In-situ Electrochemical Synthesis of H2O2 for p-nitrophenol Degradation Utilizing a Flow-through Three-dimensional Activated Carbon Cathode with Regeneration Capabilities.

The growing ubiquity of recalcitrant organic contaminants in the aqueous environment poses risks to effective and efficient water treatment and reuse. A novel three-dimensional (3D) electrochemical flow-through reactor employing activated carbon (AC) encased in a stainless-steel (SS) mesh as a cathode is proposed for the removal and degradation of a model recalcitrant contaminant p-nitrophenol (PNP), a toxic compound that is not easily biodegradable or naturally photolyzed, can accumulate and lead to adverse environmental health outcomes, and is one of the more frequently detected pollutants in the environment. As a stable 3D electrode, granular AC supported by a SS mesh frame as a cathode is hypothesized to 1) electrogenerate H2O2 via a 2-electron oxygen reduction reaction on the AC surface, 2) initiate decomposition of this electrogenerated H2O2 to form hydroxyl radicals on catalytic sites of the AC surface 3) remove PNP molecules from the waste stream via adsorption, and 4) co-locate the PNP contaminant on the carbon surface to allow for oxidation by formed hydroxyl radicals. Additionally, this design is utilized to electrochemically regenerate the AC within the cathode that is significantly saturated with PNP to allow for environmentally friendly and economic reuse of this material. Under flow conditions with optimized parameters, the 3D AC electrode is nearly 20% more effective than traditional adsorption in removing PNP. 30 grams of AC within the 3D electrode can remove 100% of the PNP compound and 92% of TOC under flow. The carbon within the 3D cathode can be electrochemically regenerated in the proposed flow system and design thereby increasing the adsorptive capacity by 60%. Moreover, in combination with continuous electrochemical treatment, the total PNP removal is enhanced by 115% over adsorption. It is anticipated this platform holds great promises to eliminate analogous contaminants as well as mixtures.

Polarity reversal for enhanced in-situ electrochemical synthesis of H2O2 over banana-peel derived biochar cathode for water remediation.

The fabrication of a cost-efficient cathode is critical for in-situ electrochemical generation of hydrogen peroxide (H2O2) to remove persistent organic pollutants from groundwater. Herein, we tested a stainless-steel (SS) mesh wrapped banana-peel derived biochar (BB) cathode for in-situ H2O2 electrogeneration to degrade bromophenol blue (BPB) and Congo red (CR) dyes. Furthermore, polarity reversal is evaluated for the activation of BB surface via introduction of various oxygen containing functionalities that serve as active sites for the oxygen reduction reaction (ORR) to generate H2O2. Various parameters including the BB mass, current, as well as the solution pH have been optimized to evaluate the cathode performance for efficient H2O2 generation. The results reveal formation of up to 9.4 mg/L H2O2 using 2.0 g BB and 100 mA current in neutral pH with no external oxygen supply with a manganese doped tin oxide deposited nickel foam (Mn-SnO2@NF) anode to facilitate the oxygen evolution reaction (OER). This iron-free electrofenton (EF) like process enabled by the SSBB cathode facilitates efficient degradation of BPB and CR dyes with 87.44 and 83.63% removal efficiency, respectively after 60 min. A prolonged stability test over 10 cycles demonstrates the effectiveness of polarity reversal toward continued removal efficiency as an added advantage. Moreover, Mn-SnO2@NF anode used for the OER was also replaced with stainless steel (SS) mesh anode to investigate the effect of oxygen evolution on H2O2 generation. Although Mn-SnO2@NF anode exhibits better oxygen evolution potential with reduced Tafel slope, SS mesh anode is discussed to be more cost-efficient for further studies.

Hematite and Magnetite Nanostructures for Green and Sustainable Energy Harnessing and Environmental Pollution Control: A Review.

The optoelectrical and magnetic characteristics of naturally existing iron-based nanostructures, especially hematite and magnetite nanoparticles (H-NPs and M-NPs), gained significant research interest in various applications, recently. The main purpose of this Review is to provide an overview of the utilization of H-NPs and M-NPs in various environmental remediation. Iron-based NPs are extensively explored to generate green energy from environmental friendly processes such as water splitting and CO2 conversion to hydrogen and low molecular weight hydrocarbons, respectively. The latter part of the Review provided a critical overview to use H-NPs and M-NPs for the detection and decontamination of inorganic and organic contaminants to counter the environmental pollution and toxicity challenge, which could ensure environmental sustainability and hygiene. Some of the future perspectives are comprehensively presented in the final portion of the script, optimiztically, and it is supported by some relevant literature surveys to predict the possible routes of H-NPs and M-NPs modifications that could enable researchers to use these NPs in more advanced environmental applications. The literature collection and discussion on the critical assessment of reserving the environmental sustainability challenges provided in this Review will be useful not only for experienced researchers but also for novices in the field.

Visible-Light Photoreduction of CO2 to CH4 over ZnTe-Modified TiO2 Coral-Like Nanostructures.

Rapidly depleting fossil fuels and the related environmental issues are two alarming global concerns the world is facing today. To address these issues efficiently, future energy requirements need to be fulfilled by renewable and environmentally friendly resources. In this context, we report the ZnTe-modified TiO2 photocatalysts with varying amounts of ZnTe (1.96, 16, and 65 %) for the photoreduction of carbon dioxide into methane under visible light. The hydrothermally synthesized photocatalysts have been characterized by using various techniques, such as X-ray diffraction, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, transmission electron microscopy, UV/Vis spectroscopy, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller (BET) analysis for surface-area measurements. The photocatalyst with 1.96 % ZnTe shows the best results, which are attributed to its high BET specific surface area and the formation of a heterojunction at the interface, which can facilitate efficient charge transfer.

In-situ groundwater remediation of contaminant mixture of As(III), Cr(VI), and sulfanilamide via electrochemical degradation/transformation using pyrite.

Electrochemical advanced oxidation processes (EAOPs) are effective in removing persistent contaminants from groundwater. However, their practical applicability depends significantly on various site-specific characteristics. Therefore, the primary objective of this investigation was to study the feasibility of EAOPs and pyrite, which is a sulfide mineral, to effectively remove the mixture of arsenic (As (III)), chromium (Cr (VI)), and sulfanilamide in groundwater. We conducted a comparison of three systems: (1) EAOP alone, (2) pyrite alone, and (3) a combined EAOP and pyrite system. In EAOP alone, sulfanilamide was effectively oxidized (80%), while the electrochemical transformation of As(III)/Cr(VI) into As(V)/Cr(III) was limited. In just the pyrite system, As(III), Cr(VI), and sulfanilamide were adsorbed onto the surface of pyrite (60%, 20%, and 18%). Neither the EAOP nor the pyrite system alone could effectively treat the contaminants mixture. Nonetheless, the combined system completely removed As(III), Cr(VI), and sulfanilamide by the synergistic reaction. This could be attributed to the formation of green rust, a natural adsorbent mineral produced as a reaction of dissolved iron, generated via electrochemical pyrite oxidation, with the groundwater electrolyte (e.g., CO3 or SO4). This system harmonized the combined approach of EAOP and pyrite to effectively eliminate both organic and inorganic contaminants. ENVIRONMENTAL IMPLICATION: A paper proposed electrochemical oxidation (EO) with pyrite to remove both organic and inorganic contaminants from groundwater. The removal performance of the combined system was evaluated, and the synergistic mechanism was revealed. The combination of EO and pyrite with synergistic removal effectively removed the mixture of both contaminants. This could be attributed by the formation of green-rust by electrochemical activation for pyrite. Compared to the single system of EO and pyrite alone, the combined system with EO and pyrite improved removal performance. Results suggested that the combined system could be used for green groundwater remediation.

Synthesis of NiMn2O4/PANI nanosized composite with increased specific capacitance for energy storage applications.

Polyaniline (PANI) stands out as a highly promising conducting polymer with potential for advanced utilization in high-performance pseudocapacitors. Therefore, there exists a pressing need to bolster the structural durability of PANI, achievable by developing composite materials that can enhance its viability for supercapacitor applications. In this particular study, a pioneering approach was undertaken to produce a novel NiMn2O4/PANI supercapacitor electrode material. A comprehensive array of analytical techniques was employed to ascertain the structural configuration, morphology, oxidation states of elements, composition, and surface characteristics of the electrode material. The electrochemical evaluation of the NiMn2O4/PANI composite shows a specific capacitance (Cs) of 1530 ± 2 F g-1 at 1 A g-1. Significantly, the composite material displays an outstanding 93.61% retention of its capacity after an extensive 10 000 cycles, signifying remarkable cycling stability, while the 2-electrode configuration reveals a Cs value of 764 F g-1 at 5 mV s-1 and 826 F g-1 at 1 A g-1 with a smaller charge transfer resistance (Rct) value of 0.67 Ω. Chronoamperometric tests showed excellent stability of the fabricated material up to 50 h. This significant advancement bears immense promise for its potential implementation in high-efficiency energy storage systems and heralds a new phase in the development of supercapacitor technology with improved stability and performance metrics.

New Insights on Designing the Next-Generation Materials for Electrochemical Synthesis of Reactive Oxidative Species Towards Efficient and Scalable Water Treatment: A Review and Perspectives.

Electrochemical water remediation technologies offer several advantages and flexibility for water treatment and degradation of contaminants. These technologies generate reactive oxidative species (ROS) that degrade pollutants. For the implementation of these technologies at an industrial scale, efficient, scalable, and cost-effective in-situ ROS synthesis is necessary to degrade complex pollutant mixtures, treat large amount of contaminated water, and clean water in a reasonable amount of time and cost. These targets are directly dependent on the materials used to generate the ROS, such as electrodes and catalysts. Here, we review the key design aspects of electrocatalytic materials for efficient in-situ ROS generation. We present a mechanistic understanding of ROS generation, including their reaction pathways, and integrate this with the key design considerations of the materials and the overall electrochemical reactor/cell. This involves tunning the interfacial interactions between the electrolyte and electrode which can enhance the ROS generation rate up to ~ 40% as discussed in this review. We also summarized the current and emerging materials for water remediation cells and created a structured dataset of about 500 electrodes and 130 catalysts used for ROS generation and water treatment. A perspective on accelerating the discovery and designing of the next generation electrocatalytic materials is discussed through the application of integrated experimental and computational workflows. Overall, this article provides a comprehensive review and perspectives on designing and discovering materials for ROS synthesis, which are critical not only for successful implementation of electrochemical water remediation technologies but also for other electrochemical applications.

In-situ hydrogen peroxide formation and persulfate activation over banana peel-derived biochar cathode for electrochemical water treatment in a flow reactor.

Electrochemical advanced oxidation processes (EAOPs) are effective for the removal of organic contaminants from groundwater. The choice of an affordable cathode material that can generate reactive oxygen species (ROS) such as hydrogen peroxide (H2O2) and hydroxyl radicals (•OH) will increase practicality and cost effectiveness of EAOPs. Carbon enriched biochar (BC), which is derived from pyrolysis of biomass, has emerged as an inexpensive and environmentally-friendly electrocatalyst for removing contaminants from groundwater. In this study, a banana peel-derived biochar (BP-BC) cathode packed in a stainless steel (SS) mesh was used in a continuous flow reactor to degrade the ibuprofen (IBP), as a model contaminant. The BP-BC cathodes generate H2O2 via a 2-electron oxygen reduction reaction, initiate the H2O2 decomposition to generate •OH, adsorb IBP from contaminated water, and oxidize IBP by formed •OH. Various reaction parameters such as pyrolysis temperature and time, BP mass, current, and flow rate, were optimized to maximize IBP removal. Initial experiments showed that H2O2 generation was limited (∼3.4 mg mL-1), resulting in only âˆ¼ 40% IBP degradation, due to insufficient surface functionalities on the BP-BC surface. The addition of persulfate (PS) into the continuous flow system significantly improves the IBP removal efficiency via PS activation. The in-situ H2O2 formation and PS activation over BP-BC cathode results in concurrent generation of •OH and sulfate anion radicals (SO4•-, a reactive oxidant), respectively, which collectively achieve âˆ¼ 100% IBP degradation. Further experiments with methanol and tertiary butanol as potential scavengers for •OH and SO4•- confirm their combined role in complete IBP degradation.

α-Fe2O3-based nanocomposites: synthesis, characterization, and photocatalytic response towards wastewater treatment.

Recently, rising distress over ecological pollution owing to water contamination by coloring effluents primarily due to dyes is of growing concern. The development of semiconductor/magnetic oxide-based nanomaterials has verified to be a potent remediation means for water pollution. In the present article, the fabrication of nanocomposites was carried out by the facile hydrothermal method. The ZnO and ZnSe nanoparticles were in situ formed on the α-Fe2O3 layer, thereby forming a heterojunction. The prepared α-Fe2O3/ZnSe nanocomposite possessed a degradation of 98.9% for a Congo red aqueous solution of 100 ppm. The α-Fe2O3/ZnO nanocomposite showed only 26% degradation of 100 ppm dye solution depicting a poor photocatalytic performance. This is attributed to the formation of recombination-enhanced configuration (type-I heterostructure) in the α-Fe2O3/ZnO nanocomposite (NC). In contrast, α-Fe2O3/ZnSe NC accomplished a higher and enhanced photocatalytic response. The key rationale for elevated photocatalytic response is the establishment of a recombination-free configuration (type-II heterostructure). Thus, α-Fe2O3/ZnSe NC known as one of outstanding nanoparticle-nanocomposite photocatalysts was synthesized under mild conditions exclusive of some multifaceted post-treatment, for dye abatement process.

Impedance Spectroscopy Analysis of PbSe Nanostructures Deposited by Aerosol Assisted Chemical Vapor Deposition Approach.

This research endeavor aimed to synthesize the lead (II) diphenyldiselenophosphinate complex and its use to obtain lead selenide nanostructured depositions and further the impedance spectroscopic analysis of these obtained PbSe nanostructures, to determine their roles in the electronics industry. The aerosol-assisted chemical vapor deposition technique was used to provide lead selenide deposition by decomposition of the complex at different temperatures using the glass substrates. The obtained films were revealed to be a pure cubic phase PbSe, as confirmed by X-ray diffraction analysis. SEM and TEM micrographs demonstrated three-dimensionally grown interlocked or aggregated nanocubes of the obtained PbSe. Characteristic dielectric measurements and the impedance spectroscopy analysis at room temperature were executed to evaluate PbSe properties over the frequency range of 100 Hz-5 MHz. The dielectric constant and dielectric loss gave similar trends, along with altering frequency, which was well explained by the Koops theory and Maxwell-Wagner theory. The effective short-range translational carrier hopping gave rise to an overdue remarkable increase in ac conductivity (σac) on the frequency increase. Fitting of a complex impedance plot was carried out with an equivalent circuit model (Rg Cg) (Rgb Qgb Cgb), which proved that grains, as well as grain boundaries, are responsible for the relaxation processes. The asymmetric depressed semicircle with the center lower to the impedance real axis provided a clear explanation of non-Debye dielectric behavior.

Impedance Spectroscopic Study of Nickel Sulfide Nanostructures Deposited by Aerosol Assisted Chemical Vapor Deposition Technique.

This research aims to synthesize the Bis(di-isobutyldithiophosphinato) nickel (II) complex [Ni(iBu2PS2)] to be employed as a substrate for the deposition of nickel sulfide nanostructures, and to investigate its dielectric and impedance characteristics for applications in the electronic industry. Various analytical tools including elemental analysis, mass spectrometry, IR, and TGA were also used to further confirm the successful synthesis of the precursor. NiS nanostructures were grown on the glass substrates by employing an aerosol assisted chemical vapor deposition (AACVD) technique via successful decomposition of the synthesized complex under variable temperature conditions. XRD, SEM, TEM, and EDX methods were well applied to examine resultant nanostructures. Dielectric studies of NiS were carried out at room temperature within the 100 Hz to 5 MHz frequency range. Maxwell-Wagner model gave a complete explanation of the variation of dielectric properties along with frequency. The reason behind high dielectric constant values at low frequency was further endorsed by Koops phenomenological model. The efficient translational hopping and futile reorientation vibration caused the overdue exceptional drift of ac conductivity (σac) along with the rise in frequency. Two relaxation processes caused by grains and grain boundaries were identified from the fitting of a complex impedance plot with an equivalent circuit model (Rg Cg) (Rgb Qgb Cgb). Asymmetry and depression in the semicircle having center present lower than the impedance real axis gave solid justification of dielectric behavior that is non-Debye in nature.

Synthesis and characterization of an α-Fe2O3/ZnTe heterostructure for photocatalytic degradation of Congo red, methyl orange and methylene blue.

The leading challenge towards environmental protection is untreated textile dyes. Tailoring photocatalytic materials is one of the sustainable remediation strategies for dye treatment. Hematite (α-Fe2O3), due to its favorable visible light active band gap (i.e. 2.1 eV), has turned out to be a robust material of interest. However, impoverished photocatalytic efficiency of α-Fe2O3 is ascribable to the short life span of the charge carriers. Consequently, the former synthesized heterostructures possess low degradation efficiency. The aim of the proposed endeavor is the synthesis of a novel zinc telluride-modified hematite (α-Fe2O3/ZnTe) heterostructure, its characterization and demonstration of its enhanced photocatalytic response. The promising heterostructure as well as bare photocatalysts were synthesized via a hydrothermal approach. All photocatalysts were characterized by the X-ray diffraction technique (XRD), scanning electron microscopy (SEM), and electron diffraction spectroscopy (EDX). Moreover, the selectivity and activity of the photocatalyst are closely related to the alignment of its band energy levels, which were estimated by UV-Vis diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). Nanomaterials, specifically α-Fe2O3 and α-Fe2O3/ZnTe, were used for the degradation of Congo red (97.9%), methyl orange (84%) and methylene blue (73%) under light irradiation (>200 nm) for 60 min. The results suggested that with the aforementioned optimized fabricated heterostructure, the degradation efficiency was improved in comparison to bare hematite (α-Fe2O3). The key rationale towards such improved photocatalytic response is the establishment of a type-II configuration in the α-Fe2O3/ZnTe heterostructure.

Efficient Photoelectrochemical Water Splitting by Tailoring MoS2/CoTe Heterojunction in a Photoelectrochemical Cell.

Solar energy conversion through photoelectrochemical water splitting (PEC) is an upcoming promising technique. MoS2/CoTe heterostructures were successfully prepared and utilized for PEC studies. MoS2 and CoTe were prepared by a hydrothermal method which were then ultrasonicated with wt. % ratios of 1:3, 1:1 and 3:1 to prepare MoS2/CoTe (1:3), MoS2/CoTe (1:1) and MoS2/CoTe (3:1) heterostructure, respectively. The pure materials and heterostructures were characterized by XRD, UV-vis-DRS, SEM, XPS, PL and Raman spectroscopy. Photoelectrochemical measurements were carried out by linear sweep voltammetry and electrochemical impedance spectroscopic measurements. A maximum photocurrent density of 2.791 mA/cm2 was observed for the MoS2/CoTe (1:1) heterojunction which is about 11 times higher than the pristine MoS2. This current density was obtained at an applied bias of 0.62 V vs. Ag/AgCl (1.23 V vs. RHE) under the light intensity of 100 mW/cm2 of AM 1.5G illumination. The enhanced photocurrent density may be attributed to the efficient electron-hole pair separation. The solar to hydrogen conversion efficiency was found to be 0.84% for 1:1 MoS2/CoTe, signifying the efficient formation of the p-n junction. This study offers a novel heterojunction photocatalyst, for PEC water splitting.