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Recently, polymeric carbon nitride (g-C3 N4 ) as a proficient photo-catalyst has been effectively employed in photocatalysis for energy conversion, storage, and pollutants degradation due to its low cost, robustness, and environmentally friendly nature. The critical review summarized the recent development, fundamentals, nanostructures design, advantages, and challenges of g-C3 N4 (CN), as potential future photoactive material. The review also discusses the latest information on the improvement of CN-based heterojunctions including Type-II, Z-scheme, metal/CN Schottky junctions, noble metal@CN, graphene@CN, carbon nanotubes (CNTs)@CN, metal-organic frameworks (MOFs)/CN, layered double hydroxides (LDH)/CN heterojunctions and CN-based heterostructures for H2 production from H2 O, CO2 conversion and pollutants degradation in detail. The optical absorption, electronic behavior, charge separation and transfer, and bandgap alignment of CN-based heterojunctions are discussed elaborately. The correlations between CN-based heterostructures and photocatalytic activities are described excessively. Besides, the prospects of CN-based heterostructures for energy production, storage, and pollutants degradation are discussed.
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This study marks a significant stride in enhancing photoelectrochemical (PEC) water splitting applications through the development of a type II nano-heterojunction comprising HfO2 and α - Fe2O3. Fabricated via Physical Vapor Deposition/Radio Frequency (PVD/RF) sputtering, this nano-heterojunction effectively addresses the efficiency limitations inherent in traditional α - Fe2O3photoanodes. The integration of HfO2 leads to a substantial increase in photocurrent density, soaring from 62 µA/cm2 for pure α - Fe2O3 to 1.46 mA cm-2 at 1.23 V versus the Reversible Hydrogen Electrode (RHE). This enhancement, a 23-fold increase, is primarily attributed to the improved absorption of photons in the visible range and the facilitation of more efficient charge transfer. The enhanced performance and long-term stability of the HfO2/α - Fe2O3 nano-heterojunction, validated through XRD, XPS, Raman Spectroscopy, EDS, SEM, EIS, and UPS analyses, demonstrate its potential as a promising and cost-effective solution for PEC water splitting applications, leveraging renewable energy sources.
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Critical to boosting photoelectrochemical (PEC) performance is improving visible light absorption, accelerating carrier separation, and reducing electron-hole pair recombination. In this investigation, the PVD/RF method was employed to fabricate WO3 thin films that were subsequently treated using the surface treatment process, and the film surface was modified by introducing varying concentrations of cobalt nanoparticles, a non-noble metal, as an effective Co catalyst. The results show that the impact of loaded cobalt nanoparticles on the film surface can explain the extended absorption spectrum of visible light, efficiently capturing photogenerated electrons. This leads to an increased concentration of charge carriers, promoting a faster rate of carrier separation and enhancing interface charge transfer efficiency. Compared with a pristine WO3 thin film photoanode, the photocurrent of the as-prepared Co/WO3 films shows a higher PEC activity, with more than a one-fold increase in photocurrent density from 1.020 mA/cm2 to 1.485 mA/cm2 under simulated solar radiation. The phase, crystallinity, and surface of the prepared films were analysed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The PVD/RF method, scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscopy (HR-TEM) were employed to assess the surface morphology of the fabricated film electrode. Optical properties were studied using UV-vis absorbance spectroscopy. Simultaneously, the photoelectrochemical properties of both films were evaluated using linear sweep voltammetry and electrochemical impedance spectroscopy (EIS). These results offer a valuable reference for designing high-performance photoanodes on a large scale for photoelectrochemical (PEC) applications.
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Photoelectrochemical water splitting via solar irradiation has garnered significant interest due to its potential in large-scale renewable hydrogen production. Heterostructure materials have emerged as an effective strategy, demonstrating enhanced performance in photoelectrochemical water-splitting applications compared to individual photocatalysts. In this study, to augment the performance of sprayed TiVO4 thin films, a hydrothermally prepared WO3 underlayer was integrated beneath the spray pyrolised TiVO4 film. The consequent heterostructure demonstrated notable enhancements in optical, structural, microstructural attributes, and photocurrent properties. This improvement is attributed to the strategic deposition of WO3 underlayer, forming a heterostructure composite electrode. This led to a marked increase in photocurrent density for the WO3/TiVO4 photoanode, reaching a peak of 740 µA/cm2 at an applied potential of 1.23 V vs RHE, about nine-fold that of standalone TiVO4. Electrochemical impedance spectroscopy revealed a reduced semicircle for the heterostructure, indicating improved charge transfer compared to bare TiVO4. The heterostructure photoelectrode exhibited enhanced charge carrier conductivity at the interface and sustained stability over 3 h. The distinct attributes of heterostructure photoelectrode present significant opportunities for devising highly efficient sunlight-driven water-splitting systems.
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In the pursuit of finding efficient D-π-A organic dyes as photosensitizers for dye-sensitized solar cells (DSSCs), first-principles calculations of guanidine-based dyes [A1-A18] were executed using density functional theory (DFT). The various electronic and optical properties of guanidine-based organic dyes with different D-π-A structural modifications were investigated. The structural modification of guanidine-based dyes largely affects the properties of molecules, such as excitation energies, the oscillator strength dipole moment, the transition dipole moment, and light-harvesting efficiencies. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) is responsible for the reduction and injection of electrons. Modification of the guanidine subunit by different structural modifications gave a range of HOMO-LUMO energy gaps. Chemical and optical characteristics of the dyes indicated prominent charge transfer and light-harvesting efficiencies. The wide electronic absorption spectra of these guanidine-based dyes computed by TD-DFT-B3LYP with 6-31G, 6-311G, and cc-PVDZ basis sets have been observed in the visible region of spectra due to the presence of chromophore groups of dye molecules. Better anchorage of dyes to the surface of TiO2 semiconductors helps in charge-transfer phenomena, and the results suggested that -COOH, -CN, and -NO2 proved to be proficient anchoring groups, making dyes very encouraging candidates for DSSCs. Molecular electrostatic potential explained the electrostatic potential of organic dyes, and IR spectrum and conformational analyses ensured the suitability of organic dyes for the fabrication of DSSCs.
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To optimize the semiconductor properties of TiVO4 thin films and enhance their performance, we incorporated cobalt nanoparticles as an effective co-catalyst consisting of a non-noble metal. Through an investigation into the impact of cobalt loading on spray pyrolyzed TiVO4 thin films, we observed a significant enhancement in the photoelectrochemical (PEC) performance. This was accomplished by carefully optimizing the concentrations of Co2+ (3 mM) to fabricate a composite electrode, resulting in a higher photocurrent density for the TiVO4:Co photoanode. When an applied potential of 1.23 V (vs RHE) was used, the photocurrent density reached 450 µA/cm2, approximately 5 times higher than that of bare TiVO4. We conducted a thorough characterization of the composite structure and optical properties. Additionally, electrochemical impedance spectroscopy analysis indicated that the TiVO4/Co thin film exhibited a smaller semicircle, indicating a significant improvement in charge transfer at the interface. In comparison to bare TiVO4, the TiVO4/Co composite exhibited a notable improvement in photocatalytic activity when degrading methylene blue (MB) dye, a widely employed model dye. Under light illumination, a TiVO4/Co thin film exhibited a notable dye degradation rate of 97% within a 45 min duration. The scalability of our fabrication method makes it suitable for large-area devices intended for sunlight-driven PEC seawater splitting studies.
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Balancing thermal and visual comfort in buildings necessitates effective insulation to counteract heat loss and gain, especially with temperature variances. One promising approach is to combine phase change materials, such as poly(ethylene glycol) (PEG), with high-performance insulators like silica aerogel (Siag). To bolster opto-thermal performance in building envelopes, we introduce a smart insulation composite material through PEG integration, i.e., PEGalyation with Siag. Central to this thermal behavior is the PEG's phase change properties, which foster a shape-stabilized framework with Siag through their porous confinement. Preliminary observations indicate notable capabilities of obstructing near-infrared light while preserving satisfactory visible transparency. An optimized Siag@PEG composite with 5% loading of PEG has the visible range transmission of â¼92%, a decrease of â¼72% in thermal conductivity which is lower than pure glass and PEG, leading to a temperature dependent switchable hydrophobic to hydrophilic wettability characteristics. As a prototype window, the thermal performance evaluation of the synthesized composite, through experimental and computational studies, shows a decrease in indoor temperature of â¼20% with a higher temperature difference of â¼20 °C between outdoor and indoor weather conditions. This lightweight composite can act as sponge media to fill inside the double-paned window and for retrofitting existing glazing to boost the energy efficiency of buildings with facile manufacturing and scalability.
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Herein, a ZrO2 added α-Fe2O3 photoanode that can split water at low applied potential is reported. First, the pristine hematite α-Fe2O3 photoanode was synthesized using an aerosol-assisted chemical vapour deposition (AACVD) method followed by modification with various amounts of ZrO2 (2 to 40%) in the form of thin films on conducting glass substrate. The XRD, Raman spectroscopy and scanning electron microscopy (SEM) analyses confirmed the presence of the monoclinic phase of ZrO2 in the composites with multifaceted particles of compact morphology. The optical analysis showed an increase in the absorbance and variation in band gap of the composites ascribed to the heterogeneity of the material. The photoelectrochemical studies gave a photocurrent density of 1.23 mA cm-2 at 1.23 V vs. RHE for the pristine hematite and remarkably higher value of 3.06 mA cm-2 for the optimized amount of ZrO2 in the modified α-Fe2O3 photoanode. To the best of our knowledge, this is the highest photocurrent reported for a ZrO2 containing photoanode. The optimized composite electrode produced nine times more oxygen than that produced by pristine hematite.
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Photocatalytic hydrogen evolution represents a transformative avenue in addressing the challenges of fossil fuels, heralding a renewable and pristine alternative to conventional fossil fuel-driven energy paradigms. Yet, a formidable challenge is crafting a high-efficacy, stable photocatalyst that optimizes solar energy transduction and charge partitioning even under adversarial conditions. Within the scope of this investigation, tantalum-iron heterojunction composites characterized by intricate, discoidal nanostructured materials were meticulously synthesized using a solvothermal-augmented calcination protocol. The X-ray diffraction, coupled with Rietveld refinements delineated the nuanced alterations in phase constitution and structural intricacies engendered by disparate calcination thermal regimes. An exhaustive study encompassing nano-morphology, electronic band attributes, bandgap dynamics, and a rigorous appraisal of their photocatalytic prowess has been executed for the composite array. Intriguingly, the specimen denoted as 1000-1, a heterojunction composite of TaO2/Ta2O5/FeTaO4, manifested an exemplary photocatalytic hydrogen evolution capacity, registering at 51.24 µmol/g, which eclipses its counterpart, 1100-1 (Ta2O5/FeTaO4), by an impressive margin. Such revelations amplify the prospective utility of these tantalum iron matrices, endorsing their candidacy as potent agents for sustainable hydrogen production via photocatalysis.
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Pristine ZnO and Co-doped ZnO photocatalyst thin films were fabricated on a ceramic substrate by spray pyrolysis. The optical, morphological and structural properties of the fabricated nanophotocatalyst thin films were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Operational parameters, including dye concentration, oxidant concentration, irradiation time and pH for dye degradation, were optimized by response surface methodology (RSM). The maximum degradation obtained was 93% under ideal conditions, such as pH 7, 3 h of direct sunlight irradiation, 30 mM concentration of oxidant and 10 ppm concentration of dye (MB). The evaluation of the extent of degradation was done using the UV/visible spectrophotometry technique. The reusability of the fabricated thin film was examined under optimized conditions. Density functional theory (DFT) with the B3LYP/LanL2DZ method was used for the theoretical modelling of the fabricated nanomaterials. The optimized structure, theoretical band gaps, IR spectra and Raman spectra of the fabricated pristine ZnO and Co:ZnO nanophotocatalysts were determined.
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Amidst the global challenges posed by pollution, escalating energy expenses, and the imminent threat of global warming, the pursuit of sustainable energy solutions has become increasingly imperative. Thermoelectricity, a promising form of green energy, can harness waste heat and directly convert it into electricity. This technology has captivated attention for centuries due to its environmentally friendly characteristics, mechanical stability, versatility in size and substrate, and absence of moving components. Its applications span diverse domains, encompassing heat recovery, cooling, sensing, and operating at low and high temperatures. However, developing thermoelectric materials with high-performance efficiency faces obstacles such as high cost, toxicity, and reliance on rare-earth elements. To address these challenges, this comprehensive review encompasses pivotal aspects of thermoelectricity, including its historical context, fundamental operating principles, cutting-edge materials, and innovative strategies. In particular, the potential of one-dimensional nanostructuring is explored as a promising avenue for advancing thermoelectric technology. The concept of one-dimensional nanostructuring is extensively examined, encompassing various configurations and their impact on the thermoelectric properties of materials. The profound influence of one-dimensional nanostructuring on thermoelectric parameters is also thoroughly discussed. The review also provides a comprehensive overview of large-scale synthesis methods for one-dimensional thermoelectric materials, delving into the measurement of thermoelectric properties specific to such materials. Finally, the review concludes by outlining prospects and identifying potential directions for further advancements in the field.
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Offshore hydrogen production through water electrolysis presents significant technical and economic challenges. Achieving an efficient hydrogen evolution reaction (HER) in alkaline and natural seawater environments remains daunting due to the sluggish kinetics of water dissociation. To address this issue, we synthesized electrocatalytic WO3-x@CdS1-x nanocomposites (WCSNCs) using ultrasonic-assisted laser irradiation. The synthesized WCSNCs with varying CdS contents were thoroughly characterized to investigate their structural, morphological, and electrochemical properties. Among the samples tested, the WCSNCs with 20 wt % CdS1-x in WO3-x (Wx@Sx-20%) exhibited superior electrocatalytic performance for hydrogen evolution in a 1 M KOH solution. Specifically, the Wx@Sx-20% catalyst demonstrated an overpotential of 0.191 V at a current density of -10 mA/cm2 and a Tafel slope of 61.9 mV/dec. The Wx@Sx-20% catalysts demonstrated outstanding stability and durability, maintaining their performance after 24 h and up to 1000 CV cycles. Notably, when subjected to natural seawater electrolysis, the Wx@Sx-20% catalysts outperformed in terms of electrocatalytic HER activity and stability. The remarkable performance enhancement of the prepared electrocatalyst can be attributed to the combined effect of sulfur vacancies in CdS1-x and oxygen vacancies in WO3-x. These vacancies promote the electrochemically active surface area, enhance the rate of charge separation and transfer, increase the number of electrocatalytic active sites, and accelerate the HER process in alkaline and natural seawater environments.
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Photoelectrochemical (PEC) water splitting is one of the promising, environmentally friendly, carbon emission-free strategies for the cost-effective production of hydrogen. The interest in developing effective approaches for solar-to-hydrogen production with stable and visible light active semiconductors directed many researchers to develop stable and efficient materials. For the first time, a nanostructured TiVO4 photoanode was fabricated at a substrate temperature of 250 °C and further annealed at 600 °C using the spray pyrolysis technique and it obtained an optical band gap of â¼2.18 eV. The photoanode underwent photoelectrochemical testing, where it exhibited a high photocurrent density of 0.080 mA cm-2 at 1.23 V (vs. reversible hydrogen electrode), which can be stable up to 110 min. Further, various physicochemical characterizations were employed to understand the phase purity and thin film growth mechanism. A systematic substrate and annealed temperatures were monitored during the fabrication process. The transmission electron microscopy (TEM) studies revealed agglomeration of TiVO4 nanoparticles with an average size of â¼100 nm accompanying dendritic orientation at the outer edge. This study envisages the design and development of a novel photocatalyst for water splitting under visible light irradiation, an ideal route to a cost-effective, large-scale, sustainable route for hydrogen production.
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Green hydrogen production is one of the most desirable sustainable goals of the United Nations. Thus, for that purpose, we developed hematite (α-Fe2O3), an n-type semiconductor, a desirable candidate for photoelectrochemical (PEC) water splitting, enabling hydrogen evolution. High recombination losses, low efficiency, and large-scale production hinder its potential. To address these issues, we have fabricated optimized bare and cadmium oxide (CdO)-decorated hematite thin film nanorod arrays using a throughput radio frequency (RF) sputtering with efficient water splitting behavior. To the best of our knowledge, no work has been done so far on the synthesis of CdO/α-Fe2O3 via RF sputtering for PEC application. Bare α-Fe2O3 samples, with a morphology of vertically aligned nanorods, were fabricated with optimized parameters such as as-deposited 70 nm of Fe, an angle of deposition of 70°, and an annealing temperature of 600 °C, which showed a photocurrent density of 0.38 mA/cm2 at 1.65 V vs reversible hydrogen electrode (RHE). Characterizations depicted that this unique morphology with high crystallinity directly enhanced the performance of hematite photoanodes. Further, deposition of 30 nm of cadmium (CdO) on the α-Fe2O3 nanorods produced a corn-like morphology with CdO nanoparticles (â¼2 nm), resulting in 4-times enhancement of the PEC performance (1.2 mA/cm2 at 1.65 V vs RHE). CdO acted as a co-catalyst, responsible for satisfactory suppression of recombination and facilitating the hole transfer, directly enhancing the overall photocurrent density. This photoanode showed an extremely stable behavior over a period of 26 h when kept under constant illumination. Furthermore, the CdO-modified photoanode showed a better dye degradation (98% in 40 min) than the bare hematite (60% in 40 min), proving to be an efficient photoanode.
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The thermal performance of window glazing requires improvement for a sustainable built environment at an acceptable cost. The current work demonstrates a multifold smart composite consisting of an optimized In2O3/ZnO-polymethyl methacrylate-paraffin composite to reduce heat exchange through the combined self-cleaning and energy-saving envelope of the smart built environment. This work has attempted to develop a smart composite coating that combines photosensitive metal oxide and phase change materials and investigate their thermal comfort performance as a glazed window. It is observed that the In2O3/ZnO (5 wt %) multifold composite film experienced better transmittance and thermal performance compared to its other wt % composite samples. Moreover, the multifold composite-coated glass integrated into a prototype glazed window was further investigated for its thermal performance, where a steady average indoor temperature of â¼30 °C was achieved when the outside temperature reached â¼55 °C, while maintaining good visibility. Interestingly, the transparency reached â¼86% at 60 °C and exhibited a hydrophobic water contact angle (WCA) of â¼138°. In contrast, a similar film exhibits â¼64% transparency at 22 °C, where the WCA becomes moderately hydrophilic (â¼68°). Temperature dependency on transparency and wettability properties was examined for up to 60 cycles, resulting in excellent indoor thermal comfort. In addition, a thermal simulation study was executed for the smart multifold glazing composite. Moreover, this study offers dynamic glazing development options for energy saving in the smart built environment.
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Substitutional doping and different nanostructures of ZnO have rendered it an effective sensor for the detection of volatile organic compounds in real-time atmosphere. However, the low selectivity of ZnO sensors limits their applications. Herein, hafnium (Hf)-doped ZnO (Hf-ZnO) nanostructures are developed by the hydrothermal method for high selectivity of hazardous NOX gas in the atmosphere, substantially portraying the role of doping concentration on the enhancement of structural, optical, and sensing behavior. ZnO microspheres with 5% Hf doping showed excellent sensing and detected 22 parts per billion (ppb) NOX gas in the atmosphere, within 24 s, which is much faster than ZnO (90 s), and rendered superior sensing ability (S = 67) at a low temperature (100 °C) compared to ZnO (S = 40). The sensor revealed exceptional stability under humid air (S = 55 at 70% RH), suggesting a potential of 5% Hf-ZnO as a new stable sensing material. Density functional theory (DFT) and other characterization analyses revealed that the high sensing activity of 5% Hf-ZnO is attributed to the accessibility of more adsorption sites arising due to charge distortion, increased oxygen vacancies concentration, Lewis acid base, porous morphology, small particle size (5 nm), and strong bond interaction amidst NO2 molecule with ZnO-Hf-Ovacancy sites, resulting from the substitution of the host cation (Zn2+) with doping cation (Hf4+).
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Doping plays a significant role in affecting the physical and chemical properties of two-dimensional (2D) dichalcogenide materials. Controllable doping is one of the major factors in the modification of the electronic and mechanical properties of 2D materials. MoS2 2D materials have gained significant attention in gas sensing owing to their high surface-to-volume ratio. However, low response and recovery time hinder their application in practical gas sensors. Herein, we report the enhanced gas response and recovery of Nb-doped MoS2 gas sensor synthesized through physical vapor deposition (PVD) toward NO2 at different temperatures. The electronic states of MoS2 and Nb-doped MOS2 monolayers grown by PVD were analyzed based on their work functions. Doping with Nb increases the work function of MoS2 and its electronic properties. The Nb-doped MoS2 showed an ultrafast response and recovery time of t rec = 30/85 s toward 5 ppm of NO2 at their optimal operating temperature (100 °C). The experimental results complement the electron difference density functional theory calculation, showing both physisorption and chemisorption of NO2 gas molecules on niobium substitution doping in MoS2.
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The photocatalytic performance of g-C3N4 for CO2 conversion is still inadequate by several shortfalls including the instability, insufficient solar light absorption and rapid charge carrier's recombination rate. To solve these problems, herein, noble metals (Pt and Au) decorated Sr-incorporated g-C3N4 photocatalysts are fabricated via the simple calcination and photo-deposition methods. The Sr-incorporation remarkably reduced the g-C3N4 band gap from 2.7 to 2.54 eV, as evidenced by the UV-visible absorption spectra and the density functional theory results. The CO2 conversion performance of the catalysts was evaluated under visible light irradiation. The Pt/0.15Sr-CN sample produced 48.55 and 74.54 µmol h-1 g-1 of CH4 and CO, respectively. These amounts are far greater than that produced by the Au/0.15Sr-CN, 0.15Sr-CN, and CN samples. A high quantum efficiency of 2.92% is predicted for the Pt/0.15Sr-CN sample. Further, the stability of the photocatalyst is confirmed via the photocatalytic recyclable test. The improved CO2 conversion performance of the catalyst is accredited to the promoted light absorption and remarkably enhanced charge separation via the Sr-incorporated mid gap states and the localized surface plasmon resonance effect induced by noble metal nanoparticles. This work will provide a new approach for promoting the catalytic efficiency of g-C3N4 for efficient solar fuel production.
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3D porous, thin sheet-like rGO aerogel was fabricated to explore its antimony (Sb) removal potential from wastewater. Langmuir isothermal and pseudo-second-order kinetic model best-suited the adsorption process. The maximum adsorption capacities were 168.59 and 206.72 mg/g for Sb (III and V) at pH 6.0 respectively. The thermodynamic parameters designated the process to be thermodynamically spontaneous, endothermic reaction, a result of dissociative chemisorption. The rGO aerogel bestowed good selectively among competing ions and reusability with 95% efficiency. rGO posed excellent practicability with Sb-spiked tap water and fixed-bed column experiments showing 97.6% of Sb (III) (3.6 µg/L) and 96.8% of Sb (V) (4.7 µg/L) removal from tap water and from fixed column bed experiments breakthrough volumes (BV) for the Sb (III) and Sb (V) ions were noted to be 540 BV and 925 BV respectively, until 5 ppb, which are below the requirement of MCL for Sb in drinking water (6 µg/L). XPS and DFT analyses explained adsorption mechanism and depicted a higher affinity of Sb (V) towards rGO surface than Sb (III).
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Grafite , Poluentes Químicos da Água , Adsorção , Antimônio , Águas ResiduáriasRESUMO
Electrochemical CO2 reduction reaction (CO2RR) provides a promising approach to curbing harmful emissions contributing to global warming. However, several challenges hinder the commercialization of this technology, including high overpotentials, electrode instability, and low Faradic efficiencies of desirable products. Several materials have been developed to overcome these challenges. This mini-review discusses the recent performance of various cobalt (Co) electrocatalysts, including Co-single atom, Co-multi metals, Co-complexes, Co-based metal-organic frameworks (MOFs), Co-based covalent organic frameworks (COFs), Co-nitrides, and Co-oxides. These materials are reviewed with respect to their stability of facilitating CO2 conversion to valuable products, and a summary of the current literature is highlighted, along with future perspectives for the development of efficient CO2RR.