Hydrogen-bonded organic frameworks for membrane separation.

Hydrogen-bonded organic frameworks (HOFs) are a new class of crystalline porous materials that are formed through the interconnection of organic or metal-organic building units via intermolecular hydrogen bonds. The remarkable flexibility and reversibility of hydrogen bonds, coupled with the customizable nature of organic units, endow HOFs with mild synthesis conditions, high crystallinity, solvent processability, and facile self-healing and regeneration properties. Consequently, these features have garnered significant attention across various fields, particularly in the realm of membrane separation. Herein, we present an overview of the recent advances in HOF-based membranes, including their advanced fabrication strategies and fascinating applications in membrane separation. To attain the desired HOF-based membranes, careful consideration is dedicated to crucial factors such as pore size, stability, hydrophilicity/hydrophobicity, and surface charge of the HOFs. Additionally, diverse preparation methods for HOF-based membranes, including blending, in situ growth, solution-processing, and electrophoretic deposition, have been analyzed. Furthermore, applications of HOF-based membranes in gas separation, water treatment, fuel cells, and other emerging application areas are presented. Finally, the challenges and prospects of HOF-based membranes are critically pointed out.

MOF-Based Photocatalytic Membrane for Water Purification: A Review.

Photocatalytic membranes can effectively integrate membrane separation and photocatalytic degradation processes to provide an eco-friendly solution for efficient water purification. It is of great significance to develop highly efficient photocatalytic membranes driven by visible light to ensure the long-term stability of membrane separation systems and the maximum utilization of solar energy. Metal-organic framework (MOF) is an emerging photocatalyst with a well-defined structure and tunable chemical properties, showing a broad application prospect in the construction of high-performance photocatalytic membranes. Herein, this work provides a comprehensive review of recent advancements in MOF-based photocatalytic membranes. Initially, this work outlines the main tailoring strategies that facilitate the enhancement of the photocatalytic activity of MOF-based photocatalysts. Next, this work introduces commonly used methods for fabricating MOF-based photocatalytic membranes. Subsequently, this work discusses the application and mechanisms of MOF-based photocatalytic membranes toward organic pollutant degradation, metal ion removal, and membrane fouling mitigation. Finally, challenges in developing MOF-based photocatalytic membranes and their practical applications are presented, while also pointing out future research directions toward overcoming these existing limitations.

Assembling 99% MOFs into Bioinspired Rigid-Flexible Coupled Membrane with Significant Permeability: The Impacts of Defects.

Assembling metal-organic frameworks (MOFs) into high-performance macroscopic membranes is crucial but still challenging. MOF-containing hybrid membranes can effectively integrate the advantages of flexible guest materials and MOFs. Nevertheless, the inherent limitations in fully harnessing the distinct characteristics of MOFs persist due to the substantial guest material content necessitated in membrane fabrication. Herein, inspired by the rigid and flexible structures in biological systems, rigid MIP-202(Zr) and defective MIP-202(Zr) (D-MIP-202(Zr)) modified flexible graphene oxide (GO) sheets are synthesized in situ and then assembled into a rigid-flexible coupled MOF-based membrane. The defects in D-MIP-202(Zr) are introduced by using acetic acid as the modulation agent. The obtained GO@MIP-202(Zr) membrane possesses a hierarchical porous structure with a 99 wt% MOF proportion, which is higher than the GO@D-MIP-202(Zr) (75 wt%) membrane with a compact bulge-structured surface. The water permeability of the GO@MIP-202(Zr) membrane attains remarkedly 5762.92 L h-1 m-2 bar-1 , which is 960 and 2.6 times higher than that of the GO membrane and GO@D-MIP-202(Zr) membrane. Additionally, benefiting from the superhydrophilicity and underwater superoleophobicity, the resultant membrane not only demonstrates high rejection for oil-water emulsions but also exhibits exceptional recyclability and anti-fouling ability. These findings provide valuable insights into the assembly of MOFs into high-performance membranes.

Carbonaceous Materials-Based Photothermal Process in Water Treatment: From Originals to Frontier Applications.

The photothermal process has attracted considerable attention in water treatment due to its advantages of low energy consumption and high efficiency. In this respect, photothermal materials play a crucial role in the photothermal process. Particularly, carbonaceous materials have emerged as promising candidates for this process because of exceptional photothermal performance. While previous research on carbonaceous materials has primarily focused on photothermal evaporation and sterilization, there is now a growing interest in exploring the potential of photothermal effect-assisted advanced oxidation processes (AOPs). However, the underlying mechanism of the photothermal effect assisted by carbonaceous materials remains unclear. This review aims to provide a comprehensive review of the photothermal process of carbonaceous materials in water treatment. It begins by introducing the photothermal properties of carbonaceous materials, followed by a discussion on strategies for enhancing these properties. Then, the application of carbonaceous materials-based photothermal process for water treatment is summarized. This includes both direct photothermal processes such as photothermal evaporation and sterilization, as well as indirect photothermal processes that assisted AOPs. Meanwhile, various mechanisms assisted by the photothermal effect are summarized. Finally, the challenges and opportunities of using carbonaceous materials-based photothermal processes for water treatment are proposed.

Covalent Organic Framework/Graphene Hybrids: Synthesis, Properties, and Applications.

To address current energy crises and environmental concerns, it is imperative to develop and design versatile porous materials ideal for water purification and energy storage. The advent of covalent organic frameworks (COFs), a revolutionary terrain of porous materials, is underscored by their superlative features such as divinable structure, adjustable aperture, and high specific surface area. However, issues like inferior electric conductivity, inaccessible active sites impede mass transfer and poor processability of bulky COFs restrict their wider application. As a herculean stride forward, COF/graphene hybrids amalgamate the strengths of their constituent components and have in consequence, enticed significant scientific intrigue. Herein, the current progress on the structure and properties of graphene-based materials and COFs are systematically outlined. Then, synthetic strategies for preparing COF/graphene hybrids, including one-pot synthesis, ex situ synthesis, and in situ growth, are comprehensively reviewed. Afterward, the pivotal attributes of COF/graphene hybrids are dissected in conjunction with their multifaceted applications spanning adsorption, separation, catalysis, sensing, and energy storage. Finally, this review is concluded by elucidating prevailing challenges and gesturing toward prospective strides within the realm of COF/graphene hybrids research.

Recent Advancement in Emerging MXene-Based Photocatalytic Membrane for Revolutionizing Wastewater Treatment.

MXene-based photocatalytic membranes provide significant benefits for wastewater treatment by effectively combining membrane separation and photocatalytic degradation processes. MXene represents a pioneering 2D photocatalyst with a variable elemental composition, substantial surface area, abundant surface terminations, and exceptional photoelectric performance, offering significant advantages in producing high-performance photocatalytic membranes. In this review, an in-depth overview of the latest scientific progress in MXene-based photocatalytic membranes is provided. Initially, a brief introduction to the structure and photocatalytic capabilities of MXene is provided, highlighting their pivotal role in promoting the photocatalytic process. Subsequently, in pursuit of the optimal MXene-based photocatalytic membrane, critical factors such as the morphology, hydrophilicity, and stability of MXenes are meticulously taken into account. Various preparation strategies for MXene-based photocatalytic membranes, including blending, vacuum filtration, and dip coating, are also discussed. Furthermore, the application and mechanism of MXene-based photocatalytic membranes in micropollutant removal, oil-water separation, and antibacterial are examined. Lastly, the challenges in the development and practical application of MXene-based photocatalytic membranes, as well as their future research direction are delineated.

Thiol-Ene Click Reaction in Constructing Liquid Separation Membranes for Water Treatment.

In the evolving landscape of water treatment, membrane technology has ascended to an instrumental role, underscored by its unmatched efficacy and ubiquity. Diverse synthesis and modification techniques are employed to fabricate state-of-the-art liquid separation membranes. Click reactions, distinguished by their rapid kinetics, minimal byproduct generation, and simple reaction condition, emerge as a potent paradigm for devising eco-functional materials. While the metal-free thiol-ene click reaction is acknowledged as a viable approach for membrane material innovation, a systematic elucidation of its applicability in liquid separation membrane development remains conspicuously absent. This review elucidates the pre-functionalization strategies of substrate materials tailored for thiol-ene reactions, notably highlighting thiolation and introducing unsaturated moieties. The consequential implications of thiol-ene reactions on membrane properties-including trade-off effect, surface wettability, and antifouling property-are discussed. The application of thiol-ene reaction in fabricating various liquid separation membranes for different water treatment processes, including wastewater treatment, oil/water separation, and ion separation, are reviewed. Finally, the prospects of thiol-ene reaction in designing novel liquid separation membrane, including pre-functionalization, products prediction, and solute-solute separation membrane, are proposed. This review endeavors to furnish invaluable insights, paving the way for expanding the horizons of thiol-ene reaction application in liquid separation membrane fabrication.

Covalent Organic Frameworks: The Rising-Star Platforms for the Design of CO2 Separation Membranes.

Membrane-based carbon dioxide (CO2 ) capture and separation technologies have aroused great interest in industry and academia due to their great potential to combat current global warming, reduce energy consumption in chemical separation of raw materials, and achieve carbon neutrality. The emerging covalent organic frameworks (COFs) composed of organic linkers via reversible covalent bonds are a class of porous crystalline polymers with regular and extended structures. The inherent structure and customizable organic linkers give COFs high and permanent porosity, short transport channel, tunable functionality, and excellent stability, thereby enabling them rising-star alternatives for developing advanced CO2 separation membranes. Therefore, the promising research areas ranging from development of COF membranes to their separation applications have emerged. Herein, this review first introduces the main advantages of COFs as the state-of-the-art membranes in CO2 separation, including tunable pore size, modifiable surfaces property, adjustable surface charge, excellent stability. Then, the preparation approaches of COF-based membranes are systematically summarized, including in situ growth, layer-by-layer stacking, blending, and interface engineering. Subsequently, the key advances of COF-based membranes in separating various CO2 mixed gases, such as CO2 /CH4 , CO2 /H2 , CO2 /N2 , and CO2 /He, are comprehensively discussed. Finally, the current issues and further research expectations in this field are proposed.

Ultrahigh Performance H2 O2 Generation by Single-Atom Fe Catalysts with N/O Bidentate Ligand via Oxalic Acid and Oxygen Molecules Activation.

Single-atom catalysts (SACs) for photocatalytic hydrogen peroxide (H2 O2 ) generation are researched but it is still challenging to obtain high H2 O2 yields. Herein, graphite carbon nitride (FeSA /CN) confined single Fe atoms with N/O coordination is prepared, and FeSA /CN shows high H2 O2 production via oxalic acid and O2 activation. Under visible light illumination, the concentration of H2 O2 generated by FeSA /CN can achieve 40.19 mM g-1 h-1 , which is 10.44 times higher than that of g-C3 N4 . The enhanced H2 O2 generation can be attributed to the formation of metal-organic complexes and rapid electron transfer. Moreover, the O2 activation of photocatalysts is revealed by 3,3',5,5'-tetramethylbenzidine oxidation. The results display that the O2 activation capacity of FeSA /CN is higher than that of g-C3 N4 , which facilitates the formation of H2 O2 . Finally, density functional theory calculation demonstrates that O2 is chemically adsorbed on Fe atomic sites. The adsorption energy of O2 is enhanced from -0.555 to -1.497 eV, and the bond length of OO is extended from 1.235 to 1.292 Å. These results exhibit that the confinement of single Fe atoms can promote O2 adsorption and activation. Finally, the photocatalytic mechanism is elaborated, which provides a deep understanding for SACs-catalyzed H2 O2 generation.

Advances in technology and utilization of natural resources for achieving carbon neutrality and a sustainable solution to neutral environment.

The greatest environmental issue of the twenty-first century is climate change. Human-caused greenhouse gas emissions are increasing the frequency of extreme weather. Carbon dioxide (CO2) accounts for 80% of human greenhouse gas emissions. However, CO2 emissions and global temperature have risen steadily from pre-industrial times. Emissions data are crucial for most carbon emission policymaking and goal-setting. Sustainable and carbon-neutral sources must be used to create green energy and fossil-based alternatives to reduce our reliance on fossil fuels. Near-real-time monitoring of carbon emissions is a critical national concern and cutting-edge science. This review article provides an overview of the many carbon accounting systems that are now in use and are based on an annual time frame. The primary emphasis of the study is on the recently created carbon emission and eliminating sources and technology, as well as the current application trends for carbon neutrality. We also propose a framework for the most advanced naturally available carbon neutral accounting sources capable of being implemented on a large scale. Forming relevant data and procedures will help the "carbon neutrality" plan decision-making process. The formation of pertinent data and methodologies will give robust database support to the decision-making process for the "carbon neutrality" plan for the globe. In conclusion, this article offers some opinions, opportunities, challenges and future perspectives related to carbon neutrality and carbon emission monitoring and eliminating resources and technologies.

MXenes as Superexcellent Support for Confining Single Atom: Properties, Synthesis, and Electrocatalytic Applications.

Single atom catalysts (SACs) have shown their noticeable potential and gradually become a new favorite in catalytic field due to the particular selectivity, high catalytic performance, and strong durability. The most important factor in the synthesis of SACs is the selection of appropriate support and formation of metal-support interaction. Among a large number of nanomaterials, MXenes can be utilized as benign supports for fixing SACs because of their expansive specific surface area, regulable bandgap, superior electronic conductivity, and strong mechanical stability. The structure and property of MXenes can be manipulated by changing transition metal elements and surface termination. Here, the uniqueness and superiority of MXenes as superexcellent supports for confining SACs are analyzed from structure and property. The synthetic strategy of MXene-supported SACs is also summarized, especially emphasizing the immobilization of isolated atom against aggregation by utilizing the formidable metal-support covalent coordination interaction. In addition, the applications of MXene-supported SACs in electrocatalytic field are highlighted, including hydrogen evolution reaction, oxygen evolution reaction, overall water splitting, oxygen reduction reaction, and nitrogen reduction reaction. Finally, the challenges and prospects are pointed out for the further understanding and practical application of MXene-supported SACs in electrocatalysis.

Recent development of advanced biotechnology for wastewater treatment.

The importance of highly efficient wastewater treatment is evident from aggravated water crises. With the development of green technology, wastewater treatment is required in an eco-friendly manner. Biotechnology is a promising solution to address this problem, including treatment and monitoring processes. The main directions and differences in biotreatment process are related to the surrounding environmental conditions, biological processes, and the type of microorganisms. It is significant to find suitable biotreatment methods to meet the specific requirements for practical situations. In this review, we first provide a comprehensive overview of optimized biotreatment processes for treating wastewater during different conditions. Both the advantages and disadvantages of these biotechnologies are discussed at length, along with their application scope. Then, we elaborated on recent developments of advanced biosensors (i.e. optical, electrochemical, and other biosensors) for monitoring processes. Finally, we discuss the limitations and perspectives of biological methods and biosensors applied in wastewater treatment. Overall, this review aims to project a rapid developmental path showing a broad vision of recent biotechnologies, applications, challenges, and opportunities for scholars in biotechnological fields for "green" wastewater treatment.

Recent advances in covalent organic frameworks (COFs) as a smart sensing material.

As a newly emerging kind of porous material, covalent organic frameworks (COFs) have drawn much attention because of their fascinating structural features (e.g., divinable structure, adjustable porosity and total organic backbone). Since the seminal work of Yaghi and co-workers reported in 2005, the COF materials have shown superior potential in diverse applications, such as gas storage, adsorption, optoelectronics, catalysis, etc. Recently, COF materials have shown a new trend in sensing fields. This critical review briefly describes the synthesis routes for COF powders and thin films. What's more, the most fascinating and significant applications of COFs in sensing fields including explosive sensing, humidity sensing, pH detection, biosensing, gas sensing, metal ion sensing, and other substance sensing are summarized and highlighted. Finally, the major challenges and future trends of COFs with respect to their preparation and sensing applications are discussed.

Peroxidase-Like Activity of Smart Nanomaterials and Their Advanced Application in Colorimetric Glucose Biosensors.

Diabetes is a dominating health issue with 425 million people suffering from the disease worldwide and 4 million deaths each year. To avoid further complications, the diabetic patient blood glucose level should be strictly monitored despite there being no cure for diabetes. Colorimetric biosensing has attracted significant attention because of its low cost, simplicity, and practicality. Recently, some nanomaterials have been found that possess unexpected peroxidase-like activity, and great advances have been made in fabricating colorimetric glucose biosensors based on the peroxidase-like activity of these nanomaterials using glucose oxidase. Compared with natural horseradish peroxidase, the nanomaterials exhibit flexibility in structure design and composition, and have easy separation and storage, high stability, simple preparation, and tunable catalytic activity. To highlight the significant progress in the field of nanomaterial-based peroxidase-like activity, this work discusses the various smart nanomaterials that mimic horseradish peroxidase and its mechanism and development history, and the applications in colorimetric glucose biosensors. Different approaches for tunable peroxidase-like activity of nanomaterials are summarized, such as size, morphology, and shape; surface modification and coating; and metal doping and alloy. Finally, the conclusion and challenges facing peroxidase-like activity of nanomaterials and future directions are discussed.

Black Phosphorus, a Rising Star 2D Nanomaterial in the Post-Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications.

Semiconductor photocatalysis, a sustainable and renewable technology, is deemed to be a new path to resolve environmental pollution and energy shortage. The development of effective photocatalysts, especially the metal-free photocatalysts, is a critical determinant of this technique. The recently emerged 2D material of black phosphorus with distinctive properties of tunable direct bandgap, ultrahigh charge mobility, fortified optical absorption, large specific surface area, and anisotropic structure has captured enormous attention since the first exfoliation of bulk black phosphorus into mono- or few layered phosphorene in 2014. In this article, the state-of-the-art preparation methods are first summarized for bulk black phosphorus, phosphorene, and black phosphorus quantum dot and then the fundamental structure and electronic and optical properties are analyzed to evaluate its feasibility as a metal-free photocatalyst. Various modifications on black phosphorus are also summarized to enhance its photocatalytic performance. Furthermore, the multifarious applications such as solar to energy conversion, organic removal, disinfection, nitrogen fixation, and photodynamic therapy are discussed and some of the future challenges and opportunities for black phosphorus research are proposed. This review reveals that the rising star of black phosphorus will be a multifunctional material in the postgraphene era.

Electrochemical biosensor for amplified detection of Pb2+ based on perfect match of reduced graphene oxide-gold nanoparticles and single-stranded DNAzyme.

In this study, a sensitive amplification strategy for Pb2+ detection using reduced graphene oxide (RGO) and gold nanoparticles (AuNPs) was proposed. Thiol-modified DNAzyme is specific for Pb2+ self-assembly on RGO-AuNPs-modified electrode surface. Ferrocene labeled single-stranded DNAzyme (Fc-ssDNAzyme) self-hybridizes to form a DNA hairpin structure. The amount of Fc adsorbed on the electrode surface changes after the appearance of Pb2+, leading to a change of electrical signal. This change can be sensitively identified by differential pulse voltammetry (DPV) assisted by ferricyanide ([Fe(CN)6]3-/4-) in the electrolyte. The high conductivity and specific surface area of RGO and the strong chemical bond adsorption effect between DNAzyme and AuNPs are responsible for the amplified detection of Pb2+, which realize a detection range of 0.05-400,000.0 nM and a minimum detection limit of 0.015 nM. Moreover, the selectivity test results indicated that the biosensor had specificity for Pb2+, even if there was interference from other high-concentration metal ions. This simple biosensor also exhibited good responsiveness in actual sample detection, which provides a good application prospect for field detection of Pb2+ in water. Graphical abstract.

Colorimetric determination of mercury(II) using gold nanoparticles and double ligand exchange.

A colorimetric assay is described for highly selective and sensitive determination of Hg(II) ions by using gold nanoparticles (AuNPs) functionalized with dithioerythritol (DETL). This method relies on the unique optical properties of DETL-functionalized AuNPs as well as the thiophilicity of both AuNPs and Hg(II). In the presence of DETL, the AuNPs aggregate due to ligand exchange between thiol groups of DETL and the citrate ions on the surface of AuNPs. This induces a color change from red to blue. On addition of Hg(II), the thiol groups preferably interact with Hg(II) rather than with AuNPs. Thus, the DETL is released from the surface of the AuNPs and binds to Hg(II). This triggers the redispersion of the AuNPs. The ratio of absorbances at 650 and 525 nm drops linearly in two Hg(II) concentration ranges (viz. from 0.1 to 0.5 µM, and from 0.5 to 5 µM). The ions Cu(II), Pb(II), and Cd(II) do not interfere even in the absence of masking agents. The detection limit is as low as 24 nM. Graphical abstract A highly selective colorimetric method based on gold nanoparticles via double ligand exchange reaction is described for determination of Hg2+. This assay can selective detect Hg2+ with no response to major interfering metal ions such as Cu2+, Pb2+, and Cd2+ in the absence of masking agents compared with previous works.

Atomically dispersed dual-atom catalysts: A new rising star in environmental remediation.

Single-atom catalysts, characterized by individual metal atoms as active centers, have emerged as promising candidates owing to their remarkable catalytic efficiency, maximum atomic utilization efficiency, and robust stability. However, the limitation of single-atom catalysts lies in their inability to cater to multistep reactions using a solitary active site. Introducing an additional metal atom can amplify the number of active sites, modulate the electronic structure, bolster adsorption ability, and enable a gamut of core reactions, thus augmenting their catalytic prowess. As such, dual-atom catalysts have risen to prominence. However, a comprehensive review elucidating the realm of dual-atom catalysts in environmental remediation is currently lacking. This review endeavors to bridge this gap, starting with a discourse on immobilization techniques for dual-atom catalysts, which includes configurations such as adjacent atoms, bridged atoms, and co-facially separated atoms. The review then delves into the intrinsic activity mechanisms of these catalysts, elucidating aspects like adsorption dynamics, electronic regulation, and synergistic effects. Following this, a comprehensive summarization of dual-atom catalysts for environmental applications is provided, spanning electrocatalysis, photocatalysis, and Fenton-like reactions. Finally, the existing challenges and opportunities in the field of dual-atom catalysts are extensively discussed. This work aims to be a beacon, illuminating the path towards the evolution and adoption of dual-atom catalysts in environmental remediation.

Mxenes for membrane separation: from fabrication strategies to advanced applications.

Transition metal carbides/nitrides/carbonitrides, commonly referred to as MXenes, have gained widespread attention since their discovery in 2011 as a promising family of two-dimensional (2D) materials. Their impressive chemical, electrical, thermal, mechanical, and biological properties have fueled a surge in research focused on the synthesis and application of MXenes in various fields, including membrane-based separation. By engineering the materials and membrane structures, MXene-based membranes have demonstrated remarkable separation performance and added functionalities, such as antifouling and photocatalytic properties. In this review, we aim to have a timely and critical review of research on their fabrication strategy and performance in advanced molecular separation and ion exchange, beginning with a brief introduction of the preparation and physicochemical properties of MXenes. Finally, outlooks and future works are outlined with the aims to provide valuable insights and guidance for advancing membranes' applications in different separation domains.

Molecular oxygen activation: Innovative techniques for environmental remediation.

Molecular oxygen as a green, non-toxic, and inexpensive oxidant has displayed numerous advantages compared with other oxidants for more sustainable and environmentally benign pollutant degradation. Molecular oxygen activation stands as a groundbreaking approach in advanced oxidation processes, offering efficient environmental remediation with minimal environmental impact with the production of high-oxidation reactive oxygen species (ROS). The adaptability and energy efficiency of molecular oxygen activation significantly contribute to the progression of sustainable water remediation technologies. This review meticulously explores the principles and mechanisms of molecular oxygen activation, shedding light on the diverse ROS production pathways. Subsequently, this review comprehensively details contemporary activation approaches, including photocatalytic activation, electrocatalytic activation, piezoelectric activation, and photothermal activation, explicating their distinct activation mechanisms. Additionally, it delves into the promising applications of molecular oxygen activation in the degradation of water pollutants, primary air pollutants, and volatile organic compounds, providing an in-depth analysis of the associated degradation pathways and mechanisms. Moreover, this review also addresses the imminent challenges and emerging opportunities in environmental remediation. It is envisioned that this comprehensive analysis will spur ongoing exploration and innovation in the use of molecular oxygen activation for environmental remediation and beyond.