Unusual catalytic effect of the two-dimensional molecular space with regular triphenylphosphine groups

A novel organic-inorganic hybrid 2D molecular space with regular triphenylphosphine groups (triphenylphosphineamidephenylsilica, PPh(3)APhS) was successfully synthesized through grafting triphenylphosphine groups in the 2D structure of layered aminophenylsilica dodecyl sulfate (APhTMS-DS), which was developed in our previous research, with regular ammonium groups. The 2D structures were kept after the grafting reaction of triphenylphosphine groups in PPh(3)APhS. The catalytic potentials of 2D molecular space with regular triphenylphosphine groups were investigated. An unusual catalytic effect was found in a carbon-phosphorus ylide reaction. The PPh(3)-catalyzed reaction of modified allylic compounds, including bromides and chlorides with tropone yielded a [3 + 6] annulation product. However, an unusual [8 + 3] cycloadduct was obtained in the reaction of modified allylic compounds, including bromides and chlorides with tropone catalyzed by PPh(3)APhS. Otherwise, the stable catalytic intermediate was successfully separated, and the reaction activity of the catalytic intermediate was confirmed in the reaction of modified allylic compounds with tropone catalyzed by PPh(3)APhS. This research is the first successful example of directly influencing catalytic reaction processes and product structures by utilizing the chemical and geometrical limits of 2D molecular spaces with regular catalyst molecules and affords a novel method for controlling catalytic reaction processes and catalyst design.     

Transformative two-dimensional layered nanocrystals

Regioselective chemical reactions and structural transformations of two-dimensional (2D) layered transition-metal chalcogenide (TMC) nanocrystals are described. Upon exposure of 2D TiS(2) nanodiscs to a chemical stimulus, such as Cu ion, selective chemical reaction begins to occur at the peripheral edges. This edge reaction is followed by ion diffusion, which is facilitated by interlayer nanochannels and leads to the formation of a heteroepitaxial TiS(2)-Cu(2)S intermediate. These processes eventually result in the generation of a single-crystalline, double-convex toroidal Cu(2)S nanostructure. Such 2D regioselective chemical reactions also take place when other ionic reactants are used. The observations made and chemical principles uncovered in this effort indicate that a general approach exists for building various toroidal nanocrystals of substances such as Ag(2)S, MnS, and CdS.     

Reactive groups on polymer-covered electrodes

Polythiophene films containing ester groups on the surface of electrodes are interesting potential carrier materials for reagents. Methyl thiophene-3-acetate (3) can be copolymerized with 3-methylthiophene (1) and 3-butylthiophene (2) by means of cyclic voltammetry (CV) at potentials of 0–2.2 V. Higher potentials (0–2.4 V) lead to overoxidation of the copolymers. The ester groups were confirmed by FTIR spectra. Electrochemical investigations of 2,2′-bithiophene (6) and 3 at equimolar ratios showed no successful copolymerization at potentials of 0–1.3 V. If the copolymerization experiments of 6 with 1 or 3 were carried out at molar ratios of 1:50 at 1.3 V, 6 with its low oxidation potential was polymerized without copolymerization of the other monomers. However, if the oxidation potential was increased stepwise from 1.3 V, the oxidation of 1 or 3 occurred, forming copolymers containing both monomer components. HPLC investigations of solutions containing mixtures of 6 and 3 and also 6 and 1 in acetonitrile/TEABF₄ showed, after exhaustive oxidation at a potential of 1.3 V, the complete absence of 6; 1 and the ester 3 were not oxidized and copolymerized at these potentials. From the results of the copolymerization experiments, as well as the HPLC investigations, it can be concluded that the dominant mechanism of the electrochemical polymerization is radical cation dimerization. Received: 21 August 1998 / Accepted: 11 January 2000     

The chlorine evolution reaction promoted by organocatalysts with amide functional groups

<正>Since the nineteenth century, the chlor-alkali process entails the electrochemical oxidation of sodium chloride solutions to Cl₂ by the chlorine evolution reaction(CER) and the simultaneous production of sodium hydroxide and H₂ at the cathode, of which sodium hydroxide and Cl₂ are widely used as important chemicals [1]. Currently, Cl₂ production relies heavily on the chlor-alkali process, which is implemented on an industrial scale worldwide,     

水中氯离子溶液标准物质的研制

以氯化钠纯度标准物质为原料,超纯水为溶剂,采用重量–容量法制备了水中氯离子溶液标准物质,系统阐述了水中氯离子溶液标准物质的研制方法.采用离子色谱法对制备的水中氯离子溶液标准物质进行分析,通过F–检验和回归曲线法对色谱数据进行计算,方差分析和线性拟合结果表明该溶液标准物质具有良好的均匀性和稳定性.研制的水中氯离子溶液标准...     

Photoelectrochemistry of two-dimensional and layered materials: a brief review

Journal of Solid State Electrochemistry - Two-dimensional (2D) materials have unique band structure and show a great promise for optoelectronic and solar energy harvesting applications....     

Electrical conductivity in a non-covalent two-dimensional porous organic material with high crystallinity

Electroactive macrocycle building blocks are a promising route to new types of functional two-dimensional porous organic frameworks. Our strategy uses conjugated macrocycles that organize into two dimensional porous sheets via non-covalent van der Waals interactions, to make ultrathin films that are just one molecule thick. In bulk, these two-dimensional (2D) sheets stack into a three-dimensional van der Waals crystal, where relatively weak alkyl–alkyl interactions constitute the interface between these sheets. With the liquid-phase exfoliation, we are able to obtain films as thin as two molecular layers. Further using a combination of liquid-phase and mechanical exfoliation, we are able to create non-covalent sheets over a large area (>100 μm²). The ultrathin porous films maintain the single crystal packing from the macrocyclic structure and are electrically conductive. We demonstrate that this new type of 2D non-covalent porous organic framework can be used as the active layer in a field effect transistor device with graphene source and drain contacts along with hexagonal boron nitride as the gate dielectric interface.

Ultrathin porous films held together by non-covalent van der Waals interactions was obtained by a top-down approach, which is then utilized as channel material in a two-dimensional planar field-effect transistor device through easy stamp transfer.

We describe a new type of two-dimensional (2D), molecularly-thin porous organic framework that is formed from macrocyclic building blocks that assemble, through non-covalent interactions, into a porous two-dimensional plane. Covalent organic frameworks (COFs) are promising in applications due to their ability to host other functional molecules in the voids.^1–7 Many porous frameworks have been demonstrated to be useful in energy storage,⁸ catalysis,^9–11 separation,^12,13 optoelectronics^4,14 and sensing.^15,16 In order to construct nanodevices with porous channels, ultrathin films of porous frameworks has been prepared with bottom-up^4,17–20 and top-down^1,21 approaches. The top-down approaches to these materials are enabled by strong covalent bonds in the two-dimensional plane and weak van der Waals interactions between them, similar to what is seen in two-dimensional materials such as graphene and TMDs.^22–27 For porous ultrathin films, the electrical conductance has not been extensively investigated.^2,7,20,28,29Here, we explore making molecularly thin layers in which conjugated macrocycles are used as building blocks and non-covalent van der Waals interactions are the adhesive that assembles these molecules into rigid, porous layers. By adjusting the relative strengths of the interactions that direct the assembly within the plane and those holding the two-dimensional layers with respect to each other, we can exfoliate these non-covalent porous frameworks using the same means employed for traditional two-dimensional van der Waals materials.³⁰ Using liquid-phase and mechanical exfoliation, we create porous films that are as thin as two-layers of molecules. These new results are exciting and useful because previously we were not able to obtain such high-ordered thin porous film directly from its bulk crystal and were limited to investigating the electronic properties of this hollow organic capsules in spin-coated films. These ultrathin porous films are ordered over large areas and maintain the single crystal packing from the macrocyclic building blocks. To demonstrate the utility of this new type of ultrathin material, we fabricated 2D field effect transistor (FET) devices in which graphene is the source/drain contacts, hexagonal boron nitride is the gate dielectric interface, and the exfoliated molecular sheet is the active layer. These ultrathin self-assembled materials are efficacious at transporting electrons and will find utility in gas sensing and applications similar to traditional two-dimensional materials. Fig. 1 displays the molecular building block (1). Characterization is contained in the ESI^† and a previous report.³¹1 has several important molecular features in its solid-state assembly. It is a rigid and shape persistent macrocycle that has an interior and an exterior (Fig. 1a), and in bulk, has a pore of ∼11.4 Å in diameter and a surface area of 20 m² g⁻¹ from BET measurements.³¹ When it assembles in the crystalline state, it forms two-dimensional porous sheets with two types of cavities (Fig. 1b), one molecule thick, that are held together by relatively strong π–π contacts and Br–PDI interaction between the bromine atoms on the thiophenes and adjacent PDI molecules (Fig. 1c), which plays a crucial role in the self-assembly of the films. The close proximity of the molecules in the 2D plane together with the conjugation within the macrocycle facilitate charge transport of electrons in the 2D plane. These electrically conductive porous sheets then stack into a three-dimensional crystal in which adjacent sheets are separated from one another by the alkane sidechains of the perylene diimide (Fig. 1d). It is in this alkane gallery that we see an opportunity for exfoliation to yield ultrathin 2D sheets.Open in a separate windowFig. 1Structure and packing of molecule 1. (a) Chemical structure, side view and top view of molecular structure of 1. C, N, O, S, Br are colored in grey, blue, red, yellow and green, respectively. The vertical distance of one macrocycle is about 1.5 nm. (b) Face-on view and edge-on view of one layer of 1. The internal cavity of 1 and the cavity formed by the packing of 1 are labeled as i and i′, respectively. (c) Interactions binding two adjacent macrocycles from neighboring brominated thiophene rings. (d) View of packing of 1 along the c axis through the interaction of alkane sidechains. Exfoliation takes place at the alkyl–alkyl interface. One layer of 1 is about 2 nm in thickness.We isolated crystals of this material that were grown from solution and then tested whether they can be exfoliated. Fig. 2a displays a representative micrograph of one of the crystals. The crystal has a pseudo-hexagonal packing of the molecular building blocks in the two-dimensional plane, and this symmetry is mirrored in the hexagonally-shaped crystals. The simplest method for exfoliation is mechanical exfoliation, which is most commonly performed using scotch-tape.^32,33 We place the single crystals onto clean scotch-tape and repeat the mechanical exfoliation process for a few repetitions, and then we transfer the exfoliated crystals onto a clean silicon wafer. Fig. 2b displays an atomic force microscopy (AFM) micrograph of the typical non-covalent porous 2D sheet of 1 we obtained from this method. The porous sheets are flat and smooth and a few micrometers in diameter with a thickness of ∼8 nm; this thickness corresponds to a stack of five molecular layers of 1. This result demonstrates that non-covalent interactions are strong enough to hold molecules together to form ultrathin porous materials. Just as with traditional two-dimensional materials, the non-covalent porous organic 2D sheets of 1 are flexible as evidenced by the wrinkles and folds in the micrograph in Fig. 2b and S2.^†Open in a separate windowFig. 2Mechanical exfoliation of 1. (a) Optical microscopy and scanning electron microscope (SEM) (inset) images of a single crystal of macrocycle 1. (b) AFM and optical microscope (inset) images of the ultrathin non-covalent porous sheet of 1 on a silicon wafer obtained from mechanical exfoliation.We were unable to obtain porous films as thin as a single layer and also large-area samples using mechanical exfoliation, and thus we next explored if liquid-phase exfoliation^34,35 could produce them. Because the halogen bonds that hold the sheets together should be most robust in solvents with a low-dielectric constant that lack heteroatoms, and because the groups holding the sheets together are the alkane sidechains, we chose saturated hydrocarbons (hexane or heptane) as the solvents for exfoliation. Fig. 3a shows the process we follow for the liquid-phase exfoliation. We suspend single crystals of 1 in heptane and sonicate the mixture for five minutes. We drop cast the supernatant solution on silicon wafer and examine them with AFM. Remarkably, we are able to obtain non-covalent porous organic frameworks as thin as only two molecular layers (Fig. 3b).³⁶ Nevertheless, the lateral size of the porous 2D sheets of 1 we could obtain using this method are quite small, making it difficult to fabricate devices from them.Open in a separate windowFig. 3Liquid-phase exfoliation and combination of liquid-phase and mechanical exfoliation. (a) Schematic showing the liquid-phase exfoliation process. (b) AFM image of the ultrathin sheet of 1 on a silicon wafer obtained from liquid-phase exfoliation method. The sheets in this micrograph are two molecular layers (left) and three molecular layers (right) in thickness. (c) AFM image of the ultrathin sheet of 1 on a silicon wafer obtained from combination of liquid-phase and mechanical exfoliation, inset: optical microscope image of the ultrathin sheet 1. (d) AFM image showing the height change across the ultrathin sheet of 1 on silicon wafer obtained with combination methods, inset: optical microscope image of the ultrathin sheet of 1.To get large-area films characteristic of the mechanical exfoliation and thin films characteristic of the liquid-phase exfoliation, we combined the two methods. We first immerse the crystal of 1 in heptane for a few minutes to let the solvent seep into the gallery between the sheets and weaken the interlayer interactions. Then, we use mechanical exfoliation to isolate the ultrathin films. With this method, we obtained sheets of 1 with a lateral size of over ten micrometers, as shown in Fig. 3c. By carefully examining the exfoliated non-covalent porous 2D sheets of 1, we were also able to observe the height change across the sheet (Fig. 3d) with integer values of the layer thickness after the exfoliation steps. As marked red in Fig. 3d, we could identify a single layer of 1 with a height difference between these two surfaces of about 1.5 nm, corresponding to monolayer of molecule 1.We conducted transmission electron microscopy (TEM) studies to characterize the crystallinity of the as-prepared non-covalent porous 2D sheets of 1. As shown in Fig. 4a (inset), the 2D sheets exhibit a layered structure after liquid-phase exfoliation. The selected area electron diffraction (SAED) in the area (marked by the red circle) reveals a hexagonal diffraction pattern, with the bright reflections corresponding to the (2 1(−) 0) plane, with a spacing of 11.3 Å. This diffraction pattern confirms that the non-covalent, porous 2D sheets of 1 retain the single crystal packing and are stable to the liquid-phase processing.Open in a separate windowFig. 4TEM characterization and device fabrication. (a) SEAD pattern and TEM image (inset) of the non-covalent porous ultrathin sheet 1 obtained by liquid-phase exfoliation. (b) Schematic showing the structure of the hBN/Graphene/1 device based on the non-covalent porous ultrathin sheet 1 with graphene as electrodes and hBN as the dielectric layer. (c) Optical microscope image showing the as-fabricated hBN/Graphene/1 device. (d) Transfer curve of the hBN/Graphene/1 device.We next sought to determine the ability of these non-covalent porous ultrathin layers to transport charge. Because these films are van der Waals materials, we sought to make devices with van der Waals interfaces. [The ESI^† contains the current/voltage curves for 1 in a more traditional organic FET with Au contacts and trichloro(octadecyl)silane coated SiO₂ as the gate dielectric.] The source-drain contacts were fabricated from graphene and the dielectric interface was hexagonal boron nitride (hBN). A schematic of the device is shown in Fig. 4b. To create this device, we first exfoliate graphene and hBN onto a silicon substrate. We then follow a published procedure³⁷ to first pick up hBN and then graphene to make the hBN/graphene stack. We transfer this hBN/graphene stack onto another clean silicon substrate. Then the graphene was cut using electron beam lithography and an oxygen plasma to open a 300 nm gap between graphene electrodes (see Fig. S4^† for the AFM details of graphene electrodes). In order to transfer the non-covalent porous ultrathin sheets of 1 onto the graphene electrodes, we exploit the combined liquid/mechanical exfoliation method above to obtained 2D sheet of 1 with polydimethylsiloxane (PDMS) polymer as the substrate, which was then used for the stamp transferring. In this manner, we were able to transfer the ultrathin sheets (∼20 nm) onto the graphene electrodes. Fig. 4c displays the optical microscope image of the device, and Fig. 4d displays the FET transfer curves revealing that the material is an efficacious, n-type transistor. Several features of the device are noteworthy. The electron mobility in the linear regime was estimated to be 1.6 × 10⁻⁴ cm² V⁻¹ s⁻¹ from the transfer curve. As expected, it is somewhat lower than the electron mobility estimated from the saturation regime of the traditional OFET shown in Fig. S3.^†38 Despite the small size and the nanoscale thickness, the material exhibits over 3 orders of magnitude difference in current between the off and on state of the device. The threshold voltage is about 39 V, implying that the device turns on at relatively high voltage. We surmise that the contact, through the alkane sidechains is an impediment to more efficient charge transport.     

Synthesis of new liquid crystalline compounds with side chains containing hydroxy groups or chlorine atom

Catalytic hydrogenation of the oxo group in 3-hydroxy-1-(4-hydroxyphenyl)octan-1-one gave 1-(4-hydroxyphenyl)octane-1,3-diol and 1-(4-hydroxyphenyl)octan-3-ol which were converted into the corre-sponding benzyl ethers containing a hydroxy group, 1,3-diol fragment, or chlorine atom in the side chain. The products were shown to possess liquid crystalline properties.     

Linear molecules based on dimethylgermanium and dimethylsilicon groups bridged with oxygen atoms and terminated with chlorine atoms

This article deals with the equilibrated system (CH₃)₂SiCl₂–(CH₃)₂GeCl₂–[(CH₃)₂SiO]–[(CH₃)₂GeO], which consists of a range of various chain, and some ring, molecules resulting from scrambling of the bridging oxygen with the monofunctional chlorine atoms between the dimethylgermanium and dimethylsilicon moieties. The proton nuclear magnetic resonance of the methyl groups (which do not exchange appreciably under the conditions employed) bonded to the germanium and silicon atoms shows that there is a strong preference of the chlorine atoms for being on the dimethylgermanium and the bridging group for being on the dimethlysilicon moiety at equilibrium. This means that thermodynamic factors alone cause the germanium atoms to be found as “unreacted” dimethyldichlorogermane with siloxane polymers or to be preferentially arranged at the ends of the chain molecules in the case of the mixed germoxane–siloxanes. The NMR fine structure is interpreted in these terms, and it is shown that the experimental data may be fitted by appropriate calculations based on only four equilibrium constants, which define the arrangement of neighboring atoms about any given atom in a molecule and the size distribution of the linear molecules.     

Intercalation compound of diclofenac sodium with layered inorganic compounds as a new drug material

The intercalation reaction of diclofenac sodium (DFS) with layered inorganic compounds, gamma-titanium phosphate (gamma-TiP), proton type titanium oxide (H-TiO2) and sodium type synthetic mica (Na-TSM), was examined on. The direct reaction of DFS in ethanol-water mixed solvent resulted in the large amount accommodation of DFS. The amount of intercalated DFS was the order of gamma-TiP>H-TiO2>Na-TSM corresponding to the order of acidity. The intercalation using phospholiopids was also examined to assist the intercalation reaction. However, the amount of intercalated DFS was rather small in comparison with those in the direct reaction. DFS accommodated in gamma-TiP dissolved into neutral and basic buffer solution stoichiometry while scarcely dissolved in the acidic solution. The mechanism of the intercalation and reverse dissolution was successfully accounted according to the ion-exchange mechanism between Na+ in DFS and H+ in gamma-TiP. The dissolution from tablet of DFS/gamma-TiP intercalation compound was examined by using a disintegrator. It was found that the dissolution rate appropriately controlled by mixing the disintegrator. The present results suggested the different possibilities in the clinical field to use layered inorganic compounds such as drug delivery system (DDS).     

Synthesis of a new PET/layered niobate hybrid material

A new organic/inorganic hybrid material was prepared by the polymerization of bis(hydroxyethyl) terephthalate (BHET) with a layered niobate compound, H₄Nb₆O₁₇, modified by 11-aminoundecanoic acid (AUA). The hybrid polymer films of BHET with H₄Nb₆O₁₇/AUA exhibited favorable characteristics, particularly of being optically clear, indicating the exfoliation and homogeneous dispersion of H₄Nb₆O₁₇ into the PET/niobate hybrid.     

Study of an alternative material to manufacture layered hydraulic hoses

Hydraulic hoses are components of umbilical cables and others subsea equipments. They are manufactured from thermoplastic polymers and are susceptible to collapse under external pressure, which can cause plastic strains around the circumference, leading to failure under internal pressure (bursting). This work studies an alternative hydraulic hose liner capable of support such load history, even after long time exposure to the hydraulic fluid. It is based on the comparison between the material currently used (Polyamide 11) and a fluorinated elastomer, Viton^®. Mechanical characterization, ageing tests as well as nonlinear finite elements simulations were accomplished to issue both performances. The results obtained showed that Viton^® liners are mechanically more suitable than Polyamide 11 liners to such hoses. The ageing tests showed compatibility between Viton^® and the hydraulic fluid. Considering that the external aramid layer is responsible to withstand the internal pressure in both cases, Viton^® can successfully replace Polyamide 11 for this application as well as others involving layered hoses under combined internal and external pressure.     

The assignment of diastereotopic menthyl groups by two-dimensional NMR

The ¹³C and ¹H NMR spectra of (–)-bis[1R, 3 R, 4S]menthylphosphine (1) are assigned by two-dimensional double quantum NMR and ¹³C? ¹H shift correlation diagrams. The variable temperature spectra of 1 indicate hindered rotation about the P? C bonds.     

Spongy gel-like layered double hydroxide-alkaline phosphatase nanohybrid as a biosensing material

Formation of new bio-nanohybrid material was obtained by immobilization of alkaline phosphatase within a Mg(2)Al LDH by "soft chemistry" coprecipitation synthesis, resulting in an original spongy gel-like morphology allowing the preservation of the enzyme structure and activity even at low pH values thanks to the buffering property of the basic host structure.     

Rapid development in two-dimensional layered perovskite materials and their application in solar cells

This review summarized recent research progresses of two-dimensional layered organic-inorganic hybrid perovskite materials and their photovoltaic performances in 2D perovskite solar cells.     

Neutron activation analysis for chlorine in Zr-2.5 wt% Nb coolant tube material

Zr-2.5 wt% Nb has been found to be better compared to Zircaloy-2 as coolant tube material in Canadu-PHW reactors but has a stringent specification of less than 0.5 mg/kg of chlorine. Instrumental neutron activation analysis (INAA) for the determination of chlorine in Zr-2.5 wt% Nb is not possible because of the high activity produced due to the determination of the matrix. Hence a radiochemical neutron activation analysis (RNAA) procedure has been developed for the determination of chlorine in this material. For the first time the chlorine determination at less than a ppm level by NAA is being reported in this paper, in a number of Zr-2.5 wt% Nb samples ranging from 0.1 to 2 mg/kg.     

Conflicting roles of Na-doped layered cathode material LiCoO2 for Li-ion batteries

In this work, the electrochemical performance of Na-doped layered cathode material LiCoO₂ for Li-ion batteries is studied using first-principles calculations. The results show that the doped Na ion acts as a pillar, which can greatly increase the diffusion rate of Li ions, but it is not conducive to improving cycle performance and delithiation potential. These research results provide a theoretical reference for the study of Li-ion batteries with high-rate performance. Due to the conflicting role of single element doping, the multi-element co-doping strategy will be the best way to develop high-performance Li-ion batteries.

Graphical abstract