ABSTRACT
NH2-functionalized metal-organic frameworks (NH2-functionalized MOFs) can abate organic pollutants, predominantly favored by their chemical, mechanical, and thermal stabilities. The present review stated the chemistry of identifying NH2-functionalization and its role in enhancing the properties of bare MOFs. The integration of the amine group bestows several advantages: 1.) enabling band structure modification, 2.) establishing strong metal-NH2 bonds, 3.) preserving MOF structures from reactive oxygen species, and 4.) shielding MOF structures against pH alterations. Consequently, the NH2-functionalized MOFs are promising materials for the photodegradation of organic contaminants. The following section illustrates the two approaches (pre-synthetic and post-synthetic) for NH2-functionalized MOFs. Nevertheless, specific intrinsic limitations, entailing a high recombination rate of charge carriers and inadequate optical adsorption, restrain the applicability of NH2-functionalized MOFs. Accordingly, the succeeding segment presents strategies to elevate the photocatalytic activities of NH2-functionalized MOFs via heterojunction fabrication. The importance of the NH2-functionalized MOFs-based heterojunction has been evaluated in terms of the effect on the enhancement of charge separation, optical adsorption, and redox ability of charge carriers. Subsequently, the potential application for organic pollutant degradation via NH2-functionalized MOFs-based heterojunctions has been scrutinized, wherein the organic pollutants. Eventually, the review concluded with challenges and potential opportunities in engaging and burgeoning domains of the NH2-functionalized MOFs-based heterojunctions.
ABSTRACT
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.
ABSTRACT
Titanium dioxide (TiO2) based photocatalysts have been widely used as a photocatalyst for the degradation of various persistent organic compounds in water and air. The degradation mechanism involves the generation of highly reactive oxygen species, such as hydroxyl radicals, which react with organic compounds to break down their chemical bonds and ultimately mineralize them into harmless products. In the case of pharmaceutical and pesticide molecules, TiO2and modified TiO2photocatalysis effectively degrade a wide range of compounds, including antibiotics, pesticides, and herbicides. The main downside is the production of dangerous intermediate products, which are not frequently addressed in the literature that is currently available. The degradation rate of these compounds by TiO2photocatalysis depends on factors such as the chemical structure of the compounds, the concentration of the TiO2catalyst, the intensity, the light source, and the presence of other organic or inorganic species in the solution. The comprehension of the degradation mechanism is explored to gain insights into the intermediates. Additionally, the utilization of response surface methodology is addressed, offering a potential avenue for enhancing the scalability of the reactors. Overall, TiO2photocatalysis is a promising technology for the treatment of pharmaceutical and agrochemical wastewater, but further research is needed to optimize the process conditions and to understand the fate and toxicity of the degradation products.
Subject(s)
Pesticides , Photochemical Processes , Titanium , Titanium/chemistry , Catalysis , Pesticides/chemistry , Pharmaceutical Preparations/chemistry , LightABSTRACT
A variety of bacteria, including beneficial probiotic lactobacilli, produce antibacterials to kill competing bacteria. Lactobacilli secrete antimicrobial peptides (AMPs) called bacteriocins and organic acids. In the food industry, bacteriocins, but even whole cell-free supernatants, are becoming more and more important as bio-preservatives, while, in orthopedics, bacteriocins are introducing new perspectives in biomaterials technologies for anti-infective surfaces. Studies are focusing on Lactiplantibacillus plantarum (previously known as Lactobacillus plantarum). L. plantarum exhibits great phenotypic versatility, which enhances the chances for its industrial exploitation. Importantly, more than other lactobacilli, it relies on AMPs for its antibacterial activity. In this study, Response Surface Methodology (RSM) through a Box-Behnken experimental design was used to estimate the optimal conditions for the production of antibacterials by L. plantarum. A temperature of 35 °C, pH 6.5, and an incubation time of 48 h provided the highest concentration of antibacterials. The initial pH was the main factor influencing the production of antibacterials, at 95% confidence level. Thanks to RSM, the titer of antibacterials increased more than 10-fold, this result being markedly higher than those obtained in the very few studies that have so far used similar statistical methodologies. The Box-Behnken design turned out to be a valid model to satisfactorily plan a large-scale production of antibacterials from L. plantarum.
ABSTRACT
Etching technology - one of the representative modern semiconductor device makers - serves as a broad descriptor for the process of removing material from the surfaces of various materials, whether partially or entirely. Meanwhile, thinning technology represents a novel and highly specialized approach within the realm of etching technology. It indicates the importance of achieving an exceptionally sophisticated and precise removal of material, layer-by-layer, at the nanoscale. Notably, thinning technology has gained substantial momentum, particularly in top-down strategies aimed at pushing the frontiers of nano-worlds. This rapid development in thinning technology has generated substantial interest among researchers from diverse backgrounds, including those in the fields of chemistry, physics, and engineering. Precisely and expertly controlling the layer numbers of 2D materials through the thinning procedure has been considered as a crucial step. This is because the thinning processes lead to variations in the electrical and optical characteristics. In this comprehensive review, the strategies for top-down thinning of representative 2D materials (e.g., graphene, black phosphorus, MoS2, h-BN, WS2, MoSe2, and WSe2) based on conventional plasma-assisted thinning, integrated cyclic plasma-assisted thinning, laser-assisted thinning, metal-assisted splitting, and layer-resolved splitting are covered in detail, along with their mechanisms and benefits. Additionally, this review further explores the latest advancements in terms of the potential advantages of semiconductor devices achieved by top-down 2D material thinning procedures.
ABSTRACT
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.
Subject(s)
Arsenic , Iron , Metal-Organic Frameworks , Water Pollutants, Chemical , Water Purification , Arsenic/chemistry , Arsenic/analysis , Adsorption , Water Pollutants, Chemical/chemistry , Iron/chemistry , Water Purification/methods , Metal-Organic Frameworks/chemistry , Catalysis , Oxidation-Reduction , Groundwater/chemistryABSTRACT
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.
Subject(s)
Ciprofloxacin , Oxygen , Photolysis , Wastewater , Water Pollutants, Chemical , Ciprofloxacin/chemistry , Water Pollutants, Chemical/chemistry , Wastewater/chemistry , Oxygen/chemistry , Bismuth/chemistry , Anti-Bacterial Agents/chemistry , Tungsten/chemistry , Catalysis , Light , Density Functional TheoryABSTRACT
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.
Subject(s)
Nanostructures , Water Pollutants, Chemical , Water Purification , Carbon , EcosystemABSTRACT
To date, intensive emphasis is required to develop advanced postharvest technologies to ensure food security, increase nutrition, and improve farmers toward cleaner production. How to effectively degrade the harmful gaseous ethylene (C2H4) biosynthesis, which distributes heavy losses of fresh-cut fruits and vegetables, has received considerable attention. Among various advanced techniques, photocatalytic degradation of biological C2H4 is proposed as the most promising method to solve this issue. In this context, the recent studies on the photodegradation of C2H4 have been critically summarized and highlighted. Many photocatalysts, including TiO2-based and non-TiO2-based (metal oxides (ZnO, WO3, Ga2O3), molybdates (ß-Ag2MoO4), phosphides (Ag3PO4), perovskite oxides (Bi2WO6)) nanomaterials, have been revealed with credible performance results. Also, varying reaction parameters to optimize the photocatalytic degradation efficacy in the literature are summarized. We also discussed the current status, challenges, and prospects for enhanced photodegradation of C2H4 in this study. The efficacy and economics of photodegradation have played an essential role in selecting a particular type of photocatalyst. Although many efforts have been made, significant improvements are still required for photocatalysis. In this work, we have also successfully suggested some strategies to further promote this concept for controlling and degrading plant-generated C2H4 in fruit and vegetable postharvest in a sustainable and economically feasible manner.
ABSTRACT
Two-dimensional transition metal dichalcogenides (2D-TMDCs) with various physical characteristics have attracted significant interest from the scientific and industrial worlds in the years following Moore's law. The p-n junction is one of the earliest electrical components to be utilized in electronics and optoelectronics, and modern research on 2D materials has renewed interest in it. In this regard, device preparation and application have evolved substantially in this decade. 2D TMDCs provide unprecedented flexibility in the construction of innovative p-n junction device designs, which is not achievable with traditional bulk semiconductors. It has been investigated using 2D TMDCs for various junctions, including homojunctions, heterojunctions, P-I-N junctions, and broken gap junctions. To achieve high-performance p-n junctions, several issues still need to be resolved, such as developing 2D TMDCs of superior quality, raising the rectification ratio and quantum efficiency, and successfully separating the photogenerated electron-hole pairs, among other things. This review comprehensively details the various 2D-based p-n junction geometries investigated with an emphasis on 2D junctions. We investigated the 2D p-n junctions utilized in current rectifiers and photodetectors. To make a comparison of various devices easier, important optoelectronic and electronic features are presented. We thoroughly assessed the review's prospects and challenges for this emerging field of study. This study will serve as a roadmap for more real-world photodetection technology applications.
ABSTRACT
Recently, there has been a significant increase in the interest of using photocatalysis for environmental clean-up applications. In this research, potassium, and phosphorus co-doped graphitic carbon nitride (KPCN) photocatalyst modified with graphene oxide (GO) and heterostructured with ZnFe2O4 was synthesized via the hydrothermal method (KPCN/GO/ZnFe2O4). The photoactivity of KPCN/GO/ZnFe2O4 photocatalyst was examined for the photocatalytic degradation of target pollutants such as methylene blue (MB) dye, rhodamine B (RhB) dye, and tetracycline (TC) antibiotic. Furthermore, the chemical oxygen demand (COD) removal efficiency for real wastewater was determined to explore the practical application of KPCN/GO/ZnFe2O4 photocatalyst. The degradation efficiencies of bare graphitic carbon nitride, KPCN, KPCN/GO, and KPCN/GO/ZnFe2O4 photocatalysts for tetracycline antibiotics were 30%, 42%, 57%, and 87% within 60 min, respectively. Moreover, KPCN/GO/ZnFe2O4 photocatalyst showed 71% COD removal efficiency within 240 min. The â¢OH and â¢O2- were the major reactive species in the photocatalytic process. Results showed that the degradation efficiencies of graphitic carbon nitride were greatly enhanced upon doping and further improved with the addition of GO and ZnFe2O4. Doping improved light harvesting, GO enhanced the adsorption ability and heterojunction with ZnFe2O4 enhanced the charge separation as well as the reusability of synthesized KPCN/GO/ZnFe2O4 photocatalyst.
Subject(s)
Anti-Bacterial Agents , Water Purification , Adsorption , Tetracyclines , Light , CatalysisABSTRACT
Covalent organic frameworks (COFs) based on core@shell nanohybrids have recently received significant attention and have become one of the most promising strategies for improving the stability and catalytic activity of COFs. Compared with traditional core@shell, COF-based core@shell hybrids own remarkable advantages, including size-selective reactions, bifunctional catalysis, and integration of multiple functions. These properties could enhance the stability and recyclability, resistance to sintering, and maximize the electronic interaction between the core and the shell. The activity and selectivity of COF-based core@shell could be simultaneously improved by taking benefit of the existing synergy between the functional encapsulating shell and the covered core material. Considering that, we have highlighted various topological diagrams and the role of COFs in COF-based core@shell hybrid for activity and selectivity enhancement. This concept article provides all-inclusive advances in the design and catalytic applications of COF-based core@shell hybrids. Various synthetic techniques have been developed for the facile tailoring of functional core@shell hybrids, including novel seed growth, in-situ, layer-by-layer, and one-pot method. Importantly, charge dynamics and structure-performance relationships are investigated through different characterization techniques. Different COF-based core@shell hybrids with established synergistic interactions have been detailed, and their influence on stability and catalytic efficiency for various applications is explained and discussed in this contribution. A comprehensive discussion on the remaining challenges associated with COF-based core@shell nanoparticles and research directions has also been provided to deliver insightful ideas for additional future developments.
Subject(s)
Metal-Organic Frameworks , Nanoparticles , Nanostructures , Catalysis , ReproductionABSTRACT
Over the past several decades, the increase in industrialization provoked the discharge of harmful pollutants into the environment, affecting human beings and ecosystems. ZnO-based photocatalysts seem to be the most promising photocatalysts for treating harmful pollutants. However, fast charge carrier recombination, photo corrosion, and long reaction time are the significant factors that reduce the photoactivity of ZnO-based photocatalysts. In order to enhance the photoactivity of such photocatalysts, a combined process i.e., sonocatalysis + photocatalysis = sonophotocatalysis was used. Sonophotocatalysis is one of several different AOP methods that have recently drawn considerable interest, as it produces high reactive oxygen species (ROS) which helps in the oxidation of pollutants by acoustic cavitation. This combined technique enhanced the overall efficiency of the individual method by overcoming its limiting factors. The current review aims to present the theoretical and fundamental aspects of sonocatalysis and photocatalysis along with a detailed discussion on the benefits that can be obtained by the combined process i.e., US + UV (sonophotocatalysis). Also, we have provided a comparison of the excellent performance of ZnO to that of the other metal oxides. The purpose of this study is to discuss the literature concerning the potential applications of ZnO-based sonophotocatalysts for the degradation of pollutants i.e., dyes, antibiotics, pesticides, phenols, etc. That are carried out for future developments. The role of the produced ROS under light and ultrasound stimulation and the degradation mechanisms that are based on published literature are also discussed. In the end, future perspectives are suggested, that are helpful in the development of the sonophotocatalysis process for the remediation of wastewater containing various pollutants.
Subject(s)
Environmental Pollutants , Zinc Oxide , Humans , Reactive Oxygen Species , Ecosystem , Catalysis , WaterABSTRACT
In this work, CQDs decorated MnIn2S4/CdS/Bi2S3 heterojunction was prepared successfully by hydrothermal technique for photocatalytic disinfection of Escherichia coli (E. coli) and mineralization of methyl orange (MO) dye. The charge transferal route and mineralization process in CQDs-MnIn2S4/CdS/Bi2S3 heterojunction were comprehensively investigated by advanced spectroscopic techniques. The improved visible-light activity and enhanced photo-generated charge transferal efficacy caused dual Z-scheme CQDs-MnIn2S4/CdS/Bi2S3 heterojunction to achieve boosted photodegradation ability. The catalytic degradation trend was followed as CQDs-MnIn2S4/CdS/Bi2S3 > MnIn2S4 > CdS > Bi2S3. The dye was mineralized within 180 min under visible light irradiation. The effect of reaction parameters, pH effect, catalyst dosage, and H2O2 addition on MO degradation was also investigated. The degradation rate was maximal at pH 4 with a pseudo-first-order rate constant, 0.0438 min-1. The assessment of antibacterial properties revealed that CQDs-MnIn2S4/CdS/Bi2S3 composite effectively inactivated E. coli under visible light. Scavenging experiments, transient photocurrent response, and electron spin resonance spectroscopy suggested that â¢[Formula: see text] and holes were the dominant reactive species. The Z-scheme heterojunction is recyclable up to ten photocatalytic cycles according to recycling experiments. This research indicates the importance of dual Z-scheme CQDs decorated MnIn2S4/CdS/Bi2S3 heterojunction in wastewater remediation.
Subject(s)
Carbon , Quantum Dots , Quantum Dots/chemistry , Escherichia coli , Hydrogen Peroxide , Anti-Bacterial Agents/chemistry , LightABSTRACT
Doping-induced vacancy engineering of graphitic carbon nitride (GCN) is beneficial for bandgap modulation, efficient electronic excitation, and facilitated charge carrier migration. In this study, synthesis of oxygen and sulphur co-doped induced N vacancies (OSGCN) by the hydrothermal method was performed to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) antibiotic degradation and H2 production. The results from experimental and DFT simulation studies validate the synergistic effects of co-dopants and N-vacancies, i.e., bandgap lowering, electron-hole pairs separation, and high solar energy utilization. The substitution of sp2 N atom by O and S co-dopants causes strong delocalization of HOMO-LUMO distribution, enhancing carrier mobility, increasing reactive sites, and facilitating charge-carrier separation. Remarkably, OSGCN/PMS photocatalytic system achieved 99.4% SMX degradation efficiency and a high H2 generation rate of 548.23 µ mol g-1 h-1 within 60 min and 36 h, respectively under visible light irradiations. The SMX degradation kinetics was pseudo-first-order with retained recycling efficiency up to 4 catalytic cycles. The results of EPR and chemical scavenging experiments revealed the redox action of reactive oxidative species, wherein 1O2 was the dominant reactive species in SMX degradation. The identification of formed intermediates and the SMX stepwise degradation pathway was investigated via LC-MS analysis and DFT studies, respectively. The results from this work anticipated deepening the understanding of PMS activation by substitutional co-doping favoring N-vacancy formation in GCN lattice for improved photocatalytic activity.
Subject(s)
Graphite , Sulfamethoxazole , Sulfamethoxazole/chemistry , Peroxides/chemistry , Graphite/chemistry , OxygenABSTRACT
This work successfully fabricated graphitic carbon nitride and magnetically recoverable α-Fe2O3/g-C3N4/SiO2 photo-Fenton catalysts using thermal polycondensation and in situ-simple precursor drying-calcination process, respectively, was examined for model synthetic rhodamine B (RhB) dye in the presence of H2O2 and acidic pH under simulated visible light irradiation. An aqueous suspension of the reaction mixture of dye-containing wastewater was fully degraded and reached 97% of photo-Fenton degradation efficiency within 120 min followed by the production of hydroxyl radical (â¢OH). The dominant hydroxyl radical position generated surface charge, electrostatic potential distribution, and average local ionization potential, which contributed to the complete mineralization of RhB dye, according to the density functional theory (DFT) calculations. HPLC and GCMS experiments were performed to examine the degradation fragments of RhB and draw a plausible mechanistic pathway which showed that RhB degradation generated a series of N-deethylated products, followed by a one-time ring-opening, which indicated that photosensitization induced a photocatalysis reaction mechanism.
Subject(s)
Hydrogen Peroxide , Silicon Dioxide , Hydrogen Peroxide/chemistry , Hydroxyl Radical/chemistry , Light , CatalysisABSTRACT
Architecting a desirable and highly efficient nanocomposite for applications like adsorption, catalysis, etc. has always been a challenge. Metal Organic Framework (MOF)-based hierarchical composite has perceived popularity as an advanced adsorbent and catalyst. Hierarchically structured MOF material can be modulated to allow the surface interaction (external or internal) of MOF with the molecules of interest. They are well endowed with tunable functionality, high porosity, and increased surface area epitomizing mass transfer and mechanical stability of the fabricated nanostructure. Additionally, the anticipated optimization of nanocomposite can only be acquired by a thorough understanding of the synthesis techniques. This review starts with a brief introduction to MOF and the requirement for advanced nanocomposites after the setback faced by conventional MOF structures. Further, we discussed the background of MOF-based hierarchical composites followed by synthetic techniques including chemical and thermal treatment. It is important to rationally validate the successful nanocomposite fabrication by characterization techniques, an overview of challenges, and future perspectives associated with MOF-based hierarchically structured nanocomposite.
Subject(s)
Metal-Organic Frameworks , Nanocomposites , Water Purification , Nanocomposites/chemistry , Catalysis , AdsorptionABSTRACT
In recent times, green chemistry or "green world" is a new and effective approach for sustainable environmental remediation. Among all biomaterials, cellulose is a vital material in research and green chemistry. Cellulose is the most commonly used natural biopolymer because of its distinctive and exceptional properties such as reproducibility, cost-effectiveness, biocompatibility, biodegradability, and universality. Generally, coupling cellulose with other nanocomposite materials enhances the properties like porosity and specific surface area. The polymer is environment-friendly, bioresorbable, and sustainable which not only justifies the requirements of a good photocatalyst but boosts the adsorption ability and degradation efficiency of the nanocomposite. Hence, knowing the role of cellulose to enhance photocatalytic activity, the present review is focused on the properties of cellulose and its application in antibiotics, textile dyes, phenol and Cr(VI) reduction, and degradation. The work also highlighted the degradation mechanism of cellulose-based photocatalysts, confirming cellulose's role as a support material to act as a sink and electron mediator, suppressing the charge carrier's recombination rate and enhancing the charge migration ability. The review also covers the latest progressions, leanings, and challenges of cellulose biomaterials-based nanocomposites in the photocatalysis field.
Subject(s)
Cellulose , Environmental Pollutants , Cellulose/chemistry , Reproducibility of Results , Polymers/chemistry , Biocompatible MaterialsABSTRACT
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.
Subject(s)
Environmental Pollutants , Environmental Restoration and Remediation , Graphite , Electricity , Physical PhenomenaABSTRACT
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.