Synthesis of novel and stable g-C3N4/N-doped SrTiO3 hybrid nanocomposites with improved photocurrent and photocatalytic activity under visible light irradiation

Hybrid nanocomposites based on N-doped SrTiO3 nanoparticles wrapped in g-C3N4 nanosheets were successfully prepared by a facile and reproducible polymeric citrate and thermal exfoliation method. The results clearly indicated that the N-doped SrTiO3 nanoparticles are successfully wrapped in layers of the g-C3N4 nanosheets. The g-C3N4/N-doped SrTiO3 nanocomposites showed absorption edges at longer wavelengths compared with the pure g-C3N4 as well as N-doped SrTiO3. The hybrid nanocomposites exhibit an improved photocurrent response and photocatalytic activity under visible light irradiation. Interestingly, the hybrid nanocomposite possesses high photostability and reusability. Based on experimental results, the possible mechanism for prolonged lifetime of the photoinduced charge carrier was also discussed. The high performance of the g-C3N4/N-doped SrTiO3 photocatalysts is due to the synergic effect at the interface of g-C3N4 and N-doped SrTiO3 hetero/nanojunction including the high separation efficiency of the charge carrier, band energy matching and the suppressed recombination rate. Therefore, the hybrid photocatalyst could be of potential interest for water splitting and environmental remediation under natural sunlight.

Synthetic strategies to nanostructured photocatalysts for CO2 reduction to solar fuels and chemicals

Artificial photosynthesis represents one of the great scientific challenges of the 21st century, offering the possibility of clean energy through water photolysis and renewable chemicals through CO2 utilisation as a sustainable feedstock. Catalysis will undoubtedly play a key role in delivering technologies able to meet these goals, mediating solar energy via excited generate charge carriers to selectively activate molecular bonds under ambient conditions. This review describes recent synthetic approaches adopted to engineer nanostructured photocatalytic materials for efficient light harnessing, charge separation and the photoreduction of CO2 to higher hydrocarbons such as methane, methanol and even olefins.

A solar-powered reverse osmosis system for high recovery of freshwater from saline groundwater

Desalination of groundwater is essential in arid regions that are remote from both seawater and freshwater resources. Desirable features of a groundwater desalination system include a high recovery ratio, operation from a sustainable energy source such as solar, and high water output per unit of energy and land. Here we propose a new system that uses a solar-Rankine cycle to drive reverse osmosis (RO). The working fluid such as steam is expanded against a power piston that actuates a pump piston which in turn pressurises the saline water thus passing it through RO membranes. A reciprocating crank mechanism is used to equalise the forces between the two pistons. The choice of batch mode in preference to continuous flow permits maximum energy recovery and minimal concentration polarisation in the vicinity of the RO membrane. This study analyses the sizing and efficiency of the crank mechanism, quantifies energy losses in the RO separation and predicts the overall performance. For example, a system using a field of linear Fresnel collectors occupying 1000 m2 of land and raising steam at 200 °C and 15.5 bar could desalinate 350 m3/day from saline water containing 5000 ppm of sodium chloride with a recovery ratio of 0.7.

Synthesis of highly efficient and recyclable visible-light responsive mesoporous g-C3N4 photocatalyst via facile template-free sonochemical route

Herein we demonstrate a facile template-free sonochemical strategy to synthesize mesoporous g-C3N4 with a high surface area and enhanced photocatalytic activity. The TEM and nitrogen adsorption–desorption studies confirm mesoporous structure in g-C3N4 body. The photocatalytic activity of mesoporous g-C3N4 is almost 5.5 times higher than that of bulk g-C3N4 under visible-light irradiation. The high photocatalytic performance of the mesoporous g-C3N4 was attributed to the much higher specific surface area, efficient adsorption ability and the unique interfacial mesoporous structure which can favour the absorption of light and separation of photoinduced electron–hole pairs more effectively. A possible photocatalytic mechanism was discussed by the radicals and holes trapping experiments. Interestingly, the synthesized mesoporous g-C3N4 possesses high reusability. Hence the mesoporous g-C3N4 can be a promising photocatalytic material for practical applications in water splitting as well as environmental remediation.

Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red

A family of titania derived nanocomposites synthesized via sol-gel and hydrothermal routes exhibit excellent performance for the photocatalytic degradation of two important exemplar water pollutants, oxytetracycline and Congo Red. Low loadings of Co3O4 nanoparticles dispersed over the surfaces of anatase TiO2 confer visible light photoactivity for the aqueous phase decomposition of organics through the resulting heterojunction and reduced band gap. Subsequent modification of these Co3O4/TiO2 composites by trace amounts of graphene oxide nanosheets in the presence of a diamine linker further promotes both oxytetracycline and Congo Red photodegradation under simulated solar and visible irradiation, through a combination of enhanced photoresponse and consequent radical generation. Radical quenching and fluorescence experiments implicate holes and hydroxyl radicals as the respective primary and secondary active species responsible for oxidative photodegradation of pollutants.

Synthesis of Cr and La-codoped SrTiO3 nanoparticles for enhanced photocatalytic performance under sunlight irradiation

In this study, we report a facile polymeric citrate strategy for the synthesis of Cr,La-codoped SrTiO3 nanoparticles. The synthesized samples were well characterized by various analytical techniques. The UV-vis DRS studies reveal that the absorption edge shifts towards the visible light region after doping with Cr, which is highly beneficial for absorbing the visible light in the solar spectrum. More attractively, codoping with La exhibits greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The optimum photocatalytic activity at 1 atom% of Cr,La-codoped SrTiO3 nanoparticles is almost 6 times higher than that of pure SrTiO3 nanoparticles and 3 times higher than that of Cr-doped SrTiO3 nanoparticles. The high photocatalytic performance in the present photocatalytic system is due to codoping with La, which acts as a most effective donor for stabilizing Cr3+ in Cr,La-codoped SrTiO3 nanoparticles. More importantly, the synthesized photocatalysts possess high reusability. A proposed mechanism for the enhanced photocatalytic activity of Cr,La-codoped SrTiO3 nanoparticles was also investigated by trapping experiments. Therefore, our results not only demonstrate the highly efficient visible light photocatalytic activity of the Cr,La-codoped SrTiO3 photocatalyst, but also enlighten the codoping strategy in the design and development of advanced photocatalytic materials for energy and environmental applications.

In situ growth strategy for highly efficient Ag2CO3/g-C3N4 hetero/nanojunctions with enhanced photocatalytic activity under sunlight irradiation

Developing novel heterojunction photocatalysts is a powerful strategy for improving the separation efficiency of photogenerated charge carriers, which is attracting the intense research interest in photocatalysis. Herein we report a highly efficient hetero/nanojunction consisting of Ag2CO3 nanoparticles grown on layered g-C3N4 nanosheets synthesized via a facile and template free in situ precipitation method. The UV–vis diffuse reflectance studies revealed that the synthesized Ag2CO3/g-C3N4 hetero/nanojunctions exhibit a broader and stronger light absorption in the visible light region, which is highly beneficial for absorbing the visible light in the solar spectrum. The optimum photocatalytic activity of Ag2CO3/g-C3N4 at a weight content of 10% Ag2CO3 for the degradation of Rhodamine B was almost 5.5 and 4 times as high as that of the pure Ag2CO3 and g-C3N4, respectively. The enhanced photocatalytic activity of the Ag2CO3/g-C3N4 hetero/nanojunctions is due to synergistic effects including the strong visible light absorption, large specific surface area, and high charge transfer and separation efficiency. More importantly, the high photostability and low use of the noble metal silver which reduces the cost of the material. Therefore, the synthesized Ag2CO3/g-C3N4 hetero/nanojunction photocatalyst is a promising candidate for energy storage and environment protection applications.

Colloidal dual-band gap cell for photocatalytic hydrogen generation

We report that the internal quantum efficiency for hydrogen generation in spherical, Pt-decorated CdS nanocrystals can be tuned by quantum confinement, resulting in higher efficiencies for smaller than for larger nanocrystals (17.3% for 2.8 nm and 11.4% for 4.6 nm diameter nanocrystals). We attribute this to a larger driving force for electron and hole transfer in the smaller nanocrystals. The larger internal quantum efficiency in smaller nanocrystals enables a novel colloidal dual-band gap cell utilising differently sized nanocrystals and showing larger external quantum efficiencies than cells with only one size of nanocrystals (9.4% for 2.8 nm particles only and 14.7% for 2.8 nm and 4.6 nm nanocrystals). This represents a proof-of-principle for future colloidal tandem cell.

Pore confinement effects and stabilization of carbon nitride oligomers in macroporous silica for photocatalytic hydrogen production

An ordered macroporous host (mac-SiO2) has been used to prevent aggregation of layered photocatalysts based on carbon nitride. Using typical carbon nitride synthesis conditions, cyanamide was condensed at 550 °C in the presence and absence of mac-SiO2. Condensation in the absence of mac-SiO2 results in materials with structural characteristics consistent with the carbon nitride, melon, accompanied by ca. 2 wt% carbonization. For mac-SiO2 supported materials, condensation occurs with greater carbonization (ca. 6 wt%). On addition of 3 wt% Pt cocatalyst photocatalytic hydrogen production under visible light is found to be up to 10 times greater for the supported composites. Time-resolved photoluminescence spectroscopy shows that excited state relaxation is more rapid for the mac-SiO2 supported materials suggesting faster electron-hole recombination and that supported carbon nitride does not exhibit improved charge separation. CO2 temperature programmed desorption indicates that enhanced photoactivity of supported carbon nitride is attributable to an increased surface area compared to bulk carbon nitride and an increase in the concentration of weakly basic catalytic sites, consistent with carbon nitride oligomers.

Photodeposition as a facile route to tunable Pt photocatalysts for hydrogen production:on the role of methanol

Photodeposition of H2PtCl6 in the presence of methanol promotes the formation of highly dispersed, metallic Pt nanoparticles over titania, likely via capture of photogenerated holes by the alcohol to produce an excess of surface electrons for substrate-mediated transfer to Pt complexes, resulting in a high density of surface nucleation sites for Pt reduction. Photocatalytic hydrogen production from water is proportional to the surface density of Pt metal co-catalyst, and hence photodeposition in the presence of high methanol concentrations affords a facile route to optimising photocatalyst design and highlights the importance of tuning co-catalyst properties in photocatalysis.

Facile synthesis of hierarchical Cu2O nanocubes as visible light photocatalysts

Hierarchically structured Cu2O nanocubes have been synthesized by a facile and cost-effective one-pot, solution phase process. Self-assembly of 5 nm Cu2O nanocrystallites induced through reduction by glucose affords a mesoporous 375 nm cubic architecture with superior visible light photocatalytic performance in both methylene blue dye degradation and hydrogen production from water than conventional non-porous analogues. Hierarchical nanocubes offer improved accessible surface active sites and optical/electronic properties, which act in concert to confer 200–300% rate-enhancements for the photocatalytic decomposition of organic pollutants and solar fuels.

Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight

Herein, we demonstrate the synthesis of highly efficient Fe-doped graphitic carbon nitride (g-C3N4) nanosheets via a facile and cost effective method. The synthesized Fe-doped g-C3N4 nanosheets were well characterized by various analytical techniques. The results revealed that the Fe exists mainly in the +3 oxidation state in the Fe-doped g-C3N4 nanosheets. Fe doping of g-C3N4 nanosheets has a great influence on the electronic and optical properties. The diffuse reflectance spectra of Fe-doped g-C3N4 nanosheets exhibit red shift and increased absorption in the visible light range, which is highly beneficial for absorbing the visible light in the solar spectrum. More significantly, the Fe-doped g-C3N4 nanosheets exhibit greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The photocatalytic activity of 2 mol% Fe-doped g-C3N4 nanosheets is almost 7 times higher than that of bulk g-C3N4 and 4.5 times higher than that of pure g-C3N4 nanosheets. A proposed mechanism for the enhanced photocatalytic activity of Fe-doped g-C3N4 nanosheets was investigated by trapping experiments. The synthesized photocatalysts are highly stable even after five successive experimental runs. The enhanced photocatalytic performance of Fe-doped g-C3N4 nanosheets is due to high visible light response, large surface area, high charge separation and charge transfer. Therefore, the Fe-doped g-C3N4 photocatalyst is a promising candidate for energy conversion and environmental remediation.

Studies of solar radiation and its measurement

A mathematical model has been developed for predicting the spectral distribution of solar radiation incident on a horizontal surface. The solar spectrum in the wavelength range 0.29 to 4.0 micrometers has been divided in 144 intervals. Two variables in the model are the atmospheric water vapour content and atmospheric turbidity. After allowing for absorption and scattering in the atmosphere, the spectral intensity of direct and diffuse components of radiation are computed. When the predicted radiation levels are compared with the measured values for the total radiation and the values with glass filters RG715, RG630 and OG530, a close agreement (± 5%) has been achieved under clear sky conditions. A solar radiation measuring facility, close to the centre of Birmingham, has been set up utilising a microcomputer based data logging system. A suite of computer programs in the BASIC programming language has been developed and extensively tested for solar radiation data, logging, analysis and plotting. Two commonly used instruments, the Eppley PSP pyranometer and the Kipp and Zonen CM5 pyranometer, have been compared under different experimental conditions. Three models for computing the inclined plane irradiation, using total and diffuse radiation on a horizontal surface, have been tested for Birmingham. The anisotropic-alI-sky model, proposed by Klucher, provides a good agreement between the measured and the predicted radiation levels. Measurements of solar spectral distribution, using glass filters, are also reported for a number of inclines facing South.

Desalination of brackish water by a batch reverse osmosis desalink system for use with solar thermal energy

For remote, semi-arid areas, brackish groundwater (BW) desalination powered by solar energy may serve as the most technically and economically viable means to alleviate the water stresses. For such systems, high recovery ratio is desired because of the technical and economical difficulties of concentrate management. It has been demonstrated that the current, conventional solar reverse osmosis (RO) desalination can be improved by 40–200 times by eliminating unnecessary energy losses. In this work, a batch-RO system that can be powered by a thermal Rankine cycle has been developed. By directly recycling high pressure concentrates and by using a linkage connection to provide increasing feed pressures, the batch-RO has been shown to achieve a 70% saving in energy consumption compared to a continuous single-stage RO system. Theoretical investigations on the mass transfer phenomena, including dispersion and concentration polarization, have been carried out to complement and to guide experimental efforts. The performance evaluation of the batch-RO system, named DesaLink, has been based on extensive experimental tests performed upon it. Operating DesaLink using compressed air as power supply under laboratory conditions, a freshwater production of approximately 300 litres per day was recorded with a concentration of around 350 ppm, whilst the feed water had a concentration range of 2500–4500 ppm; the corresponding linkage efficiency was around 40%. In the computational aspect, simulation models have been developed and validated for each of the subsystems of DesaLink, upon which an integrated model has been realised for the whole system. The models, both the subsystem ones and the integrated one, have been demonstrated to predict accurately the system performance under specific operational conditions. A simulation case study has been performed using the developed model. Simulation results indicate that the system can be expected to achieve a water production of 200 m3 per year by using a widely available evacuated tube solar collector having an area of only 2 m2. This freshwater production would satisfy the drinking water needs of 163 habitants in the Rajasthan region, the area for which the case study was performed.