Nanosized tubular clay minerals as inorganic nanoreactors for energy and environmental applications: A review to fill current knowledge gaps.

Modern society pays further and further attention to environmental protection and the promotion of sustainable energy solutions. Heterogeneous photocatalysis is widely recognized as one of the most economically viable and ecologically sound technologies to combat environmental pollution and the global energy crisis. One challenge is finding a suitable photocatalytic material for an efficient process. Inorganic nanotubes have garnered attention as potential candidates due to their optoelectronic properties, which differ from their bulk equivalents. Among them, clay nanotubes (halloysite, imogolite, and chrysotile) are attracting renewed interest for photocatalysis applications thanks to their low production costs, their unique physical and chemical properties, and the possibility to functionalize or dope their structure to enhance charge-carriers separation into their structure. In this review, we provide new insights into the potential of these inorganic nanotubes in photocatalysis. We first discuss the structural and morphological features of clay nanotubes. Applications of photocatalysts based on clay nanotubes across a range of photocatalytic reactions, including the decomposition of organic pollutants, elimination of NOx, production of hydrogen, and disinfection of bacteria, are discussed. Finally, we highlight the obstacles and outline potential avenues for advancing the current photocatalytic system based on clay nanotubes. Our aim is that this review can offer researchers new opportunities to advance further research in the field of clay nanotubes-based photocatalysis with other vital applications in the future.

Ba3(PO4)2 Photocatalyst for Efficient Photocatalytic Application.

Barium phosphate (Ba3(PO4)2) is a class of material that has attracted significant attention thanks to its chemical stability and versatility. However, the use of Ba3(PO4)2 as a photocatalyst is scarcely reported, and its use as a photocatalyst has yet to be reported. Herein, Ba3(PO4)2 nanoflakes synthesis is optimized using sol-gel and hydrothermal methods. The as-prepared Ba3(PO4)2 powders are investigated using physicochemical characterizations, including XRD, SEM, EDX, FTIR, DRS, J-t, LSV, Mott-Schottky, and EIS. In addition, DFT calculations are performed to investigate the band structure. The oxidation capability of the photocatalysts is investigated depending on the synthesis method using rhodamine B (RhB) as a pollutant model. Both Ba3(PO4)2 samples prepared by the sol-gel and hydrothermal methods display high RhB photodegradation of 79% and 68%, respectively. The Ba3(PO4)2 obtained using the sol-gel process exhibits much higher stability under light excitation after four regeneration cycles. The photocatalytic oxidation mechanism is proposed based on the active species trapping experiments where O2 •‒ is the most reactive species. The finding shows the promising potential of Ba3(PO4)2 photocatalysts and opens the door for further investigation and application in various photocatalytic applications.

Ti-Modified Imogolite Nanotubes as Promising Photocatalyst 1D Nanostructures for H2 Production.

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500 µmol g-1 after 5 h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO2 -P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications.

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.

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.

Application of calcium alginate-PANI@sawdust wood hydrogel bio-beads for the removal of orange G dye from aqueous solution.

This work aims to investigate the adsorption performance of orange G (OG) dye from aqueous solutions employing PANI@sawdust biocomposite enrobed by calcium-alginate bio-beads (Alg-PANI@SD). The as-prepared adsorbent was characterized by scanning-electron-microscopy (SEM), X-ray energy-dispersive spectroscopy (EDS), and Fourier transforms infrared (FT-IR) spectroscopy and used to remove orange G dye from aqueous water. Batch tests were performed as a function of adsorbent dosage, pH, contact time, interfering ions, and initial OG dye concentration. Experimental results show that the kinetic model of pseudo-first-order (PFO) and Freundlich isotherm perfectly fit the entire experimental data. Additionally, the prepared composite exhibited an excellent regeneration capacity and reusability for OG dye removal. The results revealed that the as-prepared Alg-PANI@SD bio-beads have the potential to be applied as a low-cost adsorbent for the adsorption of OG dye from aqueous media.

Effectiveness of a novel polyaniline@Fe-ZSM-5 hybrid composite for Orange G dye removal from aqueous media: Experimental study and advanced statistical physics insights.

A polyaniline@Fe-ZSM-5 composite was synthesized via an in situ interfacial polymerization procedure. The morphology, crystallinity, and structural features of the as-developed PANI@Fe-ZSM-5 composite were assessed using scanning electron microscopy - energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The composite was efficiently employed for the first time as an adsorbent Orange G (OG) dyestuff from water. The OG dye adsorption performance was investigated as a function of several operating conditions. The kinetic study demonstrated that a pseudo-second-order model was appropriate to anticipate the OG adsorption process. The maximum adsorption capacity was found to be 217 mg/g. The adsorption equilibrium data at different temperatures were calculated via advanced statistical physics formalism. The entropy function indicated that the disorder of OG molecules improved at low concentrations and lessened at high concentrations. The free enthalpy and internal energy functions suggested that the OG adsorption was a spontaneous process and physisorption in nature. Regeneration investigation showed that the PANI@Fe-ZSM-5 could be effectively reused up to five cycles. The main results of this work provided a deep insight on the experimental study supported by advanced statistical physics prediction for the adsorption of Orange G dye onto the novel polyaniline@Fe-ZSM-5 hybrid composite. Additionally, the experimental and advanced statistical physics findings stated in this study may arouse research interest in the field of wastewater treatment.

Effect of heat treatment on the photocatalytic activity of α-Fe2O3 nanoparticles: towards diclofenac elimination.

α-Fe2O3 nanoparticles were synthesized via a straightforward method. XRD, FTIR, SEM, ESR, and DRS techniques investigated the influence of various calcination temperatures on the crystal structure, optical, and photocatalytic properties of the samples. The obtained results demonstrated that the average crystallite size increased with the increase in the calcination temperature. Measured and computed optical properties were in accordance and the bandgap energy decreased with the increase in the calcination temperature. The highest photocatalytic degradation efficiency for diclofenac (DCF) was obtained with the sample calcinated at 300 °C (96%). The photocatalytic process occurs because of the presence of OH• radicals. The addition of H2O2 led to the inhibition of OH• radicals that H2O2 scavenged.

Efficient detoxification of Cr(VI)-containing effluents by sequential adsorption and reduction using a novel cysteine-doped PANi@faujasite composite: Experimental study supported by advanced statistical physics prediction.

Nowadays, the global spreading of hazardous heavy metals becomes a top-priority environmental challenge, owing to its serious detrimental health outcomes. Herein, a novel cysteine-doped polyaniline@faujasite hybrid composite (Cys-PANi@FAU-50) was synthesized via a facile in-situ polymerization route for the effective detoxification of Cr(VI)-bearing wastewaters. The Cys-PANi@FAU-50 composite displayed an open mesoporous structure richly decorated with nitrogen/oxygen-containing functional groups, which consequently boosted the diffusion, adsorption and reduction of Cr(VI) oxyanions. The Cr(VI) adsorption behavior was satisfactorily tailored via pseudo-second-order law and Langmuir model with a maximum uptake capacity of 384.6 mg/g. Based on the advanced statistical physics theory, the monolayer model with two distinct receptor sites provided a reliable microscopic and macroscopic prediction of the Cr(VI) adsorption process. Stereographically, the Cr(VI) ions were adsorbed through horizontal multi-anchorage and vertical multi-molecular mechanisms on the amine and hydroxyl groups of Cys-PANi@FAU-50, respectively. The thermodynamic functions evidenced that the Cr(VI) adsorption was an endothermic spontaneous process. XPS analysis proved that Cr(VI) ions were electrostatically adsorbed, and subsequently reduced to Cr(III), which were in turn immobilized by chelation with imine/sulfonate groups and electrostatic interactions with carboxylate groups. The Cys-PANi@FAU-50 featured an effortless regenerability and good reusability. Overall, the Cys-PANi@FAU-50 composite owns outstanding potentiality for detoxifying Cr(VI)-laden effluents.

Synthesis and characterization of arginine-doped heliotrope leaves with high clean-up capacity for crystal violet dye from aqueous media.

A novel arginine-modified Heliotrope leaf (Arg@HL) was used as adsorbent for the crystal violet (CV) dye adsorption in a batch process. The physicochemical and morphological composition of Arg@HL were characterized by field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The experiments were carried out to investigate the factors that influence the dye uptake by the adsorbent, such as the contact time under agitation, adsorbent amount, initial dye concentration, temperature and pH of dye solution. The optimum conditions of adsorption were found on the batch scale as followed: CV concentration of 20 mg·L-1, an amount of 0.75 g·L-1 of the adsorbent, 90 min contact time, 6 pH and 25 °C temperature for Arg@HL. The results confirmed a second-order model explaining the dye crystal violet's adsorption's kinetics by Arg-Heliotrope leaves. The Langmuir model effectively defines the adsorption isotherms. The results revealed that the Arg@HL has the potential to be used as a low-cost adsorbent for the removal of CV dye from aqueous solutions.

Polyaniline coated tungsten trioxide as an effective adsorbent for the removal of orange G dye from aqueous media.

In this work, the core-shell PANI@WO3 composite was obtained from the reaction of aniline monomer polymerization with WO3 particles; sodium persulfate was used as an oxidant. Various analytical techniques such as scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS) were used to characterize the as-prepared PANI@WO3 adsorbent, which well confirmed that the WO3 particles were coated by polyaniline polymer. The PANI@WO3 composite was tested as an adsorbent to remove reactive orange G (OG) for the first time. pH, adsorbent dose, contact time, initial dye concentration, and temperature were systematically investigated in order to study their effect on the adsorption process. The experimental findings showed that the PANI@WO3 composite has considerable potential to remove an aqueous OG dye. Langmuir and Freundlich's models were used to analyze the equilibrium isotherms of OG dye adsorption on the PANI@WO3 composite. As a result, the best correlation of the experimental data was provided by the Langmuir model, and the maximum capacity of adsorption was 226.50 mg g-1. From a thermodynamic point of view, the OG dye adsorption process occurred spontaneously and endothermically. Importantly, PANI@WO3 still exhibited an excellent adsorption capability after four regeneration cycles, indicating the potential reusability of the PANI@WO3 composite. These results indicate that the as prepared PANI@WO3 composite could be employed as an efficient adsorbent and was much better than the parent material adsorption of OG dye.

Novel citric acid-functionalized brown algae with a high removal efficiency of crystal violet dye from colored wastewaters: insights into equilibrium, adsorption mechanism, and reusability.

Synthetic dye waste is one of the world's key ecological concerns. The algal biomass has emerged as a promising alternative adsorbent for wastewater treatment. The present study deals with the functionalization of brown algae (BA) by citric acid in order to improve its adsorption ability for textile dye removal in aqueous solutions. The morphological texture (SEM and BET) and surface chemistry (FTIR, EDS-mapping, and PZC) of the novel functionalized brown algae (designated as BA-CA) were analyzed. The performance of BA-CA for crystal violet (CV) dye removal from wastewater was investigated. The isotherm and kinetic adsorption modeling indicate the good fit of Langmuir isotherm and pseudo-second-order models. Optimum monolayer uptake capacity was 279.14 mg/g for BA-CA, which was about two times higher than that of unmodified BA. The thermodynamic parameters clearly indicated that CV removal process was physiosorption, exothermic, and spontaneous in nature. The regeneration study showed excellent reusability of the BA-CA up to five cycles. Overall, the experimental findings lead us to conclude that the BA-CA can be used as an eco-friendly, cost-effective and easily regenerated adsorbent for the purification of textile effluents.

Facile synthesis and characterization of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate nanocomposite for highly efficient removal of hazardous hexavalent chromium ions from water.

The present study describes the preparation of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate (BTCA-PANI@ZnP) nanocomposite via a facile two-step procedure. Thereafter, the as-prepared composite material adsorption characteristics for Cr(VI) ions removal were evaluated under batch adsorption. Kinetic approach studies for Cr(VI) removal, clearly demonstrated that the results of the adsorption process followed the pseudo second order and Langmuir models. The thermodynamic study indicated a spontaneous and endothermic process. Furthermore, higher monolayer adsorption was determined to be 933.88 mg g-1. In addition, the capability study regarding Cr(VI) ions adsorption over BTCA-PANI@ZnP nanocomposite clearly revealed that our method is suitable for large scale application. X-ray photoelectron spectroscopy (XPS) analysis confirmed Cr(VI) adsorption on the BTCA-PANI@ZnP surface, followed by its subsequent reduction to Cr(III). Thus, the occurrence of external mass transfer, electrostatic attraction and reduction phenomenon were considered as main mechanistic pathways of Cr(VI) ions removal. The superior adsorption performance of the material, the multi-dimensional characteristics of the surface and the involvement of multiple removal mechanisms clearly demonstrated the potential applicability of the BTCA-PANI@ZnP material as an effective alternative for the removal of Cr(VI) ions from wastewater.