Sonoprocessing: From Concepts to Large-Scale Reactors.

Intensification of ultrasonic processes for diversified applications, including environmental remediation, extractions, food processes, and synthesis of materials, has received attention from the scientific community and industry. The mechanistic pathways involved in intensification of ultrasonic processes that include the ultrasonic generation of cavitation bubbles, radical formation upon their collapse, and the possibility of fine-tuning operating parameters for specific applications are all well documented in the literature. However, the scale-up of ultrasonic processes with large-scale sonochemical reactors for industrial applications remains a challenge. In this context, this review provides a complete overview of the current understanding of the role of operating parameters and reactor configuration on the sonochemical processes. Experimental and theoretical techniques to characterize the intensity and distribution of cavitation activity within sonoreactors are compared. Classes of laboratory and large-scale sonoreactors are reviewed, highlighting recent advances in batch and flow-through reactors. Finally, examples of large-scale sonoprocessing applications have been reviewed, discussing the major scale-up and sustainability challenges.

Boosting Hydroxyl Radical Yield via Synergistic Activation of Electrogenerated HOCl/H2O2 in Electro-Fenton-like Degradation of Contaminants under Chloride Conditions.

Hydroxyl radical production via catalytic activation of HOCl is a new type of Fenton-like process. However, metal-chlorocomplex formation under high chloride conditions could deactivate the catalyst and reduce the process efficiency. Herein, in situ electrogenerated HOCl was activated to •OH via a metal-free, B/N-codoped carbon nanofiber cathode for the first time to degrade contaminant under high chloride condition. The results show 98% degradation of rhodamine B (RhB) within 120 min (k = 0.036 min-1) under sulfate conditions, while complete degradation (k = 0.188 min-1) was obtained in only 30 min under chloride conditions. An enhanced degradation mechanism consists of an Adsorb & Shuttle process, wherein adsorption concentrates the pollutants at the cathode surface and they are subsequently oxidized by the large amount of •OH produced via activation of HOCl and H2O2 at the cathode. Density functional theory calculations verify the pyridinic N as the active site for the activation of HOCl and H2O2. The process efficiency was also evaluated by treating tetracycline and bisphenol A as well as high chloride-containing real secondary effluents from a pesticide manufacturing plant. High yields of •OH and HOCl allow continuous regeneration of the cathode for several cycles, limiting its fast deactivation, which is promising for real application.

Through converting the surface complex on TiO2 nanorods to generate superoxide and singlet oxygen to remove CN.

Cyanide (CN-) is extensively used in the process of plating devices and for surface treatment in the electroplating industry and is extremely hazardous to humans and the environment. Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) hold considerable promise for CN- removal. However, the activity of sulfate radical and hydroxyl radical generated in the PMS activation process is low in the base condition, leading to a drop in its efficiency in CN- removal. Thus, a photo-electrocatalytic system (PEC), developed using a TiO2 photoanode and a carbon aerogel cathode, was used to activate PMS for the removal of CN- from wastewater through the generation of radicals and non-radicals. The PEC/PMS system could effectively remove CN-, with the removal efficiency reaching 98.5% within 2 min, when PMS concentration was at the 0.25 mmol/L level, and the applied bias voltage was -0.5 V. The main active species in the PEC/PMS system were superoxide radicals and singlet oxygen, which was proved through electron paramagnetic resonance detection and quenching experiments. Results obtained through in-situ Raman measurements, photocurrent tests, and electrochemical impedance spectroscopy measurements indicated that the TiO2 could activate PMS to generate active species. Following many cycles of experimentation, it was discovered that the system displayed high catalytic performance and possessed satisfactory stability to remove CN- economically and efficiently.

Radical-Mediated Photocatalysis for Lignocellulosic Biomass Conversion into Value-Added Chemicals and Hydrogen: Facts, Opportunities and Challenges.

Photocatalytic biomass conversion into high-value chemicals and fuels is considered one of the hottest ongoing research and industrial topics toward sustainable development. In short, this process can cleave Cß -O/Cα -Cß bonds in lignin to aromatic platform chemicals, and further conversion of the polysaccharides to other platform chemicals and H2 . From the chemistry point of view, the optimization of the unique cooperative interplay of radical oxidation species (which are activated via molecular oxygen species, ROSs) and substrate-derived radical intermediates by appropriate control of their type and/or yield is key to the selective production of desired products. Technically, several challenges have been raised that face successful real-world applications. This review aims to discuss the recently reported mechanistic pathways toward selective biomass conversion through the optimization of ROSs behavior and materials/system design. On top of that, through a SWOT analysis, we critically discussed this technology from both chemistry and technological viewpoints to help the scientists and engineers bridge the gap between lab-scale and large-scale production.

Engineering carbon nanotubes for sensitive viral detection.

Viral infections have been proven a severe threat to human beings, and the pandemic of Coronavirus Disease 2019 (COVID-19) has become a societal health concern, including mental distress and morbidity. Therefore, the early diagnosis and differentiation of viral infections are the prerequisite for curbing the local and global spread of viruses. To this end, carbon nanotubes (CNTs) based virus detection strategies are developed that provide feasible alternatives to conventional diagnostic techniques. Here in this review, an overview of the design and engineering of CNTs-based sensors for virus detection is summarized, followed by the nano-bio interactions used in developing biosensors. Then, we classify the viral sensors into covalently engineered CNTs, non-covalently engineered CNTs, and size-tunable CNTs arrays for viral detection, based on the type of CNTs-based nano-bio interfaces. Finally, the current challenges and prospects of CNTs-based sensors for virus detection are discussed.

Advances in 2D MXenes-based materials for water purification and disinfection: Synthesis approaches and photocatalytic mechanistic pathways.

MXenes two-dimensional materials have recently excited researchers' curiosity for various industrial applications. MXenes are promising materials for environmental remediation technologies to sense and mitigate various intractable hazardous pollutants from the atmosphere due to their inherent mechanical and physicochemical properties, such as high surface area, increased hydrophilicity, high conductivity, changing band gaps, and robust electrochemistry. This review discusses the versatile applications of MXenes and MXene-based nanocomposites in various environmental remediation processes. A brief description of synthetic procedures of MXenes nanocomposites and their different properties are highlighted. Afterward, the photocatalytic abilities of MXene-based nanocomposites for degrading organic pollutants, removal of heavy metals, and inactivation of microorganisms are discussed. In addition, the role of MXenes anti-corrosion support in the lifetime of some semiconductors was addressed. Current challenges and future perspectives toward the application of MXene materials for environmental remediation and energy production are summarized for plausible real-world use.

Oxidative Inactivation of SARS-CoV-2 on Photoactive AgNPs@TiO2 Ceramic Tiles.

The current SARS-CoV-2 pandemic causes serious public health, social, and economic issues all over the globe. Surface transmission has been claimed as a possible SARS-CoV-2 infection route, especially in heavy contaminated environmental surfaces, including hospitals and crowded public places. Herein, we studied the deactivation of SARS-CoV-2 on photoactive AgNPs@TiO2 coated on industrial ceramic tiles under dark, UVA, and LED light irradiations. SARS-CoV-2 inactivation is effective under any light/dark conditions. The presence of AgNPs has an important key to limit the survival of SARS-CoV-2 in the dark; moreover, there is a synergistic action when TiO2 is decorated with Ag to enhance the virus photocatalytic inactivation even under LED. The radical oxidation was confirmed as the the central mechanism behind SARS-CoV-2 damage/inactivation by ESR analysis under LED light. Therefore, photoactive AgNPs@TiO2 ceramic tiles could be exploited to fight surface infections, especially during viral severe pandemics.

Recovery of Phosphorus from Hypophosphite-Laden Wastewater: A Single-Compartment Photoelectrocatalytic Cell System Integrating Oxidation and Precipitation.

Recovery of phosphorus through precipitation from hypophosphite-laden wastewater is more difficult than from orthophosphate-laden wastewater because of the higher solubility of hypophosphite (H2PO2-). Herein, a single-compartment photoelectrocatalytic (PEC) cell system consisting of a TiO2/Ni-Sb-SnO2 bifunctional photoanode and an activated carbon fiber (ACF) cathode with dosing Fe2+ ions was developed for recovery of phosphorus in the form of FePO4 from hypophosphite-laden wastewater. In the PEC process, H2PO2- with an initial concentration of 1.0 mM was completely oxidized and recovered within 30 min at 3.0 V, and the pseudo-first-order rate constant of H2PO2- oxidation was ∼4 times than that in the electrocatalytic process and even ∼89 times than that in the photocatalytic process. The bifunctional photoanode can simultaneously generate •OH radicals and O3; the ACF cathode can electrogenerate H2O2; H2O2, O3, and the added Fe2+ can interact with each other to produce •OH radicals and Fe3+ ions. •OH radicals mainly from the Fenton process were responsible for oxidation of H2PO2- to PO43-, which immediately combined with Fe3+ to form FePO4 at the optimized conditions to realize recovery of phosphorus. The long-term stability of this system was demonstrated. The efficiency for actual electroless nickel plating effluents was exhibited.

Strategies to reduce mass and photons transfer limitations in heterogeneous photocatalytic processes: Hexavalent chromium reduction studies.

The current work presents different approaches to overcome mass and photon transfer limitations in heterogeneous photocatalytic processes applied to the reduction of hexavalent chromium to its trivalent form in the presence of a sacrificial agent. Two reactor designs were tested, a monolithic tubular photoreactor (MTP) and a micro-meso-structured photoreactor (NETmix), both presenting a high catalyst surface area per reaction liquid volume. In order to reduce photon transfer limitations, the tubular photoreactor was packed with transparent cellulose acetate monolithic structures (CAM) coated with the catalyst by a dip-coating method. For the NETmix reactor, a thin film of photocatalyst was uniformly deposited on the front glass slab (GS) or on the network of channels and chambers imprinted in the back stainless steel slab (SSS) using a spray system. The reaction rate for the NETmix photoreactor was evaluated for two illumination sources, solar light or UVA-LEDs, using the NETmix with the front glass slab or/and back stainless steel slab coated with TiO2-P25. The reusability of the photocatalytic films on the NETmix walls was also evaluated for three consecutive cycles using fresh Cr(VI) solutions. The catalyst reactivity in combination with the NETmix-SSS photoreactor is almost 70 times superior to one obtained with the MTP.

Cu nanoparticles grafting on the surface of ZnO nanostructures to boost the porosity and surface area for effective removal of manganese ions from aqueous solutions.

Designing highly adsorptive materials for wastewater treatment via facile approaches is still challenging. To boost the recovery of heavy metals from wastewater, surface and structure modification are considered a successful route. Herein, we report the design of ZnO nanoparticles by a simple thermal decomposition method followed by grafting Cu nanoparticles (Cu NPs) over the ZnO surface. Cu/ZnO was prepared with different Cu ratios, 0.01 and 1%. It was found that incorporating Cu into ZnO improved the porosity and surface area of ZnO. The adsorption ability of Cu/ZnO compared with bare ZnO was studied towards removing manganese ions from wastewater. The effects of several parameters, such as pH, temperature, contact time, and initial ion concentrations, were studied. The maximum removal of manganese was found at pH 2, 20 °C after 60 min in the presence of 1 g/L adsorbent. The role of Cu grafted on the surface of ZnO was discussed. The rates of adsorption were found to follow the pseudo-second-order model. The results showed better fitting to Freundlich isotherm. The thermodynamic study revealed that the sorption process is spontaneous, exothermic, and favorable at low temperatures. The free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were calculated to predict the nature of adsorption.

Easy-handling semi-floating TiO2-based aerogel for solar photocatalytic water depollution.

One of the capital issues of photocatalytic technology is how to use photocatalytic materials in real world conditions. Suspension photocatalysts are the most effective, while the handling and recovery of nanoparticles are very challenging and costly. Herein, we report the design of semi-floating aerogel TiO2-based photocatalyst for the oxidation of dyes and photoreduction of Cr(VI). TiO2 aerogel-based photocatalyst was fabricated through in situ polymerization using borax, poly(vinyl alcohol) and polyvinylidene in the presence of H2O2 as a catalyst. Cubic TiO2 aerogel of few centimetres was designed for the photocatalytic tests under solar light irradiation. TiO2 aerogel showed a good photoactivity against the oxidation of three types of dyes and Cr(VI) photoreduction. In terms of dyes, the kinetics of methylene blue oxidation was the fastest as compared to rhodamine B and methyl red, while, a total reduction of Cr(VI) at 10 ppm was obtained within 30 min after the addition of tartaric acid as hole scavenger. TiO2 aerogel can be easily recovered, washed and recycled. TiO2 aerogel can move freely from the top to the deep solution. The semi-floating property could be an advantage to enhance the mass transfer along with bulk solution, as compared to totally floating-based photocatalysts.

Fast g-C3N4 sonocoated activated carbon for enhanced solar photocatalytic oxidation of organic pollutants through Adsorb & Shuttle process.

To solve low mass transfer in photocatalytic technology for water treatment, the combination of photoactive nanoparticles with highly adsorptive materials has been regarded as a successful approach. The optimization of photoactive particle coating in terms of dispersion on the surface of adsorbing support is the main key to reach a maximum synergism for pollutants removal. This study discusses the coating of as-prepared biomass based activated carbon by g-C3N4 using three routes, namely ball milling (AC-CN@BM), physical stirring (AC-CN@Phy) and ultrasonic assisted coating (AC-CN@US). The coating mechanisms by different processes were discussed using different characterization techniques. Ball milling based coating provides good g-C3N4 dispersion on the surface of AC, however, a partial degradation of g-C3N4 structure and a lower surface area were confirmed by FTIR, XRD and BET analysis. Physically designed sample shows a significant agglomeration of particles on the surface of AC. However, ultrasonic coating provides excellent distribution of g-C3N4 and high surface of the composite. In terms of photoactivity, AC-CN@BM exhibits the lowest adsorption and photocatalytic activity under solar light for the removal of ciprofloxacin. AC-CN@Phy showed medium performance, but less physical stability of g-C3N4 particles on AC, leading to their partial release. AC-CN@US showed the highest efficiency and stability after using; suggesting the good combination between g-C3N4 and AC, which in turn maximizes the removal of ciprofloxacin via Adsorb & shuttle process. The overall costs of composite, including the starting elements and the coating ultrasonic process are relatively low and green as compared to commonly reported routes.

Combined conversion of lignocellulosic biomass into high-value products with ultrasonic cavitation and photocatalytic produced reactive oxygen species - A review.

The production of high-value products from lignocellulosic biomass is carried out through the selective scission of crosslinked CC/CO bonds. Nowadays, several techniques are applied to optimize biomass conversion into desired products with high yields. Photocatalytic technology has been proven to be a valuable tool for valorizing biomass at mild conditions. The photoproduced reactive oxygen species (ROSs) can initiate the scission of crosslinked bonds and form radical intermediates. However, the low mass transfer of the photocatalytic process could limit the production of a high yield of products. The incorporation of ultrasonic cavitation in the photocatalytic system provides an exceptional condition to boost the fragmentation and transformation of biomass into the desired products within a lesser reaction time. This review critically discusses the main factors governing the application of photocatalysis for biomass valorization and tricks to boost the selectivity for enhancing the yield of desired products. Synergistic effects obtained through the combination of sonolysis and photocatalysis were discussed in depth. Under ultrasonic vibration, hot spots could be produced on the surface of the photocatalysts, improving the mass transfer through the jet phenomenon. In addition, shock waves can assist the dissolution and mixing of biomass particles.

Valorization of lignocellulosic biomass into sustainable materials for adsorption and photocatalytic applications in water and air remediation.

An exponential rise in global pollution and industrialization has led to significant economic and environmental problems due to the insufficient application of green technology for the chemical industry and energy production. Nowadays, the scientific and environmental/industrial communities push to apply new sustainable ways and/or materials for energy/environmental applications through the so-called circular (bio)economy. One of today's hottest topics is primarily valorizing available lignocellulosic biomass wastes into valuable materials for energy or environmentally related applications. This review aims to discuss, from both the chemistry and mechanistic points of view, the recent finding reported on the valorization of biomass wastes into valuable carbon materials. The sorption mechanisms using carbon materials prepared from biomass wastes by emphasizing the relationship between the synthesis route or/and surface modification and the retention performance were discussed towards the removal of organic and heavy metal pollutants from water or air (NOx, CO2, VOCs, SO2, and Hg0). Photocatalytic nanoparticle-coated biomass-based carbon materials have proved to be successful composites for water remediation. The review discusses and simplifies the most raised interfacial, photonic, and physical mechanisms that might take place on the surface of these composites under light irradiation. Finally, the review examines the economic benefits and circular bioeconomy and the challenges of transferring this technology to more comprehensive applications.

Heat and ZnCl2 chemical carbonization of date stone as an adsorbent: optimization of material fabrication parameters and adsorption studies.

In the present study, the optimization of factors for the fabrication of highly adsorptive activated carbon from agricultural waste (date stone) was investigated by using ZnCl2 as a chemical agent during the heat treatment. ZnCl2 acts as a dehydration agent during the heat treatment, allowing a better porosity. In addition, it boosts the fragmentation of the lignocellulosic structure and the condensation of carbon rings. The findings of this investigation showed that the synthesis conditions for better ZnCl2 chemical/heat carbonization to fabricate an adsorbent from date stone are 700 °C, 120 min, and 2.0 g/g. The characterization analysis showed that the as-prepared activated carbon exhibits a surface area of 1036 m2/g, an iodine number of 928.5 mg/g, and phenol number of 2.1 mmol/g, which are comparable to commercial activated carbons. Batch sorption tests to remove methylene blue (MB) from water showed a maximum adsorption capacity of 384.6 mg/g using the prepared activated carbon. Equilibrium data was best fitted by the Langmuir isotherm model. It was found also that the kinetic adsorption data obeyed the pseudo-first order, and both external diffusion and intra-particle diffusion control the adsorption. Based on the obtained results, the optimization of synthesis conditions may help the transfer of technology in terms of agriculture-based material valorization towards the environmental remediation.

Doped-polyaniline based sorbents for the simultaneous removal of heavy metals and dyes from water: Unravelling the role of synthesis method and doping agent.

Recently, the engineering of alternative adsorbents with better functional and sorbing ability towards the purification of wastewaters has received much attention from the scientific community. Currently polymers, in particular, are regarded as attractive soft materials in the field of environmental remediation due to their several unique properties. In this regard, the synthesis method is key point to fabricate polymer-based adsorbent with targeted characteristics. In the present work, four polyaniline (PANIs) samples were synthesized by two alternative chemical approaches, a traditional one and an eco-friendly one, and two different dopants were used, HCl and H2SO4, respectively. All PANIs were characterized for their thermal, optical, morphological, and structural properties and their capability to remove simultaneously dyes and heavy metals from water have been investigated. It was deduced that the sorption ability is dependent on the as-synthesized PANI using different procedures and dopants. All the PANIs from traditional method showed high levels of pollutants removal (from 89 to 97%). Even though the materials obtained from the green way are overall less active, H2SO4-doped corresponding polymer showed high sorption capability (75-97%). Finally, the most performing PANIs were selected for recycling tests exhibiting high sorption efficiency retention up to four runs without any regeneration treatment. Most important, the cycling tests were stopped well before the sample sorption limit could be reached.

A review of advances in multifunctional XTiO3 perovskite-type oxides as piezo-photocatalysts for environmental remediation and energy production.

Over more than three decades, the field of engineering of photocatalytic materials with unique properties and enhanced performance has received a huge attention. In this regard, different classes of materials were fabricated and used for different photocatalytic applications. Among these materials, recently multifunctional XTiO3 perovskites have drawn outstanding interest towards environmental remediation and energy conversion thanks to their unique structural, optical, physiochemical, electrical and thermal characteristics. XTiO3 perovskites are able to initiate different surface catalytic reactions. Under ultrasonic vibration or heating, XTiO3 perovskites can induce piezo-catalytic reactions due to the titling of their conduction and valence bands, resulting in the formation of separated charge carriers in the medium. In addition, under light irradiation, XTiO3 perovskites are considered as a new class of photocatalysts for environmental and energy related applications. Herein, we addressed the recent advances on variously synthesized, doped and formulated XTiO3 perovskite-type oxides showing piezo- and/or photocatalytic exploitation in environmental remediation and energy conversion. The control of structural crystallite size and phase, conductivity, morphology, oxygen vacancy control, doping agents and ratio has a significant role on the photocatalytic and piezocatalytic activities. The different piezo or/and photocatalytic processes mechanistic pathways towards varying applications were discussed. The current challenges facing these materials and future trends were addressed at the end of the review.

Recent advances of bismuth titanate based photocatalysts engineering for enhanced organic contaminates oxidation in water: A review.

Over more than three decades, the scientific community has been contentiously interested in structuring varying photocatalytic materials with unique properties for appropriate technology transfer. Most of the existing reported photocatalysts in the literature show pros and cons by considering the type of application and working conditions. Bismuth titanate oxides (BTO) are novel photocatalysts that raised recently towards energy and environmental-related applications. Most recent advances to developing bismuth titanate-based photocatalysts for the oxidation of organic pollutants in the water phase were reviewed in this report. To counter the potential drawbacks of BTO materials, i.e., rapid recombination of photoproduced charges, and further promote the photoactivity, most reported approaches were discussed, including creating direct Z-scheme junctions, conventional heterojunctions, metal/non-metal doping, coupling with carbon materials, surface modification and construction of oxygen vacancies. In the end, the review addresses the future trends for better engineering and application of BTO based photocatalysts towards the photodegradation of organic pollutants in water under controlled lab and large scales conditions.

Recent advancement in conjugated polymers based photocatalytic technology for air pollutants abatement: Cases of CO2, NOx, and VOCs.

According to World Health Organization (WHO) survey, air pollution has become the major reason of several fatal diseases, which had led to the death of 7 million peoples around the globe. The 9 people out of 10 breathe air, which exceeds WHO recommendations. Several strategies are in practice to reduce the emission of pollutants into the air, and also strict industrial, scientific, and health recommendations to use sustainable green technologies to reduce the emission of contaminants into the air. Photocatalysis technology recently has been raised as a green technology to be in practice towards the removal of air pollutants. The scientific community has passed a long pathway to develop such technology from the material, and reactor points of view. Many classes of photoactive materials have been suggested to achieve such a target. In this context, the contribution of conjugated polymers (CPs), and their modification with some common inorganic semiconductors as novel photocatalysts, has never been addressed in literature till now for said application, and is critically evaluated in this review. As we know that CPs have unique characteristics compared to inorganic semiconductors, because of their conductivity, excellent light response, good sorption ability, better redox charge generation, and separation along with a delocalized π-electrons system. The advances in photocatalytic removal/reduction of three primary air-polluting compounds such as CO2, NOX, and VOCs using CPs based photocatalysts are discussed in detail. Furthermore, the synergetic effects, obtained in CPs after combining with inorganic semiconductors are also comprehensively summarized in this review. However, such a combined system, on to better charges generation and separation, may make the Adsorb & Shuttle process into action, wherein, CPs may play the sorbing area. And, we hope that, the critical discussion on the further enhancement of photoactivity and future recommendations will open the doors for up-to-date technology transfer in modern research.

Correction: Ultrafast conversion of carcinogenic 4-nitrophenol into 4-aminophenol in the dark catalyzed by surface interaction on BiPO4/g-C3N4 nanostructures in the presence of NaBH4.

[This corrects the article DOI: 10.1039/D1RA02852A.].