the dendrimer structure. The platinum nanoparticles formed appear to have high mobility because subsequent thermal treatment in O2/H2, used to remove the dendrimer component, led to further sintering.  相似文献   

20.
CdS-sensitized Pt/TiO(2) nanosheets with exposed (001) facets were prepared by hydrothermal treatment of a Ti(OC(4)H(9))(4)-HF-H(2)O mixed solution followed by photochemical reduction deposition of Pt nanoparticles (NPs) on TiO(2) nanosheets (TiO(2) NSs) and chemical bath deposition of CdS NPs on Pt/TiO(2) NSs, successively. The UV and visible-light driven photocatalytic activity of the as-prepared samples was evaluated by photocatalytic H(2) production from lactic acid aqueous solution under UV and visible-light (λ ≥ 420 nm) irradiation. It was shown that no photocatalytic H(2)-production activity was observed on the pure TiO(2) NSs under UV and/or visible-light irradiation. Deposition of CdS NPs on Pt/TiO(2) NSs caused significant enhancement of the UV and visible-light photocatalytic H(2)-production rates. The morphology of TiO(2) particles had also significant influence on the visible-light H(2)-production activity. Among TiO(2) NSs, P25 and the NPs studied, the CdS-sensitized Pt/TiO(2) NSs show the highest photocatalytic activity (13.9% apparent quantum efficiency obtained at 420 nm), exceeding that of CdS-sensitized Pt/P25 by 10.3% and that of Pt/NPs by 1.21%, which can be attributed to the combined effect of several factors including the presence of exposed (001) facets, surface fluorination and high specific surface area. After many replication experiments of the photocatalytic hydrogen production in the presence of lactic acid, the CdS-sensitized Pt/TiO(2) NSs did not show great loss in the photocatalytic activity, confirming that the CdS/Pt/TiO(2) NSs system is stable and not photocorroded.  相似文献   

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