Comparison of Titanium Dioxide and Zinc Oxide Photocatalysts for the Inactivation of Escherichia coli in Water Using Slurry and Rotating-Disk Photocatalytic Reactors.

The application of photocatalysis for the disinfection of water has been extensively reported over the past 30 years. Titanium dioxide (TiO2) has been the most widely and successfully used photocatalyst to date; however, it is not without its limitations. Frequently observed long lag times, sometimes up to 60 min, before bacterial inactivation begins and the presence of residual microorganisms, for example, up to 104 colony forming units, remaining after treatment are ongoing challenges with this particular photocatalyst. It is therefore important to find alternative photocatalysts that can address these issues. In this study, we compared the disinfection capacity of TiO2 with that of zinc oxide (ZnO) using Escherichia coli as a model organism in both a suspended and immobilized catalyst system. Our results showed that ZnO was superior to TiO2 in a number of areas. Not only were bacterial rates of destruction much quicker with ZnO, but no lag time was observed prior to inactivation in suspended systems. Furthermore, complete bacterial destruction was observed within the treatment times under investigation. The greater efficiency of ZnO is believed to be due to the decomposition of the bacterial cell wall being driven by hydrogen peroxide as opposed to hydroxyl radicals. The results reported in this paper show that ZnO is a more efficient and cost-effective photocatalyst than TiO2 and that it represents a viable alternative photocatalyst for water disinfection processes.

Mechanistic Study of Glucose Photoreforming over TiO2-Based Catalysts for H2 Production.

Glucose is a key intermediate in cellulose photoreforming for H2 production. This work presents a mechanistic investigation of glucose photoreforming over TiO2 and Pt/m-TiO2 catalysts. Analysis of the intermediates formed in the process confirmed the α-scission mechanism of glucose oxidation forming arabinose (Cn-1 sugar) and formic acid in the initial oxidation step. The selectivity to sugar products and formic acid differed over Pt/TiO2 and TiO2, with Pt/TiO2 showing the lower selectivity to formic acid due to enhanced adsorption/conversion of formic acid over Pt/TiO2. In situ ATR-IR spectroscopy of glucose photoreforming showed the presence of molecular formic acid and formate on the surface of both catalysts at low glucose conversions, suggesting that formic acid oxidation could dominate surface reactions in glucose photoreforming. Further in situ ATR-IR of formic acid photoreforming showed Pt-TiO2 interfacial sites to be key for formic acid oxidation as TiO2 was unable to convert adsorbed formic acid/formate. Isotopic studies of the photoreforming of formic acid in D2O (with different concentrations) showed that the source of the protons (to form H2 at Pt sites) was determined by the relative surface coverage of adsorbed water and formic acid.

Enhanced Monitoring of Photocatalytic Reactive Oxygen Species: Using Electrochemistry for Rapid Sensing of Hydroxyl Radicals Formed during the Degradation of Coumarin.

Many recent research studies have reported indirect methods for the detection and quantification of OH radicals generated during photocatalysis. The short lifespan and high reactivity of these radicals make indirect detection using probes such as coumarin a more viable quantification method. Hydroxyl radical production is commonly monitored using fluorescence spectroscopy to determine the concentration of the compound 7-hydroxycoumarin, which is formed from hydroxyl radical attack on coumarin. There are, however, a number of additional hydroxylated coumarins generated during this process, which are less amenable to detection by fluorescence spectroscopy. Consequently, limitations and inaccuracies of this method have previously been reported in the literature. As an alternative approach to those previously reported, this work has developed an electrochemical screening method using coumarin as a OH radical trap, that is capable of in situ monitoring of not only 7-hydroxycoumarin, but all the main mono-hydroxylated products formed. As a result, this technique is a more representative and comprehensive method for the quantification of OH radicals produced by photocatalysts using coumarin as a probe molecule. Moreover, the electroanalytical method provides a portable, rapid, sensitive, and accurate in situ method for the monitoring of OH radical formation without the need for sample preparation.

Oxidation of Sulphur pollutants in model and real fuels using hydrodynamic cavitation.

Hydrodynamic Cavitation (HC) offers an attractive platform for intensifying oxidative desulphurization of fuels. In the first part of this work, we present new results on oxidising single ring thiophene in a model fuel over the extended range of volume fraction of organic phase from 2.5 to 80 v/v %. We also present influence of type and scale of HC device on performance of oxidative desulphurization. Further experiments revealed that oxidising radicals generated in-situ by HC alone were not able to oxidise dual ring thiophenes. External catalyst (formic acid) and oxidising agents (hydrogen peroxide, H2O2) were therefore used with HC. Based on our prior work with acoustic cavitation (AC), the volumetric ratios for H2O2 and formic acid were identified as 0.95 v/v % and 6.25 v/v % respectively. The data of oxidation of dual ring thiophenes with n-dodecane and n-hexane as model fuels and typical transport fuels (diesel, kerosene, and petrol) using these oxidant and catalyst is presented. The observed performance with HC was compared with results obtained from a stirred tank and AC set-up. The presented data indicates that HC is able to intensify oxidation of sulphur species. The presented results provide a sound basis for further developments on HC based oxidative desulphurization processes.

Solar-driven semi-conductor photocatalytic water treatment (TiO2, g-C3N4, and TiO2+g-C3N4) of cyanotoxins: Proof-of-concept study with microcystin-LR.

Cyanobacteria and their toxins are a threat to drinking water safety as increasingly cyanobacterial blooms (mass occurrences) occur in lakes and reservoirs all over the world. Photocatalytic removal of cyanotoxins by solar light active catalysts is a promising way to purify water at relatively low cost compared to modifying existing infrastructure. We have established a facile and low-cost method to obtain TiO2 and g-C3N4 coated floating photocatalysts using recycled glass beads. g-C3N4 coated and TiO2+g-C3N4 co-coated beads were able to completely remove microcystin-LR in artificial fresh water under both natural and simulated solar light irradiation without agitation in less than 2 h. TiO2 coated beads achieved complete removal within 8 h of irradiation. TiO2+g-C3N4 beads were more effective than g-C3N4 beads as demonstrated by the increase reaction rate with reaction constants, 0.0485 min-1 compared to 0.0264 min-1 respectively, with TiO2 alone found to be considerably slower 0.0072 min-1. g-C3N4 based photocatalysts showed a similar degradation pathway to TiO2 based photocatalysts by attacking the C6-C7 double bond on the Adda side chain.

Quantifying OH radical generation in hydrodynamic cavitation via coumarin dosimetry: Influence of operating parameters and cavitation devices.

Hydrodynamic cavitation (HC) has been extensively investigated for effluent treatment applications. Performance of HC devices or processes is often reported in terms of degradation of organic pollutants rather than quantification of hydroxyl (OH) radicals. In this study, generation of OH radicals in vortex based cavitation device using coumarin dosimetry was quantified. Coumarin was used as the chemical probe with an initial concentration of 100 µM (15 ppm). Generation of OH radicals was quantified by analysing generated single hydroxylated products. The influence of operating parameters such as pH and type of acid used to adjust pH, dissolved oxygen, and inlet and outlet pressures was investigated. Acidic pH was found to be more conducive for generating OH radicals and therefore subsequent experiments were performed at pH of 3. Sulphuric acid was found to be more than three times effective than hydrochloric acid in generating OH radicals. Effect of initial levels of dissolved oxygen was found to influence OH radical generation. Performance of vortex based cavitation device was then compared with other commonly used cavitation devices based on orifice and venturi. The vortex based cavitation device was found to outperform the orifice and venturi based devices in terms of initial per-pass factor. Influence of device scale (nominal flow rate through the device) on performance was then evaluated. The results presented for these devices unambiguously quantifies their cavitational performance. The presented results will be useful for evaluating computational models and stimulate further development of predictive computational models in this challenging area.

Suppressing cyanobacterial dominance by UV-LED TiO2-photocatalysis in a drinking water reservoir: A mesocosm study.

Cyanobacteria and their toxic secondary metabolites present challenges for water treatment globally. In this study we have assessed TiO2 immobilized onto recycled foamed glass beads by a facile calcination method, combined in treatment units with 365 nm UV-LEDs. The treatment system was deployed in mesocosms within a eutrophic Brazilian drinking water reservoir. The treatment units were deployed for 7 days and suppressed cyanobacterial abundance by 85% while at the same time enhancing other water quality parameters; turbidity and transparency improved by 40 and 81% respectively. Genomic analysis of the microbiota in the treated mesocosms revealed that the composition of the cyanobacterial community was affected and the abundance of Bacteroidetes and Proteobacteria increased during cyanobacterial suppression. The effect of the treatment on zooplankton and other eukaryotes was also monitored. The abundance of zooplankton decreased while Chrysophyte and Alveolata loadings increased. The results of this proof-of-concept study demonstrate the potential for full-scale, in-reservoir application of advanced oxidation processes as complementary water treatment processes.

Toward the Photocatalytic Valorization of Lignin: Conversion of a Model Lignin Hexamer with Multiple Functionalities.

The valorization of biomass via photocatalysis is an area of expanding research with advances in new technologies and materials with a view toward enhanced sustainability being reported. A significant challenge within this field, however, is understanding the impact photocatalysis has on more recalcitrant compounds present in biomass, such as lignin. Moreover, the current state of lignin model compound research is still largely focused on the breakdown of small models containing typically only one linkage. Described herein is the use of TiO2-mediated photocatalysis for the degradation of a representative hexameric lignin model compound which contains multiple linkages (e.g., 5-5', ß-5, and ß-O-4). The results revealed that while cleavage of the ß-5 and ß-O-4 occurred, the 5-5' appeared to remain intact within the identified reaction intermediates. To understand some of the more fundamental questions, a dimeric compound with a biphenyl linkage was synthesized and studied under photocatalytic conditions. The proposal of intermediates and pathways of degradation based on the studies conducted is presented and discussed herein.

Removal of single and dual ring thiophene's from dodecane using cavitation based processes.

Utilising cavitation for enhancing oxidative desulphurization has been investigated for nearly-two decades with recent investigations shifting focus from low-capacity acoustic cavitation (AC) to scalable hydrodynamic cavitation (HC). This work focuses on developing a viable means for removing thiophene's from fuels. In the first phase of this work, use of vortex based HC devices for removal of single and dual ring thiophenes from dodecane was investigated. HC was shown to be able to remove single ring thiophene from dodecane without using any external catalyst or additives. However, in absence of catalyst or additives, it was not possible to remove dual ring thiophenes such as dibenzothiophene using HC. Therefore, in the second phase of this work, various strategies based on use of catalyst or additives to augment cavitation based process were investigated. AC based experiments were opted for shortlisting suitable catalysts and additives for intensifying cavitation based processes. The influence of using oxidant (H2O2) and carboxylic acid catalysts on efficacy of removal of dual ring thiophenes is presented. Several conditions were tested, and the optimal volumetric ratios of 0.95 v/v % H2O2 and 6.25 v/v % HCOOH was identified and utilised throughout the remainder of the study. Regeneration of extractant which accumulates oxidised sulphur species from dodecane was also investigated using AC. The additives and process conditions reported in this work are useful for enhancing desulphurization performance.

Photocatalytic Reforming of Biomass: What Role Will the Technology Play in Future Energy Systems.

Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as 'hydrogen' and 'visible' becoming prominent research topics. There are likely two primary drivers behind this, the first of which is that biomass represents a more sustainable photocatalytic feedstock for reforming to value-added products and energy. The second is the transition towards achieving net zero emission targets, which has increased focus on the development of technologies that could play a role in future energy systems. Therefore, this review provides a perspective on not only the current state of the research but also a future outlook on the potential roadmap for photocatalytic reforming of biomass. Producing energy via photocatalytic biomass reforming is very desirable due to the ambient operating conditions and potential to utilise renewable energy (e.g., solar) with a wide variety of biomass resources. As both interest and development within this field continues to grow, however, there are challenges being identified that are paramount to further advancement. In reviewing both the literature and trajectory of the field, research priorities can be identified and utilised to facilitate fundamental research alongside whole systems evaluation. Moreover, this would underpin the enhancement of photocatalytic technology with a view towards improving the technology readiness level and promoting engagement between academia and industry.

Comparison of UV-A photolytic and UV/TiO2 photocatalytic effects on Microcystis aeruginosa PCC7813 and four microcystin analogues: A pilot scale study.

To date, the high cost of supplying UV irradiation has prevented the widespread application of UV photolysis and titanium dioxide based photocatalysis in removing undesirable organics in the water treatment sector. To overcome this problem, the use of UV-LEDs (365 nm) for photolysis and heterogeneous photocatalysis applying TiO2 coated glass beads under UV-LED illumination (365 nm) in a pilot scale reactor for the elimination of Microcystis aeruginosa PCC7813 and four microcystin analogues (MC-LR, -LY, -LW, -LF) with a view to deployment in drinking water reservoirs was investigated. UV-A (365 nm) photolysis was shown to be more effective than the UV/TiO2 photocatalytic system for the removal of Microcystis aeruginosa cells and microcystins. During photolysis, cell density significantly decreased over 5 days from an initial concentration of 5.8 × 106 cells mL-1 until few cells were left. Both intra- and extracellular microcystin concentrations were significantly reduced by 100 and 92 %, respectively, by day 5 of the UV treatment for all microcystin analogues. During UV/TiO2 treatment, there was great variability between replicates, making prediction of the effect on cyanobacterial cell and toxin behavior difficult.

Isotope Effects in Photocatalysis: An Underexplored Issue.

In order to improve the performance of well-established photocatalysts and to develop new potential photocatalyst materials, an understanding of the underlying mechanisms of photocatalytic reactions is of the utmost importance. An often neglected method for studying the mechanism is the investigation of isotope effects. Although just a few studies related to isotope effects exist, it has been shown to be a powerful tool for exploring mechanisms of photocatalytic processes. Most of the reports are focused on TiO2, which is the most studied photocatalyst, while there is a lack of data for other photocatalyst materials. This mini-review represents an overview of research utilizing isotope effects in the area of photocatalysis. The benefits and the importance of these studies will be highlighted, and the potential for these processes to be applied for the study of further photocatalytic reactions and different photocatalyst materials will be shown.

Enhanced photocatalytic degradation of 2-methyl-4-chlorophenoxyacetic acid (MCPA) by the addition of H2O2.

Photocatalytic remediation technology has been shown to be a favorable approach for the removal of a range of environmental pollutants in water treatment. While this approach can often achieve complete degradation, often overlooked are reaction intermediates that are potentially as harmful as the original parent compound. In the case of photocatalytic oxidation of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA), we have recently shown that 4-chloro-2-methylphenol (CMP) is formed as the primary intermediate. To ensure the continued development of the technology, it is crucial to ensure the removal of both MCPA and CMP can be achieved by photocatalysis. Reported here is the enhanced photocatalytic removal and subsequent suppression of MCPA and CMP respectively, by the addition of small quantities of H2O2. While the addition of H2O2 often accelerates degradation rates (via increased OH radical production), it was found to restrict the formation of CMP in this study through competitive adsorption at the surface of TiO2. Based on the combination of MCPA removal coupled with supressed CMP formation, 0.5% H2O2 was determined to be an optimal loading for the process. Under these conditions 100% MCPA removal was achieved (to the limit of HPLC detection) after 45 min irradiation at a degradation rate of ∼1 mg L-1 min-1 (ƞphoton = 4.4), which also resulted in a ∼83% reduction in CMP formation when compared to a system with no H2O2 present.

Removal of phthalates from aqueous solution by semiconductor photocatalysis: A review.

While phthalate esters are commonly used as plasticizers to improve the flexibility and workability of polymeric materials, their presence and detection in various environments has become a significant concern. Phthalate esters are known to have endocrine-disrupting effects, which affects reproductive health and physical development. As a result, there is now increased focus and urgency to develop effective and energy efficient technologies capable of removing these harmful compounds from the environment. This review explores the use of semiconductor photocatalysis as an efficient and promising solution towards achieving removal and degradation of phthalate esters. A comprehensive review of photocatalysts reported in the literature demonstrates the range of materials including commercial TiO2, solar activated catalysts and composite materials capable of enhancing adsorption and degradation. The degradation pathways and kinetics are also considered to provide the reader with an insight into the photocatalytic mechanism of removal. In addition, through the use of two key platforms (the technology readiness level scale and electrical energy per order), the crucial parameters associated with advancing photocatalysis for phthalate ester removal are discussed. These include enhanced surface interaction, catalyst platform development, improved light delivery systems and overall system energy requirements with a view towards pilot scale and industrial deployment.

Photocatalytic removal of the cyanobacterium Microcystis aeruginosa PCC7813 and four microcystins by TiO2 coated porous glass beads with UV-LED irradiation.

Cyanobacteria and their toxic secondary metabolites are a challenge in water treatment due to increased biomass and dissolved metabolites in the raw water. Retrofitting existing water treatment infrastructure is prohibitively expensive or unfeasible, hence 'in-reservoir' treatment options are being explored. In the current study, a treatment system was able to photocatalytically inhibit the growth of Microcystis aeruginosa and remove released microcystins by photocatalysis using titanium dioxide coated, porous foamed glass beads and UV-LEDs (365 nm). A 35% reduction of M. aeruginosa PCC7813 cell density compared to control samples was achieved in seven days. As a function of cell removal, intracellular microcystins (microcystin-LR, -LY, -LW, and -LF) were removed by 49% from 0.69 to 0.35 µg mL-1 in seven days. Microcystins that leaked into the surrounding water from compromised cells were completely removed by photocatalysis. The findings of the current study demonstrate the feasibility of an in-reservoir treatment unit applying low cost UV-LEDs and porous foamed beads made from recycled glass coated with titanium dioxide as a means to control cyanobacteria and their toxins before they can reach the water treatment plant.

Removal of microcystins from a waste stabilisation lagoon: Evaluation of a packed-bed continuous flow TiO2 reactor.

Photocatalysis has been shown to successfully remove microcystins (MC) in laboratory experiments. Most research to date has been performed under ideal conditions in pure or ultrapure water. In this investigation the efficiency of photocatalysis using titanium dioxide was examined in a complex matrix (waste stabilisation lagoon water). A flow-through photocatalytic reactor was used for the photocatalytic removal of four commonly occurring microcystin analogues (MC-YR, MC-RR, MC-LR, and MC-LA). Up to 51% removal for single MC analogues in waste lagoon water was observed. Similar removal rates were observed when a mixture of all four MC analogues was treated. Although treatment of MC-containing cyanobacterial cells of Microcystis aeruginosa resulted in no decline in cell numbers or viability with the current reactor design and treatment regime, the photocatalytic treatment did improve the overall quality of waste lagoon water. This study demonstrates that despite the presence of natural organic matter the microcystins could be successfully degraded in a complex environmental matrix.

Halogen-bond mediated efficient storage of extremely volatile perfluoroiodides in ionic liquids.

Highly volatile and valuable reagents, perfluoroiodides were shown to complex with ionic liquids with the aid of a halogen-bond between a diverse set of anions and the electrophilic iodine atoms in perfluorinated iodides. The affinity of anions in various ionic liquids towards perfluoroiodides was examined by 19F NMR. Making use of the non-volatility of ionic liquids, we demonstrate here that perfluoroiodides can be stored and released controllably, on demand, from an ionic liquid matrix.

Simultaneous cellulose conversion and hydrogen production assisted by cellulose decomposition under UV-light photocatalysis.

Photocatalytic conversion of cellulose to sugars and carbon dioxide with simultaneous production of hydrogen assisted by cellulose decomposition under UV or solar light irradiation was achieved upon immobilization of cellulose onto a TiO2 photocatalyst. This approach enables production of hydrogen from water without using valuable sacrificial agents, and provides the possibility for recovering sugars as liquid fuels.

In situ ATR-FTIR study of H2O and D2O adsorption on TiO2 under UV irradiation.

The adsorption of water and deuterium oxide on TiO2 surfaces was investigated in the dark as well as under UV(A) irradiation using in situ ATR-FTIR spectroscopy under oxygen and oxygen free conditions. Adsorption of H2O-D2O mixtures revealed an isotopic exchange reaction occurring onto the surface of TiO2 in the dark. Under UV(A) irradiation, the amount of both OH and OD groups was found to be increased by the presence of molecular oxygen. Furthermore, the photocatalytic formation of hydroperoxide under oxygenated condition has been recorded utilizing Attenuated Total Reflection Fourier Transformed Infrared (ATR-FTIR) spectroscopy which appeared as new band at 3483 cm(-1). Different possible mechanisms are discussed in terms of the source of hydroxyl groups formed and/or hydration water on the TiO2 surface for the photocatalytic reaction and photoinduced hydrophilicity.

Photocatalytic degradation of eleven microcystin variants and nodularin by TiO2 coated glass microspheres.

Microcystins and nodularin are toxic cyanobacterial secondary metabolites produced by cyanobacteria that pose a threat to human health in drinking water. Conventional water treatment methods often fail to remove these toxins. Advanced oxidation processes such as TiO2 photocatalysis have been shown to effectively degrade these compounds. A particular issue that has limited the widespread application of TiO2 photocatalysis for water treatment has been the separation of the nanoparticulate powder from the treated water. A novel catalyst format, TiO2 coated hollow glass spheres (Photospheres™), is far more easily separated from treated water due to its buoyancy. This paper reports the photocatalytic degradation of eleven microcystin variants and nodularin in water using Photospheres™. It was found that the Photospheres™ successfully decomposed all compounds in 5 min or less. This was found to be comparable to the rate of degradation observed using a Degussa P25 material, which has been previously reported to be the most efficient TiO2 for photocatalytic degradation of microcystins in water. Furthermore, it was observed that the degree of initial catalyst adsorption of the cyanotoxins depended on the amino acid in the variable positions of the microcystin molecule. The fastest degradation (2 min) was observed for the hydrophobic variants (microcystin-LY, -LW, -LF). Suitability of UV-LEDs as an alternative low energy light source was also evaluated.