Enhanced Methane Storage in Graphene Oxide Induced by an External Electric Field: A Study by MD Simulations and DFT Calculation.

To improve the methane (CH4) storage performance of graphene oxide (GO), molecular dynamics (MD) simulations and density functional theory (DFT) calculation were employed to investigate the effect of electric field (EF) on the adsorption and desorption performances of monolayer graphene modified with three oxygen-containing functional groups (hydroxyl, carboxyl, and epoxy) as the CH4 storage material. Through the calculation and analysis of the radial distribution function (RDF), adsorption energy, adsorption weight percentage, and the amount of CH4 released, the mechanisms of influence on adsorption and desorption performances caused by an external EF were revealed. The study results showed that the external EF can significantly enhance the adsorption energy of CH4 on hydroxylated graphene (GO-OH) and carboxylated graphene (GO-COOH), making it easier to adsorb CH4, and improve the adsorption capacity. Whereas the EF severely weakened the adsorption energy of CH4 on epoxy-modified graphene (GO-COC) and reduced the adsorption capacity of GO-COC. For the desorption process, applying the EF can decrease the CH4 release of GO-OH and GO-COOH but increase the CH4 release of GO-COC. To sum up, when an EF is present, the adsorption properties of -COOH and -OH and desorption properties of -COC will be improved, but the desorption properties of -COOH and -OH and the adsorption properties of -COC will be weakened. The findings in this study are expected to propose a novel non-chemical method to improve the storage capacity of GO for CH4.

Influence of an External Electric Field on Electronic and Optical Properties of a g-C3N4/TiO2 Heterostructure: A First-Principles Perspective.

In this study, calculations based on density functional theory (DFT) were utilized to examine how electrostatic fields affect the electrical and optical characteristics of g-C3N4/TiO2 heterostructures. The binding energy, density of states, difference in charge density, and optical absorption spectra of the heterostructure were calculated and analyzed to reveal the mechanism of the influence of the external electric field (EF) on the properties of the heterostructure. The results show that the binding energy of the heterogeneous structure is reduced due to the imposed electric field in X- and Y-directions, and the optical absorption spectrum is slightly enhanced, but the BG and charge transfer number are basically unchanged. On the contrary, applying the electric field in the Z-direction increases the binding energy of the heterogeneous structure, decreases the BG, increases the number of charge transfers, and red shifts the optical absorption spectrum, which improves the photocatalytic ability of the g-C3N4/TiO2 heterostructure.

Selenocystine and Photo-Irradiation Directed Growth of Helically Grooved Gold Nanoarrows.

The fabrication of discrete nanostructures with both plasmonic circular dichroism (PCD) and chiral features is still a challenge. Here, gold nanoarrows (GNAs) with both chiroptical responses and chiral morphologies are achieved by using L-selenocystine (L-SeCys2 ) as a chiral inducer. While L-SeCys2 generates GNAs with a weak PCD signal, the irradiated L-SeCys2 (irr-L-SeCys2 ) leads to GNAs with featured helical grooves (HeliGNAs) accompanying with a strong PCD signal. It is revealed that when L-SeCys2 is photo-irradiated, the emergence of selenyl radicals plays an important role in the formation of HeliGNAs and enhancement of the chiroptical signal. In comparison with L-SeCys2 and the other kinds of sulfur-containing amino acids, the formation mechanism of helical grooves on the surface of GNAs is proposed. Both HeliGNAs and GNAs are used to discriminate amino acids by utilizing surface enhanced Raman scattering (SERS) effect. In the presence of either GNAs or HeliGNAs as the substrate, Fmoc-L-Phe shows more significant SERS than Fmoc-D-Phe. This study may advance the design of discrete plasmonic nanomaterials with both chiral morphology and potential applications in discrimination of chiral molecules.

Reversible Chiral Optical Switching Based on Co-Assembled Spiropyran Gels.

In recent years, it has been very interesting to dynamically adjust the emission of circularly polarized luminescence (CPL) materials through external stimulation due to their applications and the fundamental interest in them. In this work, luminescence-tunable and light-responsive supramolecular co-assembly CPL-active materials are fabricated by mixing an achiral functional spiropyran (SP-COOH) molecule with a chiral gelator. The spiropyran achieves a reversible change between a white closed ring state spiropyran and a purple zwitterionic merocyanine state in supramolecular co-assembly gels under alternate visible (vis) and ultraviolet (UV) light irradiation. The gel shows strong CPL signals due to the chirality transfer in co-assembly systems. These signals could change reversibly under alternate exposure to UV and vis light. Therefore, utilizing the multistimulus-responsive CPL signals in different states, a CPL switch of the supramolecular system signal according to the combinatorial control of UV-vis light irradiation is constructed.

Gas-Responsive and Self-Powered Visual Composite Langmuir-Blodgett Films for Ultrathin Gas Sensors.

The complex and variable environments are challenging the development of related detection and analysis. Ammonia (NH3) and hydrogen chloride (HCl) gases are both commonly used in industry, but they are considered to be toxic and corrosive substances that can threaten human health and the environment. Therefore, it is necessary here to develop a convenient, sensitive, and reliable sensor device for acid-alkali gas detection. Herein, we propose the synthesis strategy of an ultrathin film gas sensor based on the pH-responsive, self-powered, and visible composite Langmuir-Blodgett (LB) films. In our work, the LB films with nanometric thicknesses are obtained based on the sensitive materials of two novel carbazole structural sensitizers (abbreviated as CS-35 and CS-37) and several dye molecules. The composite LB films are formed with Carbazole samples and dye molecules through hydrogen bonding, π-π stacking, synergistic electrostatic interactions, and hydrophobic interactions, existing as J-aggregate or H-aggregate. The formation of high-quality and uniform Langmuir films is confirmed with transmission electron microscope (TEM), UV-vis spectrum, atomic force microscopy (AFM), and other measurements. In addition, based on the simple protonation and deprotonation, the prepared LB films can be assembled into a visual sensor for the response of pH gases. The response is confirmed by the study of ultraviolet spectroscopy and electrical output in vertical contact separation mode, which potentially unlocks a sustainable future for the application of ultrathin self-powered gas sensors.

Biomimetic Nanozymes Based on Coassembly of Amino Acid and Hemin for Catalytic Oxidation and Sensing of Biomolecules.

Nanoassemblies based on self-assembly of biological building blocks are promising in mimicking the nanostructures, properties, and functionalities of natural enzymes. However, it remains a challenge to design of biomimetic nanozymes with tunable nanostructures and enhanced catalytic activities starting from simple biomolecules. Herein, the construction of nanoassemblies through coassembly of an amphiphilic amino acid and hemin is reported. The nanostructures and morphologies of the resulting nanoassemblies are readily controlled by tuning the molar ratio between the amino acid and hemin, thus leading to tailored peroxidase-mimicking activities of the nanoassemblies. Importantly, the optimized nanoassemblies exhibit a remarkable catalytic efficiency that is comparable to the natural counterpart when considering molecular mass along with good robustness in multiple catalytic cycles. The nanoassemblies are effectively integrated as biomimetic nanozymes in a sensing system for catalytic detection of glucose. Therefore, this work demonstrates that nanozymes with advanced catalytic capabilities can be constructed by self-assembly of minimalist biological building blocks and may thus promote the rational design and catalytic applications of biomimetic nanozymes.

Improve optical properties by modifying Ag nanoparticles on a razor clam SERS substrate.

Irregular substrates are inappropriate for enhancing surface enhanced Raman scattering (SERS) due to their poor performances in terms of uniformity, enhancement performance, and polarization characteristics. However, in this work, we purposely employed a natural biological razor clam material with messy and irregular structures to improve the SERS. The rough surface was achieved by magnetron sputtering Ag nanoislands on the prism layer of the razor clams, and the Ag nanoparticles were treated using the method of oil-water interface self-assembly to form relatively uniform structures. Compared to the substrate without Ag nanoparticles, the presented substrate has better reproducibility, polarization-independence, and higher SERS intensity, and the detect limitation of R6G can be decreased from 10-12 M to 10-18 M. The ultrasensitive detection of thiram gives our structures potential for high sensitivity biosensors.

Self-Assembled Sandwich-like MXene-Derived Composites as Highly Efficient and Sustainable Catalysts for Wastewater Treatment.

Photocatalysts play an increasingly important role in environmental remediation polluted by industrial wastewater. However, the preparation of adsorbents and catalysts with high activity by simple and easy methods is still a great challenge. Here, sandwich-like composite catalyst Cu2O/TiO2/Ti3C2 was prepared by an easily available solvent reduction measure for the highly efficient catalytic nitro compounds. In particular, sandwich-like composite catalyst Cu2O/TiO2/Ti3C2 exhibits excellent catalysis for 2-nitroaniline (2-NA) and 4-nitrophenol (4-NP), and its pseudo-first-order reaction rate constants (k) are 0.163 and 0.114 min-1, respectively. Interestingly, even after eight consecutive cycles of catalytic experiments, the conversion rates of catalytic 2-NA and 4-NP are still greater than 95 and 92%, respectively, demonstrating that the obtained catalyst has excellent catalytic capability and a high reutilization rate. The excellent catalytic performances of Cu2O/TiO2/Ti3C2 can be attributed to the fact that Ti3C2 provides a greater reaction site for the formation of Cu2O and reduces the aggregation during the formation of Cu2O by in situ synthesis. Therefore, ternary composite catalyst Cu2O/TiO2/Ti3C2 prepared by solvent reduction not only supplies a technical method for the catalytic reaction of MXene-based material but also lays the foundation for the development of new photocatalysts.

Construction of Multifunctional and Adjustable Langmuir-Blodgett Composite Films Containing Black Phosphorus with High Stability for Optically Electrical Applications.

Fabrication of composite thin-film materials based on black phosphorus (BP) will greatly broaden the applications of BP in various areas. However, it is still a challenge to prepare a BP-based composite film with good stability and controllable structure. In this work, a series of BP-based composite Langmuir-Blodgett (LB) films are prepared by the self-assembly of polyethyleneimine (PEI)-modified BP nanosheets (BPNSs) (BPNS-PEI) and dye molecules. The presence of PEI greatly improves the stability of BPNSs. As for BPNS-PEI and dye molecules, the electrostatic interactions or π-π stacking interactions ensure the formation of stable composite LB films. Due to the protonation and deprotonation of amino groups, the synthesized BPNS-PEI/dye composite films show a sensitive response to acid and alkali gases, which shows wide application prospects as a highly sensitive gas sensor. Furthermore, surface-enhanced Raman scattering (SERS) proves that the prepared LB films exhibit good reproducibility and obvious Raman enhancement effect on rhodamine 6G molecules. In addition, due to the high carrier transfer rate of the obtained composite films, they possess enhanced photocurrent generation performance than pure BPNS-PEI and pure dye films. The current work demonstrates an effective method for preparing the ordered self-assembled BP-based composite LB films with good SERS and photoelectric conversion performance.

Multifunctional Antimicrobial Biometallohydrogels Based on Amino Acid Coordinated Self-Assembly.

There is a real need for new antibiotics against self-evolving bacteria. One option is to use biofriendly broad-spectrum and mechanically tunable antimicrobial hydrogels that can combat multidrug-resistant microbes. Whilst appealing, there are currently limited options. Herein, broad-spectrum antimicrobial biometallohydrogels based on the self-assembly and local mineralization of Ag+ -coordinated Fmoc-amino acids are reported. Such biometallohydrogels have the advantages of localized delivery and sustained release, reduced drug dosage and toxicity yet improved bioavailability, prolonged drug effect, and tunable mechanical strength. Furthermore, they can directly interact with the cell walls and membrane, resulting in the detachment of the plasma membrane and leakage of the cytoplasm. This leads to cell death, triggering a significant antibacterial effect against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria in cells and mice. This study paves the way for developing a multifunctional integration platform based on simple biomolecules coordinated self-assembly toward a broad range of biomedical applications.

Effect of an Electric Field on Surface Properties of Hydrophobic Particles during a Flotation Process in Salt Water.

Under air flotation conditions, the effect of an electric field (EF) to the interfacial properties of hydrophobic particles in salt solution was investigated by using molecular dynamics simulation. The varieties of thickness of the hydrophobic layer on the surface of the hydrophobic particles, radial distribution function of Na+, diffusivity of CO2 and H2O, residence time of H2O in the solvent shell of Na+, and the distribution of CO2 near the graphene caused by the applied EF in different NaCl systems were calculated, and all those results were compared with those where there is no EF applied. The results reveal that the thickness of the hydrophobic layer near the hydrophobic particles is decreased under an EF. The coordination number and residence time of H2O in the solvent shell of Na+ are also decreased, which indicates that the restraint of Na+ on surrounding H2O is weakened, and the H2O molecules are more mobile. Under an external EF, the diffusion coefficient of CO2 and H2O is increased, and the quantity of CO2 near the surface of graphene is decreased according to the numerical results of the radial distribution of graphene-CO2. All the results indicate that the EF will decrease the thickness of the hydrophobic layer near hydrophobic particles, which can therefore weaken the adsorption between the hydrophobic particles and the gas molecules. The simulation results in the present study can provide theoretical support for brine mineral flotation under an external EF.

Chemical Vapor Deposition-Assisted Fabrication of Self-Assembled Co/MnO@C Composite Nanofibers as Advanced Anode Materials for High-Capacity Li-Ion Batteries.

Constructing the nanostructure of transition metal oxides for high energy density lithium-ion batteries has been widely studied recently. Prompted by the idea that the transition metal can serve as a catalyzer influence on the reversibility of solid-electrolyte interphase films, Co/MnO@C composite nanofibers were designed by electrospinning and chemical vapor deposition methods. The Co/MnO@C electrode showed superior electrochemical performance with a large capacity increase for the first 400 cycles and a high rate performance of 1345 mA h g-1 at 1000 mA g-1. There was no obvious decay of capacity over the whole 1000 cycles, demonstrating the excellent cycling stability of the samples. The new design and synthesis of the anodic materials may offer a prototype for high-performance and strong-stability batteries.

Preparation and High Photocurrent Generation Enhancement of Self-Assembled Layered Double Hydroxide-Based Composite Dye Films.

Understanding photocurrent conversion of layered double hydroxide (LDH) materials will be a key step in the future application of these materials to light-capturing molecular devices. In the present study, ultrathin nickel-iron layered double hydroxide/dye (NF-LDH/dye) Langmuir-Blodgett (LB) semiconductor films were prepared using an LB device and deposited on an indium tin oxide (ITO) substrate as a photoanode. The photoelectric conversion efficiency of the prepared LB semiconductor film materials was tested. A comparative experiment was performed to effectively explore the photoelectric conversion performances of the LB semiconductor film materials. Specifically, the NF-LDH cast film electrode, the dye cast film electrode, and an ultrathin composite LB film electrode were used as typical samples to explore photoelectric conversion performances. The electrochemical workstation was used to study the photocurrent density, linear scanning voltammetry curve, and electrochemical impedance spectroscopy of LB film electrodes with different layers. The results show that the film electrode cast by LDH alone or dye alone produces weak photocurrent. The photoelectric conversion efficiency of the LB film electrode is enhanced due to the different dyes' molecular structures and/or aggregations on the surface of LDH with various morphological patterns. The combined NF-LDH/dye composite LB film photoelectrode can generate a photocurrent that is 2-5 times stronger than the raw material, and the stable use efficiency is more than 92%. Present obtained composite LB films demonstrated a uniform morphology and good photoelectric conversion ability. This work provides a useful reference for the field of LDH semiconductor optoelectronic devices and solar cells.

Porous FeO x /carbon nanocomposites with different iron oxidation degree for building high-performance lithium ion batteries.

Transition metal oxides have attracted lots of interest for lithium ion battery (LIB) due to the high theoretical capacity, however, the large specific volume change, low electrical conductivity and slow intrinsic lithiation/delithiation still limit the practical applications. In order to overcome the challenge, a novel type of high temperature annealing treatment for the synthesis of 3D porous FeO x nanocrystals embedded in a partially carbon matrix as an example for high-performance LIB is reported. The FeO x /carbon nanocomposites with coral-like architecture achieved at 700 °C (F700) exhibit good long term cyclability with a reversible capacity 1012 mAh g-1 remain after 500 cycles at 1.0 A g-1 and the high rate capacity with a reversible capacity of 233 mAh g-1 even at extremely high current density of 20 A g-1. These excellent electrochemical performances could be attributed to the 3D porous structure and carbon coating, which could not only provide excellent electronic conductivity and enough elastic buffer space to accommodate volume changes upon lithium insertion/extraction, but also effectively avoid agglomeration of the Fe3O4 nanocrystals and maintain the structural integrity of the electrode during the charge/discharge process.

Fabrication of hierarchical SrTiO3@MoS2 heterostructure nanofibers as efficient and low-cost electrocatalysts for hydrogen-evolution reactions.

The construction of low-cost, high-performance electrocatalysts instead of platinum catalysts is critical to solving the energy crisis. Here, using simple electrospinning and hydrothermal methods, new MoS2 nanosheets on SrTiO3 nanofibers (NFs) and 2D SrTiO3@MoS2 heterostructure NFs are synthesized. In addition, SrTiO3@MoS2 heterostructure NFs are compared with bare SrTiO3 NFs and MoS2 nanosheets. Importantly, the prepared SrTiO3@MoS2 heterostructure shows better hydrogen-evolution reaction performance than other MoS2-based electrocatalysts with an overpotential of 165 mV at 10 mA cm-2, a Tafel slope of 81.41 mV dec-1, and long-term electrochemical durability of 3000 cycles. Therefore, the present work strongly demonstrates the positive synergy between SrTiO3 NFs and layered MoS2, and also provides a strategy for preparing low-cost and high-activity water-decomposition electrocatalysts.

Chiral Nanostructured Composite Films via Solvent-Tuned Self-Assembly and Their Enantioselective Performances.

Chiral nanostructures exhibited distinctive functions and attractive applications in complex biological systems, which demonstrated the subject of many outstanding research studies. In this work, various hierarchical composite film nanostructures were designed via supramolecular self-assembly using chiral amphiphilic glutamate derivatives and achiral porphyrin derivatives and their macroscopic enantioselective recognition properties were investigated. We have found that intermolecular hydrogen-bonding interactions between water (donor and acceptor) and N, N-dimethylformamide (DMF) as well as chloroform (CHCl3) (acceptor only) and DMF could subtly alter the molecular packing and significantly affected the supramolecular self-assembled nanostructures and triggered circular dichroism (CD) signal reversal. Present research work exemplified a feasible method to fabricate chiral flower-like and brick-like nanostructure films in different mixed solvents and large-scale chiral transfer from the molecular level to complex structures, which also provided a facile approach to identify certain l-/d-amino acids by means of contact angle detection using present obtained self-assembled composted films.

Facile preparation of self-assembled hydrogels constructed from poly-cyclodextrin and poly-adamantane as highly selective adsorbents for wastewater treatment.

Self-assembled hydrogel materials constructed from cyclodextrin polymer (P-CD)/adamantane-modified poly acrylic acid (PAA-Ad) were designed and prepared via host-guest interactions. It was observed that the prepared supramolecular hydrogels had an interconnected three-dimensional porous network. In addition, the obtained hydrogels showed a recovery performance and it was confirmed that the host-guest interactions between ß-cyclodextrin and adamantane were the main driving force for the formation of the hydrogels. The mechanical properties of the hydrogels could be adjusted by varying the concentrations of PAA-Ad. In particular, the prepared supramolecular hydrogels exhibited superior performances in water purification. The results demonstrated that the hydrogels possessed different mechanisms in the adsorption of the four typical poisonous organic dye molecules used, including bisphenol A (BPA), 4-aminoazobenzene (N-Azo), methylene blue (MB), and rhodamine B (RhB). The hydrogels mainly adsorbed N-Azo by host-guest interaction and adsorbed BPA by host-guest interaction and hydrogen bond synergy. They also adsorbed MB and RhB by hydrogen bonding and electrostatic interaction.

Facile preparation of a self-assembled Artemia cyst shell-TiO2-MoS2 porous composite structure with highly efficient catalytic reduction of nitro compounds for wastewater treatment.

The catalytic reduction of nitro compounds is currently a hot research area, how to efficiently and stably degrade such toxic and harmful substances has become the research goal of many researchers. In this work, an Artemia cyst shell (ACS)-TiO2-MoS2 ternary porous structure was proposed and prepared as a catalyst for the reduction of 2-nitroaniline (2-NA) and 4-nitrophenol (4-NP). The ACS has a large number of porous structures, exhibits a good binding ability with TiO2 and MoS2, and provides a large number of active sites for the catalytic reduction process. The obtained composite material has a good reduction effect on 4-NP and 2-NA, with a good stability and recyclability, which is obviously higher than the reduction effect of ACS-TiO2 and MoS2 under the same conditions. This work provides ideas for the design of porous catalytic materials.

The porous structure effects of skeleton builders in sustainable sludge dewatering process.

Dewatering from sludge is an important sustainable issue in recent years, in this work, we found the unique behavior: Skeleton builder additions can improve the dewatering performance greatly, which related to the different pore structure of skeleton builder. As compared to the coal ash, sawdust and rice husk char are easier to construct porous channels in the sludge body, which is responsible for the discharge of water. the dewatering efficiency can increased from approximately 30%-65% by pipe network effect and interlayer channel effect, a sufficient amount of skeleton builders establish a complete pipe drainage network in the sludge body, allowing the water to be discharged fluently. Moreover, the skeleton builders can cause the sludge body to form a layered structure. Under the combined action of pipe network effect and interlayer channel effect, the deep-dewatering effect increased largely by the addition of skeleton builders.

Facile synthesis of self-assembled carbon nanotubes/dye composite films for sensitive electrochemical determination of Cd(II) ions.

A new type of voltammetric sensor material has been fabricated via a facile self-assembled method. A modified glassy carbon electrode (GCE) by phenylsulfonic groups grafted multi-walled carbon nanotubes (CNT-SO3H) with dye molecules via Langmuir-Blodgett (LB) assembling (CNT-SO3H/dye-LB/GCE) were prepared for detecting trace levels of cadmium (Cd2+) ions by square wave anodic stripping voltammetry. The synergy effect between CNT-SO3H and dye as well as orderly aggregates in composite LB films contributed to greatly enhancing the determination performance. Under selected conditions, voltammetric response of the fabricated electrochemical sensor in 0.1 M acetate buffer solution containing Bi3+ ions for Cd2+ ions was linear with its concentration in the range 0.1 to 1.2 µM, with a detection limit of 0.08 µM. In addition, the preparation process of self-assembled composite film modified electrodes was simple, non-toxic, exhibiting higher sensitivity and potential application prospects in aspects of heavy metal ions detection and environmental analysis.