Solar photocatalytic degradation of azo dye: comparison of photocatalytic efficiency of ZnO and TiO2

The photocatalytic activity of commercial ZnO powder has been investigated and compared with that of Degussa P25 TiO₂. Laboratory experiments with acid brown 14 as the model pollutant have been carried out to evaluate the performance of both ZnO and TiO₂ catalysts. Solar light was used as the energy source for the photocatalytic experiments. These catalysts were examined for surface area, particle size and crystallinity. The effect of initial dye concentration, catalyst loading, irradiation time, pH, adsorption of acid brown 14 on ZnO and TiO₂, intensity of light and comparison of photocatalytic activity with different commercial catalysts were studied. The progress of photocatalytic degradation of the acid brown 14 has been observed by monitoring the change in substrate concentration of the model compound employing HPLC and measuring the absorbance in UV–Visible spectrophotometer for decolourisation. The photodegradation rate was determined for each experiment and the highest values were observed for ZnO suggesting that it absorbs large fraction of the solar spectrum and absorption of more light quanta than TiO₂. The complete mineralisation was confirmed by total organic carbon (TOC) analysis, COD measurement and estimation of the formation of inorganic ions such as NH₄⁺, NO₃⁻, Cl⁻ and SO₄²⁻.     

Biological hydrogen production from phenol-containing wastewater using Clostridium butyricum

Toxicity renders certain industrial effluents unfit for recovering its bioenergy content. An enriched single strain, Clostridium butyricum, was herein applied to fermentatively produce hydrogen from glucose in the presence of 200–1500 mg L⁻¹ of phenol. The enriched C. butyricum yielded hydrogen at approximately 1.4 mol H₂ mol⁻¹ glucose in the presence of 200–400 mg L⁻¹ phenol. Significant inhibition of cell metabolism was noted at phenol concentration >1000 mg L⁻¹. During glucose fermentation, phenol dosed at 200–400 mg L⁻¹ was partly co-degraded. Ethanol and acetate were the primary metabolites, whose yields increased with increasing phenol concentration. The present results revealed the potential to harvest hydrogen from a toxic (phenol-containing) wastewater.     

Effect of loaded silver nanoparticles on TiO2 for photocatalytic degradation of Acid Red 88

Nanometer sized Ag–TiO₂ nanoparticles were prepared (by photoreduction of Ag⁺ ions) in order to assess its photocatalytic degradation ability of target pollutant (textile dye; Acid red 88) upon visible light irradiation. Furthermore, oxidative reagents such as peroxomonosulfate (PMS), peroxodisulfate (PDS) and hydrogen peroxide (H₂O₂) were added to the photocatalytic system, which may act as an alternative electron acceptor and result in a notably enhanced degradation rate (seven-fold increase with PMS as oxidant) of pollutant destruction. Mineralization of target pollutant was also performed by total organic carbon (TOC) analysis and from the results, it was confirmed that 65% mineralization was achieved in 7 h using PMS as electron acceptor. Overall, this system is relatively inexpensive, reproducible, extremely stable and efficient in complete degradation of dye in aqueous solution. In order to obtain maximum information about the performance of Ag–TiO₂ photocatalyst, we did experiments under different operating conditions, i.e., variation of amount of catalyst, concentration of dye and electron acceptors. In addition to the above, a comparative study on the photocatalytic activities of TiO₂ was also made.     

Photocatalytic colour and COD removal in the distillery effluent by solar radiation

The photodegradation of distillery effluent has been studied for removal of colour and COD reduction in the presence of solar radiation. The influence of experimental parameters such as H₂O₂ concentration dosage, effluent COD concentration, TiO₂ catalyst and pH on colour and COD removal efficiency through solar photochemical process has been investigated. Maximum colour removal of the distillery effluent achieved was 79% at an H₂O₂ concentration of 0.3 M, pH 6, effluent COD concentration of 500 ppm and catalyst dosage of 0.1 g/L. The TiO₂/H₂O₂ system seems to be more efficient in comparison to the synergetic action that appears when using H₂O₂ and TiO₂. The photocatalytic degradation process using solar light as an irradiation source showed potential application for the colour removal of the distillery effluent treatment. Solar radiation can be an considered as an alternative, effective and economic energy carrier for the treatment of industrial effluent.     

TiO2-assisted degradation of acid orange 7 textile dye under solar light

Photocatalytic degradation of acid orange 7 (AO7) in aqueous systems was successfully achieved by the combination of TiO₂ with potassium persulphate under solar light using a photochemical reactor with recirculation. Degradation of AO7 involves color removal and mineralization. The employment of TiO₂ removed 85% of color from the 0.2 mM AO7 aqueous solution under solar light; while, 66% of color was abated using the persulphate ion as oxidant in the absence of TiO₂ under similar conditions in 2 h. However, over 90% of color removal was achieved by combining TiO₂ and the persulphate ion for the same solution under similar conditions. Color removal was faster at pH 3. Mineralization of AO7 was followed by measuring chemical oxygen demand (COD). Negligible COD abatement of the textile dye was observed in the absence of persulphate ions (S₂O₈²⁻) while over 70% of COD abatement was observed for the initial dye concentrations of 0.2–0.7 mM employing a mix of TiO₂–S₂O₈²⁻ under solar light.     

Solar chemical reactor technology for industrial production of lime

We developed the solar chemical reactor technology to effect the endothermic calcination reaction CaCO₃(s) → CaO(s) + CO₂(g) at 1200–1400 K. The indirect heating 10 kW_th multi-tube rotary kiln prototype processed 1–5 mm limestone particles, producing high purity lime that is not contaminated with combustion by-products. The quality of the solar produced quicklime meets highest industrial standards in terms of reactivity (low, medium, and high) and degree of calcination (exceeding 98%). The reactor’s efficiency, defined as the enthalpy of the calcination reaction at ambient temperature (3184 kJ kg⁻¹) divided by the solar energy input, reached 30–35% for quicklime production rates up to 4 kg h⁻¹. The solar lime reactor prototype operated reliably for more than 100 h at solar flux inputs of about 2000 kW m⁻², withstanding the thermal shocks that occur in solar high temperature applications. By substituting concentrated solar energy for fossil fuels as the source of process heat, one can reduce by 20% the CO₂ emissions in a state-of-the-art lime plant and by 40% in a conventional cement plant. The cost of solar lime produced in a 20 MW_th industrial solar calcination plant is estimated in the range 131–158 $/t, i.e. about 2–3 times the current selling price of conventional lime.     

Visible-light-driven TiO2 catalysts doped with low-concentration nitrogen species

Visible-light-driven nitrogen-doped TiO₂ was synthesized using a novel nitrogen-ion donor of hydrazine hydrate. Low-concentration (0.2 at%) nitrogen species and Ti³⁺ were detected in the TiO₂-based photocatalyst by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectroscopy. The trace amount of Ti–N would contribute to the minor band-gap narrowing of about 0.02 eV. Those nitrogen-containing species, especially the NO₂²⁻ species, form surface states, which make the catalysts possible to degrade 4-chlorophenol (4-CP) under visible irradiation (λ>400 nm). Moreover, Ti³⁺ species induce oxygen vacancy states between the valence and the conduction bands, which would also contribute to the visible response. The photocatalytic activity of the nitrogen-doped TiO₂ catalyst was thought to be the synergistic effect of nitrogen and Ti³⁺ species. The catalysts showed higher photocatalytic activity for degradation of 4-CP than pure TiO₂ under not only visible but also UV irradiation. The visible response and the higher UV activity of the nitrogen-doped TiO₂ make it possible to utilize solar energy efficiently to execute photocatalysis processes.     

Solar photocatalytic degradation of methylene blue in carbon-doped TiO2 nanoparticles suspension

Carbon-doped TiO₂ nanoparticles were prepared by sol–gel auto-combustion method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Brunauer–Emmett–Teller method (BET), UV–vis diffuses reflectance spectroscopy (DRS). UV–vis diffuse reflectance spectra showed that carbon-doped TiO₂ exhibited obvious absorption in the visible light range. The visible light photocatalytic activity of carbon-doped TiO₂ was ascribed to the presence of oxygen vacancy state between the valence and the conduction bands because of the formation of Ti³⁺ species in the as-synthesized carbon-doped TiO₂. The sample calcined at 873 K showed the highest photocatalytic activity under solar irradiation. The effects of photocatalyst concentration, initial concentration of methylene blue, and pH value in aqueous solution were also presented.     

Hydrogen–methane production from swine manure: Effect of pretreatment and VFAs accumulation on gas yield

A two-phase anaerobic process to produce hydrogen and methane from swine manure was investigated, using pretreated sludge with heat, acid and alkali treatment as inoculum. The relative order of pretreatment methods of H₂ productivity effectiveness and CH₄ productivity effectiveness produced by the residua of the first phase was heat treatment > alkali treatment > acid treatment. When the inoculum sludge was heat-treated at 80°C for 30 min, the H₂ and CH₄ production rate was the highest of 36.6, 201.7 ml (g TS)_added⁻¹. There were significant correlations between biogas production and accumulation of acetic acid and butyric acids. When propionic acid and total VFA concentrations reached about 2850 mg L⁻¹ and 10.0 g L⁻¹, respectively, the average H₂ production rate and H₂ content decreased from 7.6 ml d⁻¹(g VS)_added⁻¹ and 55.3% to 1.4 ml d⁻¹(g VS)_added⁻¹ and 43.2%, respectively. The activity of methanogenic bacteria was inhibited to a significant extent when the total VFA concentration was above 10.0 g L⁻¹, but this inhibitory effect weakened when the VFA concentration fell to 6200–8500 mg L⁻¹. Correspondingly, average CH₄ production rate increased from 4.0 ml d⁻¹(g TS)_added⁻¹ to 12.5 ml d⁻¹(g TS)_added⁻¹. Propionic acid was degraded rapidly only when acetic and butyric acid concentrations dropped to 2500 mg L⁻¹ and 1000 mg L⁻¹, respectively.     

The photoinduced evolution of O2 and H2 from a WO3 aqueous suspension in the presence of Ce/Ce

This is a report on the production of O₂ and H₂ from photocatalytic and photochemical processes in the WO₃–H₂O–Ce⁴⁺_aq–hν system. The photoproduction of O₂ and H₂ was studied over the range of WO₃ concentrations from 2 to 8 g dm⁻³, and conduction band electron scavenger concentrations 1–20 mM Ce_aq⁴⁺. Medium and high concentrations of the electron scavenger gave mainly O₂ as the main product. Dilute solutions of [Ce_aq⁴⁺]< 2 mM initially produced dioxygen, and then hydrogen after an induction period of 3–4 h. Yields of 140–250 μmol O₂  h⁻¹ and 1–7 μmol H₂ h⁻¹ were obtained and were found to depend on the physical properties and content of WO₃, the concentration of the electron scavenger, illumination period and wavelength, and the radiation geometry. The photoactivity of the suspension was correlated to the level of crystallinity of WO₃ powders. The studied system utilizes WO₃ to accomplish the initial light absorption, charge separation, and production of O₂ and H⁺ from the interaction of water molecules with photogenerated WO₃ valence band holes, in the presence of Ce⁴⁺_aq species as a scavenger of conduction band electrons. This is followed by the evolution of H₂ from a homogeneous photochemical reduction of H⁺ and/or H₂O by photoexcited Ce³⁺_aq, formed from the earlier reduction of Ce⁴⁺_aq. The obtained results show that, with an appropriate design, tungsten trioxide is a promising material that can be used as a photoactive component in energy conversion systems or in environmental photocatalysis, using artificial or solar light.     

Direct methanol fuel cell operation with pre-stretched recast Nafion

Direct methanol fuel cell operation with uniaxially pre-stretched recast Nafion^® membranes (draw ratio of 4) was investigated and compared to that with commercial (un-stretched) Nafion^®. The effects of membrane thickness (60–250 μm) and methanol feed concentration (0.5–10.0 M) on fuel cell power output were quantified for a cell temperature of 60 °C, ambient pressure air, and anode/cathode catalyst loadings of 4.0 mg cm⁻². Pre-stretched recast Nafion^® in the 130–180 μm thickness range produced the highest power at 0.4 V (84 mW cm⁻²), as compared to 58 mW cm⁻² for Nafion^® 117. MEAs with pre-stretched recast Nafion^® consistently out-performed Nafion^® 117 at all methanol feed concentrations, with 33–48% higher power densities at 0.4 V, due to a combination of low area-specific resistance (the use of a thinner pre-stretched membrane, where the conductivity was the same as that for commercial Nafion^®) and low methanol crossover (due to low methanol solubility in the membrane). Very high power was generated with a 180-μm thick pre-stretched recast Nafion^® membrane by increasing the cell temperature to 80 °C, increasing the anode/cathode catalyst loading to 8.0 mg cm⁻², and increasing the cathode air pressure to 25 psig. Under these conditions the power density at 0.4 V for a 1.0-M methanol feed solution was 240 mW cm⁻² and the maximum power density was 252 mW cm⁻².     

Simulation and model validation of a horizontal shallow basin solar concentrator

Salt removal from drainage water is becoming increasingly important for sustainable irrigated arid land agriculture, where inadequate drainage infrastructure exists. Solar evaporation and concentration systems are currently in development in California for this purpose. The thermal behavior and evaporation rates of a horizontal shallow basin solar concentrator were modeled for design purposes and investigated experimentally in order to validate the model. Three different evaporation rate models were evaluated and compared. Measured and predicted peak brine temperatures differed by as much as 5 °C when using prescribed literature coefficients without calibration. Model prediction was improved by calibration so that peak brine temperature deviated less than 3 °C when tested against independent data sets.Minimum root mean square error was used to calibrate the mass transfer coefficient and absorptance of the collector surface for solar radiation, which are the main factors affecting the heat transfer associated with the solar concentrator. Calibrated collector surface absorptance for solar radiation declined while mass transfer coefficients were increased from reported literature values. Under calibration, the absorptance of the collector surface was adjusted from 0.8 to 0.61, and mass transfer coefficients estimated by Newell et al. [Newell, T.A., Smith, M.K., Cowie, R.G., Upper, J.M., Cler, C.L., 1994. Characteristics of a solar pond brine reconcentration system. Journal of Solar Energy Engineering 116 (2), 69–73] from 1.36 × 10⁻⁶(1.9 + 1.065V) to 1.70 × 10⁻⁶(1.84 + 1.0V) kg m⁻² s⁻¹ mm Hg⁻¹, by Manganaro and Schwartz [Manganaro, J.L., Schwartz, J.C., 1985. Simulation of an evaporative solar salt pond. Industrial & Engineering Chemistry Process Design and Development 24, 1245–1251] from 0.0208(1 + 0.224V) to 0.0233(1 + 0.214V) kg m⁻² h⁻¹ mm Hg⁻¹, and by Alagao et al. [Alagao, F.B., Akbarzadeh, A., Johnson, P.W., 1994. The design, construction, and initial operation of a closed-cycle, salt-gradient solar pond. Solar Energy 53 (4), 343–351] from 2.8 + 3.0V to 3.0 + 3.33V W m⁻² °C⁻¹. The calibrated models were tested using an independent data set. Maximum deviation between measured and predicted brine temperatures differed by less than 3 °C. The measured and predicted peak evaporation rates were between 1.2 and 1.4 kg m⁻² h⁻¹.The calibrated Newell model was used to predict the monthly productivity and daily maximum evaporation rates at Five Points, California for the year 2004. The productivity from April to September and from March to October was 80.7% and 94.3% of the total annual productivity, respectively.     

Assessment and influence of operational parameters on the TiO2 photocatalytic degradation of sodium benzene sulfonate under highly concentrated solar light illumination

Sodium benzene sulfonate (BS) was decomposed in aqueous TiO₂ dispersions under highly concentrated solar light illumination to examine the photocatalytic characteristics of a parabolic round concentrator (PRC) reactor to degrade the pollutant without visible light absorption. The effects of such operational parameters as initial concentration, volume of the aqueous BS solution, oxygen purging, and TiO₂ loading on the kinetics of decomposition of BS were investigated. An effective photodegradation necessitates a suitable combination of initial volume and concentration of BS solution. Relative to atmospheric air, oxygen purging significantly accelerates the degradation process at high initial concentrations of BS (0.40 mM or 1.0 mM). Optimal TiO₂ loading was 9 g l⁻¹, greater than previously reported. Elimination of TOC (total organic carbon) followed pseudo first-order kinetics in the initial stages of the photodegradation process. The relative photonic efficiency for the photodegradation of BS is ζ_rel=1.0.     

Photocatalysis of 4-chlorophenol mediated by TiO2 fixed to concrete surfaces

Titanium dioxide (TiO₂) powder was mixed with varying concrete sealer formulations and applied to prepared concrete surfaces within PVC batch reactors. A solution of 4-chlorophenol in de-ionized water, with an initial 4-chlorophenol concentration of 4 mg/L, was added to each open reactor. The photocatalytic efficiency of each TiO₂-sealer was determined through bulk solution sampling while a reactor was exposed to continuous UV light. Through analysis of mean 4-chlorophenol concentrations, the disappearance of 4-chlorophenol from solution was attributed solely to the presence of TiO₂ in the sealed concrete surface of a UV exposed reactor. The rate of disappearance increased when the mass percent of TiO₂ in the sealer was increased. The zero-order reaction rate constants ranged from 0.135 to 0.2873 mg L⁻¹ h⁻¹.     

Influence of electrolyte on the photovoltaic performance of a dye-sensitized TiO2 solar cell based on a Ru(II) terpyridyl complex photosensitizer

We have investigated the influence of electrolyte composition on the photovoltaic performance of a dye-sensitized nanocrystalline TiO₂ solar cell (DSSC) based on a Ru(II) terpyridyl complex photosensitizer (the black dye). We have also spectroscopically investigated the interaction between the electrolyte components and the adsorbed dye. The absorption peaks attributed to the metal-to-ligand charge transfer transitions of the black dye in solution and adsorbed on a TiO₂ film, were red-shifted in the presence of Li cations, which led to an expansion of the spectral response of the solar cell toward the near-IR region. The photovoltaic performance of the DSSC based on the black dye depended remarkably on the electrolyte composition. We developed a novel efficient organic liquid electrolyte containing an imidazolium iodide such as 1,2-dimethyl-3-n-propylimidazolium iodide or 1-ethyl-3-methylimidazolium iodide (EMImI) for a DSSC based on the black dye. A high solar energy-to-electricity conversion efficiency of 9.2% (J_sc=19.0 mA cm⁻², V_oc=0.67 V, and FF=0.72) was attained under AM 1.5 irradiation (100 mW cm⁻²) using a novel electrolyte consisting of 1.5 M EMImI, 0.05 M iodine, and acetonitrile as a solvent with an antireflection film.     

The effect of temperature on the charge transport and transient absorption properties of K27 sensitized DSSC

The charge transport and transient absorption properties of K27 dye-sensitized solar cell have been investigated. The current–voltage (I–V) characteristics of the solar cell were analyzed by the thermionic emission theory. The ideality factor, barrier height and series resistance values of the solar cell were determined. The ideality factor higher than unity indicated the presence of non-ideal behavior in current–voltage characteristics at lower voltages. At the higher voltages, the charge transport mechanism for the solar cell is controlled by a space-charge limited current (SCLC) with an exponential distribution of traps. The built potential values are determined from capacitance–voltage plot and were found to be 0.14 and 0.58 V, respectively. The transient absorption data of K27 DSSC device suggest that the fast and slow phases are taking place. While the fast phase corresponds to regeneration of the dye cation by the iodide redox couple, the slow phase corresponds to the decay of long-lived I₂⁻/ TiO₂ electron absorption. The best conversion efficiency for K27 DSSC was found to be 0.317% under 100 mW/cm² (FF=0.584, V_oc=480 mV, I_sc=1.131 mA). The photocurrent results indicate that the photogeneration of charge carriers is a monophotonic process.     

Stability of thin film solar cells having less-hydrogenated amorphous silicon i-layers

In this study, highly stabilized hydrogenated amorphous silicon films and their solar cells were developed. The films were fabricated using the triode deposition system, where a mesh was installed between the cathode and the anode (substrate) in a plasma-enhanced chemical vapor deposition system. At a substrate temperature of 250 °C, the hydrogen concentration of the resulting film (Si–H=4.0 at%, Si–H₂<1×10²⁰ cm⁻³) was significantly less than that of conventionally prepared films. The films were used to develop the i-layers of solar cells that exhibited a significantly low degradation ratio of 7.96%.     

Drying of hot chilli using solar tunnel drier

A mixed mode type forced convection solar tunnel drier was used to dry hot red and green chillies under the tropical weather conditions of Bangladesh. The drier consisted of transparent plastic covered flat-plate collector and a drying tunnel connected in series to supply hot air directly into the drying tunnel using two fans operated by a photovoltaic module. The drier had a loading capacity of 80 kg of fresh chillies. Moisture content of red chilli was reduced from 2.85 to 0.05 kg kg⁻¹ (db) in 20 h in solar tunnel drier and it took 32 h to reduce the moisture content to 0.09 and 0.40 kg kg⁻¹ (db) in improved and conventional sun drying methods, respectively. In case of green chilli, about 0.06 kg kg⁻¹ (db) moisture content was obtained from an initial moisture content of 7.6 kg kg⁻¹ (db) in 22 h in solar tunnel drier and 35 h to reach the moisture content to 0.10 and 0.70 kg kg⁻¹ (db) in improved and conventional sun drying methods, respectively. The use of a solar tunnel drier and blanching of sample led to a considerable reduction in drying time and dried products of better quality in terms of colour and pungency in comparison to products dried under the sun. The solar tunnel drier and blanching of chilli are recommended for drying of both red and green chillies.     

Sol–gel preparation and characterization of anti-reflective and self-cleaning SiO2–TiO2 double-layer nanometric films

Glass substrates were first coated with SiO₂ and then TiO₂ by dipping into sols which were prepared by two different methods involving complex formation and hydrolysis, using ethanol (EtOH) or butyl glycol (BG). Concentration of TiO₂ in the sols was kept at 0.1 and 0.5 wt%. Prepared coatings were investigated by field-emission scanning electron microscope (FESEM), atomic force microscope (AFM), hazemeter, UV–visible spectrophotometer and goniometer. Rhodamine B (RhB) photodegradation tests were performed in order to evaluate photocatalytic activity. Application of SiO₂ as the bottom layer increased the transmittance by 6% points, thereby compensated for the loss of transmittance caused by the TiO₂ self-cleaning top layer. Pencil-hardness values of the obtained coatings were in 5B–3H range. TiO₂ coatings obtained from sols containing 0.5% TiO₂ and BG solvent represented the highest photocatalytic activity, with a rate constant of 0.44 ppm⁻¹ h⁻¹ and a half period of 5.5 h. Self-cleaning surfaces were obtained while maintaining the anti-reflectance.     

Dye sensitization of antimony-doped CdS photoelectrochemical solar cell

Sb-doped CdS single crystal was used as a photoanode to fabricate a photoelectrochemical solar (PECS) cell. The three organic dyes; eosin, thymol blue and rhodamin 6G were used as sensitizers in (PECS) cell. In the absence of the dye, the results showed that with Sb-doped CdS single crystal electrode, a higher power conversion efficiency 9.27% has been achieved compared to 5.7–7.4% for pure crystal. Application of the dye in PECS cell increases the efficiency to about 13%. The efficiency reaches its maximum value when the dye concentration is (2.5×10⁻⁵)M, sufficient to cover the surface of the semiconductor electrode with a continuous monolayer of the dye. Exceeding this value resulted in a gradual decrease of the efficiency from its maximum value. Mott–Schottky plots gave a doping density of 3.14×10¹⁷ cm⁻³ and a space charge width of 4.95×10⁻⁶ cm for the sample used. A flat-band potential equal to −0.84 V, independent of both frequency and pH, was also predicted. Cyclic voltammetry (c.v.) measurements showed an anodic current peak at 0.4 V vs. SCE. The disappearance of this peak after excess addition of the reducing agent Na₂S, indicates that this peak is due to the PEC corrosion of the semiconductor electrode.