0000000000204153
AUTHOR
Giuseppe Vasapollo
Photocatalytic Degradation of 4-Nitrophenol by Using Porphyrin/Fe-Loaded TiO2 Composites Under Heterogeneous Photo Fenton Process
A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities toward the degradation of 4-nitrophenol (4-NP) by heterogeneous photo Fenton-like processes.
Turning lipophilic phthalocyanines/TiO2 composites into efficient photocatalysts for the conversion of CO2 into formic acid under UV–vis light irradiation
Metal-free, Cu(II)- or Zn(II) tetrakis [4-(2,4-bis-(1,1-dimethylpropyl)phenoxy)]phthalocyanines loaded over TiO2 (anatase) proved to be active in the photoreduction of CO2 to formic acid (HCO2H) in water under UV-vis light. CuPc/TiO2 is catalyst of choice, allowing to reach a maximum yield of HCO2H, unequalled by any other similar catalytic systems. Because of their low environmental impact, low potential cost, and efficient power conversion, these multipurpose materials show promise in the setup of sustainable methods for CO2 valorization. (C) 2014 Elsevier B.V. All rights reserved.
Degradation of 4-nitrophenol (4-NP) using Fe–TiO2 as a heterogeneous photo-Fenton catalyst
Photocatalytic degradation of 4-nitrophenol was investigated using Fe-doped (1, 3, 5 and 8 wt.% Fe) TiO(2) catalysts under UV light irradiation in aqueous dispersions in the presence of H(2)O(2). Photocatalysts with the lowest Fe content (1%) showed a considerably better behavior with respect to the unloaded TiO(2) and the catalysts with higher Fe contents. Photocatalytic degradation was studied under different conditions such as amounts of 1% Fe-TiO(2) catalyst, H(2)O(2) dose and initial pH of 4-NP solution. The results indicated that about 67.53% total organic carbon of a solution containing 20 mg L(-1) 4-NP was removed at pH 6.17 by using 4.9 mM of H(2)O(2) and 0.4 g L(-1) of the catalys…
New Porphyrin/Fe-Loaded TiO2 Composites as Heterogeneous Photo-Fenton Catalysts for the Efficient Degradation of 4-Nitrophenol
A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP) as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. The combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2.
Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with functionalised Cu(II)-porphyrin or Cu(II)-phthalocyanine
The photocatalytic activity of polycrystalline TiO2 samples impregnated with functionalized Cu(II)- or metal-free porphyrins has been investigated. A probe reaction, i.e., 4-nitrophenol (4-NP) photodegradation in aqueous suspension, has been used. The results indicated that the presence of the sensitizers is beneficial for the photoactivity and suggest an important role of Cu(II). A comparison with similar samples impregnated with modified Cu(II)- and metal-free phthalocyanines showed that the presence of porphyrin is more beneficial both for the decomposition rate of 4-nitrophenol and for the disappearance of nonpurgeable organic carbon (NPOC). Experiments were carried out by using cutoff …
Efficient Degradation of 4-Nitrophenol by Using Functionalized Porphyrin TiO2 Photocatalysts Under Visible Irradiation
Abstract The novel porphyrins 5,10,15,20-tetra-[4-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(a) and 5,10,15,20-tetra-[2-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(b) and their corresponding copper(II) complexes CuPp(a), CuPp(b) were synthesized and characterized by using various spectroscopic techniques. The photocatalytic activity of polycrystalline TiO2 samples impregnated with H2Pp(a), H2Pp(b), CuPp(a) and CuPp(b) as sensitizers have been investigated by carrying out the photo-degradation of 4-nitrophenol (4-NP) as a probe reaction in aqueous suspension and under visible light. The maximum photocatalytic activity was obtained using TiO2 loaded with a monolayer of the copper porphyrin CuP…
Polycrystalline TiO2 impregnated with cardanol-based porphyrins for the photocatalytic degradation of 4-nitrophenol
Hydrogenated cardanol (3-n-pentadecylphenol), a renewable organic resource obtained by vacuum distillation of roasted “cashew nut shell liquid” (CNSL), a by-product of the cashew industry, has been used to synthesize novel lipophilic porphyrins. Polycrystalline TiO2 impregnated with these novel “cardanol-based” porphyrins as sensitizers has been investigated in the photodegradation of 4-nitrophenol (4-NP) in aqueous suspension. The results indicated that the presence of the sensitizer enhances the photoactivity of polycrystalline bare TiO2 in the process. The activating effect was higher in the case of the Cu-complex.
Photoreduction of carbon dioxide to formic acid in aqueous suspension: a comparison between phthalocyanine/TiO2 and porphyrin/TiO2 catalysed processes
Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II)- and metal-free phthalocyanines or porphyrins, which have been used in the past as photocatalysts for photodegradative processes, have been successfully tested for the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid. The results indicated that the presence of the sensitizers is beneficial for the photoactivity, confirming the important role of Cu(II) co-ordinated in the middle of the macrocycles. A comparison between Cu(II) phthalocyanines and Cu(II) porphyrins indicated that the Cu(II)- phthalocyanine sensitizer was more e…
TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle
Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO2-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO2 systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO2. A significant improvement of the photoreactivity was observed in the case of TiO2 impregnated with copper porphyrin, while only a slight bene…
Cyclocarbonylation reactions of allylphenols and allylnaphthols catalyzed by Pd/C- 1,4-bis(diphenylphosphine)butane
Palladium/activated carbon (Pd/C) in the presence of 1,4-bis(diphenylphosphino)butane is an efficient heterogeneous catalyst for cyclocarbonylation reactions of 2-allyl phenols affording five-, six-, and seven-membered ring lactones. Various examples of cyclocarbonylation are reported and the regioselectivity is compared with the homogeneous system. Both commercial Pd/C and Pd/C prepared from activated carbons obtained from vegetable and polymeric wastes are investigated.
Novel meso-substituted porphyrins: Synthesis, characterization and photocatalytic activity of their TiO2-based composites
Abstract Two series of novel meso-substituted porphyrins, namely 5,10,15,20-tetra[4-(3-phenoxy)-propoxy]phenyl porphyrin, the structural analogue 5,10,15,20-tetra[2-(3-phenoxy)-propoxy]phenyl porphyrin and their Co(II) Cu(II) and Zn(II) complexes were synthesized. The compounds were characterized using various spectroscopic techniques and their molecular structure was proposed based on density functional theory calculations. The diverse properties of the porphyrin derivatives result from the different stereochemistry of the particular substituents at the meso site on the macrocycle and are controlled also by the coordinated metal. The 1H NMR spectrum of the free-base porphyrin showed a comp…
Photocatalytic Degradation of 4-nitrophenol in aqueous suspension by using polycristalline TiO2 samples impregnated with a Cu(II)-phthalocyanine
In this paper, the preparation of polycrystalline TiO2 samples impregnated with a modified Cu(II)-phthalocyanine (TiO2–CuPc) is reported along with an investigation on the photocatalytic behavior of this system compared with bare TiO2 (both in the anatase and rutile form) and with TiO2 samples impregnated with not functionalized commercial phthalocyanine (TiO2–CuPc) or with metal free phthalocyanine (TiO2–Pc). The photocatalytic degradation of 4-nitrophenol (4-NP) was studied as a probe reaction. The presence of modified CuPc showed to be beneficial only for TiO2 (anatase) while the commercial not functionalized CuPc also slightly for both TiO2 (anatase) and TiO2 (rutile). The metal free Pc…
The Photocatalytic Activity of Novel, Substituted Porphyrin/TiO2-Based Composites
Four novel porphyrins, 5-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-[3-(3-phenoxy)-propoxy] phenyl porphyrin, 5,10,15-tri-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,10,15,20-tetra-[3-(3-phenoxy)- propoxy]phenyl porphyrin, and their corresponding Cu(II) porphyrins, were synthesized and characterized spectroscopically. The photodegradation of 4-nitrophenol in aq. suspension was used to determine the photocatalytic activity of polycrystalline TiO2 samples which had been impregnated with the Cu(II) porphyrins, as sensitizers. The photocatalytic activity of the composite depends mainly on the amount of sensitizer on the TiO2 surface rather than the nature of the substituted porphyrins.