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.     

Two‐Dimensional Covalent Organic Frameworks for Carbon Dioxide Capture through Channel‐Wall Functionalization

Ordered open channels found in two‐dimensional covalent organic frameworks (2D COFs) could enable them to adsorb carbon dioxide. However, the frameworks’ dense layer architecture results in low porosity that has thus far restricted their potential for carbon dioxide adsorption. Here we report a strategy for converting a conventional 2D COF into an outstanding platform for carbon dioxide capture through channel‐wall functionalization. The dense layer structure enables the dense integration of functional groups on the channel walls, creating a new version of COFs with high capacity, reusability, selectivity, and separation productivity for flue gas. These results suggest that channel‐wall functional engineering could be a facile and powerful strategy to develop 2D COFs for high‐performance gas storage and separation.     

A New Dimension in Separation Science: Comprehensive Two‐Dimensional Gas Chromatography

The introduction and development of comprehensive two‐dimensional gas chromatography offers greatly enhanced resolution and identification of organic analytes in complex mixtures compared to any one‐dimensional separation technique. Initially promoted by the need to resolve highly complex petroleum samples, the technique’s enormous separation power and enhanced ability to gather information has rapidly attracted the attention of analysts from all scientific fields. In this Minireview, we highlight the fundamental theory, recent advances, and future trends in the instrumentation and application of comprehensive two‐dimensional column separation.     

Controllable Synthesis of Hexagonal WO3 Nanoplates for Efficient Visible‐Light‐Driven Photocatalytic Oxygen Production

Facilitating charge‐carrier separation and transfer is fundamentally important to improve the photocatalytic performance of semiconductor materials. Herein, two‐dimensional hexagonal WO₃ nanoplates were synthesized by a two‐step route: rapid evaporation and solid‐phase sintering. The as‐prepared WO₃ exhibits an enhanced activity of photocatalytic water oxidation compared to bulk monoclinic WO₃. The electron dynamics analysis reveals that a more efficient charge‐carrier separation in the former can be obtained, the origin of which can be attributed to an increased number of surface defects in hexagonal WO₃ nanoplates. This work not only presents a novel and simple method to produce two‐dimensional hexagonal WO₃ nanoplates, but also demonstrates that surface defects and two‐dimensional geometric structures can promote the charge separation, which may be extended to the design of other efficient photocatalysts.     

Template‐ and Metal‐Free Synthesis of Nitrogen‐Rich Nanoporous “Noble” Carbon Materials by Direct Pyrolysis of a Preorganized Hexaazatriphenylene Precursor

The targeted thermal condensation of a hexaazatriphenylene‐based precursor leads to porous and oxidation‐resistant (“noble”) carbons. Simple condensation of the pre‐aligned molecular precursor produces nitrogen‐rich carbons with C₂N‐type stoichiometry. Despite the absence of any porogen and metal species involved in the synthesis, the specific surface areas of the molecular carbons reach up to 1000 m² g^?1 due to the significant microporosity of the materials. The content and type of nitrogen species is controllable by the carbonization temperature whilst porosity remains largely unaffected at the same time. The resulting noble carbons are distinguished by a highly polarizable micropore structure and have thus high adsorption affinity towards molecules such as H₂O and CO₂. This molecular precursor approach opens new possibilities for the synthesis of porous noble carbons under molecular control, providing access to the special physical properties of the C₂N structure and extending the known spectrum of classical porous carbons.     

Preparation and Characterization of Adsorption-Selective Carbon Membranes for Gas Separation

The preparation and characterisation of adsorption-selective carbon membranes (ASCMs) is described. ASCMs can separate the components of a gas mixture depending on their adsorption strength. These membranes allow the separation of non-adsorbable or weakly adsorbable components (e.g. N₂, H₂, O₂, etc) from the more strongly adsorbable components (e.g. hydrocarbons) in a gas mixture. They are prepared from the deposition of a thin film of a phenolic resin on the inner face of an alumina tube. Air oxidative treatment at temperatures in the range of 300–400°C, prior to carbonisation (pre-oxidation) or after carbonisation (under vacuum at 700°C) (post-oxidation) gives rise to an adsorption-selective carbon membrane. This membrane shows a high permeability and selectivity towards the separation of gas mixtures formed by hydrocarbons and N₂. Taking into account the permeation and separation properties of the membranes, post-oxidation treatment is shown to be more effective than pre-oxidation. The separation characteristics of the carbon membranes are dependent on the composition of the gas mixture (i.e. proportion of more strongly adsorbable components) and temperature.     

Pseudo‐Membrane Jackets: Two‐Dimensional Coordination Polymers Achieving Visible Phase Separation in Cell Membrane

Cell membranes contain lateral systems that consist of various lipid compositions and actin cytoskeleton, providing two‐dimensional (2D) platforms for chemical reactions. However, such complex 2D environments have not yet been used as a synthetic platform for artificial 2D nanomaterials. Herein, we demonstrate the direct synthesis of 2D coordination polymers (CPs) at the liquid‐cell interface of the plasma membrane of living cells. The coordination‐driven self‐assembly of networking metal complex lipids produces cyanide‐bridged CP layers with metal ions, enabling “pseudo‐membrane jackets” that produce long‐lived micro‐domains with a size of 1–5 μm. The resultant artificial and visible phase separation systems remain stable even in the absence of actin skeletons in cells. Moreover, we show the cell application of the jackets by demonstrating the enhancement of cellular calcium response to ATP.     

甲烷二氧化碳转化制备富含一氧化碳合成气

研究了甲烷二氧化碳转化反应的热力学特性,计算了反应平衡常数及平衡组成,分析和确定了抑制积碳的生成条件,采用固定床流动和脉冲反应装置研究了Ni/Al_2O_3催化剂对甲烷二氧化碳转化的催化性能。     

在多孔γ-Al2O3氧化铝载体上微波合成NaA分子筛膜及气体渗透分离性能

The paper presented novel synthesis of NaA zeolite membrane with good performance using microwave heating. The method involved two steps, prior seeding 120 nm of LTA crystals on substrate and then employing a secondary hydrothermal synthesis. Effects of seeding times, synthesis time and synthesis times were investigated in this work. The quality evaluation of membranes respectively used single component gases (HE and N2) and H2/N2 (equivalent volume) mixture. The ideal H2,/N2 selectivity increased from 1.90 of the substrate to 6.37 of the three-stage synthesized membrane, which was distinctly higher than the corresponding Knudsen diffusion selectivity of 3.74. However, the real H2/N2 selectivity of the three-stage synthesis was much lower than the corresponding ideal selectivity and close to the corresponding Knudsen diffusion selectivity of 3.74.     

A Highly Permeable Aligned Montmorillonite Mixed‐Matrix Membrane for CO2 Separation

Highly permeable montmorillonite layers bonded and aligned with the chain stretching orientation of polyvinylamineacid are immobilized onto a porous polysulfone substrate to fabricate aligned montmorillonite/polysulfone mixed‐matrix membranes for CO₂ separation. High‐speed gas‐transport channels are formed by the aligned interlayer gaps of the modified montmorillonite, through which CO₂ transport primarily occurs. High CO₂ permeance of about 800 GPU is achieved combined with a high mixed‐gas selectivity for CO₂ that is stable over a period of 600 h and independent of the water content in the feed.     

Thermal‐ and Photo‐Induced Phase‐Transition Behaviors of a Tapered Dendritic Liquid Crystal with Photochromic Azobenzene Mesogens and a Bicyclic Chiral Center

A ribbon‐shaped chiral liquid crystalline (LC) dendrimer with photochromic azobenzene mesogens and an isosorbide chiral center (abbreviated as AZ₃DLC) was successfully synthesized and its major phase transitions were studied by using differential scanning calorimetry (DSC) and linear polarized optical microscopy (POM). Its ordered structures at different temperatures were further identified through structure‐sensitive diffraction techniques. Based on the experimental results, it was found that the AZ₃DLC molecule exhibited the low‐ordered chiral smectic (Sm*) LC phase with 6.31 nm periodicity at a high‐temperature phase region. AZ₃DLC showed the reversible photoisomerization in both organic solvents and nematic (N) LC media. As a chiral‐inducing agent, it exhibited a good solubility, a high helical‐twisting power, and a large change in the helical‐twisting power due to its photochemical isomerization in the commercially available N LC hosts. Therefore, we were able to reversibly “remote‐control” the colors in the whole visible region by finely tuning the helical pitch of the spontaneously formed helical superstructures.     

Topochemical Transformations of CaX2 (X=C,Si, Ge) to Form Free‐Standing Two‐Dimensional Materials

Topochemical transformations of layered materials CaX₂ (X=Si, Ge) are the method of choice for the high‐yield synthesis of pristine, defect‐free two‐dimensional systems silicane and germanane, which have advanced electronic properties. Based on solid‐state dispersion‐corrected calculations, mechanisms for such transformations are elucidated that provide an in‐depth understanding of phase transition in these layered materials. While formation of such layered materials is highly favorable for silicane and germanane, a barrier of 1.2 eV in the case of graphane precludes its synthesis from CaC₂ topochemically. The energy penalty required for distorting linear acetylene into a trans‐bent geometry accounts for this barrier. In contrast it is highly favorable in the heavier analogues, resulting in barrierless topochemical generation of silicane and germanane. Photochemical generation of the trans‐bent structure of acetylene in its first excited state (S₁) can directly generate graphane through a barrierless condensation. Unlike the buckled structure of silicene, the phase‐h of CaSi₂ with perfectly planar silicene layers exhibits the Dirac cones at the high symmetry points K and H. Interestingly, topochemical acidification of the cubic phase of calcium carbide is predicted to generate the previously elusive platonic hydrocarbon, tetrahedrane.     

A Facile Molten‐Salt Route for Large‐Scale Synthesis of NiFe2O4 Nanoplates with Enhanced Lithium Storage Capability

Binary metal oxides have been deemed as a promising class of electrode materials for high‐performance lithium ion batteries owing to their higher conductivity and electrochemical activity than corresponding monometal oxides. Here, NiFe₂O₄ nanoplates consisting of nanosized building blocks have been successfully fabricated by a facile, large‐scale NaCl and KCl molten‐salt route, and the changes in the morphology of NiFe₂O₄ as a function of the molten‐salt amount have been systemically investigated. The results indicate that the molten‐salt amount mainly influences the diameter and thickness of the NiFe₂O₄ nanoplates as well as the morphology of the nanosized building blocks. Cyclic voltammetry (CV) and galvanostatic charge–discharge measurements have been conducted to evaluate the lithium storage properties of the NiFe₂O₄ nanoplates prepared with a Ni(NO₃)₂/Fe(NO₃)₃/KCl/NaCl molar ratio of 1:2:20:60. A high reversible capacity of 888 mAh g^?1 is delivered over 100 cycles at a current density of 100 mA g^?1. Even at a current density of 5000 mA g^?1, the discharge capacity could still reach 173 mAh g^?1. Such excellent electrochemical performances of the NiFe₂O₄ nanoplates are contributed to the short Li⁺ diffusion distance of the nanosized building blocks and the synergetic effect of the Ni²⁺ and Fe³⁺ ions.     

Pressure‐Suppressed Carrier Trapping Leads to Enhanced Emission in Two‐Dimensional Perovskite (HA)2(GA)Pb2I7

A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)₂(GA)Pb₂I₇ (HA=n‐hexylammonium, GA=guanidinium). This structure features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non‐luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above‐band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two‐fold higher PL emission compared with the pristine (HA)₂(GA)Pb₂I₇.     

The Need for Two‐Dimensional Gas Chromatography: Extent of Overlap in One‐Dimensional Gas Chromatograms

The need for two‐dimensional gas chromatography is justified by the extent of peak overlap in one‐dimensional gas chromatograms (GCs) of complex mixtures. Such overlap was predicted long ago by statistical‐overlap theory (SOT). In this paper, SOT is conceptually reviewed and its predictions are shown to be quantitatively accurate. GCs of complex mixtures of polychlorinated biphenyls, pyridine‐ and nitrogen‐containing polynuclear aromatic hydrocarbons, tetrachlorodibenzo‐p‐dioxins and dibenzofurans, fatty acid methyl esters, flavors and fragrances, and naphtha were simulated by commercial GC software on DB‐1, DB‐5, and Stabilwax stationary phases. The numbers of peak maxima in the GCs agreed with predictions of SOT, when the interval of time between successive peaks of pure compounds was described by Poisson statistics. This agreement was realized even though the time intervals actually are deterministic, not statistical. In addition, the numbers of mixture components were predicted with accuracy by regression of peak numbers against SOT. Similar regressions have been reported before, but the theory used here is more sophisticated and its predictions consequently are more accurate. Future directions for finalizing SOT are suggested.     

Template‐Free Synthesis and Mechanistic Study of Porous Three‐Dimensional Hierarchical Uranium‐Containing and Uranium Oxide Microspheres

A novel type of uranium‐containing microspheres with an urchin‐like hierarchical nano/microstructure has been successfully synthesized by a facile template‐free hydrothermal method with uranyl nitrate hexahydrate, urea, and glycerol as the uranium source, precipitating agent, and shape‐controlling agent, respectively. The as‐synthesized microspheres were usually a few micrometers in size and porous inside, and their shells were composed of nanoscale rod‐shaped crystals. The growth mechanism of the hydrothermal reaction was studied, revealing that temperature, ratios of reactants, solution pH, and reaction time were all critical for the growth. The mechanism study also revealed that an intermediate compound of 3 UO₃?NH₃?5 H₂O was first formed and then gradually converted into the final hydrothermal product. These uranium‐containing microspheres were excellent precursors to synthesize porous uranium oxide microspheres. With a suitable calcination temperature, very uniform microspheres of uranium oxides (UO_2+x, U₃O₈, and UO₃) were successfully synthesized.     

Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging

Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.     

Controlled Synthesis of 3D Flower‐like Ni2P Composed of Mesoporous Nanoplates for Overall Water Splitting

Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni₂P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Ni_x P_y , the 3D flower‐like Ni₂P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H₂SO₄, with a small Tafel slope of 79 mV dec⁻¹ and an overpotential of about 240 mV at a current density of 10 mA cm⁻² with a mass loading density of 0.283 mg cm⁻². In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm⁻² and a small Tafel slope of 72 mV dec⁻¹. The excellent catalytic performance of the as‐prepared Ni₂P may be ascribed to its novel 3D morphology with unique mesoporous structure.     

A Flexible Pro‐porous Coordination Polymer: Non‐conventional Synthesis and Separation Properties Towards CO2/CH4 Mixtures

The novel coordination polymers [Cu(Hoxonic)(H₂O)]_n ( 1 ) and [Cu(Hoxonic)(bpy)_0.5]_n ? 1.5 n H₂O ( 2?H₂O ) (H₃oxonic: 4,6‐dihydroxy‐1,3,5‐triazine‐2‐carboxylic acid; bpy: 4,4′‐bipyridine) have been isolated and structurally characterised by ab initio X‐ray powder diffraction. The dense phase 1 contains 1D zig‐zag chains in which Hoxonic dianions bridge square‐pyramidal copper(II) ions, apically coordinated by water molecules. On the contrary, 2?H₂O , prepared by solution and solventless methods, is based on 2D layers of octahedral copper(II) ions bridged by Hoxonic ligands, further pillared by bpy spacers. The resulting pro‐porous 3D network possesses small hydrated cavities. The reactivity, thermal, magnetic and adsorptive properties of these materials have been investigated. Notably, the adsorption studies on 2 show that this material possesses unusual adsorption behaviour. Indeed, guest uptake is facilitated by increasing the thermal energy of both the guest and the framework. Thus, neither N₂ at 77 K nor CO₂ at 195 K are incorporated, and CH₄ is only minimally adsorbed at 273 K and high pressures (0.5 mmol g^?1 at 2500 kPa). By contrast, CO₂ is readily incorporated at 273 K (up to 2.5 mmol g^?1 at 2500 kPa). The selectivity of 2 towards CO₂ over CH₄ has been investigated by means of variable‐temperature zero coverage adsorption experiments and measurement of breakthrough curves of CO₂/CH₄ mixtures. The results show the highly selective incorporation of CO₂ in 2 , which can be rationalised on the basis of the framework flexibility and polar nature of its voids.