Photocatalytic hydrogen production with iron oxide under solar irradiation

As solar hydrogen is a sustainable and environmental friendly energy carrier, it is considered to take the place of fossil fuels in the near future. Solar hydrogen can be generated by splitting of water under solar light illumination. In this study, the use of nanostructured hematite thin-film electrodes in photocatalytic water splitting was investigated. Hematite (á-Fe2O3) has a narrow band-gap of 2.2 eV, which is able to utilise approximately 40% of solar radiation. However, poor photoelectrochemical performance is observed for hematite due to low electrical conductivity and a high rate of electron-hole recombination. An extensive review of useful measures taken to overcoming the disadvantages of hematite so as to enhance its performance was presented including thin-film structure, nanostructuring, doping, etc. Since semiconductoring materials which exhibit an inverse opal structure are expected to have a high surface-volume ratio, unique optical characteristics and a shorter distance for photogenerated holes to travel to the electrode/electrolyte interface, inverse opals of hematite thin films deposited on FTO glass substrate were successfully prepared by doctor blading using PMMA as a template. However, due to the poor adhesion of the films, an acidic medium (i.e., 2 M HCl) was employed to significantly enhance the adhesion of the films, which completely destroyed the inverse opal structure. Therefore, undoped, Ti and Zn-doped hematite thin films deposied on FTO glass substrate without an inverse opal structure were prepared by doctor blading and spray pyrolysis and characterised using SEM, EDX, XRD, TGA, UV-Vis spectroscopy and photoelectrochemical measurements. Regarding the doped hematite thin films prepared by doctor blading, the photoelectrochemical activity of the hematite photoelectrodes was improved by incorporation of Ti, most likely owing to the increased electrical conductivity of the films, the stabilisation of oxygen vacancies by Ti4+ ions and the increased electric field of the space charge layer. A highest photoresponse was recorded in case of 2.5 at.% Ti which seemed to be an optimal concentration. The effect of doping content, thickness, and calcination temperature on the performance of the Ti-doped photoelectrodes was investigated. Also, the photoactivity of the 2.5 at.% Ti-doped samples was examined in two different types of electrochemical cells. Zn doping did not enhance the photoactivity of the hematite thin films though Zn seemed to enhance the hole transport due to the slow hole mobility of hematite which could not be overcome by the enhancement. The poor performance was also obtained for the Ti-doped samples prepared by spray pyrolysis, which appeared to be a result of introduction of impurities from the metallic parts of the spray gun in an acidic medium. Further characterisation of the thin-film electrodes is required to explain the mechanism by which enhanced performance was obtained for Ti-doped electrodes (doctor blading) and poor photoactivity for Zn and Ti-doped samples which were synthesised by doctor blading and spray pyrolysis, respectively. Ti-doped hematite thin films will be synthesised in another way, such as dip coating so as to maintain an inverse opal structure as well as well adhesion. Also, a comparative study of the films will be carried out.

High photoconductive combustion synthesized TiO2 derived nanobelts for photocatalytic water purification under solar irradiation

Drinking water scarcity is a major issue that needs to be addressed seriously. Water needs to be purified from organic pollutants and bacterial contamination. In this study, sunlight driven photocatalysis for the degradation of dyes and bacterial inactivation has been conducted over TiO2 nanoparticles (CST) and TiO2 nanobelts (CSTNB). TiO2 nanoparticles were synthesized by a solution combustion process using ascorbic acid as a fuel. Acid etched TiO2 nanobelts (CSTNB) were synthesized using combustion synthesized TiO2 as a novel precursor. The mechanism of formation of TiO2 nanobelts was hypothesized. The antibacterial activity of combustion synthesized TiO2 and acid etched TiO2 nanobelts were evaluated against Escherichia coli and compared against commercial TiO2. Various characterization studies like X-ray diffraction analysis, BET surface area analysis, diffused reflectance measurements were performed. Microscopic structures and high resolution images were analyzed using scanning electron microscopy, transmission electron microscopy. The extent of photo-stability and reusability of the catalyst was evaluated by conducting repeated cycles of photo degradation experiments and was compared to the commercial grade TiO2. The reactive radical species responsible for high photocatalytic and antibacterial activity has been determined by performing multiple scavenger reactions. The excellent charge transfer mechanism, high generation of hydroxyl and hole radicals resulted in enhanced photocatalytic activity of the acid etched TiO2 nanobelts compared to commercial TiO2 and nanobelts made from commercial TiO2.

The application of a novel fluidised photo reactor under UV-Visible and natural solar irradiation in the photocatalytic generation of hydrogen

With advancements in the development of visible light responsive catalysts for H2 production frequently being reported, photocatalytic water splitting has become an attractive method as a potential ‘solar fuel generator’. The development of novel photo reactors which can enhance the potential of such catalyst, however, is rarely reported. This is particularly important as many reactor configurations are mass transport limited, which in term limits the efficiency of more effective photocatalysts in larger scale applications. This paper describes the performance of a novel fluidised photo reactor for the production of H2 over two catalysts under UV-Visible light and natural solar illumination. Catalysts Pt-C3N4 and NaTaO3.La were dispersed in the reactor and the rate of H2 was determined by GC-TCD analysis of the gas headspace. The unit was an annular reactor constructed from stainless steel 316 and quartz glass with a propeller located in the base to control fluidisation of powder catalysts. Reactor properties such as propeller rotational speed were found to enhance the photo activity of the system through the elimination of mass transport limitations and increasing light penetration. The optimum conditions for H2 evolution were found to be a propeller rotational speed of 1035 rpm and 144 W of UV-Visible irradiation, which produced a rate of 89 µmol h-1 g-1 over Pt-C3N4. Solar irradiation was provided by the George Ellery Hale Solar Telescope, located at the California Institute of Technology.

Photocatalytic Decolorization of Commercial Acid Dyes using Solar Irradiation

This work investigates the solar heterogeneous photocatalytic degradation of three commercial acid dyes: Blue 9 (C.I. 42090), Red 51 (C.I. 45430), and Yellow 23 (C.I. 19140). TiO(2) P25 from Degussa was used as the photocatalyst. The dyes were completely degraded within 120 min of treatment in the following increasing order of removal rate: Blue 9 < Yellow 23 < Red 51. The photocatalytic color removal process was well described by a two-first-order in-series reaction, followed by another first-order reaction. Photolytic experiments showed that this process is quite inefficient and highly selective towards Red 51 only. The dyes` solution was completely decolorized and organic matter removals up to 99% were achieved with photocatalysis. The lack of selectivity and the possibility of using solar light to excite the photocatalyst are promising results regarding the feasibility of this technology.

Universal Experimental Measurement System «Sun-Walker» : Automotive measurement system for the evaluation of the solar irradiation distribution for the tests of the solar concentrated systems.

This Thesis project is a part of the research conducted in Solar industry. ABSOLICON Solar Concentrator AB has invented and started production of the prospective solar concentrated system Absolicon X10. The aims of this Thesis project are designing, assembling, calibrating and putting in operation the automatic measurement system intended to evaluate distribution of density of solar radiation in the focal line of the concentrated parabolic reflectors and to measure radiation from the artificial source of light being a calibration-testing tool.On the basis of the requirements of the company’s administration and needs of designing the concentrated reflectors the operation conditions for the Sun-Walker were formulated. As the first step, the complex design of the whole system was made and division on the parts was specified. After the preliminary conducted simulation of the functions and operation conditions of the all parts were formulated.As the next steps, the detailed design of all the parts was made. Most components were ordered from respective companies. Some of the mechanical components were made in the workshop of the company. All parts of the Sun-Walker were assembled and tested. The software part, which controls the Sun-Walker work and conducts measurements of solar irradiation, was created on the LabVIEW basis. To tune and test the software part, the special simulator was designed and assembled.When all parts were assembled in the complete system, the Sun-Walker was tested, calibrated and tuned.

Discrepancies in solar irradiation data for Stockholm and Athens

The aim of this study is to evaluate the variation of solar radiation data between different data sources that will be free and available at the Solar Energy Research Center (SERC). The comparison between data sources will be carried out for two locations: Stockholm, Sweden and Athens, Greece. For the desired locations, data is gathered for different tilt angles: 0°, 30°, 45°, 60° facing south. The full dataset is available in two excel files: “Stockholm annual irradiation” and “Athens annual irradiation”. The World Radiation Data Center (WRDC) is defined as a reference for the comparison with other dtaasets, because it has the highest time span recorded for Stockholm (1964–2010) and Athens (1964–1986), in form of average monthly irradiation, expressed in kWh/m2. The indicator defined for the data comparison is the estimated standard deviation. The mean biased error (MBE) and the root mean square error (RMSE) were also used as statistical indicators for the horizontal solar irradiation data. The variation in solar irradiation data is categorized in two categories: natural or inter-annual variability, due to different data sources and lastly due to different calculation models. The inter-annual variation for Stockholm is 140.4kWh/m2 or 14.4% and 124.3kWh/m2 or 8.0% for Athens. The estimated deviation for horizontal solar irradiation is 3.7% for Stockholm and 4.4% Athens. This estimated deviation is respectively equal to 4.5% and 3.6% for Stockholm and Athens at 30° tilt, 5.2% and 4.5% at 45° tilt, 5.9% and 7.0% at 60°. NASA’s SSE, SAM and RETScreen (respectively Satel-light) exhibited the highest deviation from WRDC’s data for Stockholm (respectively Athens). The essential source for variation is notably the difference in horizontal solar irradiation. The variation increases by 1-2% per degree of tilt, using different calculation models, as used in PVSYST and Meteonorm. The location and altitude of the data source did not directly influence the variation with the WRDC data. Further examination is suggested in order to improve the methodology of selecting the location; Examining the functional dependence of ground reflected radiation with ambient temperature; variation of ambient temperature and its impact on different solar energy systems; Im pact of variation in solar irradiation and ambient temperature on system output.

Photo-Fenton degradation of the herbicide tebuthiuron under solar irradiation: Iron complexation and initial intermediates

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Homogeneous photodegradation of CI Reactive Blue 4 using a photo-Fenton process under artificial and solar irradiation

The oxidation of C.I. Reactive Blue 4 (RB4) by photo-Fenton process mediated by lerrioxalate was investigated under artificial and solar irradiation. The RB4 degradation in acidic medium (pH 2.5) was evaluated by the decrease in Total Organic Carbon (TOC) content and color, measured by the decrease in chromophore absorption band (600 nm). The influence of ferrioxalate and H2O2 concentrations on the dye degradation was studied and best results were obtained using 1.0 mM ferrioxalate and 10 nM of hydrogen peroxide. Under these experimental conditions, 80% of TOC and 100% of color removal were obtained for a 0.1 mM RB4 dye in 35 min of solar irradiation. (c) 2006 Elsevier Ltd. All rights reserved.

Degradation of tetracycline by photo-Fenton process - Solar irradiation and matrix effects

The degradation of the antibiotic tetracycline (TC) by the photo-Fenton process was evaluated under black-light and solar irradiation. The influences of iron source (Fe(NO3)(3) or ferrioxalate), hydrogen peroxide and matrix (pure water, surface water and a sewage treatment plant effluent-STP) were evaluated. Under black-light irradiation, TC degradation was favored in the presence of Fe(NO3)(3), achieving total degradation after 1 min irradiation, while under solar light the use of ferrioxalate favors the degradation. Nevertheless, no significant difference in total organic carbon removal was observed between these two iron sources, achieving a residual concentration of around 5 mg L-1 under black-light and 2 mg L-1 under solar light irradiation. No decrease of the degradation efficiency relative to pure water was observed when TC was irradiated in a sample of surface water, under either black-light or solar irradiation. However, lower efficiency was obtained under black-light when TC was present in a sample of STP effluent, indicating the interference of the constituents of this sample on the overall efficiency of the process. on the other hand, under solar irradiation in the presence of ferrioxalate, no influence of the matrix was observed, even in the sample of STP effluent, achieving total degradation of TC in 1.5 min. (c) 2006 Elsevier B.V. All rights reserved.

Annual and monthly mean global, direct and diffuse solar irradiation in Botucatu/SP/Brazil

This paper presents a climatic and statistical analysis of global, direct horizontal and diffuse radiation from a database of solar radiation measured from 1996 to 2006 in the city of Botucatu, SP, Brazil. Variation intervals of hourly and daily irradiation, annual mean 〈H̄G〉, 〈H̄bh〉 and 〈H̄d〉 irradiation, monthly mean 〈H̄G〉, 〈H̄ bh〉 and 〈H̄d〉 irradiation and monthly mean 〈K̄t〉, 〈K̄bh〉 and 〈K̄d〉 fractions were determined. Results showed that values of hourly and daily annual mean irradiation were as follows: 〈H̄G〉=1.49MJ/m2 and 〈H̄ G〉=17.74MJ/m2; 〈H̄bh〉=0. 90MJ/m2 and 〈H̄bh〉=10.33MJ/m2 and 〈H̄d〉=0.57 MJ/m2 and 〈H̄d〉=7.09MJ/m2, respectively. Variation intervals of hourly monthly mean irradiation were as follows: 〈H̄G〉 ranged from 1.65MJ/m2 in March to 1.16MJ/m2 in June; 〈H̄bh〉 ranged from 1.06MJ/m2 in April to 0.79MJ/m2 in June, and 〈H̄d〉 ranged from 0.70MJ/m2 in January to 0.37MJ/m2 in June and July. Similarly, daily 〈H̄ G〉 irradiation ranged from 21.35MJ/m2 in November to 12.94MJ/m2 in June; 〈H̄bh〉 ranged from 11.83MJ/m2 in April to 8.49MJ/m2 in June, and 〈H̄d〉 ranged from 10.29MJ/m2 in December to 4.38MJ/m2 in June. Variation intervals of hourly monthly mean fractions were as follows: 〈K̄t〉 ranged from 43.5% in January to 54.2% in April; 〈K̄bh〉 ranged from 33.6% in January to 58.0% in April and 〈K̄d〉 ranged from 66.4% in January to 42.0% in April. In the same way, daily 〈K̄ t〉 fractions ranged from 45.5% in January to 59.8% in August; 〈K̄bh〉 ranged from 38.9% in January to 62.0% in August and 〈K̄d〉 ranged from 61.1% in January to 37.7% in July.

Assessing the solar irradiation potential for solar photovoltaic applications in buildings at low latitudes ¿ Making the case for Brazil

In Brazil, a low-latitude country characterized by its high availability and uniformity of solar radiation, the use of PV solar energy integrated in buildings is still incipient. However, at the moment there are several initiatives which give some hints that lead to think that there will be a change shortly. In countries where this technology is already a daily reality, such as Germany, Japan or Spain, the recommendations and basic criteria to avoid losses due to orientation and tilt are widespread. Extrapolating those measures used in high latitudes to all regions, without a previous deeper analysis, is standard practice. They do not always correspond to reality, what frequently leads to false assumptions and may become an obstacle in a country which is taking the first step in this area. In this paper, the solar potential yield for different surfaces in Brazilian cities (located at latitudes between 0° and 30°S) are analyzed with the aim of providing the necessary tools to evaluate the suitability of the buildings’ envelopes for photovoltaic use

Evaluation and improvement of empirical models of global solar irradiation: Case study northern Spain

This paper presents a new methodology to build parametric models to estimate global solar irradiation adjusted to specific on-site characteristics based on the evaluation of variable im- portance. Thus, those variables higly correlated to solar irradiation on a site are implemented in the model and therefore, different models might be proposed under different climates. This methodology is applied in a study case in La Rioja region (northern Spain). A new model is proposed and evaluated on stability and accuracy against a review of twenty-two already exist- ing parametric models based on temperatures and rainfall in seventeen meteorological stations in La Rioja. The methodology of model evaluation is based on bootstrapping, which leads to achieve a high level of confidence in model calibration and validation from short time series (in this case five years, from 2007 to 2011). The model proposed improves the estimates of the other twenty-two models with average mean absolute error (MAE) of 2.195 MJ/m2 day and average confidence interval width (95% C.I., n=100) of 0.261 MJ/m2 day. 41.65% of the daily residuals in the case of SIAR and 20.12% in that of SOS Rioja fall within the uncertainty tolerance of the pyranometers of the two networks (10% and 5%, respectively). Relative differences between measured and estimated irradiation on an annual cumulative basis are below 4.82%. Thus, the proposed model might be useful to estimate annual sums of global solar irradiation, reaching insignificant differences between measurements from pyranometers.

Downscaling of global solar irradiation in R

A methodology for downscaling solar irradiation from satellite-derived databases is described using R software. Different packages such as raster, parallel, solaR, gstat, sp and rasterVis are considered in this study for improving solar resource estimation in areas with complex topography, in which downscaling is a very useful tool for reducing inherent deviations in satellite-derived irradiation databases, which lack of high global spatial resolution. A topographical analysis of horizon blocking and sky-view is developed with a digital elevation model to determine what fraction of hourly solar irradiation reaches the Earth's surface. Eventually, kriging with external drift is applied for a better estimation of solar irradiation throughout the region analyzed. This methodology has been implemented as an example within the region of La Rioja in northern Spain, and the mean absolute error found is a striking 25.5% lower than with the original database.

A free real-time hourly tilted solar irradiation data Website for Europe

The engineering of solar power applications, such as photovoltaic energy (PV) or thermal solar energy requires the knowledge of the solar resource available for the solar energy system. This solar resource is generally obtained from datasets, and is either measured by ground-stations, through the use of pyranometers, or by satellites. The solar irradiation data are generally not free, and their cost can be high, in particular if high temporal resolution is required, such as hourly data. In this work, we present an alternative method to provide free hourly global solar tilted irradiation data for the whole European territory through a web platform. The method that we have developed generates solar irradiation data from a combination of clear-sky simulations and weather conditions data. The results are publicly available for free through Soweda, a Web interface. To our knowledge, this is the first time that hourly solar irradiation data are made available online, in real-time, and for free, to the public. The accuracy of these data is not suitable for applications that require high data accuracy, but can be very useful for other applications that only require a rough estimate of solar irradiation.