UV-Visible ار راد ن .د TiO2 ( تیفرظ راون مان هب نورتکلا یاراد یژرنا زارت لماش VB و ) رگید زارت ی یژرنا اب ( ییاناسر راون مان هب نورتکلا زا یلاخ و رتلااب VB یم ) .دشاب ت ود نیا نیب یژرنا توافت یژرنا فاکش زار ، پگ دناب هدیمان یم .دوش هک ینامز زا نورتکلا لاقتنا VB هب VB یم ماجنا دریگ ، TiO2 اب ودح یژرنا بذج د ev 2 / 3 ، نورتکلا تفج کی دیلوت یم هرفح .دیامن و نورتکلا هرفح ی نا اب هدش دیلوت یم کرتشم حطس هب لاقت ثعاب دناوت شنکاو ماجنا اه یی ددرگ . TiO2 دربراک ،دراد یدایز یاه هلمج زا یم ناوت اوه یگدولآ هیفصت یارب (CO2) و بآ و ... نآ زا هدافتسا درک .

Advanced Nanoarchitectures for Solar Photocatalytic Applications

A surface science perspective on TiO2 photocatalysis

Sulfate radical-based advanced oxidation technologies (SR-AOTs) are attracting considerable attention due to the high oxidizing ability of SRs to degrade organic pollutants in aqueous environments This study was carried out to respond to current concerns and challenges in SR-AOTs, including (i) need of heterogeneous activation of sulfate salts using transition metal oxides, (ii) nanoscaling of the metal oxide catalysts for high catalytic activity and promising properties with respect to leaching, and (iii) easy removal and recovery of the catalytic materials after their applications for water and wastewater treatments In this study, we report a novel approach of using Fe–Co mixed oxide nanocatalysts for the heterogeneous activation of peroxymonosulfate (PMS) to generate SRs targeting the decomposition of 2,4-dichlorophenol, and especially focus on some synthesis parameters such as calcination temperature, Fe/Co contents, and TiO 2 support The physicochemical properties of the catalysts were investigated using porosimetry, XRD, HR-TEM, H 2 -TPR, and XPS Ferromagnetic CoFe 2 O 4 composites formed by thermal oxidation of a mixed phase of Fe and Co exhibited significant implications for the efficient and environmentally friendly activation of PMS, including (i) the cobalt species in CoFe 2 O 4 are of Co(II), unlike Co 3 O 4 showing some detrimental effects of Co(III) on the PMS activation, (ii) CoFe 2 O 4 possesses suppressed Co leaching properties due to strong Fe–Co interactions (ie Fe–Co linkages), and (iii) Fe–Co catalysts in form of CoFe 2 O 4 are easier to recover due to the unique ferromagnetic nature of CoFe 2 O 4  In addition, the presence of Fe was found to be beneficial for enriching hydroxyl group content on the Fe–Co catalyst surface, which is believed to facilitate the formation of Co(II)-OH complexes that are vital for heterogeneous PMS activation

Iron–cobalt mixed oxide nanocatalysts: Heterogeneous peroxymonosulfate activation, cobalt leaching, and ferromagnetic properties for environmental applications

In order to generate sulfate radicals (SRs) as oxidizing species for the degradation of 2,4-dichlorophenol (2,4-DCP) in water, we explored heterogeneous activation of peroxymonosulfate (PMS) by supported cobalt catalysts. More attention was given to the effect of support materials (Al2O3, SiO2, TiO2) and cobalt precursors (Co(NO3)2, CoCl2, CoSO4) on cobalt–support interaction, cobalt leaching, and reactivity of the catalysts. Especially, the feasibility of simultaneous generation of SRs and hydroxyl radicals (HRs) in PMS-Co/TiO2 systems was first studied under ultraviolet (UV) radiation. Much lower cobalt leaching was observed in Co/Al2O3 and Co/TiO2 systems than that of Co/SiO2 most probably due to their relatively strong cobalt-support interaction. Co/TiO2 catalyst prepared with Co(NO3)2, compared to CoCl2 or CoSO4 (where Cl− and SO42−, respectively, were not completely removed upon heat treatment at 500 °C), showed strong cobalt–support interaction, and thereby exhibited negligible cobalt leaching. Under UV radiation, Co/TiO2 at Co/Ti molar ratio of 0.001 showed significant improvement in the degradation of 2,4-DCP due to HRs. The effective generation of HRs in the system can be explained with Co(III)-mediated charge transfer from the photoinduced electrons to PMS, inducing facilitation of photoinduced electron-hole separation. However, high cobalt loading (i.e., Co/Ti molar ratio of 0.1) on TiO2 surface exhibited negligible enhancement of 2,4-DCP transformation under UV radiation since the penetration of UV light to TiO2 was prohibited by the cobalt.

Heterogeneous activation of peroxymonosulfate by supported cobalt catalysts for the degradation of 2,4-dichlorophenol in water: The effect of support, cobalt precursor, and UV radiation

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol–gel method and sol–gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The non-aqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Two different synthesis routes were applied to prepare TiO2–XSiO2 (X denotes mol% of silica in titania–silica mixed oxides) with different silica concentrations by using ammonia water as hydrolysis catalyst. Through comparing the photocatalytic performance of two sets of mixed oxides, we found that the photocatalytic activity of mixed oxides prepared via the route which can promote homogeneity, was significantly enhanced as compared with that of counterparts prepared via the another route, and the highest photocatalytic activity obtained by adding about 9.1 mol% silica into titania was much higher than that of pure TiO2. The mixed oxides were investigated by means of XRD, thermal analysis, UV–vis, FT-IR and XPS. The characterization results suggest that, in comparison with pure TiO2, the mixed oxides exhibit smaller crystallite size and higher thermal stability which can elevate the temperature of anatase to rutile phase transformation due to the addition of silica. Furthermore, Bronsted acidity, which is associated with the formation of Ti O Si hetero linkages where tetrahedrally coordinated silica is chemically mixed with the octahedral titania matrix, may be a very important contribution to the enhanced photocatalytic activity of titania–silica mixed oxides as well.

Enhanced photocatalytic activity of titania–silica mixed oxide prepared via basic hydrolyzation

Highly active sulfate-promoted rutile titania (SO(4)(2-)/TiO(2)) with smaller band gap was prepared by an in situ sulfation method, that is, under moderate conditions, sulfate-promoted rutile titania was directly obtained via precipitating Ti(SO(4))(2) in NaOH solution followed by peptizing in HNO(3) without the phase transformation from anatase to rutile. Thus, the negative impacts of phase transformation from anatase to rutile on the structure, surface, and photoactivity properties of the catalysts due to higher calcination temperature can be avoided. The catalysts were characterized by means of thermal analysis, Brunauer-Emmett-Teller analysis (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, FT-IR pyridine adsorption, and temperature-programmed desorption (TPD). The results show sulfate species are sensitive to the variation of calcination temperature. In the process of peptizing, sulfate species are homogeneously dispersed throughout the bulk of catalysts, allowing sulfate species to penetrate into the network of TiO(2) effectively. After being calcined at 300 degrees C, sulfate species occupy oxygen sites to form Ti-S bonds, as evidenced by XPS results. As calcination temperature is further increased to 600 degrees C or above, the active sulfate species on the catalyst surface are destroyed, and the sulfate species in the network of TiO(2) are expelled out onto the surface to form inactive sulfate species. Thus, Ti(3+) defects will be produced on the catalyst surface. Accompanying this process, surface area is decreased promptly, and crystalline size is greatly increased via two fast growth phases due to the decomposition of sulfate species with different binding forces. Most importantly, the band gap of SO(4)(2-)/TiO(2) is remarkably shifted to the visible light region due to the formation of Ti-S bonds, and with increasing calcination temperature the visible light absorption capability is reduced due to breakage of Ti-S bonds. The excellent photoactivity of 300 degrees C calcined SO(4)(2-)/TiO(2) can be explained by its small crystalline size, high surface area, loose and porous microstructure, and the generation of Bronsted acidity on its surface.

Synthesis of highly active sulfate-promoted rutile titania nanoparticles with a response to visible light.

Structure, luminescence properties and photocatalytic activity of europium doped-TiO2 nanoparticles

A simple and efficient approach has been set up for fabricating highly active sulfated titania−silica (SO42-/TiO2−SiO2):  Ti(SO4)2 was hydrolyzed in the presence of silica, making it possible to sulfate titania and form titania−silica mixed oxide in one step. This study was focused on investigating the roles of sulfate species and silica in improving the physicochemical properties and photoactivity of SO42-/TiO2−SiO2 through comparison with sulfated titania (SO42-/TiO2) and sulfate-free catalysts (TiO2 and TiO2−SiO2). Various characterization methods, including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and surface photovoltage spectroscopy (SPS), were employed to test these materials. The results revealed that for SO42-/TiO2 and TiO2−SiO2 the sole presence of either sulfate species or silica imposes negative effects on the photocatalysis behavior of titania, leading them to have negligible photoactivities. On the contrary, in the case...

New route to synthesize highly active nanocrystalline sulfated titania-silica : Synergetic effects between sulfate species and silica in enhancing the photocatalysis efficiency

Gas–solid heterogeneous photocatalytic oxidation (PCO) of heptane and toluene over UV-illuminated pure titania, titania–silica mixed oxides and sulfated titania was investigated at room temperature in a batch reactor. By comparing the photocatalytic activities of the different catalysts, we draw the following two conclusions: (1) there is no clear relationship between the crystalline phase and photocatalytic activity; (2) larger surface area is not always effective in the photocatalytic process and its effects on the photocatalytic activity strongly depend on the nature of the reactant used. In addition, the study on the behavior of catalyst deactivation and regeneration shows that titania–silica mixed oxide is deactivated more slowly than pure titania and sulfated titania, and for sulfated titania the regeneration temperature can be lowered due to the presence of SO42−.

Qiujing Yang

Papers

Enhanced photocatalytic activity of titania–silica mixed oxide prepared via basic hydrolyzation

Synthesis of highly active sulfate-promoted rutile titania nanoparticles with a response to visible light.

Structure, luminescence properties and photocatalytic activity of europium doped-TiO2 nanoparticles

New route to synthesize highly active nanocrystalline sulfated titania-silica : Synergetic effects between sulfate species and silica in enhancing the photocatalysis efficiency

Comparative studies of heterogeneous photocatalytic oxidation of heptane and toluene on pure titania, titania–silica mixed oxides and sulfated titania