Unraveling the synergism mechanistic insight of O-vacancy and interfacial charge transfer in WO3-x decorated on Ag2CO3/BiOBr for photocatalysis of water pollutants: Based on experimental and density functional theory (DFT) studies.

Photocatalysis has been widely used as one of the most promising approaches to remove various pollutants in liquid or gas phases during the last decade. The main emphasis of the study is on the synergy of vacancy engineering and heterojunction formation, two widely used modifying approaches, to significantly alter photocatalytic performance. The vacancy-induced Ag2CO3/BiOBr/WO3-x heterojunction system has been fabricated using a co-precipitation technique to efficiently abate methylene blue (MB) dye and doxycycline (DC) antibiotic. The as-fabricated Ag2CO3/BiOBr/WO3-x heterojunction system displayed improved optoelectronic characteristic features because of the rational combination of dual charge transferal route and defect modulation. The Ag2CO3/BiOBr/WO3-x system possessed 97% and 74% photodegradation efficacy for MB and DC, respectively, with better charge isolation and migration efficacy. The ternary photocatalyst possessed a multi-fold increase in the reaction rate for both MB and DC, i.e., 0.021 and 0.0078 min-1, respectively, compared to pristine counterparts. Additionally, more insightful deductions about the photodegradation routes were made possible by the structural investigations of MB and DC using density functional theory (DFT) simulations. This study advances the understanding of the mechanisms forming visible light active dual Z-scheme heterojunction for effective environmental remediation.

Fe-based MOFs as promising adsorbents and photocatalysts for re-use water contained arsenic: Strategies and challenges.

Arsenic (As) contaminated water, especially groundwater reservoirs, is a major issue worldwide owing to its hazardous consequences on human health and the global environment issues. Also, irrigating agricultural fields with As-contaminated water not only produces an accumulation of As in the soil but also compromises food safety due to As entering into agricultural products. Hence, there is an urgent need to develop an efficient method for As removal in water. Fe-based MOFs have attained special attention due to their low toxicity, high water stability, better physical and chemical properties, and high abundance of iron. The arsenic species removal by Fe-MOF follows the adsorption and oxidation mechanism where As (III) converts into As (V). Moreover, the adsorption mechanism is facilitated by electrostatic interactions, H-bonding, acid-base interaction, hydrophobic interactions, van der Waals forces, π-π stacking interactions, and coordinative bindings responsible for Fe-O-As bond generation. This review thoroughly recapitulates and analyses recent advancements in the facile synthesis and potential application of Fe-based MOF adsorbents for the elimination of As ions. The most commonly employed hydro/solvothermal, ultrasonic, microwave-assisted, mechanochemical, and electrochemical synthesis for Fe-MOF has been discussed along with their adsorptive and oxidative mechanisms involved in arsenic removal. The effects of factors like pH and coexisting ions have also been discussed. Lastly, the article also proposed the prospects for developing the application of Fe-based MOF in treating As-contaminated water.

Sustainability, performance, and production perspectives of waste-derived functional carbon nanomaterials towards a sustainable environment: A review.

The survival of humanity is severely threatened by the massive accumulation of waste in the ecosystem. One plausible solution for the management and upcycling of waste is conversing waste at the molecular level and deriving carbon-based nanomaterial. The field of carbon nanomaterials with distinctive properties, such as exceptionally large surface areas, good thermal and chemical stability, and improved propagation of charge carriers, remains a significant area of research. The study demonstrates recent developments in high-value carbon-based photocatalysts synthesis from various waste precursors, including zoonotic, phytogenic, polyolefinic, electronic, and biomedical, highlighting the progression as photocatalysts and adsorbents for wastewater treatment and water splitting applications. This review highpoints the benefits of using waste as a precursor to support sustainability and circular economy and the risks associated with their use. Finally, we support that a sustainable society will eventually be realized by exploring present obstacles and potential steps for creating superior carbon-based nanomaterials in the future.

DFT and experimental studies of the facet-dependent oxygen vacancies modulated WS2/BiOCl-OV S-scheme structure for enhanced photocatalytic removal of ciprofloxacin from wastewater.

The present study explores visible light-assisted photodegradation of ciprofloxacin hydrochloride (CIP) antibiotic as a promising solution to water pollution. The focus is on transforming the optical and electronic properties of BiOCl through the generation of oxygen vacancies (OVs) and the exposure of (110) facets, forming a robust S-scheme heterojunction with WS2. The resultant OVs mediated composite with an optimal ratio of WS2 and BiOCl-OV (4-WS2/BiOCl-OV) demonstrated remarkable efficiency (94.3%) in the visible light-assisted photodegradation of CIP antibiotic within 1.5 h. The CIP degradation using 4-WS2/BiOCl-OV followed pseudo-first-order kinetics with the rate constant of 0.023 min-1, outperforming bare WS2, BiOCl, and BiOCl-OV by 8, 6, and 4 times, respectively. Density functional theory (DFT) analysis aligned well with experimental results, providing insights into the structural arrangement and bandgap analysis of the photocatalysts. Liquid chromatography-mass spectrometry (LC-MS) analysis utilized for identifying potentially degraded products while scavenging experiments and electron paramagnetic resonance (EPR) spin trapping analysis elucidated the S-scheme charge transfer mechanism. This research contributes to advancing the design of oxygen vacancy-mediated S-scheme systems in the realm of photocatalysis, with potential implications for addressing water pollution concerns.

MXene Hybrid Nanosheet of WS2/Ti3C2 for Electrocatalytic Hydrogen Evolution Reaction.

Designing low-cost hybrid electrocatalysts for hydrogen production is of significant importance. Recently, MXene-based materials are being increasingly employed in energy storage devices owing to their layered structure and high electrical conductivity. In this study, we propose a facile hydrothermal strategy for producing WS2/Ti3C2 nanosheets that function as electrocatalysts in the hydrogen evolution reaction (HER). WS2 provides a high surface area and active sites for electrocatalytic activity, whereas MXene Ti3C2 facilitates charge transfer. As a result, the synthesized WS2/Ti3C2 offers an increased surface area and exhibits an enhanced electrocatalytic activity in acidic media. The WS2/Ti3C2 (10%) catalyst exhibited a low onset potential of -150 mV versus RHE for the HER and a low Tafel slope of ∼62 mV dec-1. Moreover, WS2/Ti3C2 (10%) exhibited a double-layer capacitance of 1.2 mF/cm-2, which is 3 and 6 times greater than those of bare WS2 and Ti3C2, respectively. This catalyst also maintained a steady catalytic activity for the HER for over 1000 cycles.

Chitosan-supported metal nanocatalysts for the reduction of nitroaromatics.

The second most abundant natural polymer in the earth's crust is chitosan (CS). The unique physical, chemical, structural, and mechanical features of this natural polymer have led to its increased application in a variety of fields such as medicine, catalysis, removal of pollutants, etc. To eliminate various pollutants, it is preferable to employ natural compounds as their use aids the removal of contaminants from the environment. Consequently, employing CS to eliminate contaminants is a viable choice. For this aim, CS can be applied as a template and support for metal nanoparticles (MNPs) and prevent the accumulation of MNPs as well as a reducing and stabilizing agent for the synthesis of MNPs. Among the pollutants present in nature, nitro compounds are an important and wide category of biological pollutants. 4-Nitrophenol (4-NP) is one of the nitro pollutants. There are different ways for the removal of 4-NP, but the best and most effective method for this purpose is the application of a metallic catalyst and a reducing agent. In this review, we report the recent developments regarding CS-supported metallic (nano)catalysts for the reduction of nitroaromatics such as nitrophenols, nitroaniline compounds, nitrobenzene, etc. in the presence of reducing agents. The metals investigated in this study include Ag, Au, Ni, Cu, Ru, Pt, Pd, etc.

Recent catalytic applications of MXene-based layered nanomaterials.

The urgent issues related to the catalytic processes and energy applications have accelerated the development of hybrid and smart materials. MXenes are a new family of atomic layered nanostructured materials that require considerable research. Tailorable morphologies, strong electrical conductivity, great chemical stability, large surface-to-volume ratios, tunable structures, among others are some significant characteristics that make MXenes appropriate for various electrochemical reactions, including dry reforming of methane, hydrogen evolution reaction, methanol oxidation reaction, sulfur reduction reaction, Suzuki-Miyaura coupling reaction, water-gas shift reaction, and so forth. MXenes, on the other hand, have a fundamental drawback of agglomeration, as well as poor long-term recyclability and stability. One possibility for overcoming the restrictions is the fusion of nanosheets or nanoparticles with MXenes. Herein, the relevant literature on the synthesis, catalytic stability and reusability, and applications of several MXene-based nanocatalysts are deliberated including the merits and cons of the newer MXene-based catalysts.

Hollow Ni/NiO/C composite derived from metal-organic frameworks as a high-efficiency electrocatalyst for the hydrogen evolution reaction.

Metal-organic frameworks (MOFs) constitute a class of crystalline porous materials employed in storage and energy conversion applications. MOFs possess characteristics that render them ideal in the preparation of electrocatalysts, and exhibit excellent performance for the hydrogen evolution reaction (HER). Herein, H-Ni/NiO/C catalysts were synthesized from a Ni-based MOF hollow structure via a two-step process involving carbonization and oxidation. Interestingly, the performance of the H-Ni/NiO/C catalyst was superior to those of H-Ni/C, H-NiO/C, and NH-Ni/NiO/C catalysts for the HER. Notably, H-Ni/NiO/C exhibited the best electrocatalytic activity for the HER, with a low overpotential of 87 mV for 10 mA cm-2 and a Tafel slope of 91.7 mV dec-1. The high performance is ascribed to the synergistic effect of the metal/metal oxide and hollow architecture, which is favorable for breaking the H-OH bond, forming hydrogen atoms, and enabling charge transport. These results indicate that the employed approach is promising for fabricating cost-effective catalysts for hydrogen production in alkaline media.

Rational design, structure properties, and synthesis strategies of dual-pore covalent organic frameworks (COFs) for potent applications: A review.

Dual-pore covalent organic frameworks (COFs) offer a molecular scaffold for introducing building blocks into periodically organized polygonal skeletons to produce fascinating structural features. The rapid development of this material has attracted intensive interest from researchers with diverse expertise. This review selects the leading scientific findings about dual-pore COFs and highlights their functions and perspectives on design, structure properties, and synthesis strategies. Dual-pore COFs, as newly hetero-pore COFs by integrating particular pores into one polygonal skeleton, have been compared to conventional COFs. Dual-pore COFs display hierarchical/heterogeneous porosities and homogeneous porosity, which endow them with exceptional features involving mass diffusion, charge transfer, and large surface area with abundant active sites. Additionally, the strategic dual-pore design by opting for different approaches, such as integration of [D2h + C2] symmetries, kagome-type lattices, and other symmetric arrangements of monomers, are inclusively discussed. Identification and construction of dual-pores in COFs via optimal synthetic methods, such as desymmetrization, multiple linking sites, and orthogonal reactions, are highlighted as the primary pore engineering routes to simultaneously regulate the growth and alter the characteristics of COFs for promising applications. Lastly, a focused discussion on various challenges and critical fundamentals of dual-pore engineering is successfully outlined, with potential prospects of introducing dual-pore in COFs.

Hexagonal-borocarbonitride (h-BCN) based heterostructure photocatalyst for energy and environmental applications: A review.

Formulation of heterojunction with remarkable high efficiency by utilizing solar light is promising to synchronously overcome energy and environmental crises. In this concern, hexagonal-borocarbonitride (h-BCN) based Z-schemes have proved potential candidates due to their spatially separated oxidation and reduction sites, robust light-harvesting ability, high charge pair migration and separation, and strong redox ability. H-BCN has emerged as a hotspot in the research field as a metal-free photocatalyst with a tunable bandgap range of 0-5.5 eV. The BCN photocatalyst displayed synergistic benefits of both graphene and boron nitride. Herein, the review demonstrates the current state-of-the-art in the Z-scheme photocatalytic application with a special emphasis on the predominant features of their photoactivity. Initially, fundamental aspects and various synthesis techniques are discussed, including thermal polymerization, template-assisted, and template-free methods. Afterward, the reaction mechanism of direct Z-scheme photocatalysts and indirect Z-scheme (all-solid-state) are highlighted. Moreover, the emerging Step-scheme (S-scheme) systems are briefly deliberated to understand the charge transfer pathway mechanism with an induced internal electric field. This review critically aims to comprehensively summarize the photo-redox applications of various h-BCN-based heterojunction photocatalysts including CO2 photoreduction, H2 evolution, and pollutants degradation. Finally, some challenges and future direction of h-BCN-based Z-scheme photocatalyst in environmental remediation are also proposed.

An overview on recent progress in photocatalytic air purification: Metal-based and metal-free photocatalysis.

Air pollution is becoming a distinctly growing concern and the most pressing universal problem as a result of increased energy consumption, with the multiplication of the human population and industrial enterprises, resulting in the generation of hazardous pollutants. Among these, carbon monoxide, nitrogen oxides, Volatile organic compounds, Semi volatile organic compounds, and other inorganic gases not only have an adverse impact on human health both outdoors and indoors, but have also substantially altered the global climate, resulting in several calamities around the world. Thus, the purification of air is a crucial matter to deal with. Photocatalytic oxidation is one of the most recent and promising technologies, and it has been the subject of numerous studies over the past two decades. Hence, the photocatalyst is the most reassuring aspirant due to its adequate bandgap and exquisite stability. The process of photocatalysis has provided many benefits to the atmosphere by removing pollutants. In this review, our work focuses on four main themes. Firstly, we briefly elaborated on the general mechanism of air pollutant degradation, followed by an overview of the typical TiO2 photocatalyst, which is the most researched photocatalyst for photocatalytic destruction of gaseous VOCs. The influence of operating parameters influencing the process of photocatalytic oxidation (such as mass transfer, light source and intensity, pollutant concentration, and relative humidity) was then summarized. Afterwards, the progress and drawbacks of some typical photoreactors (including monolithic reactors, microreactors, optical fiber reactors, and packed bed reactors) were described and differentiated. Lastly, the most noteworthy coverage is dedicated to different types of modification strategies aimed at ameliorating the performance of photocatalysts for degradation of air pollutants, which were proposed and addressed. In addition, the review winds up with a brief deliberation for more exploration into air purification photocatalysis.

Machine learning-assisted evaluation of potential biochars for pharmaceutical removal from water.

A popular approach to select optimal adsorbents is to perform parallel experiments on adsorbents based on an initially decided goal such as specified product purity, efficiency, or binding capacity. To screen optimal adsorbents, we focused on the max adsorption capacity of the candidates at equilibrium in this work because the adsorption capacity of each adsorbent is strongly dependent on certain conditions. A data-driven machine learning tool for predicting the max adsorption capacity (Qm) of 19 pharmaceutical compounds on 88 biochars was developed. The range of values of Qm (mean 48.29 mg/g) was remarkably large, with a high number of outliers and large variability. Modified biochars enhanced the Qm and surface area values compared with the original biochar, with a statistically significant difference (Chi-square value = 7.21-18.25, P < 0.005). K- nearest neighbors (KNN) was found to be the most optimal algorithm with a root mean square error (RMSE) of 23.48 followed by random forest and Cubist with RMSE of 26.91 and 29.56, respectively, whereas linear regression and regularization were the worst algorithms. KNN model achieved R2 of 0.92 and RMSE of 16.62 for the testing data. A web app was developed to facilitate the use of the KNN model, providing a reliable solution for saving time and money in unnecessary lab-scale adsorption experiments while selecting appropriate biochars for pharmaceutical adsorption.

Multilayered Nanocomposites Prepared through Quadruple-Layering Approach towards Enhanced Mechanical Performance.

Multilayered materials are widely studied due to their special structures and great properties, such as their mechanical ones. In this paper a novel and effective technique, a quadruple-layering approach, was used to fabricate multilayered materials. This approach increases the number of layers rapidly via simple operations. Materials with 4, 16, and 64 layers with alternating layers of polypropylene and nanocomposites were fabricated using this approach, and their film morphology and mechanical properties were studied. The influence of the number of layers on the mechanical properties of the materials and the relationship between the mechanical properties of each material were investigated. The results illustrated that the tensile modulus and strength were enhanced and elongation at the break increased when the layer numbers of the multilayered materials increased. However, this approach has a defect in that as the layer number increases, the layer thickness was not uniform, thus restricting the improvement of properties. This may need to be further studied in future work.

Recent progress on elemental sulfur based photocatalysts for energy and environmental applications.

The growing needs of the rising population and blatant misuse of resources have contributed enormously to environmental problems. Among the various methods, photocatalysis has emerged as one of the effective remediation methods. The continuous search for effective photocatalysts that can be made from abundant, cheap, non-toxic materials is going on. Although sulfur is a known insulator, recent sulfur use as a visible light photocatalyst has ushered a new era in this direction. Sulfur is a non-toxic, cheap, and abundant photocatalyst, exhibiting significant photocatalytic properties. But, hydrophobicity, poor light-harvesting and high recombination rate of charge carriers in elemental sulfur photocatalyst are some of the major drawbacks of the elemental sulfur photocatalyst. The photocatalytic activity of sulfur as a single element was low, but various methods such as nanoscaling, heterojunction formation, doping and surface modifications have been used to enhance it. The review highlights sulfur's crystal structure, electronic and optical properties, and morphological changes, making it an excellent visible light photocatalyst. The article points to the limitations of sulfur as a single photocatalyst and various strategies to improve the shortcomings. More recently, there has been an emphasis on the synthesis of metal-free photocatalysts. This review provides its readers with a comprehensive detail of sulfur being used as a dopant in improving the photocatalytic properties of metal-free photocatalysts and their environmental remediation use. Finally, the conclusion and future perspectives for sulfur-based nanostructures are presented.

Polypyrrole-based nanomaterials: A novel strategy for reducing toxic chemicals and others related to environmental sustainability applications.

Aqueous contaminants such as pharmaceuticals, dyes, personal care products, etc., are the common water contaminants that show adverse health effects. Photocatalysis is one of the well-known techniques to treat these water contaminants. Currently, most inorganic photocatalysts show a poor balance between adsorption and photocatalytic activity. In addition, heavy metal pollution and low biosafety are significant concerns in photocatalysis. Thus, environmentally friendly photocatalysts are required to avoid the secondary pollution caused by some inorganic semiconductor-photocatalysts. Organic polymer-based photocatalysts are low-cost, stable, non-toxic, and can utilize visible and NIR light for photocatalysis. In this review, we have discussed polypyrrole as a photocatalyst. Polypyrrole is a conducting organic polymer photocatalyst that is highly stable with high charge mobility and strong binding sites for photocatalytic reactions. Besides these advantages, polypyrrole has limitations, such as high charge recombination due to a small bandgap and poor dispersity. So we have explored the modifications to polypyrrole photocatalysts, such as doping and heterojunctions. Further, we have explained the applications of polypyrrole in photocatalysis as an adsorbent, sensitizer, degradation of pollutants, and energy production. Finally, the future aspects of polypyrrole photocatalysis are also explored to improve the path of future research.

Structural Characterization of Mannoglucan Isolated from Ophiocordyceps sobolifera and Its Antioxidant Activities.

A novel polysaccharide structure (PS-T80) was collected from Ophiocordyceps sobolifera biomass and characterized via a combination of chemical and spectral analyses. Employing high-performance gel permeation chromatography (HPGPC), the average molecular weight is proven to be 7.4 × 104 Da. Furthermore, a sugar composition analysis of the obtained polysaccharide suggests two main sugars, ß-d-glucose and α-d-mannose, at a molar ratio of 2:1, respectively, in the backbone. The structure analysis unveils that PS-T80 is a mannoglucan, possessing the repeating unit of [→3)-ß-d-Glcp-(1 → 3)-α-d-Manp-(1 → 3)-ß-d-Glcp-(1→] n . Such a configuration could be considered a novel polysaccharide. Impressively, in vitro antioxidant tests revealed that PS-T80 has a promising antioxidant activity. These results demonstrate that the obtained PS is a potential bioactive material for biomedical applications.

Potential of graphene based photocatalyst for antiviral activity with emphasis on COVID-19: A review.

Coronavirus disease-2019 caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has been one of the most challenging worldwide epidemics of recent times. Semiconducting materials (photocatalysts) could prove effectual solar-light-driven technology on account of variant reactive oxidative species (ROS), including superoxide (•O2 - ) and hydroxyl (•OH) radicals either by degradation of proteins, DNA, RNA, or preventing cell development by terminating cellular membrane. Graphene-based materials have been exquisitely explored for antiviral applications due to their extraordinary physicochemical features including large specific surface area, robust mechanical strength, tunable structural features, and high electrical conductivity. Considering that, the present study highlights a perspective on the potentials of graphene based materials for photocatalytic antiviral activity. The interaction of virus with the surface of graphene based nanomaterials and the consequent physical, as well as ROS induced inactivation process, has been highlighted and discussed. It is highly anticipated that the present review article emphasizing mechanistic antiviral insights could accelerate further research in this field.

Electrochemical conversion of CO2 to value-added chemicals over bimetallic Pd-based nanostructures: Recent progress and emerging trends.

Electrochemical conversion of CO2 to fuels and chemicals as a sustainable solution for waste transformation has garnered tremendous interest to combat the fervent issue of the prevailing high atmospheric CO2 concentration while contributing to the generation of sustainable energy. Monometallic palladium (Pd) has been shown promising in electrochemical CO2 reduction, producing formate or CO depending on applied potentials. Recently, bimetallic Pd-based materials strived to fine-tune the binding affinity of key intermediates is a prominent strategy for the desired product formation from CO2 reduction. Herein, the recent emerging trends on bimetallic Pd-based electrocatalysts are reviewed, including fundamentals of CO2 electroreduction and material engineering of bimetallic Pd-electrocatalysts categorized by primary products. Modern analytical techniques on these novel electrocatalysts are also thoroughly studied to get insights into reaction mechanisms. Lastly, we deliberate over the challenges and prospects for Pd-based catalysts for electrochemical CO2 conversion.

Graphitic carbon nitride based immobilized and non-immobilized floating photocatalysts for environmental remediation.

In solar photocatalysis, light utilization and recycling of powder from reaction solution are the main obstructions that hinder the photocatalytic efficacy of any photocatalyst. In this respect, a floatable system is effective for efficient solar photocatalysis by light utilization. Due to the maximum solar light absorption property, floating nanocomposite photocatalyst is an appealing substitute for effective wastewater treatment. Floating photocatalysts are a non-oxygenated and non-stirred solution that is a good light harvester, stable, non-toxic, biodegradable, naturally abundant in nature. They also have low density, a simple preparation process, no need to stir, and high porosity. Due to these characteristics, floating photocatalysts are widely favored and ideal candidates for practical environmental remediation. Several researchers have come up with new and innovative ways for immobilizing capable photocatalyst on a floatable substrate to produce floating nanocomposite photocatalytic material. In recent decades, g-C3N4-based floating photocatalysts have gained a lot of attention as g-C3N4 is a visible light active photocatalyst with unique and exceptional properties. It also has good photocatalytic activity in waste water treatment and environmental remediation. Many previous reports have studied the logical design and manufacturing method for heterojunction floating photocatalysts and immobilized floating photocatalysts. Based on those studies, we have focused on the g-C3N4 based immobilized and non-immobilized floating photocatalysts for pollutant degradation. We have also categorized immobilized floating photocatalyst based on several lightweight substrates such as expanded perlite and glass microbead. In addition, future challenges have been discussed to maximize solar light absorption and to improve the efficiency of broadband response floating photocatalysts. Floating photocatalysis is an advanced technique in energy conversion and environmental remediation thus requires special consideration.

Current perspective in metal oxide based photocatalysts for virus disinfection: A review.

Nanotechnology holds huge potential for the prevention of various viral outbreaks that have increased at a disquieting rate over the past decades. Metal oxide nanomaterials with oxidative capability are the effective materials that provide platforms as well as tools for the well understanding of the mechanism, its detection, and treatment of various viral diseases like measles, influenza, herpes, ebola, current COVID-19 etc. In this inclusive review, we survey various previous research articles on different notable photoactive transition metal oxides that possess enough potential to act as antiviral agents for the deactivation of harmful viruses. We investigated and highlighted the plausible photocatalytic oxidative mechanism of photoactive transition metal oxides in degrading viral coatings, genomic RNA using suitable free radical generation. The key finding of the present review article including the discovery of a vision on the suitable photocatalytic transition metal oxides that have been proven to be excellent against harmful viruses and consequently combatting deadly CoV-2 in the environment. This review intends to provide conclusive remarks and a realistic outlook on other advanced photocatalytic metal oxides as a potential solution in battling other similar upcoming pandemics.