Two‐Dimensional Microporous Material‐based Mixed Matrix Membranes for Gas Separation

Since the discovery of graphene and its derivatives, the development and application of two‐dimensional (2D) materials have attracted enormous attention. 2D microporous materials, such as metal‐organic frameworks (MOFs), covalent organic frameworks (COFs), graphitic carbon nitride (g‐C₃N₄) and so on, hold great potential to be used in gas separation membranes because of their high aspect ratio and homogeneously distributed nanometer pores, which are beneficial for improving gas permeability and selectivity. This review briefly summarizes the recent design and fabrication of 2D microporous materials, as well as their applications in mixed matrix membranes (MMMs) for gas separation. The enhanced separation performances of the membranes and their long‐term stability are also introduced. Challenges and the latest development of newly synthesized 2D microporous materials are finally discussed to foresee the potential opportunities for 2D microporous material‐based MMMs.     

Graphitic Carbon Nitride Nanoribbons: Graphene‐Assisted Formation and Synergic Function for Highly Efficient Hydrogen Evolution

The development of new promising metal‐free catalysts is of great significance for the electrocatalytic hydrogen evolution reaction (HER). Herein, a rationally assembled three‐dimensional (3D) architecture of 1D graphitic carbon nitride (g‐C₃N₄) nanoribbons with 2D graphene sheets has been developed by a one‐step hydrothermal method. Because of the multipathway of charge and mass transport, the hierarchically structured g‐C₃N₄ nanoribbon–graphene hybrids lead to a high electrocatalytic ability for HER with a Tafel slope of 54 mV decade^?1, a low onset overpotential of 80 mV and overpotential of 207 mV to approach a current of 10 mA cm^?2, superior to those non‐metal materials and well‐developed metallic catalysts reported previously. This work presents a great advance for designing and developing highly efficient metal‐free catalyst for hydrogen evolution.     

《新型二维纳米材料》专辑序言——新型二维纳米材料:掀起未来技术革命

Two-dimensional(2D) nanomaterials possess sheet-like structures with the thickness of nanoscale, but the lateral size is infinite. In 2004, Andre Geim and co-workers at the University of Manchester successfully exfoliated a sheet of graphene from graphite by the micromechanical cleavage technique, which marked the beginning of 2D nanomaterials. Given the ultrahigh carrier mobility, excellent mechanical property, good thermal stability, superior thermal conductivities and huge specific surface area of graphene, it causes general exploration of other graphene-like 2D nanomaterials.===The 2D feature is unique to access unprecedented physical, chemical, electronic and optical properties. For example, the electron confinement in two dimensions makes them ideal candidates for the fundamental study in condensed matter physics and electronic/optoelectronic devices; the large lateral size endows them with huge surface area and high exposure of active sites. Due to their unique properties, 2D nanomaterials have promising applications in energy storage and conversion, electronic devices, catalytic reaction, sensing and biomedicine. By now, nearly 20 types of 2D nanomaterials have been studied, such as graphene, graphitic carbon nitride(g-C₃N₄), transition metal dichalcogenides(TMDs), transition metal carbides/nitrides(MXenes), layered double hydroxides(LDHs), transition metal oxides(TMOs), Ⅲ to Ⅵ layered semiconductor(MX₄), and perovskite-type hybrids(AMX₃).===In this special issue of the novel 2D nanomaterials, we selected 12 related articles in reviews, research papers and brief communications involving supercapacitor, electrochemical catalysis, sensing, battery, fluorescence, water treatment and antiflaming performance of 2D nanomaterials. We hope that readers will have a deep understanding of the current development of 2D nanomaterials, and find it beneficial to their future researches.===Toward this end, I greatly appreciate the outstanding contribution of all authors, as well as the strenuous efforts from the editorial staff members.     

Recyclable catalysts for the synthesis of heterocyclic compounds using carbon materials

Heterogeneous catalytic reactions play a major role in the industry to produce a number of compounds that are essential in our daily life. Synthesis of heterocyclic compounds using heterogeneous catalysis is one of the rapidly growing research areas. Inherent ability to produce high selectivity and potentiality to recycle, the catalyst makes the heterogeneous systems more attractive, especially on the industrial scale. Various recyclable catalytic systems have been extensively developed for the synthesis of heterocyclic compounds via dehydration, partial oxidations, three-component couplings, dehydrogenations, and others. Different supports like polymers, metal oxides, and quite recently carbon supports like carbon nanotubes (CNTs), graphene oxide (GO), graphitic nitride (GCN), and nitrogenous carbon materials (NGr) have been widely used to synthesize diverse heterocycles. The use of GO in the synthesis of heterocyclic compounds has been reviewed recently, hence we did not focus on GO in this review. The aim of this review article is to explore the emerging areas of carbon-based heterogeneous materials such as CNTs, GCN, and NGr in the synthesis of heterocycles. This review also focused on the most recent examples, their preparation, and recycling studies of highly excited catalytic systems used for the heterocycles.     

Solar Light Responsive Graphitic Carbon Nitride Coupled Porphyrin Photocatalyst that Uses for Solar Fine Chemical Production

Photocatalysis is a defendable manner for production of several organic chemicals, energy and its storage from solar energy. For the evolution of metal free, cost-effective catalyst a 2D composite has been appear as a photocatalyst. Here, we had reported the synthesis of a light harvesting composite as a photocatalyst which was assembled by a poly-condensation mechanism between graphitic carbon nitride and tetrakis(4-nitrophenyl) porphyrin and the resulting composite manifest the excellent light harvesting properties, suitable energy band and low charge recombination. The photocatalyst [(NO₂)₄TPP@g-C₃N₄] enables the efficient photocatalytic production of nicotinamide adenine dinucleotide (NADH) from consumed NAD⁺ also the production of organic chemicals like 4-methoxybenzylimines from 4-methoxybenzylamines. The photocatalytic efficiency of the photocatalyst was estimated by the percentage of NADH regeneration and the percentage yield of organic transformations. It shows the tetrakis(4-nitrophenyl) porphyrin could enhance the charge transfer capacity of graphitic carbon nitride which shows excellent photocatalysis activities and organic transformations.     

Engineering carbon nanocatalysts towards efficient degradation of emerging organic contaminants via persulfate activation: A review

The engineering of carbon nanocatalysts for the persulfate activated elimination of emerging organic contaminants(EOCs) demonstrates promising potential compared with metal-based counterparts due to their unique advantage of high stability and low toxicity. The early reviews introduced the theoretical background of persulfate activation together with a detailed summary of different mechanisms responsible for degradation of EOCs. To further unify the state of knowledge, identify the research gaps...     

石墨烯基微电极的制备及其在电化学传感中的应用

微电极由于灵敏度高、响应快、样品用量少、操作简便等特点,近年来在化学分析、生物医学、食品安全、环境检测等领域引起人们的广泛关注。 石墨烯具有超高的比表面积、优异的电子迁移率及良好的生物相容性等优点,近年来在电化学传感领域展示出巨大的发展前景。 本文围绕石墨烯基微电极的制备及其在电化学传感中的应用展开,总结了近年来国内外同行基于石墨烯修饰微电极和石墨烯微电极在重金属离子、多巴胺、葡萄糖、H₂O₂等分子检测方面取得的研究成果。 同时探讨了石墨烯基微电极在电化学传感方面面临的挑战和发展前景。     

Helical Graphitic Carbon Nitrides with Photocatalytic and Optical Activities

Graphitic carbon nitride can be imprinted with a twisted hexagonal rod‐like morphology by a nanocasting technique using chiral silicon dioxides as templates. The helical nanoarchitectures promote charge separation and mass transfer of carbon nitride semiconductors, enabling it to act as a more efficient photocatalyst for water splitting and CO₂ reduction than the pristine carbon nitride polymer. This is to our knowledge a unique example of chiral graphitic carbon nitride that features both left‐ and right‐handed helical nanostructures and exhibits unique optical activity to circularly polarized light at the semiconductor absorption edge as well as photoredox activity for solar‐to‐chemical conversion. Such helical nanostructured polymeric semiconductors are envisaged to hold great promise for a range of applications that rely on such semiconductor properties as well as chirality for photocatalysis, asymmetric catalysis, chiral recognition, nanotechnology, and chemical sensing.     

Recent Applications of Carbon Nanomaterials for microRNA Electrochemical Sensing

MicroRNA (miRNA) is an important tumor marker in the human body, and its early detection has a great influence on the survival rate of patients. Although there are many detection methods for miRNA at present such as northern blotting, real-time quantitative polymerase chain reaction, microarrays, and others, electrochemical biosensors have the advantages of low detection cost, small instrument size, simple operation, non-invasive detection and low consumption of reagents and solvents, and thus they play an important role in the early detection of cancer. In addition, with the development of nanotechnology, nano-biosensors show great potential. The application of various nanomaterials in the development of electrochemical biosensor has greatly improved the detection sensitivity of electrochemical biosensor. Among them, carbon nanomaterials which have unique electrical, optical, physical and chemical properties have attracted increasing attention. In particular, they have a large surface area, good biocompatibility and conductivity. Therefore, carbon nanomaterials combined with electrochemical methods can be used to detect miRNA quickly, easily and sensitively. In this review, we systematically review recent applications of different carbon nanomaterials (carbon nanotubes, graphene and its derivatives, graphitic carbon nitride, carbon dots, graphene quantum dots and other carbon nanomaterials) for miRNA electrochemical detection. In addition, we demonstrate the future prospects of electrochemical biosensors modified by carbon nanomaterials for the detection of miRNAs, and some suggestions for their development in the near future.     

Directional Charge Transport in Layered Two‐Dimensional Triazine‐Based Graphitic Carbon Nitride

Triazine‐based graphitic carbon nitride (TGCN) is the most recent addition to the family of graphene‐type, two‐dimensional, and metal‐free materials. Although hailed as a promising low‐band‐gap semiconductor for electronic applications, so far, only its structure and optical properties have been known. Here, we combine direction‐dependent electrical measurements and time‐resolved optical spectroscopy to determine the macroscopic conductivity and microscopic charge‐carrier mobilities in this layered material “beyond graphene”. Electrical conductivity along the basal plane of TGCN is 65 times lower than through the stacked layers, as opposed to graphite. Furthermore, we develop a model for this charge‐transport behavior based on observed carrier dynamics and random‐walk simulations. Our combined methods provide a path towards intrinsic charge transport in a direction‐dependent layered semiconductor for applications in field‐effect transistors (FETs) and sensors.     

Highly crystalline and conductive nitrogen-doped mesoporous carbon with graphitic walls and its electrochemical performance

We present a rational and simple methodology to fabricate highly conductive nitrogen-doped ordered mesoporous carbon with a graphitic wall structure by the simple adjustment of the carbonization temperature of mesoporous carbon nitride without the addition of any external nitrogen sources. By simply controlling the heat-treatment temperature, the structural order and intrinsic properties such as surface area, conductivity, and pore volume, and the nitrogen content of ordered graphitic mesoporous carbon can be controlled. Among the materials studied, the sample heat-treated at 1000 °C shows the highest conductivity, which is 32 times higher than that for the samples treated at 800 °C and retains the well-ordered mesoporous structure of the parent mesoporous carbon nitride and a reasonable amount of nitrogen in the graphitic framework. Since these materials exhibit high conductivity with the nitrogen atoms in the graphitic framework, we further demonstrate their use as a support for nanoparticle fabrication without the addition of any external stabilizing or size-controlling agent, as well as the anode electrode catalysts. Highly dispersed platinum nanoparticles with a size similar to that of the pore diameter of the support can be fabricated since the nitrogen atoms and the well-ordered porous structure in the mesoporous graphitic carbon framework act as a stabilizing and size-controlling agent, respectively. Furthermore the Pt-loaded, nitrogen-doped mesoporous graphitic carbon sample with a high conductivity shows much higher anodic electrocatalytic activity than the other materials used in the study.     

Preparation of phosphorus-doped carbon nanospheres and their electrocatalytic performance for O2 reduction

Phosphorus-doped carbon nanospheres without any metal residues were synthesized and characterized.The results revealed that the doping phosphorus atoms could significantly improve the electrocatalytic activity of graphitic carbon for the oxygen-reduction reaction(ORR) both in acidic and alkaline media,and the materials exhibited high electrocatalytic activity,long-term stability,and excellent tolerance to crossover effects especially in alkaline media.Quantum mechanics calculations with the density functional theory demonstrated that the changes in charge density and energetic characteristics of frontier orbitals for the P-doped graphene sheet could facilitate the ORR.     

Recent Progress in LDH@Graphene and Analogous Heterostructures for Highly Active and Stable Photocatalytic and Photoelectrochemical Water Splitting

Photocatalytic (PC) and photoelectrochemical (PEC) water splitting is a plethora of green technological process, which transforms copiously available photon energy into valuable chemical energy. With the augmentation of modern civilization, developmental process of novel semiconductor photocatalysts proceeded at a sweltering rate, but the overall energy conversion efficiency of semiconductor photocatalysts in PC/PEC is moderately poor owing to the instability ariseing from the photocorrosion and messy charge configuration. Particularly, layered double hydroxides (LDHs) as reassuring multifunctional photocatalysts, turned out to be intensively investigated owing to the lamellar structure and exceptional physico-chemical properties. However, major drawbacks of LDHs material are its low conductivity, sluggish mass transfer and structural instability in acidic media, which hinder their applicability and stability. To surmount these obstacles, the formation of LDH@graphene and analogus heterostructures could proficiently amalgamate multi-functionalities, compensate distinct shortcomings, and endow novel properties, which ensure effective charge separation to result in stability and superior catalytic activities. Herein, we aim to summarize the currently updated synthetic strategies used to design heterostructures of 2D LDHs with 2D/3D graphene and graphene analogus material as graphitic carbon nitride (g-C₃N₄), and MoS₂ as mediator, or interlayer support, or co-catalyst or vice versa for superior PC/PEC water splitting activities along with long-term stabilities. Furthermore, latest characterization technique measuring the stability along with variant interface mode for imparting charge separation in LDH@graphene and graphene analogus heterostructure has been identified in this field of research with understanding the intrinsic structural features and activities.     

Molecularly defined graphitic interface toward proton manipulation

Proton plays a critical role in electrochemical systems to control electrochemical reactivity or isotopic enrichment. Graphene is intensively investigated owing to its unique electronic structure and device fabrication. Through the structural tunability of graphitic materials by chemical or physical modification of the surface, graphene is revealed to be an ideal material for proton manipulation. Here, we review the use of graphene or graphitic materials toward the manipulation of proton with regard to the following three points. (1) Electronic properties of graphene: The electronic band structure of graphene can be modified by metal contacts owing to the interaction with a metal surface. (2) Molecular control of graphitic interface: The chemical structure of graphene can be modified, as is done in molecular chemistry, and can be used as a catalytic platform. (3) Proton conduction by graphene: Proton transport through a graphene layer occurs with a unique mechanism such as tunneling. We provide a perspective on the use of graphitic materials toward controlling the behavior of protons on the basis of the aforementioned points. From the above, graphene can be used as a platform for proton manipulation.     

Smart nano-architectures as potential sensing tools for detecting heavy metal ions in aqueous matrices

The discharge of heavy metal ions into water resources as a result of human activities has become a global issue. Contamination with heavy metal ions poses a major threat to the environment and human health. Therefore, there is a dire need to probe the presence of heavy metal ions in a more selective, facile, quick, cost-effective and sensitive way. Conventional sensors are being utilized to sense heavy metal ions; however, various challenges and limitations like interference, overlapping of oxidation potential, selectivity and sensitivity are associated with them that limit their in-field applicability. Hence, nanomaterial based chemical sensors have emerged as an alternative substitute and are extensively employed for the detection of heavy metal ions as a potent analytical tool. The incorporation of nanomaterials in sensors increases their sensitivity, selectivity, portability, on-site detection capability and device performance. Nanomaterial based electrodes exhibit enhanced performance because surface of electrode at nano-scale level offers high catalytic potential, large active surface area and high conductivity. Therefore, this review addresses the recent progress on chemical sensors based on different nanomaterials such as carbon nanotubes (CNTs), metal nanoparticles, graphene, carbon quantum dots and nanocomposites for sensing heavy metals ions using different sensing approaches. Furthermore, various types of optical sensors such as fluorescence, luminescence and colorimetry sensors have been presented in detail.     

Triazine‐Based Graphitic Carbon Nitride: a Two‐Dimensional Semiconductor

Graphitic carbon nitride has been predicted to be structurally analogous to carbon‐only graphite, yet with an inherent bandgap. We have grown, for the first time, macroscopically large crystalline thin films of triazine‐based, graphitic carbon nitride (TGCN) using an ionothermal, interfacial reaction starting with the abundant monomer dicyandiamide. The films consist of stacked, two‐dimensional (2D) crystals between a few and several hundreds of atomic layers in thickness. Scanning force and transmission electron microscopy show long‐range, in‐plane order, while optical spectroscopy, X‐ray photoelectron spectroscopy, and density functional theory calculations corroborate a direct bandgap between 1.6 and 2.0 eV. Thus TGCN is of interest for electronic devices, such as field‐effect transistors and light‐emitting diodes.     

Transition‐Metal‐Ion‐Mediated Polymerization of Dopamine: Mussel‐Inspired Approach for the Facile Synthesis of Robust Transition‐Metal Nanoparticle–Graphene Hybrids

Inspired by the high transition‐metal‐ion content in mussel glues, and the cross‐linking and mechanical reinforcement effects of some transition‐metal ions in mussel threads, high concentrations of nickel(II), cobalt(II), and manganese(II) ions have been purposely introduced into the reaction system for dopamine polymerization. Kinetics studies were conducted for the Ni²⁺–dopamine system to investigate the polymerization mechanism. The results show that the Ni²⁺ ions could accelerate the assembly of dopamine oligomers in the polymerization process. Spectroscopic and electron microscopic studies reveal that the Ni²⁺ ions are chelated with polydopamine (PDA) units, forming homogeneous Ni²⁺–PDA complexes. This facile one‐pot approach is utilized to construct transition‐metal‐ion–PDA complex thin coatings on graphene oxide, which can be carbonized to produce robust hybrid nanosheets with well‐dispersed metallic nickel/metallic cobalt/manganese(II) oxide nanoparticles embedded in PDA‐derived thin graphitic carbon layers. The nickel–graphene hybrid prepared by using this approach shows good catalytic properties and recyclability for the reduction of p ‐ nitrophenol.     

二维石墨相氮化碳纳米片的制备及其在光催化领域的研究进展

二维(2D)层状石墨型氮化碳纳米片(CNNS)由于具有各向异性的2D几何形态和芳香族p-π共轭骨架,高度开放的平面结构、超高的比表面积、增强的电子迁移速率和与层厚度相关可调的半导体带隙等特征,是目前2D层状材料的研究热点之一。 本文综述了近年来氮化碳纳米片的各种制备方法、功能化改性和应用,涉及环保、能源转换及生物传感等领域。 最后指出进一步探索制备高质量氮化碳纳米片的新方法以及拓展其在光催化领域的应用是未来研究的重点。     

Exfoliation of Crystalline 2D Carbon Nitride: Thin Sheets,Scrolls and Bundles via Mechanical and Chemical Routes

The carbon nitride poly(triazine imide) with intercalated bromide ions is a layered, graphitic material of 2D covalently bonded molecular sheets with an exceptionally large gallery height of 3.52 Å due to the intercalated bromide anions. The material can be cleaved both mechanically and chemically into thin sheets and scrolls analogous to the carbon‐only systems graphite and graphene.

     

Rational Design of Carbon-Based 2D Nanostructures for Enhanced Photocatalytic CO2 Reduction: A Dimensionality Perspective

Photocatalytic CO₂ reduction is a revolutionary approach to solve imminent energy and environmental issues by replicating the ingenuity of nature. The past decade has witnessed an impetus in the rise of two-dimensional (2D) structure materials as advanced nanomaterials to boost photocatalytic activities. In particular, the use of 2D carbon-based materials is deemed as highly favorable, not only as a green material choice, but also due to their exceptional physicochemical and electrical properties. This Review article presents a diverse range of alterations and compositions derived from 2D carbon-based nanomaterials, mainly graphene and graphitic carbon nitride (g-C₃N₄), which have remarkably ameliorated the photocatalytic CO₂ performance. Herein, the rational design of the photocatalyst systems with consideration of the aspect of dimensionality and the resultant heterostructures at the interface are systematically analyzed to elucidate an insightful perspective on this pacey subject. Finally, a conclusion and outlook on the limitations and prospects of the cutting-edge research field are highlighted.