Solar photodegradation of Rhodamine B dye by Cu2O/TiO2 heterostructure: experimental and computational studies of degradation and toxicity.

CONTEXT AND RESULTS: In this study, the heterojunction Cu2O/TiO2 is used for the degradation of a cationic dye, Rhodamine B, under solar light irradiation over a wide pH range. The physical and optical properties of both semiconductors Cu2O and TiO2 are correlated with the photo-electrochemical characterization to establish the energy diagram of the heterojunction Cu2O/TiO2. X-ray diffraction, UV-visible, SEM, EDX, and BET analyses are conducted for both photocatalysts. The band gap (Eg) of 3.26 eV is obtained for TiO2 with an indirect optical transition. In the case of Cu2O, the transition is directly allowed at 2.05 eV. According to the BET analysis, the specific surface area of TiO2 particles is higher (82.65 m2 g-1) than that of Cu2O (29.81 m2 g-1). The flat band potentials, determined from the Mott-Schottky plots, are 0.3 and - 0.32 VSCE for TiO2 and Cu2O, respectively. The photocatalytic activity is directly proportional to the mass ratio, and the best result is obtained for the mass ratio 1:1 of Cu2O/TiO2. COMPUTATIONAL AND THEORETICAL TECHNIQUES: Furthermore, a theoretical study is conducted by using density functional theory to optimize the structure, reactivity sites of the RhB molecule, and physical parameters like the energy of the frontier molecular orbitals and electronegativity and to predict the proposed mechanism of RhB degradation as well as its intermediates. Also, molecular dynamics simulation is used to determine the adsorption behavior of RhB on TiO2 (101) and Cu2O (111) surfaces. The ecotoxicity evaluation showed that degradation products have significantly lower acute toxicity than RhB.

Influence of pretreatment on the properties of α-Fe2O3 and the effect on photocatalytic degradation of methylene blue under visible light.

The hematite (α-Fe2O3) nanostructures were synthesized by thermal oxidation of metal at 500 °C under atmospheric pressure. We studied the effect of the electrochemical pretreatment of the substrate before calcinations and its impact on the morphology, crystalline structure, lattice microstructural, and optical properties of α-Fe2O3. Uniform nanosheets were observed on the sample surface after calcination; their dimension and morphology were accentuated by the pretreatment, as confirmed by the SEM images. The characteristics of the nanostructures, analyzed by X-ray diffraction (XRD), revealed a rhombohedral symmetry with the space group R-3c and lattice constants: a = 0.5034 nm and c = 1.375 nm. The average crystallite size and strain, determined from the Williamson-Hall (W-H) plot, showed substantial variations after the substrate pretreatment. The Raman spectroscopy confirmed the changes in the crystal properties of the hematite submitted to pretreatment. The diffuse reflectance allowed to evaluate the optical gap which lies between 1.2 and 1.97 eV, induced by the electrochemical processing. The photocatalytic activity of α-Fe2O3 films was assessed by the degradation of methylene blue (MB) under LED light; 15% enhancement of the degradation for the pretreated specimens was noticed.

Solar photodegradation of a textile azo dye using synthesized ZnO/Bentonite.

The present work is devoted to the synthesis of a new photocatalyst ZnO (7.5%)/Bentonite prepared by impregnation method and its successful application for the degradation of Solophenyl Red 3BL (SR 3BL) under solar light (∼660 W/m2). The X-ray diffraction (XRD) indicates mixed phases of the nanocomposite catalyst (ZnO/Bentonite), characterized by scanning electron microscopy, X-ray fluorescence and attenuated total reflection. The optical properties confirm the presence of the Wurtzite ZnO phase with an optical gap of 3.27 eV. The catalyst dose (0.25-1 gL-1), pH solution (2.5-11) and initial dye concentration (5-75 mg/L) are optimized. The optimal pH (∼6.7) is close to the natural environment. The photodegradation yield increases with decreasing the SR 3BL concentration. The equilibrium is reached within 160 min and the data are well fitted by the Langmuir-Hinshelwood model; the SR 3BL disappearance obeys to a first-order kinetic with an apparent rate constant of 10-2 mn-1. The best yield of SR 3BL photodegradation (92%) is achieved for a concentration of 5 mg/L and a catalyst dose of 0.75 gL-1 at free pH.

Biosorption of Ni(II) by Fig Male: Optimization and Modeling Using a Full Factorial Design.

The fig male (FM) is successfully used as biosorbent for Ni(2+) removal. The maximum removal efficiency (96.6%) is obtained at pH ~ 5 for a concentration of 1.70 mmol L(-1) and catalyst dose of 5 g L(-1) in less than 10 minutes. The Ni(2+) uptake follows a pseudo-second-order kinetic, the rate constants increase with increasing temperature, and an activation energy of 55.48 kJ mol(-1) is found. The thermodynamic parameters indicate a spontaneous endothermic bisorption. The isotherm data are fitted by the Langmuir and Dubinin-Radushkevich models. The former indicates a maximum Ni(2+) uptake of 0.459 mmol g(-1), which is higher than that of most biosorbents investigated to date. The FTIR spectra reveal the biosorption mechanism between Ni(2+) and FM functional groups. An empirical modeling is performed by using a 2(3) full factorial design, and a regression equation for Ni(2+) biosorption is determined. The biosorbent mass and pH are the most significant parameters affecting the Ni(2+) biosorption.

Visible light CrO4(2-) reduction using the new CuAlO2/CdS hetero-system.

In this study, 64% of hexavalent chromium Cr(VI) reduction from the initial concentration (10(-4) M) is reported under visible light using the (CuAlO(2)/CdS) hetero-system. In this new hetero-system, low doped CuAlO(2) delafossite, synthesized by sol-gel works as an electrons reservoir with a wide space charge region (440 nm). In this case, the electron transfer to chromate is mediated via the hexagonal CdS variety, whose conduction band level is at -1.08 V with respect to the saturated calomel electrode which is more negative than the CrO(4)(2-)/Cr(3+) level. This high reduction rate is achieved under optimized pH and CuAlO(2) percentage. Moreover, salicylic acid gives the best performance among hole scavengers and CuAlO(2) approaches 100% photostability at pH 7.5. The photo-catalytic process follows a pseudo first order kinetic with a half life of 2h. The reaction products are identified by UV-visible spectrophotometry and linear voltametry at a platinum rotating electrode. The results reveal the presence of Cr(3+) after irradiation.

Visible light induced H2PO(4)(-) removal over CuAlO2 catalyst.

The delafossite CuAlO(2) is successfully used for the visible light driven H(2)PO(4)(-) reduction. It is prepared from the nitrates decomposition in order to increase the ratio of reaction surface per given mass. CuAlO(2) is a narrow band gap semiconductor which exhibits a good chemical stability with a corrosion rate of 1.70 µmol year(-1) at neutral pH. The flat band potential (+0.25 V(SCE)) is determined from the Mott-Schottky characteristic. Hence, the conduction band, positioned at (-1.19 V(SCE)), lies below the H(2)PO(4)(-) level yielding a spontaneous reduction under visible illumination. The photocatalytic process is investigated under mild conditions and 30% conversion occurs in less than ~6h with a quantum efficiency of 0.04% under full light. The concentration decreases by a factor of 39% after a second cycle. The photoactivity follows a first order kinetic with a rate constant of 6.6 × 10(-2)h(-1). The possibility of identifying the reaction products via the intensity-potential characteristics is explored. The decrease of the conversion rate over illumination time is due to the competitive water reduction.

Photocatalytic reduction of Cr(VI) on the new hetero-system CuAl2O4/TiO2.

Visible light driven HCrO(4)(-) reduction was successfully achieved over the new hetero-system CuAl(2)O(4)/TiO(2). The spinel, elaborated by nitrate route, was characterized photo electrochemically. The optical gap was found to be 1.70 eV and the transition is directly allowed. The conduction band (-1.05 V(SCE)) is located below that of TiO(2), more negative than the HCrO(4)(-)/Cr(3+) level (+0.58 V(SCE)) yielding a thermodynamically feasible chromate reduction upon visible illumination. CuAl(2)O(4) is stable against photo corrosion by holes consumption reaction involving salicylic acid which favors the charges separation. There is a direct correlation between the dark adsorption and the photo activity. A reduction of more than 95% of chromate was achieved after 3 h irradiation at pH 2 with an optimal mass ratio (CuAl(2)O(4)/TiO(2)) equal to 1/3. The reduction follows a first order kinetic with a half life of ∼1 h and a quantum yield of 0.11% under polychromatic light. Prolonged illumination was accompanied by a deceleration of the Cr(VI) reduction thanks to the competitive water discharge. The hydrogen evolution, an issue of energetic concern, took place with a rate of 3.75 cm(3) (g catalyst)(-1) h(-1).

Photocatalytic reduction of Cr(VI) on the novel hetero-system CuFe(2)O(4)/CdS.

The photocatalytic HCrO(4)(-) reduction was investigated in air equilibrated solution using the spinel CuFe(2)O(4) nanoparticles as sensitizers. The oxide is p-type semi conductor, prepared from nitrates decomposition. The catalytic performance increases with decreasing pH and the concomitant oxidation of salicylic acid contributes significantly to the photoactivity through the charges separation of electron/hole pairs (C(7)H(6)O(3)+6 O(2)+4h(+)+3 H(2)O → 7 CO(2)+4 H(3)O(+)). Evidence has been given to show the advantages of the hetero-system CuFe(2)O(4)/CdS in the chromate reduction. CuFe(2)O(4) acts as electrons pump and the electron transfer to chromate is mediated via CdS hexagonal variety (greenockite). A reduction of 60% occurs and the process is well described by a pseudo first order kinetic with a half life of ∼2.8h and a quantum yield of ∼0.12% for an initial HCrO(4)(-) concentration of 3 × 10(-4)M. An improvement up to 72% is obtained when the reaction occurs in a stirred reactor and no cadmium was detected after 6h illumination. The results indicate a competitive effect with the water reduction. The hydrogen evolutions are found to be 0.236 and 0.960 cm(3)mn(-1)g(-1) in presence and in absence of HCrO(4)(-), respectively.

Adsorption of Zn2+ ions onto NaA and NaX zeolites: kinetic, equilibrium and thermodynamic studies.

The adsorption of Zn(2+) onto NaA and NaX zeolites was investigated. The samples were synthesized according to a hydrothermal crystallization using aluminium isopropoxide (Al[OCH(CH(3))(2)](3)) as a new alumina source. The effects of pH, initial concentration, solid/liquid ratio and temperature were studied in batch experiments. The Freundlich and the Langmuir models were applied and the adsorption equilibrium followed Langmuir adsorption isotherm. The uptake distribution coefficient (K(d)) indicated that the Zn(2+) removal was the highest at minimum concentration. Thermodynamic parameters were calculated. The negative values of standard enthalpy of adsorption revealed the exothermic nature of the adsorption process whereas the negative activation entropies reflected that no significant change occurs in the internal structure of the zeolites solid matrix during the sorption of Zn(2+). The negative values of Gibbs free energy were indicative of the spontaneity of the adsorption process. Analysis of the kinetic and rate data revealed that the pseudo second-order sorption mechanism is predominant and the intra particle diffusion was the determining step for the sorption of zinc ions. The obtained optimal parameters have been applied to wastewater from the industrial zone (Algeria) in order to remove the contained zinc effluents.

Visible light degradation of Orange II using xCuyOz/TiO2 heterojunctions.

Cu(2)O/TiO(2), Cu/Cu(2)O/TiO(2) and Cu/Cu(2)O/CuO/TiO(2) heterojunctions were prepared and studied for their potential application as photocatalysts able to induce high performance under visible light. Orange II was used as a representative dye molecule. The effect of the amount and composition of the photosensitizers toward the activation of TiO(2) was studied. In each case, the global mechanism of Inter Particle Electrons Injection (IPEI) was discussed. The highest photocatalytic activity was observed for the system Cu/Cu(2)O/CuO (MB2 catalyst) under visible light (t(1/2)=24 min, k=159.7 x 10(-3)min(-1)) and for the heterojunction cascade Cu/Cu(2)O/CuO/TiO(2) (MB2 (50%)/TiO(2)) under UV-vis light (t(1/2)=4 min, k=1342 x 10(-3)min(-1)). In the last case, the high performance was attributed firstly to the electromotive forces developed under this configuration in which CuO energy bands mediate the electrons transfer from Cu(2)O to TiO(2). The formation of monobloc sensitizers also accounts for the decrease of the probability of the charges lost. It was demonstrated that "Cu(2)O/CuO" governs the capability of the heterojunction cascade and Cu does not play a significant role regardless of the heterojunction cascade efficiency. The electrical energy consumption per order of magnitude for photocatalytic degradation of Orange II was investigated for some representative catalytic systems. Visible/MB2 and UV/vis MB2 (50%)/TiO(2) exhibited respectively 0.340 and 0.05 kW hm(-3) demonstrating the high efficiency of the systems.

Photocatalytic removal of M(2+) (Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Ag(+)) over new catalyst CuCrO(2).

The metal ions M(2+) (Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Ag(+)) are potentially toxic. Their electro deposition has been carried out in aqueous air-equilibrated CuCrO(2) suspension upon visible illumination. The delafossite CuCrO(2) is p-type semiconductor characterized by a low band gap (1.28 eV) and a long-term chemical stability. The corrosion rate is found to be 10(-2) micromol m(-2)month(-1) in aqua regia. The oxide has been elaborated through nitrate route where the specific surface area is increased via the surface/bulk ratio. A correlation exists between the dark M(2+) adsorption, the redox potential of M(2+/0) couple and the conduction band of CuCrO(2) positioned at -1.06 V(SCE). Ag(+) cannot be photoreduced because of its positive potential located far above the valence band. By contrast, Zn(2+) is efficiently deposited due to the large driving force at the interface. The improved photoactivity of copper with a deposition percentage (90%) is attributed to the strong dark adsorption onto the surface catalyst. The results indicate a competitive effect with the water reduction; it has been observed that the M(2+) deposition goes parallel with the hydrogen evolution. Such behavior is attributed to the low H(2) over voltage when ultra fine aggregate of M islands are photodeposited onto CuCrO(2) substrate.

The physical properties of oxygen-deficient perovskite SrPbO(3-δ).

The transport properties of oxygen-deficient perovskite SrPbO(3-δ) with mixed lead valency were investigated down to 4.2 K. The small δ-value (0.059), determined from iodometry, is due to the inert lone pair Pb(2+) that does not enjoy regular octahedral coordination in spite of collective electron behaviour. The oxide exhibits a temperature-independent magnetic susceptibility consistent with itinerant electrons. The sign of carriers like polarons is that of n-type conductivity coming from the balance charge via oxygen extraction. The thermal variation of conductivity and thermopower reveal the existence of an energy gap. The conduction mechanism occurs by polaron hopping in conformity with small activation energy. The metal-insulating transition seems to be of Anderson type, resulting from the disorder of oxygen vacancies. At low temperature, the conductivity was fitted to a variable range hopping [Formula: see text]. A comparison with SrSnO(3) will be reported. The covalency of Sn-O raises the antibonding conduction state of 5s parentage and increases the forbidden gap from 1.78 to 3.30 eV.