Polymer structure‐dependent ion interaction studied by amphiphilic nonionic poly(organophosphazenes)

The relative effectiveness of anions and cations in altering macromolecular conformation was reported to be independent of the nature of the macromolecule. However, in terms of the degree of changes, macromolecule‐dependent ion action cannot be underestimated. The designed poly(organophosphazenes) have been selected for this study due to its versatility of the substitution with a fixed backbone. To set up the systematic explanation on the ion action related with molecular interactions, ions and polymers are arranged based on the water binding ability. As a characteristic factor specific in the thermothickening system, the temperature at which the viscosity of the polymer solution reaches the maximum (T_max) has been compared. Anions with strong water binding ability more effectively lower the T_max of the hydrophobic poly(organophosphazenes). Meanwhile, the T_max of the cation‐complexed poly(organophosphazenes) are lowered by the sequence of water binding ability of the complexed cations. In both the anion and cation interactions, poly(organophosphazenes) substituted by longer PEG and more hydrophilic amino acid ester, show differentiated result due to different interaction with water when compared with other polymer systems in this study. Ion interaction with poly(organophosphazenes) mediated by water supports interfacial interactions expressed by interaction parameters, which strongly depends on the polymer structure and ion type. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2022–2034, 2008     

Tuning Optimum Temperature Range of Bi2Te3‐Based Thermoelectric Materials by Defect Engineering

Bi₂Te₃‐based solid solutions, which have been widely used as thermoelectric (TE) materials for the room temperature TE refrigeration, are also the potential candidates for the power generators with medium and low‐temperature heat sources. Therefore, depending on the applications, Bi₂Te₃‐based materials are expected to exhibit excellent TE properties in different temperature ranges. Manipulating the point defects in Bi₂Te₃‐based materials is an effective and important method to realize this purpose. In this review, we focus on how to optimize the TE properties of Bi₂Te₃‐based TE materials in different temperature ranges by defect engineering. Our calculation results of two‐band model revel that tuning the carrier concentration and band gap, which is easily realized by defects engineering, can obtain better TE properties at different temperatures. Then, the typical paradigms about optimizing the TE properties at different temperatures for n‐type and p‐type Bi₂Te₃‐based ZM ingots and polycrystals are discussed in the perspective of defects engineering. This review can provide the guidance to improve the TE properties of Bi₂Te₃‐based materials at different temperatures by defects engineering.     

Poly(difluorophosphazene): A New Intermediate for the Synthesis of Poly(organophosphazenes)

Although many poly(organophosphazenes) have been synthesized, new preparative pathways are needed, especially for polymers that contain alkyl side groups. A new development involves the use of poly(difluorophosphazene), (NPC1₂) instead of poly-(dichlorophosphazene), (NPC1²)_n, as a substrate for reactions with organometallic reagents. This approach has allowed the preparation of a new class of poly(organophosphazenes) that possess substituent groups linked to the skeleton through direct phosphorus-carbon bonds. The synthesis of uncrosslinked poly-(difluorophosphazene) and its reactions with alkoxides and amines are also reviewed.     

CO2 Capture,Separation and Reduction on Boron-Doped MoS2, MoSe2 and Heterostructures with Different Doping Densities: A Theoretical Study

Designing high-performance materials for CO₂ capture and conversion is of great significance to reduce the greenhouse effect and alleviate the energy crisis. The strategy of doping is widely used to improve activity and selectivity of the materials. However, it is unclear how the doping densities influence the materials’ properties. Herein, we investigated the mechanism of CO₂ capture, separation and conversion on MoS₂, MoSe₂ and Janus MoSSe monolayers with different boron doping levels using density functional theory (DFT) simulations. The results indicate that CO₂, H₂ and CH₄ bind weakly to the monolayers without and with single-atom boron doping, rendering these materials unsuitable for CO₂ capture from gas mixtures. In contrast, CO₂ binds strongly to monolayers doped with diatomic boron, whereas H₂ and CH₄ can only form weak interactions with these surfaces. Thus, the monolayers doped with diatomic boron can efficiently capture and separate CO₂ from such gas mixtures. The electronic structure analysis demonstrates that monolayers doped with diatomic doped are more prone to donating electrons to CO₂ than those with single-atom boron doped, leading to activation of CO₂. The results further indicate that CO₂ can be converted to CH₄ on diatomic boron doped catalysts, and MoSSe is the most efficient of the surfaces studied for CO₂ capture, separation and conversion. In summary, the study provides evidence for the doping density is vital to design materials with particular functions.     

Yellow pigments based on Fe2TiO5 and TiO2

The aim of our research was to prepare yellow pigments based on structure of pseudobrookite Fe₂TiO₅. Part of Fe was substituted with Li and Ti from Fe₂TiO₅ to Li_0.05Fe_0.07Ti_2.44O₅. Synthesis and pigmentary-application properties in the Li₂O–Fe₂O₃–TiO₂ system were studied for 800 and 900°C using classical ceramic method of preparation. The main attention was aimed to usage of four different sources of titanium compounds as raw materials. We studied the influence of different sources of titanium compounds on the structural and the colour properties of the prepared pigments. The thermal analysis was used for characterization of titanium compounds and determination of their thermal stability.     

Emerging polymorphism in nanostructured TiO2: Quantum chemical comparison of anatase,rutile, and brookite clusters

Density functional theory (DFT) and time‐dependent DFT calculations have been performed on a set of 34 titanium dioxide clusters ((TiO2)_n with n ≤ 125) to investigate structural and electronic properties of nanostructured TiO₂ (nano‐TiO₂) materials. The investigated clusters include models of the three low‐energy polymorphic forms of TiO₂ anatase, rutile, and brookite. A systematic comparison of clusters of increasing size show clear trends for emerging bulk properties in the investigated systems as the surface‐to‐bulk ratio changes from small clusters dominated by undercoordinated surface atoms to more realistic model nanocrystals with significant bulk components. Differences and similarities in terms of atomic coordination, structural stability, and electronic properties for the three different polymorphic forms of nano‐TiO₂ are discussed. The calculations provide evidence for emerging polymorphism with increasing cluster sizes so that the different TiO₂ forms can be clearly distinguished based on structural characteristics associated with the local bonding environment of the constituent atoms. © 2013 Wiley Periodicals, Inc.     

Supercritical CO2-Induced Amorphization in 2D Materials: Mechanism and Applications

Supercritical carbon dioxide (SC CO₂)-assisted chemical and material processing has shown great success in the fabrication of 2D amorphous materials, while the amorphization mechanism in SC CO₂ is quite complicated to be understand. In this review, we introduce different kinds of 2D amorphous materials prepared with SC CO₂ and discuss the possible amorphization mechanism and how they affect the structures and properties of 2D materials. Their applications are further presented and discussed. In addition, the prospective of future development of SC CO₂-assisted fabrication of 2D amorphous materials is also involved. The investigation of SC CO₂ induced amorphization not only provides theoretic understanding of amorphization process, but also directs to the preparation and application of 2D amorphous materials with specific structure and property, suggesting the promising future of SC CO₂-assisted process in material design and engineering.     

CO2 adsorption on granular and monolith carbonaceous materials

We evaluated the CO₂ adsorption capacity on granular and monolith carbonaceous materials, obtained by chemical activation of African palm stones with H₃PO₄, ZnCl₂ and CaCl₂ solutions at different concentrations. Textural properties of the synthesized materials were analyzed using N₂ adsorption measurements at 77 K, the isotherms showed obtaining of materials microporous and moderately mesoporous, with surface areas between 161 and 1700 m²/g and pore volume between 0.09 and 0.64 cm³ g⁻¹. Were observed different behaviors for textural parameters in each series, associated with the activating agent used in the preparation. The materials obtained have a CO₂ adsorption capacity between ∼114 and 254 mg CO₂/g, at atmospheric pressure and 273 K. It was established that the total amount of CO₂ adsorbed under these experimental conditions is defined by the narrow micropore volume (V_n) and increased the total basicity of the materials.     

Dynamic Studies on Kinetic H2/D2 Quantum Sieving in a Narrow Pore Metal–Organic Framework Grown on a Sensor Chip

The separation of deuterium from hydrogen still remains a challenging and industrially relevant task. Compared to traditional cryogenic methods for separation, based on different boiling points of H₂ and D₂, the use of ultramicroporous materials offers a more efficient alternative method. Due to their rigid structures, permanently high porosity, tunable pore sizes and adjustable internal surface properties, metal–organic frameworks (MOFs), a class of porous materials built through the coordination between organic linkers and metal ions/clusters, are more suitable for this approach than zeolites or carbon-based materials. Herein, dynamic gas flow studies on H₂/D₂ quantum sieving in MFU-4, a metal-organic framework with ultra-narrow pores of 2.5 Å, are presented. A specially designed sensor with a very fast response based on surface acoustic waves is used. On-chip measurements of diffusion rates in the temperature range 27–207 K reveal a quantum sieving effect, with D₂ diffusing faster than H₂ below 64 K and the opposite selectivity above this temperature. The experimental results obtained are confirmed by molecular dynamic simulation regarding quantum sieving of H₂ and D₂ on MOFs for which a flexible framework approach was used for the first time.     

Dependence of the Properties of 2D Nanocomposites Generated by Covalent Crosslinking of Nanosheets on the Interlayer Separation: A Combined Experimental and Theoretical Study

Covalently cross-linked heterostructures of 2D materials are a new class of materials which possess electrochemical and photochemical hydrogen evolution properties. It was of considerable interest to investigate the role of interlayer spacing in the nanocomposites involving MoS₂ and graphene sheets and its control over electronic structures and catalytic properties. We have investigated this problem with emphasis on the hydrogen evolution properties of these structures by a combined experimental and theoretical study. We have linked MoS₂ based nanocomposites with other 2D materials with varying interlayer spacing by changing the linker and studied their hydrogen evolution properties. The hydrogen evolution activity for these composites decreases with increasing linker length, which we can link to a decrease in magnitude of charge transfer across the layers with increasing interlayer spacing. Factors such as the nature of the sheets, interlayer distance as well as the nature of the linker provide pathways to tune the properties of covalently cross-linked 2D material rendering this new class of materials highly interesting.     

Dual Plasmonic Au−Cu2−xS Nanocomposites: Design Strategies and Photothermal Properties

Coupling two different materials to create a hybrid nanostructured system is a powerful strategy for achieving synergistically enhanced properties and advanced functionalities. In the case of Au and Cu_2−xS, their combination on the nanoscale results in dual plasmonic Au−Cu_2−xS nanocomposites that exhibit intense photon absorption in both the visible and the near-infrared spectral ranges. Their strong light-absorbing properties translate to superior photothermal transduction efficiency, making them attractive in photothermal-based applications. There are several nanostructure configurations that are possible for the Au−Cu_2−xS system, and the successful fabrication of a particular architecture often requires a carefully planned synthetic strategy. In this Minireview, the different synthetic approaches that can be employed to produce rationally designed Au−Cu_2−xS nanocomposites are presented, with a focus on the experimental protocols that can lead to heterodimer, core–shell, reverse core–shell, and yolk–shell configurations. The photothermal behavior of these materials is also discussed, providing a glimpse of their potential use as photothermally active agents in therapeutic and theranostic applications.     

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2O2

The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e⁻ ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e⁻ ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H₂O₂ production. The work here gives not only new understandings on the 2e⁻ ORR catalysis, but also the robust catalyst which can be directly used in industry.     

Volatility of molten salts [Ph4P][NTf2] and Cs[NTf2]

The two ionic compounds [Ph₄P][NTf₂] and Cs[NTf₂] were qualified to be suitable liquid materials for different high temperature applications. Development and optimization of these application techniques require knowledge of the thermodynamic properties of vaporization. Vapor pressures and vaporization enthalpies have been measured by using quartz-crystal microbalance. Solubility parameters and miscibility of ionic liquids in practically relevant solvents were assessed.     

Surfactant-assisted hydrothermal crystallization of nanostructured lithium metasilicate (Li2SiO3) hollow spheres: II—Textural analysis and CO2-H2O sorption evaluation

In a previous work, the synthesis and structural-microstructural characterization of different nanocrystalline lithium metasilicate (Li₂SiO₃) samples were performed. Then, in this work, initially, a textural analysis was performed over the same samples. Li₂SiO₃ samples prepared with a non-ionic surfactant (TRITON X-114) presented the best textural properties. Therefore, this sample was selected to evaluate its water vapor (H₂O) and carbon dioxide (CO₂) sorption properties. Sorption experiments were performed at low temperatures (30-80 °C) in presence of water vapor using N₂ or CO₂ as carrier gases. Results clearly evidenced that CO₂ sorption on these materials is highly improved by H₂O vapor, and of course, textural properties enhanced the H₂O-CO₂ sorption efficiency, in comparison with the solid-state reference sample.     

The optical and gas-sensitive properties of opal-like structures based on SnO<Subscript>2</Subscript>

Opal-like materials based on tin dioxide were prepared, and their structural and sensor characteristics were studied. The optical transmission spectra of opal-like structures based on SnO₂ were recorded, and the volume fraction occupied in them by tin dioxide was estimated. It was shown that structures based on SnO₂ contained a photon stop-zone in the visible spectrum range. The sensor properties of the materials toward CO and H₂ were studied over the temperature range 375−425°C. The SnO₂ samples studied had much higher sensitivity to CO compared with SnO₂ materials without opal-like structures.     

Single- and few-layer 2H-SnS2 and 4H-SnS2 nanosheets for high-performance photodetection

The properties of two-dimensional（2D） materials are highly dependent on their phase and thickness. Various phases exist in tin disulfide（SnS₂）, resulting in promising electronic and optical properties. Hence,accurately identifying the phase and thickness of SnS₂ nanosheets is prior to their optoelectronic applications. Herein, layered 2H-SnS₂ and 4H-SnS₂ crystals were grown by chemical vapor transportation and the crystalline phase of SnS₂ w...     

Preparation and characterization of Ni(dpedt)(pddt) and Ni(dpedt)(pddt)·CS2, where dpedt is diphenylethylenedithiolate and pddt is 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate

The unsymmetrical nickel 1,2-dithiolene complex based on diphenylethylenedithiolate (dpedt) and 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate (pddt) was prepared and characterized. Depending on the conditions of crystallization, it is possible to obtain the complex in two different crystalline forms. X-ray structure studies recognize these forms as Ni(dpedt)(pddt) and Ni(dpedt)(pddt)·CS₂. The experimental optical and electrochemical parameters are in a good agreement with the calculated ones, using the corresponding parameters of the symmetrical complexes, Ni(dpedt)₂ and Ni(pddt)₂. The HOMO and LUMO energy levels, obtained from optical and electrochemical measurements, are very close to the Fermi energy of (metallic) Au. The chemical and electrochemical properties of both forms showed that they are stable in air and could be candidate materials for optics and electronics.     

Effects of cross-linkers with different molecular weights in cross-linked Matrimid 5218 and test temperature on gas transport properties

The poly(ethylene oxide) (PEO) was introduced by the cross-linking method in the commercial Matrimid 5218. The two kinds of membranes were prepared from the Matrimid 5218 and the cross-linkers poly(propylene glycol) block poly(ethylene glycol) block poly(propylene glycol) diamine (PPG/PEG/PPGDA) with different molecular weights. The cross-linking reaction process was monitored by FTIR. The cross-linked Matrimid 5218 membranes display excellent CO₂ permeability and CO₂/light gas selectivity. The effects of cross-linkers with different molecular weights on gel content, thermal properties and H₂, CO₂, N₂ and CH₄ gas transport properties were reported. The effect of temperature on gas transport properties was also reported, and the permeabilities of these materials as a function of temperature were compared with other gas membrane materials.     

Capture of toxic gases in MOFs: SO2, H2S,NH3 and NOx

MOFs are promising candidates for the capture of toxic gases since their adsorption properties can be tuned as a function of the topology and chemical composition of the pores. Although the main drawback of MOFs is their vulnerability to these highly corrosive gases which can compromise their chemical stability, remarkable examples have demonstrated high chemical stability to SO₂, H₂S, NH₃ and NO_x. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases. Thus, the interactions of such functional groups (coordinatively unsaturated metal sites, μ-OH groups, defective sites and halogen groups) with these toxic molecules, not only determines the capture properties of MOFs, but also can provide a guideline for the desigh of new multi-functionalised MOF materials. Thus, this perspective aims to provide valuable information on the significant progress on this environmental-remediation field, which could inspire more investigators to provide more and novel research on such challenging task.

MOFs are promising candidates for the capture of toxic gases such as SO₂, H₂S, NH₃ and NOx. Understanding the role of different chemical functionalities, within the pores of MOFs, is the key for accomplishing superior captures of these toxic gases.     

Exfoliated transition metal dichalcogenides (MoS2, MoSe2, WS2, WSe2): An electrochemical impedance spectroscopic investigation

Owing to the enthralling properties which transition metal dichalcogenides present, they are facing immense scientific interest from researchers. Till date, these two-dimensional materials have been assessed for a wide array of different applications and there are various synthetic methods of attaining them in their respective bulk and exfoliated forms. Herein, we explore the effects of lithium ion intercalation exfoliation process on the charge transfer resistance of transition metal dichalcogenide materials (MoS₂, MoSe₂, WS₂ and WSe₂). We also show that electrochemical activation of the transition metal dichalcogenides results in decreased resistance towards charge transfer, as demonstrated by electrochemical impedance spectroscopy.