Photocatalytic degradation of aqueous methylene blue using ca-alginate supported ZnO nanoparticles: point of zero charge role in adsorption and photodegradation.

A novel insoluble Ca-Alginate created from soluble Na-Alginate was used as a support substrate for ZnO nanoparticles producing ZnO@Ca-Alginate composite photocatalyst. Fourier Transform Infrared (FT-IR), Ultraviolet-Visible (UV-Vis), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Spectroscopy (EDX), and X-ray Diffraction (XRD) analysis techniques were used in the characterization of the prepared ZnO@Ca-Alginate. The ZnO@Ca-Alginate was tested for its potential use in the photodegradation of Methylene Blue (MB) from an aqueous solution under solar-simulated light. This composite photocatalyst efficiency in MB removal was compared with naked ZnO potential considering different conditions and parameters (e.g. pH, MB concentration, amount of photocatalyst, and irradiation time). The MB concentrations were identified using UV-vis spectrophotometric methods. While, high-performance liquid chromatography (HPLC), Total organic carbon (TOC) analysis, and other elemental analyses were used to confirm the MB complete mineralization. The MB photodegradation results were performed by using UV-vis analysis., the results showed that up to 95% of MB (40 mL, 40 ppm) was removed within 30 min of irradiation using either ZnO@Ca-Alginate or naked ZnO. The pH and the zero-charge point (Pzc) values play a main role in the adsorption and photodegradation results. The Pzc values for Ca-Alginate, ZnO, and Zn@Ca-Alginate were 6.5, 8.8, and 6.8 respectively. The prepared composite catalyst showed a maximum adsorption and photodegradation in a basic to slightly basic medium, the MB completely removed at pH of 7.7 within an hour of irradiation. The complete miniralzation of MB at the end of the photodegrdation process was confirmed. Here it is proved that the ZnO@Ca-Alginate photocatalyst can be recovered and reused without any significant decrease in its effectiveness.

Correction: Optical properties and photoactivity of carbon nanodots synthesized from olive solid wastes at different carbonization temperatures.

[This corrects the article DOI: 10.1039/D1RA09273A.].

Optical properties and photoactivity of carbon nanodots synthesized from olive solid wastes at different carbonization temperatures.

Carbon nanodots (CNDs) have many fascinating properties, such as optical properties (UV-Visible absorption and fluorescence emission), which make them good candidates in many applications, such as photocatalysts for the degradation of several organic pollutants. This study aims to synthesize CNDs from olive solid wastes at different carbonization temperatures from 300 to 900 °C and study the effect on the optical properties of the CNDs, such UV-Vis, fluorescence, quantum yield, and energy bandgap, in addition to the influence on the photoactivity of the CNDs as photocatalysts for the degradation of methylene blue (MB). CNDs were prepared from olive solid wastes (OSWs) by pyrolysis at different temperatures (300-900 °C) for conversion to carbonized material, and then oxidized chemically in the presence of hydrogen peroxide (H2O2). It was found that an increase in the carbonization temperature of the OSWs leads to an increase in the product yield with a maximum value at 500 °C, and it then decreased dramatically. On the other hand, a decrease in fluorescence due to the diminishment of oxygen groups and the destruction of the surface of the CNDs was observed. The higher quantum yield (5.17%) and bandgap (2.77 eV) were achieved for CNDs prepared from OSWs that carbonized at 300 °C. The rate and degradation efficiency of MB were studied with the different synthesized CNDs, and it was found that an increase in the carbonization temperature leads to a decrease in the rate and degradation efficiency of MB, with the highest degradation rate of 0.0575 min-1 and degradation efficiency of 100% after 120 minutes of light irradiation being realized for the sample carbonized at 300 °C.

Effective and selective electroreduction of aqueous nitrate catalyzed by copper particles on multi-walled carbon nanotubes.

Drinking-water contamination with nitrate ions is inevitable and wide spreading, which demands feasible removal. Water de-nitration by potentiostatic electroreduction is described here. A novel electrocatalyst based on nano-copper particles, supported onto multi-walled carbon nanotubes (MWCNTs), and spray-deposited onto fluorine doped tin oxide-glass substrates, is described. The Cu/MWCNT/FTO electrode has been characterized by several methods and assessed as a working electrode in aqueous nitrate ion electroreduction, in comparison with MWCNT sprayed on FTO (MWCNT/FTO) with no copper. Comparison with earlier reported electrodes is also described. XRD patterns confirm the presence of nano-copper crystallites, in the electrode, with average size ⁓45 nm. Within 2 h of electrolysis, Cu/MWVNT/FTO exhibits more than 65% removal of nitrate at -1.80 V (vs. SCE). In longer time (7 h) the electrode completely converts the nitrate into N2 (∼65%) and (NH4+) ∼35% with no NO2- ions. The kinetics show 0.76 order with respect to nitrate, and a rate constant 4.53 × 10-2 min-1 higher than earlier counterparts. The new electrode functions under various conditions of temperature, pH, electrolyte type and concentration and inter-electrode spacing, only at ambient applied potential. Moreover, the electrode exhibits stability under nitrate electroreduction conditions, and can be recovered and reused for multiple times without efficiency loss. XRD and EDS results also confirm the electrode stability after multiple reuse. Compared to earlier systems, the Cu/MWCNT/FTO is environmentally stable, safe, non-costly with high nitrate removal efficiency and selectivity.

Photocatalytic degradation of phenazopyridine contaminant in soil with direct solar light.

Photocatalytic degradation of waste pharmaceutics, with solar radiation, is described here as a feasible method to purify pre-contaminated soils. Phenazopyridine has been used as a model soil contaminant. Two different nano-size powders have been first examined as catalysts, namely commercial TiO2 (anatase) and commercial ZnO. As the ZnO showed higher catalytic efficiency, the study was then focused on it. The commercial ZnO powder was then compared with lab-prepared ZnO powder, and the latter shows relatively higher efficiency. The ZnO was used in two different ways. In one way, dry ZnO catalyst powder was spread onto the soil, while in the other way the ZnO was sprayed onto the soil surface by a wet spray method. The spray technique shows slightly higher efficiency, in addition to being easier to apply at future large scale. Depending on conditions and type of photocatalyst used, up to 90% contaminant removal can be achieved in 30 min. In case of photocatalysis experiments, the reacted contaminant molecules undergo complete degradation with no detectable side reaction organic products. Possible evaporation or escape of organic contaminant, or other possibly resulting organics, is ruled out by a series of control experiments. Photodegradation process takes place only at the catalytic sites on the soil surface, where contaminant molecules that diffuse from the soil bulk are completely degraded. Other useful organisms inside the soil are not affected as they are kept away from catalyst sites. A plausible mechanism is proposed for the degradation process.

Modes of tetra(4-pyridyl)porphyrinatomanganese(III) ion intercalation inside natural clays.

BACKGROUND: Metalloporphyrin ions, with planar shape, have been known to intercalate horizontally and diagonally between montmorillonite layers. Perpendicular intercalation inside montmorillonite has not been reported earlier. This work aims at achieving perpendicular intercalation inside montmorillonite in natural clays. Possible intercalation inside other forms of natural clay will also be investigated. METHODS: Natural clays were purified and characterized. The naked clay powder was then refluxed with tetra(4-pyridyl)porphyrinatomanganese(III) ion (MnTPyP(+)) solution in methanol with continuous stirring for different times. Electronic absorption spectra, atomic absorption spectra, Fourier Transform infrared spectra, scanning electron microscopy and X-ray diffraction were all used in clay characterization and in intercalation study. RESULTS: The natural clay involved different phases, namely montmorillonite, biotite, kaolinite, illite and traces of quartz. Montmorillonite clay allowed horizontal, diagonal and perpendicular intercalation of the metalloporphyrin ions. Biotite allowed only horizontal intercalation. The mode of intercalation was deduced by monitoring the clay inter-planar distance value change. Intercalation occurred inside both micro- and nano-size clay powders to different extents. The nano-powder (average size ~50 nm) showed uptake values up to 3.8 mg MnTPyP/g solid, whereas the micro-size powder (average size ~316 nm) exhibited lower uptake (2.4 mg MnTPyP/g solid). Non-expandable clay phases did not allow any intercalation. The intercalated MnTPyP(+) ions showed promising future supported catalyst applications. CONCLUSIONS: Depending on their phase, natural clays hosted metalloporphyrin ions. Montmorillonite can allow all three possible intercalation geometries, horizontal, diagonal and for the first time perpendicular. Biotite allows horizontal intercalation only. Non-expandable clays allow no intercalation. Graphical abstractMetalloporphyrin complexes can be intercalated into montmorillonite in horizontal, perpendicular and diagonal geometries.

Optimizing photo-mineralization of aqueous methyl orange by nano-ZnO catalyst under simulated natural conditions.

BACKGROUND: Photo-degradation of organic contaminants into non-hazardous mineral compounds is emerging as a strategy to purify water and environment. Tremendous research is being done using direct solar light for these purposes. In this paper we report on optimum conditions for complete mineralization of aqueous methyl orange using lab-prepared ZnO nanopowder catalyst under simulated solar light. RESULTS: Nano-scale ZnO powder was prepared in the lab by standard methods, and then characterized using electronic absorption spectra, photolumenscence emission (PL) spectra, XRD, and SEM. The powder involved a wurtzite structure with ~19 nm particles living in agglomerates. Photo-degradation progressed faster under neutral or slightly acidic conditions which resemble natural waters. Increasing catalyst concentration increased photodegradation rate to a certain limit. Values of catalyst turn over number and degradation percentage increased under higher light intensity, whereas the quantum yield values decreased. The photocatalytic efficiency of nano-ZnO powders in methyl orange photodegradation in water with solar light has been affected by changing the working conditions. More importantly, the process may be used under natural water conditions with pH normally less than 7, with no need to use high concentrations of catalyst or contaminant. The results also highlight the negative impact of possible high concentrations of CO2 on water purification processes. Effects of other added gaseous flows to the reaction mixture are also discussed. CONCLUSION: ZnO nano-particles are useful catalyst for complete mineralization of organic contaminants in water. Photo-degradation of organic contaminants with ZnO nano-particles, methyl orange being an example, should be considered for future large scale water purification processes under natural conditions.

Solid olive waste in environmental cleanup: enhanced nitrite ion removal by ZnCl2-activated carbon.

This communication describes how olive solid wastes can be used to prepare activated carbon (AC), with soundly high surface areas, suitable to remove nitrite ions from water. Solid olive wastes, so called Jeft, separated as unwanted bi-products from olive oil mills, have been converted into charcoal. The charcoal was then physically and/or chemically activated using different compounds namely conc. H3PO4 or ZnCl2. Charcoal carbonization was performed under inert atmosphere to avoid loss of heated carbon by oxidation with air. Surface area measurements and SEM micrographs showed that activation using ZnCl2 yields AC with highest surface area and more porous surfaces. The ZnCl2-activated carbon was then used to remove nitrite ions from water by adsorption. Effects of different parameters on value of surface area and adsorption capacity of the AC were investigated. Commercial AC materials were used as reference for comparison. The AC showed higher adsorption capacity toward nitrite than other reported adsorbents. The results suggest that using 5 g of the ZnCl2-activated carbon per liter of heavily nitrite-contaminated water (50 ppm) may bring the contaminant concentration down to the WHO accepted concentration limits within 60 min. This work highlights the future feasibility of using olive waste as feed stocks to produce useful renewable materials while keeping in mind the wisdom "make wastes work in environmental protection".

CdS-sensitized TiO2 in phenazopyridine photo-degradation: catalyst efficiency, stability and feasibility assessment.

Mineralization of phenazopyridine, 1, in water, under solar-simulator radiation was efficiently achieved using nanoparticle CdS-sensitized rutile TiO(2), TiO(2)/CdS, 2, as photo-catalysts. Despite that, 2 showed two main drawbacks. Firstly, the system was difficult to recover by simple filtration, and demanded centrifugation. Secondly, the sensitizer CdS showed relatively high tendency to leach out hazardous Cd(2+) ions under photo-degradation reaction conditions. In an attempt to solve out such difficulties, 2 was supported onto sand surface. The sand/TiO(2)/CdS system, 3, was easier to recover but showed slightly lower catalytic activity compared to 2. On the other hand, the support failed to prevent leaching of Cd(2+). This indicates limited future applicability of CdS-sensitized TiO(2) photo-catalyst systems, in solar-based water purification strategies, unless leaching out tendency is completely prevented.

Solid olive waste in environmental cleanup: oil recovery and carbon production for water purification.

A potentially-economic three-fold strategy, to use solid olive wastes in water purification, is presented. Firstly, oil remaining in solid waste (higher than 5% of waste) was recovered by the Soxhlet extraction technique, which can be useful for the soap industry. Secondly, the remaining solid was processed to yield relatively high-surface area active carbon (AC). Thirdly, the resulting carbon was employed to reversibly adsorb chromate ions from water, aiming to establish a water purification process with reusable AC. The technique used here enabled oil recovery together with the production of a clean solid, suitable for making AC. This process also has the advantage of low production cost.