Boosting the photocatalytic properties of NaTaO3 by coupling with AgBr.

AgBr/NaTaO3 composites, with different molar % of NaTaO3 (Br/NTO(X%)), have been synthesized by simple precipitation methods; bare NaTaO3 was synthesized by hydrothermal procedure, while AgBr was synthesized by a precipitation procedure using cetyl-tri-methyl-ammonium bromide (CTAB) and AgNO3. Samples have been characterized by X-ray diffraction (XRD), N2 adsorption, UV-vis diffuse reflectance spectroscopy (DRS), Fourier-transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the as-prepared photo-catalysts was evaluated through photocatalytic degradation of rhodamine B (RhB), methyl orange (MO) and caffeic acid (CAFA) under UV and visible illumination. Single AgBr material and Br/NTO(X%) composites displayed the ability to absorb light in the visible region, while NaTaO3 is only photoactive under UV irradiation. Based on the position of conduction and valence bands of AgBr and NaTaO3, the heterojunction between these two photo-catalysts corresponds to a type II junction. In the case of photocatalytic degradation of RhB and CAFA, Br/NTO(x%) composites have highest photocatalytic activity than that obtained by both parental materials under the same operational conditions. AgBr and Br/NTO(x%) composites achieve a fast degradation of MO, together with a considerable adsorption capacity, attributed to the presence of a remaining amount of residual CTAB on the AgBr surface. In summary, coupling AgBr with NaTaO3 improves the photocatalytic activity under both UV and visible illumination with respect to the parental components, but the performance of the composites is highly dependent on the type of substrate to be degraded and the illumination conditions.

Z-scheme WO3/PANI heterojunctions with enhanced photocatalytic activity under visible light: A depth experimental and DFT studies.

A WO3@PANI heterojunction photocatalyst with a various mass ratio of polyaniline to WO3 was obtained via the in situ oxidative deposition polymerization of aniline monomer in the presence of WO3 powder. The characterization of WO3@PANI composites was carried via X-ray diffraction (XRD), scanning electron microscopy (SEM-EDS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible diffuse reflection spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL). The photocatalytic efficiency of WO3@PANI photocatalysts was assessed by following the decomposition of the Rhodamine B (RhB) dye under visible light irradiation (λ >420 nm). The results evidenced the high efficiency of the WO3@PANI (0.5 wt %) nanocomposite in the photocatalytic degradation of RhB (90% within 120 min) under visible light irradiation 3.6 times compared to pure WO3. The synergistic effect between PANI and WO3 is the reason for the increased photogenerated carrier separation. The superior photocatalytic performance of the WO3@PANI catalyst was ascribed to the increased visible light in the visible range and the efficient charge carrier separation. Furthermore, the Density Functional Theory study (DFT) of WO3@PANI was performed at the molecular level, to find its internal nature for the tuning of photocatalytic efficiency. The DFT results indicated that the chemical bonds connected the solid-solid contact interfaces between WO3 and PANI. Finally, a plausible photocatalytic mechanism of WO3@PANI (0.5 wt %) performance under visible light illumination is suggested to guide additional photocatalytic activity development.

Polyaniline coated tungsten trioxide as an effective adsorbent for the removal of orange G dye from aqueous media.

In this work, the core-shell PANI@WO3 composite was obtained from the reaction of aniline monomer polymerization with WO3 particles; sodium persulfate was used as an oxidant. Various analytical techniques such as scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS) were used to characterize the as-prepared PANI@WO3 adsorbent, which well confirmed that the WO3 particles were coated by polyaniline polymer. The PANI@WO3 composite was tested as an adsorbent to remove reactive orange G (OG) for the first time. pH, adsorbent dose, contact time, initial dye concentration, and temperature were systematically investigated in order to study their effect on the adsorption process. The experimental findings showed that the PANI@WO3 composite has considerable potential to remove an aqueous OG dye. Langmuir and Freundlich's models were used to analyze the equilibrium isotherms of OG dye adsorption on the PANI@WO3 composite. As a result, the best correlation of the experimental data was provided by the Langmuir model, and the maximum capacity of adsorption was 226.50 mg g-1. From a thermodynamic point of view, the OG dye adsorption process occurred spontaneously and endothermically. Importantly, PANI@WO3 still exhibited an excellent adsorption capability after four regeneration cycles, indicating the potential reusability of the PANI@WO3 composite. These results indicate that the as prepared PANI@WO3 composite could be employed as an efficient adsorbent and was much better than the parent material adsorption of OG dye.

Facile synthesis and characterization of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate nanocomposite for highly efficient removal of hazardous hexavalent chromium ions from water.

The present study describes the preparation of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate (BTCA-PANI@ZnP) nanocomposite via a facile two-step procedure. Thereafter, the as-prepared composite material adsorption characteristics for Cr(VI) ions removal were evaluated under batch adsorption. Kinetic approach studies for Cr(VI) removal, clearly demonstrated that the results of the adsorption process followed the pseudo second order and Langmuir models. The thermodynamic study indicated a spontaneous and endothermic process. Furthermore, higher monolayer adsorption was determined to be 933.88 mg g-1. In addition, the capability study regarding Cr(VI) ions adsorption over BTCA-PANI@ZnP nanocomposite clearly revealed that our method is suitable for large scale application. X-ray photoelectron spectroscopy (XPS) analysis confirmed Cr(VI) adsorption on the BTCA-PANI@ZnP surface, followed by its subsequent reduction to Cr(III). Thus, the occurrence of external mass transfer, electrostatic attraction and reduction phenomenon were considered as main mechanistic pathways of Cr(VI) ions removal. The superior adsorption performance of the material, the multi-dimensional characteristics of the surface and the involvement of multiple removal mechanisms clearly demonstrated the potential applicability of the BTCA-PANI@ZnP material as an effective alternative for the removal of Cr(VI) ions from wastewater.

Influence of Water on the Oxidation of NO on Pd/TiO2 Photocatalysts.

Two series of new photocatalysts were synthesized based on modification with Pd of the commercial P25 photocatalyst (EVONIK®). Two techniques were employed to incorporate Pd nanoparticles on the P25 surface: photodeposition (series Pd-P) and impregnation (series Pd-I). Both series were characterized in depth using a variety of instrumental techniques: BET, DRS, XRD, XPS, TEM, FTIR and FESEM. The modified series exhibited a significant change in pore size distribution, but no differences compared to the original P25 with respect to crystalline phase ratio or particle size were observed. The Pd0 oxidation state was predominant in the Pd-P series, while the presence of the Pd2+ oxidation state was additionally observed in the Pd-I series. The photoactivity tests were performed in a continuous photoreactor with the photocatalysts deposited, by dip-coating, on borosilicate glass plates. A total of 500 ppb of NO was used as input flow at a volumetric flow rate of 1.2 L·min-1, and different relative humidities from 0 to 65% were tested. The results obtained show that under UV-vis or Vis radiation, the presence of Pd nanoparticles favors NO removal independently of the Pd incorporation method employed and independently of the tested relative humidity conditions. This improvement seems to be related to the different interaction of the water with the surface of the photocatalysts in the presence or absence of Pd. It was found in the catalyst without Pd that disproportionation of NO2 is favored through its reaction with water, with faster surface saturation. In contrast, in the catalysts with Pd, disproportionation took place through nitro-chelates and adsorbed NO2 formed from the photocatalytic oxidation of the NO. This different mechanism explains the greater efficiency in NOx removal in the catalysts with Pd. Comparing the two series of catalysts with Pd, Pd-P and Pd-I, greater activity of the Pd-P series was observed under both UV-vis and Vis radiation. It was shown that the Pd0 oxidation state is responsible for this greater activity as the Pd-I series improves its activity in successive cycles due to a reduction in Pd2+ species during the photoactivity tests.

Recent progress on the enhancement of photocatalytic properties of BiPO4 using π-conjugated materials.

Semiconductor photocatalysis is regarded as most privileged solution for energy conversion and environmental application. Recently, photocatalysis methods using bismuth-based photocatalysts, such as BiPO4, have been extensively investigated owing to their superior efficacy regarding organic pollutant degradation and their further mineralization into CO2 and H2O. It is well known that BiPO4 monoclinic phase exhibited better photocatalytic performance compared to Degussa (Evonik) P25 TiO2 in term of ultraviolet light driven organic pollutants degradation. However, its wide band gap, poor adsorptive performance and large size make BiPO4 less active under visible light irradiation. However, extensive research works have been conducted in the past with the aim of improving visible light driven BiPO4 activity by constructing a series of heterostructures, mainly coupled with π-conjugated architecture (e.g., conductive polymer, dye sensitization and carbonaceous materials). However, a critical review of modified BiPO4 systems using π-conjugated materials has not been published to date. Therefore, this current review article was designed with the aim of presenting a brief current state-of-the-art towards synthesis methods of BiPO4 in the first section, with an especial focuses onto its crystal-microstructure, optical and photocatalytic properties. Moreover, the most relevant strategies that have been employed to improve its photocatalytic activities are then addressed as the main part of this review. Finally, the last section presents ongoing challenges and perspectives for modified BiPO4 systems using π-conjugated materials.

Influence of Sr-doping on structural, optical and photocatalytic properties of synthesized Ca3(PO4)2.

Well-crystallized Ca3(PO4)2 doped and un-doped nano-particles with the maximum strontium content (40 wt% Sr) followed by calcination at 800 °C for 3 h were synthesized via facile co-precipitation method. DTA/TGA, X-ray diffraction (XRD), energy dispersive scanning electron microscopy (SEM/EDX), UV-vis diffuse reflectance spectrum (UV-vis DRS), Raman spectroscopy and photoluminescence (PL) techniques were used for material characterization. The (XRD) patterns of as-synthesized Sr-doped Ca3(PO4)2 solid solution samples exhibited a systematic shift toward lower angles by possessing a single rhombohedral crystal structure without any secondary phases. The UV light driven photocatalytic activity was assessed for rhodamine B (RhB) degradation. As a result, ultrafast photodegradation activity was observed after Sr doping. Moreover, the 30 wt% Sr-Ca3(PO4)2 sample showed the highest photocatalytic degradation among the Sr-doped Ca3(PO4)2 samples toward RhB. It was further suggested that as-synthesized 30 wt% Sr-Ca3(PO4)2 superior photocatalytic performance is ascribed to the more proficient partition of photogenerated electron-hole pairs. Furthermore, the involved mechanism of superior photocatalytic performance of the 30 wt% Sr-Ca3(PO4)2 solid solution was also investigated. In addition, regeneration cycles indicated the higher stability of the photocatalyst to be effectively recycled up to four times without any considerable reduction in photocatalytic performance. Thus, these informations further provides us a scalable pathway to fabricate Sr doped Ca3(PO4)2 and its consequent use as an efficient photocatalyst for rhodamine B (RhB) contaminated wastewater treatment.

Role of Fe(III) in aqueous solution or deposited on ZnO surface in the photoassisted degradation of rhodamine B and caffeine.

Iron (III) was incorporated, to the surface of a synthesized ZnO, using two nominal molar percentages of Fe (III): 1% and 5% Fe relative to ZnO. Samples dried and calcined at 200 °C and 400 °C for 2 h, were characterized by XRD, XPS, XRF, N2-adsorption-BET and (UV-vis)-DRS. Photocatalytic activities of the catalysts were assessed based on the degradation of rhodamine B (RhB) and caffeine (CAF) in aqueous solution under two irradiation conditions: UV and visible light illumination. Prior to the photocatalytic tests, the interaction of each one of the substrates with either Fe(III) or Fe(II) was studied in homogeneous medium under UV-illumination and oxygenated environment. It was found that Fe (III) can play an important role in homogeneous media in the photoassisted degradation, both of rhodamine B and caffeine, while Fe (II) does not exert a relevant role in the photoassisted degradation of the referred substrates. Fe-ZnO samples display similar or poorer performance than pure ZnO in the presence of UV light for both studied substrates. The phenomenon can be attributed to the formation of either goethite or ZnFe2O4 at the ZnO surface where the coupled Fe3+/Fe2+ can act as recombination centers for the photogenerated charges. On the contrary, all Fe-ZnO samples showed enhanced photocatalytic activity under visible illumination which seems to be independent of the iron content. In this context, the mechanisms for photoassisted degradation of both the substrates in homogeneous medium and photocatalytic degradation are discussed, as well as the role of Fe in the photodegradation processes.

Photocatalytic reduction of CO2 over platinised Bi2WO6-based materials.

The photocatalytic reduction of CO2 with H2O to produce CH4 in the gas phase was carried out in the presence of two Bi2WO6-based materials. For this purpose, single Bi2WO6 and a coupled Bi2WO6-TiO2 system were synthesised and metallised with Pt, through a Pt photodeposition method. Then, the samples were characterised and the photocatalytic activity was evaluated in a continuous fluidised-bed reactor irradiated with UV light. Single Bi2WO6 presents an interesting behaviour under H2O rich conditions. In particular, the metallisation improves the material's performance for CH4 formation, while the TiO2 addition to Bi2WO6 increases the CH4 yield only at low H2O/CO2 ratio. The Bi2WO6-TiO2 system metallised with a Pt photocatalyst displayed the highest CH4 yield among all the prepared photocatalysts. The stability of the system can be enhanced through the addition of a blue phosphor to the reactant mixture, especially under H2O rich conditions.

Novel Bi(2)WO(6)-TiO(2) heterostructures for Rhodamine B degradation under sunlike irradiation.

Highly efficient Bi(2)WO(6)-TiO(2) heterostructure is synthesized by means of a hydrothermal method having highly photoactivity for the degradation of Rhodamine B under sunlike irradiation. From the structural characterization it has been demonstrated that TiO(2) is incorporated on the Aurivillius structure. Interesting synergetic effect between TiO(2) and Bi(2)WO(6) leads to an improved charge carrier separation mechanism, causing the excellent photocatalytic performance under sunlike irradiation. The photocatalytic performance of Bi(2)WO(6) and Bi(2)WO(6)-TiO(2) was compared under different irradiation conditions and using increasing Rhodamine B concentration up to 25 ppm. After the photocatalytic analysis of both systems, the mineralization efficiency of the heterostructure appears significantly higher with respect to Bi(2)WO(6).

Sunlight highly photoactive Bi2WO6-TiO2 heterostructures for rhodamine B degradation.

Highly efficient Bi(2)WO(6)-TiO(2) heterostructures are synthesized by means of a hydrothermal method; they have high photoactivity for the degradation of rhodamine B under sunlike irradiation. An interesting synergetic effect between TiO(2) and Bi(2)WO(6) leads to an improved charge carrier separation mechanism, causing the excellent photocatalytic performance.

Oxidation of 6- and 8-methylquinolines upon UV-illumination in the presence of a powder of TiO2 photocatalyst.

Selective transformation of the methyl group into a formyl group in methylquinolines is of great interest because formation of the corresponding aldehydes is either very expensive or unknown. We report here results concerning the photo-oxidation of 6- and 8-methylquinolines (6-MQ and 8-MQ) suspended with TiO2 powder in oxygenated acetonitrile. The analytical study of the products generated from the TiO2-photoassisted oxidation of 6-MQ and 8-MQ in oxygenated acetonitrile suspensions indicated that in both cases, for a UV-illumination period of < 24 h, the corresponding formyl derivatives quinoline-6- and -8-carbaldehydes are detected as practically the sole products. Analysis of further photogenerated oxidation products enabled mechanistic delineation of the course of the semiconductor-mediated reaction.

EXAFS study of the Fex/ZrO2 composite nanomaterials obtained by sol-gel synthesis.

The local Zr and Fe arrangements in the nanocomposite system Fe(x)/ZrO2 (x=0-0.2) obtained by sol-gel method were studied by EXAFS. The phase composition was found to vary significantly on iron loading. For the samples calcined at 500 or 600 degrees C, at x< or =0.01, the formed ZrO2 is a mixture of monoclinic and tetragonal structures. Only tetragonal structure is revealed at x > or = 0.05 with the exception of Fe0.2/ZrO2, calcined at 500 degrees C, where new non-typically short Zr-Zr distances (3.29, 3.43A) were observed. At low iron loading (less than one monolayer) Fe3+ ions were found to localize within the pre-surface layers of ZrO2 nanoparticles showing property of isolated ions. For greater Fe loading, iron exhibits either two-dimensional layer structure or two-phase system.

[Urodynamics fundamentals. The flow curve and the isometric phase]. / Fundamentos de Urodinámica. La curva de flujo y la fase isométrica.

OBJECTIVE: To analyze the cause-effect relationship of bladder dynamics and flow rate. METHODS: A theoretical study was performed using the mathematical equations obtained by other authors. RESULTS: We have developed equations for bladder dynamics, flow rate and the detrusor, which is considered to act like a spring from experimental studies on anesthesized animals. CONCLUSIONS: The relaxation constant, urinary stream velocity and area of urethral section can now be determined from the flow rate equation.

[The Fabian prosthesis: our experience in 13 cases]. / Prótesis de Fabian: nuestra experiencia en 13 casos.

The spiral intraurethral prosthesis is a device that maintains the urinary tract expedite and overcomes the prostatic obstacle. It is used as an alternative in patients requiring permanent bladder catheters due to prostatic obstruction syndrome that are at high risk for surgery and in those patients that are on the waiting list for surgery. We report the results of a one-year follow-up of 13 patients in whom a prosthesis had been implanted. The spiral prosthesis had to be removed in 6 cases (one due to calcification two months after placement); the remaining 7 patients are still being followed. We briefly analyze the micturition hydrodynamics and the changes of the continence mechanisms and attempt to explain the poor flowmetry results and incontinence observed in these patients with the urological spiral prosthesis. We have recently abandoned the metal prosthesis and now use the so-called "intraureteral catheter" which has become available. However, further experience is warranted in order to determine its results.