Recent developments on advanced materials for photonics, sensing and energy conversion energy applications (AMPSECA'2021).

We are honored to present this special issue of the Environmental Science and Pollution Research which comprises the selected papers presented at the international conference on Advanced Materials for Photonics, Sensing and Energy Conversion Energy Applications, held in Marrakech, Morocco.

Two-dimensional layered carbon-based catalytic ozonation for water purification: Rational design of catalysts and an in-depth understanding of the interfacial reaction mechanism.

This review renewed insight into the existing complex and contradictory mechanisms of catalytic ozonation by two-dimensional layered carbon-based materials (2D-LCMs) for degradation toxic refractory organics in aqueous solution. Migration and capture of active electrons are central to catalytic ozonation reactions, which was not studied or reviewed more clearly. Based on this perspective, the catalytic ozonation potential of 2D-LCMs synthesized by numerous methods is firstly contrasted to guide the design of subsequent carbon based-catalysts, and not limited to 2D-LCMs. Matching ROS to active sites is a key step in understanding the catalytic mechanism. The structure-activity relationships between reported numerous active sites and ROS evolution is then constructed. Result showed that OH could be produced by -OH, -C=O, -COOH groups, defective sites, immobilized metal atoms, doped heteroatoms and photo-induced electrons; and O2- could be produced by -OH groups and sp2-bonded carbon. The normalized model further be used to visually compare the contribution degree of various regulatory methods to performance improvement. More importantly, this review calls for 2D-LCMs-based catalytic ozonation to be studied without circumventing the issue of structural stability, which would lead to many proposals of catalysts and its involved catalytic reaction mechanism being meaningless.

Ti-Modified LaFeO3/ß-SiC Alveolar Foams as Immobilized Dual Catalysts with Combined Photo-Fenton and Photocatalytic Activity.

Ti-modified LaFeO3/ß-SiC alveolar foams were used as immobilized, highly robust dual catalysts with combined photocatalytic wet peroxide oxidation and photocatalytic activity under UV-A light. They were prepared by incipient wetness impregnation of a ß-SiC foam support, by implementing a sol-gel Pechini synthesis at the foam surface in the presence of dried amorphous sol-gel titania as a titanium source. The physicochemical and catalytic features suggest the stabilization at the foam surface of a substituted La1-xTixFeO3 catalyst analogous to its powdery counterpart. Taking 4-chlorophenol removal in water as a model reaction, its dual nature enables both high reaction rates and full total organic carbon (TOC) conversion because of a synergy effect, while its macroscopic structure overcomes the drawback of working with powdery catalysts. Further, it yields photonic efficiencies for degradation and mineralization of ca. 9.4 and 38%, respectively, that strongly outperform those obtained with a reference TiO2 P25/ß-SiC foam photocatalyst. The enhancement of the catalyst robustness upon Ti modification prevents any Fe leaching to the solution, and therefore, the optimized macroscopic foam catalyst with 10 wt % catalyst loading operates through pure heterogeneous surface reactions, without any activity loss during reusability test cycles.

Activity enhancement pathways in LaFeO3@TiO2 heterojunction photocatalysts for visible and solar light driven degradation of myclobutanil pesticide in water.

LaFeO3@TiO2 heterojunction composites with a core-shell porous structure and LaFeO3 contents in the 2.5-25 wt.% range have been synthesized via consecutive sol-gel syntheses and tested for the photocatalytic oxidation of the myclobutanil pesticide in water under solar light and pure visible light. Whatever the light spectrum, the kinetic rate constants for both myclobutanil degradation and TOC conversion exhibited a volcano-like profile with increasing the narrow band-gap (2.1 eV) LaFeO3 content, the optimum composite strongly overperforming both single phases, with full myclobutanil mineralization achieved in 240 min in the best case. The light spectrum influenced the optimum LaFeO3 content in the composite, being observed at 5 wt.% and 12.5 wt.% under solar and visible light, respectively. This has been attributed to the existence of different light-mediated reaction mechanisms. The optimum LaFeO3/TiO2 composite photocatalyst was active and stable after several runs under solar light with leached iron concentration below 0.1 mg/L in solution.

Photocatalytic Degradation of Myclobutanil and Its Commercial Formulation with TiO2 P25 in Slurry and TiO2/ß-SiC Foams.

Viticulture is one of the crops most subject to pest control by fungicides. Their drainage towards the fresh water affects the aquatic environment, the fauna, the flora and especially the human health. It is therefore necessary to find an adequate solution to solve this problem. Heterogeneous photocatalysis is an advanced oxidation method for the degradation and mineralization of organic pollutants in water and air using semi-conductor (e.g., TiO²). TiO2 P25 in suspension (0.75 g·L-1) is used to treat Myclobutanil contaminated water and a commercial formulation Systhane™ 20EW, a fungicide produced by BASF. After 120 min of batch treatment under our conditions (pH = 6.7, Co = 10 mg ·L-1), 96% and 98% of Myclobutanil and Systhane were removed with 94% and 92% mineralization, respectively. In order to avoid the recovery of nanoparticles of TiO² P25 after treatment, we have taken care of ß-SiC foam cells. Under the same experimental conditions, 45% and 56% of Myclobutanil and Systhane degraded after 4 h with mineralization of 29% and 27%, respectively in recirculation in a fixed-light photoreactor by UV-A lamps. These results are very encouraging: filtering is not necessary to separate the catalyst from the treated water, it is very important for large-scale use of this process.

Coating-free TiO2@ß-SiC alveolar foams as a ready-to-use composite photocatalyst with tunable adsorption properties for water treatment.

Coating-free TiO2@ß-SiC photocatalytic composite foams gathered within a ready-to-use shell/core alveolar medium the photocatalytically active TiO2 phase and the ß-SiC foam structure were prepared via a multi-step shape memory synthesis (SMS) replica method. They were fabricated following a sequential two-step carburization approach, in which an external TiC skin was synthesized at the surface of a ß-SiC skeleton foam obtained from a pre-shaped polyurethane foam during a first carburization step. The adsorption behaviour of the shell/core TiO2@ß-SiC composite foams towards the Diuron pollutant in water was tuned by submitting the carbide foams to a final calcination treatment within the 550-700 °C temperature range. The controlled calcination step allowed (i) the selective oxidation of the TiC shell into a TiO2 crystallite shell owing to the ß-SiC resistance to oxidation and (ii) the amount of residual unreacted carbon in the foams to be tuned. The lower the calcination temperature, the more pronounced the adsorption profiles of the composites and the higher the Diuron amount removed by adsorption on the residual unreacted carbon. The ready-to-use TiO2@ß-SiC composite foams were active in the degradation of the Diuron pesticide, without any further post-synthesis immobilization or synthesis process at the foam surface. They displayed good reusability with test cycles and benefitted from an enhanced stability in terms of the titania release to water.

Kinetics and mechanism of Paraquat's degradation: UV-C photolysis vs UV-C photocatalysis with TiO2/SiC foams.

In this study, the photolytic and photocatalytic removal of the herbicide paraquat is investigated under UV-C (254 nm). For photocatalytic experiments, SiC foams were used with P25-TiO2 nanoparticles deposited by dip-coating. The foams were characterized by scanning electron microscopy and paraquat's degradation under UV-C photolysis or photocatalysis, followed by UV-vis spectroscopy, total organic carbon analyzer, LC-MS and ion chromatography. After 3 h of reactions by photolysis and photocatalysis, 4% and 91% of TOC removal were observed. An analysis of degradation by-products showed a similar degradation pathway with pyridinium ions observed by LC/MS and carboxylic acids (succinate, acetate, oxalate and formate) detected by ion chromatography. In conclusion, these two different photo-degradation processes are able to remove paraquat and produce similar by-products. However, the kinetics of degradation is rather slow during photolysis and it is recommended to combine the UV-C lightning with a TiO2 photocatalyst to improve the mineralization rate.

Removal of atrazine and its by-products from water using electrochemical advanced oxidation processes.

Atrazine (ATZ) is one of the most common pesticides detected in surface water in Quebec (Canada). The present study was mainly focused on the degradation of ATZ and its by-products using electrochemical advanced oxidation processes such as photo-electro-Fenton (PEF), electro-Fenton (EF) and anodic-oxidation with simultaneous H2O2 formation (AO - H2O2). The comparison of these processes showed that PEF process was found to be the most effective process in removing ATZ and its by-products from both synthetic solution (ATZ0 = 100 µg L-1) and real agricultural surface water enriched with ATZ (ATZ0 = 10 µg L-1). Different operating parameters, including wavelength of the light, pH, current density and the presence of natural organic matter (humic acids) were investigated for PEF process using boron-doped diamond (BDD) anode and graphite cathode. The current density and the wavelength of the light were the most important parameters in the ATZ degradation efficiency. The best operating conditions were recorded for the synthetic samples at a current density of 18.2 mA cm-2, a pH of 3.0 and treatment time of 45 min. Results showed that atrazine-desethyl-desisopropyl (DEDIA) was the most important by-product recorded. More than 99% of ATZ oxidation was recorded after 15 min of treatment and all the concentrations of major by-products were less than the limit of detection after 45 min of treatment. The PEF process was also tested for real surface water contaminated by ATZ: i) with and without addition of iron; ii) without pH adjustment (pH âˆ¼ 6.7) and with pH adjustment (pH âˆ¼ 3.1). In spite of the presence of radical scavenger and iron complexation the PEF process was more effective to remove ATZ from real surface water when the pH value was adjusted near to 3.0. The ATZ removal was 96.0% with 0.01 mM of iron (kapp = 0.13 min-1) and 100% with 0.1 mM of iron (kapp = 0.17 min-1).

Effect of W doping level on TiO2 on the photocatalytic degradation of Diuron.

In the present study, three compositions of W-doped titania nano-photocatalyst are synthesized via the sol-gel method. The powders obtained were characterized by X-ray diffraction, Raman spectroscopy and UV-visible diffuse reflectance spectroscopy. The photocatalytic performances of the different photocatalysts are tested with respect to the degradation of Diuron in water solutions under simulated solar light and visible light irradiation. The W0.03Ti0.97O2 catalyst exhibits better photoactivity than the pure TiO2 even under simulated solar light and visible light. This improvement in activity was attributed to photoelectron/hole separation efficiency.

Nitrogen-containing organic compounds: Origins, toxicity and conditions of their photocatalytic mineralization over TiO2.

Sustainable water management remains a global concern to meet the food needs of industrial and agricultural activities. Therefore, pollution abatement techniques, cheap and environmentally, are highly desired and recommended. The present review is devoted to the origin and the toxicity of nitrogen-containing organic compounds in water. The progress made in removing these pollutants, in recent years, is addressed. However, a prominent place is given to the photocatalytic degradation process using the TiO2 as a semiconductor, the conditions for good mineralization and especially the factors influencing it. The parameters that impact the performance of this method are the pH, the temperature, the reactor used, the light, the concentration of the pollutant, the amount of catalyst, etc. Up to now, the importance of one parameter relative to another has not been established because in the context of the photocatalytic degradation, certain parameters are often tightly coupled. Consequently, the mineralization is dependent on the initial degree of oxidation of nitrogen atom contained in the pollutant to be degraded. The hydroxyl nitrogen is primarily converted into nitrate ions (NO3-), while the amides and the primary amines are converted into ammonium ions (NH4+).

Sol-gel synthesis of TiO2 nanoparticles: effect of Pluronic P123 on particle's morphology and photocatalytic degradation of paraquat.

We report a facile method to tune TiO2 nanoparticles' morphology by modifying and an acid-catalyzed sol-gel synthesis with Pluronic P123. Synthesized particles were characterized by transmission electron microscopy, BET analysis, and X-ray diffraction spectroscopy. XRD analysis revealed a high anatase content while BET measurements showed that porous volume strongly depends on the amount of P123. We demonstrate that high amounts of P123 increase particle's aspect-ratio from spherical to rod-shape morphology. We evaluated the photocatalytic performances for the removal of methyl viologen (paraquat) and found that best performances are obtained for the following weight ratio P123/TiO2 = 7.5. Furthermore, P25 is less active than synthesized nanoparticles.

Degradation of atrazine in aqueous solution with electrophotocatalytic process using TiO2-x photoanode.

The present study investigates the efficiency of a sustainable treatment technology, the electrophotocatalytic (EPC) process using innovative photoanode TiO2-x prepared by a magnetron sputter deposition process to remove the herbicide atrazine (ATZ) from water. The coexistence of anatase and rutile were identified by X-ray diffraction (XRD) and the presence of oxygen vacancies reduce the value of the observed bandgap to 3.0 eV compared to the typical 3.2 eV TiO2, this reduction is concomitant with a partial phase transition which is probably responsible for the increase in photoactivity. The experimental results with an initial concentration of ATZ (100 µg L(-1)) show that more than 99% of ATZ oxidation was obtained after 30 min of treatment and reaction kinetic constant was about 0.146 min(-1). This good efficiency indicates that EPC process is an efficient, simple and green technique for degradation of pesticides such as ATZ in water. The analysis with liquid chromatography technique permits to identify, quantify and see the evolution of ATZ by-products which are generated by dechlorination, dealkylation and alkylic-oxidation mechanisms. Finally, the possible pathways of ATZ degradation by hydroxyl radicals were proposed.

Cerium doped red mud catalytic ozonation for bezafibrate degradation in wastewater: Efficiency, intermediates, and toxicity.

In this study, the performance of bezafibrate (BZF) degradation and detoxification in the aqueous phase using cerium-modified red mud (RM) catalysts prepared using different cerium sources and synthesis methods were evaluated. Experimental results showed that the surface cerium modification was responsible for the development of the catalytic activity of RM and this was influenced by the cerium source and the synthesis method. Catalyst prepared from cerium (IV) by precipitation was found to show the best catalytic activity in BZF degradation and detoxification. Reactive oxygen species including peroxides, hydroxyl radicals, and super oxide ions were identified in all reactions and we proposed the corresponding catalytic reaction mechanism for each catalyst that prepared from different cerium source and method. This was supported by the intermediates profiles that were generated upon BZF degradation. The surface and the structural properties of cerium-modified RM were characterized in detail by several analytical methods. Two interesting findings were made: (1) the surface texture (specific surface area and mesoporous volume) influenced the catalytic reaction pathway; and (2) Ce(III) species and oxygen vacancies were generated on the surface of the catalyst after cerium modification. This plays an important role in the development of the catalytic activity.

Effect of SiN x diffusion barrier thickness on the structural properties and photocatalytic activity of TiO2 films obtained by sol-gel dip coating and reactive magnetron sputtering.

We investigate the effect of the thickness of the silicon nitride (SiN x ) diffusion barrier on the structural and photocatalytic efficiency of TiO2 films obtained with different processes. We show that the structural and photocatalytic efficiency of TiO2 films produced using soft chemistry (sol-gel) and physical methods (reactive sputtering) are affected differentially by the intercalating SiN x diffusion barrier. Increasing the thickness of the SiN x diffusion barrier induced a gradual decrease of the crystallite size of TiO2 films obtained by the sol-gel process. However, TiO2 obtained using the reactive sputtering method showed no dependence on the thickness of the SiN x barrier diffusion. The SiN x barrier diffusion showed a beneficial effect on the photocatalytic efficiency of TiO2 films regardless of the synthesis method used. The proposed mechanism leading to the improvement in the photocatalytic efficiency of the TiO2 films obtained by each process was discussed.

H2S photocatalytic oxidation over WO3/TiO2 Hombikat UV100.

Hydrogen sulfide (H2S) is a toxic, corrosive and malodorous compound with damaging effects even when present at a low concentration in air. Consequently, the development of efficient and environmentally friendly remediation technologies as an alternative to conventional techniques is justified for environmental reasons and public concern over human health and well-being. In the context of indoor air quality control, the use of photocatalysis over semi-conductor oxides could be a valuable alternative purification technology due to its wide-ranging effect and its easy way of implementation. The superiority of the TiO2 Hombikat UV100 photocatalyst in comparison with the Aeroxide© TiO2 P25 standard was already apparent in the UV-A photocatalytic oxidation of H2S. We report here on the first use of WO3/TiO2 UV100 photocatalysts for this reaction. Associating WO3 to TiO2 UV100 was not beneficial in terms of semiconductor coupling and of charge transfer between both phases. Even if such coupled wide band-gap oxide semi-conductor photocatalysts suffered from on-flow deactivation due to the formation of poisoning sulfates as ultimate reaction products continuously stored at the surface, by contrast, their ability to strongly lower and delay the release of SO2 to the gas phase was very positive for maintaining a weak selectivity into the unwanted SO2 by-product.

Photo-degradation of butyl parahydroxybenzoate by using TiO2-supported catalyst.

The present work evaluates the potential of the photocatalysis (PC) process for the degradation of butylparaben (BPB). Relatively high treatment efficiency was achieved by comparison to photochemical process. Prior to photocatalytic degradation, adsorption (AD) of BPB occurred on the titanium dioxide (TiO2)-supported catalyst. AD was described by Langmuir isotherm (KL = 0.085 L g(-1), qm = 4.77 mg g(-1)). The influence of angle of inclination of the reactor, pH, recirculation flow rate and initial concentration of BPB were investigated. The PC process applied under optimal operating conditions (recirculation flow rate of 0.15 L min(-1), angle of inclination of 15°, pH = 7 and 5 mg L(-1) of BPB) is able to oxidize 84.9-96.6% of BPB and to ensure around 38.7% of mineralization. The Langmuir-Hinshelwood kinetic model described well the photocatalytic oxidation of BPB (k = 7.02 mg L(-1) h(-1), K = 0.364 L mg(-1)).

TiO2/ß-SiC foam-structured photoreactor for continuous wastewater treatment.

INTRODUCTION: This study of photocatalytic degradation of wastewater was carried out in alveolar cell ß-SiC foam-structured photocatalytic reactors working in a recirculation mode. The immobilization of TiO2 on ß-SiC foams was efficiently obtained through a sol-gel technique in acidic conditions. DISCUSSION: In order to optimize degradation yields obtained by the foam-structured prototype reactor for the photocatalytic water treatment, the operating conditions of the photoreactor have been investigated and the efficiency of the process was evaluated by measuring the photocatalytic degradation of Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl-urea)) under UV irradiation. Kinetic studies were carried out by investigating the influence of different parameters controlling the reaction (TiO2 loading and ß-SiC foam cell size). The ageing of TiO2/ß-SiC foam photocatalytic materials and the mineralization (TOC, Cl-, NO3- and NH4+) of Diuron were investigated.

Design and study of a cost-effective solar photoreactor for pesticide removal from water.

In order to remove pesticides from water, a basic photoreactor has been built. We evaluated the performance of this photoreactor using two commercial photocatalytic materials from Ahlstrom group and from Saint-Gobain, with solar and artificial UV-lamps. We compared the kinetics of photocatalytic degradation and mineralization of Diuron in the same reactor with of both photocatalyst supports. We showed that Diuron is easily degraded under solar or artificial irradiation, while the kinetics of mineralization in the same condition are very slow. The behaviour of these commercial materials has been studied after several uses in the same conditions. We showed the effectiveness of this basic and cheap photoreactor for the elimination of pesticide in water.