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Polymeric graphitic carbon nitride (g-CN) has emerged as a promising metal-free photocatalyst; however, the polymerization process is still poorly understood, and the synthesized g-CN shows a struc...

It is a highly relevant topic concerning how to improve the electrochemical performance of anode materials for the next generation lithium-ion batteries (LIBs). Herein, for the first time, we report a facile and controllable approach to modify MoS2 nanosheets, a typical 2D material, as an anode material for advanced LIBs via oxygen plasma engineering. An oxygen plasma treatment not only generates vacancies/defects but also incorporates heteroatom doping to form Mo–O–C bonds. This unique hybrid specialty enables the oxygen-plasma-treated MoS2 to achieve superior electrochemical performance with high reversible capacities, a long-term cycle life, and good rate capabilities. The plasma-assisted modification is believed to be applicable for other 2D materials as an efficient anode for energy storages.

Semiconductor materials are favoured in the field of photocatalysis due to their unique optoelectronic properties. When a semiconductor is excited by external energy, electrons will transition through the band gap, providing electrons or holes for the reaction. This is similar to the chemical enhancement mode of a catalytic reaction initiated by the rough noble metal on the surface excited by plasmon resonance. In this study, different types of semiconductor silicon loaded with silver nanoparticles were used as SERS substrates. SERS detection of p-aminothiophenol (PATP) and p-nitrothiophenol (PNTP) probe molecules was performed using typical surface plasmon-driven coupling reactions, and the mechanism of optical drive charge transfer in semiconductor–metal–molecular systems was investigated. Scanning electron microscopy and plasmon luminescence spectroscopy were used to characterize the silver deposited on the substrate surface. Mapping technology and electrochemistry were used to characterize the photocatalytic reaction of the probe molecules. This study proposed a mechanism for the coupling reaction of “hot electrons” and “hot holes” on the surface of plasmon-driven molecules and provides a method for preparing a stable SERS substrate.

There is much evidence that surface plasmon photocatalytic reactions can occur on organic molecules on metal surfaces. In this paper, we focus on the photocatalytic reaction of 4-ethynylaniline (PEAN) on silver nanoparticles (Ag NPs) in a liquid environment by surface-enhanced Raman spectroscopy (SERS). Our experiments used SERS to characterize p,p′-diynylazobenzene produced from PEAN via a selective catalytic coupling reaction on Ag NPs. This discovery not only achieved the expected results but also broadens the known plasmon-driven surface catalytic reaction system. In our work, we also regulated the photocatalytic coupling reaction conditions of PEAN on Ag NPs by laser power-dependent and time-dependent SERS spectra.

In this study, we demonstrate that plasma treatment can be a facile and environmentally friendly approach to perform surface modification of graphitic carbon nitride (g-CN), leading to a remarkable modulation on its photocatalytic activity. The bulk properties of g-CN, including the particle size, structure, composition, and electronic band structures, have no changes after being treated by oxygen or nitrogen plasma; however, its surface composition and specific surface area exhibit remarkable differences corresponding to an oxygen functionalization induced by the plasma post-treatment. The introduced oxygen functional groups play a key role in reducing the recombination rate of the photoexcited charge carries. As a consequence, the oxygen-plasma-treated sample shows a much superior photocatalytic activity, which is about 4.2 times higher than that of the pristine g-CN for the degradation of rhodamine B (RhB) under visible light irradiation, while the activity of nitrogen-plasma-treated sample exhibits a slight decrease. Furthermore, both of the plasma-treated samples are found to possess impressive photocatalytic stabilities. Our results suggest that plasma treatment could be a conventional strategy to perform surface modification of g-CN in forms of both powders and thin films, which holds broad interest not only for developing g-CN-based high-performance photocatalysts but also for constructing photoelectrochemical cells and photoelectronic devices with improved energy conversion efficiencies.

The effect of plating temperatures between 60 and 90°C on structure and corrosion resistance for electroless NiWP coatings on AZ91D magnesium alloy substrate was investigated. Results show that temperature has a significant influence on the surface morphology and corrosion resistance of the NiWP alloy coating. An increase in temperature will lead to an increase in coating thickness and form a more uniform and dense NiWP coatings. Moreover, cracks were observed by SEM in coating surface and interface at the plating temperature of 90°C. Coating corrosion resistance is highly dependent on temperature according to polarization curves. The optimum temperature is found to be 80 ∘ C and the possible reasons of corrosion resistance for NiWP coating have been discussed.

The interlayer interactions in nonpolar graphite and other B C N layered materials involving polar covalent bonds (h-BN, g-C3N4, graphite-like BC3 and BC2N) have been investigated by dispersion-corrected density functional calculations. Lattice parameters, bulk moduli and interlayer binding energies of these layered materials have been calculated using different dispersion correction schemes for comparison. Charge density difference plots have also been presented to elucidate the charge transfer behaviors along the nonpolar/polar covalent bonds as well as in the interlayer region. At first, graphite and h-BN were examined as benchmarks; the former contains planar graphene layers regardless of the interlayer binding, while the monolayers in the latter exhibit an asymmetric charge distribution along the B N polar bonds, leading to a slightly puckered feature induced by the interlayer interaction. Similar geometric deviations have also been observed in other layered structures involving C N and/or B C polar bonds, but with distinct characteristics directly related to their specific interlayer stacking situations. By contrast, all of the isolated monolayers free from interlayer binding show a pristine planar feature in despite of the polar covalent bonds involved. Our theoretical findings further address the necessity of considering the electron-density variations induced by specific bonding environments in polar B C N layered materials, which can be properly described by the Tkatchenko-Scheffler correction.

Understanding the intermolecular interactions in the context of crystal packing is of fundamental significance in molecular materials science. Infrared (IR) spectroscopy can provide complementary structural information; however, it still remains a great challenge to accurately predict the molecular IR vibrations in the crystalline phase. Here we report a cluster-model approach to simulate the IR spectra of triazine-based molecular crystals via density functional theory (DFT) calculations. In the properly designed cluster models, the molecular IR vibrations are expressed by a representative unit, while the nearest-neighbouring molecules are treated as a “frozen shell” to mimic the surrounding crystallographic environments. Much smaller clusters can be built by considering the crystallographic equivalence in the unit cell, which are able to perform DFT calculations on more complicated crystal structures with endurable computational costs. The simulated spectra show excellent consistencies with the experimental ones, particularly providing an in-depth understanding of the vibrational modes closely related to hydrogen bonding. Most importantly, the selectively built clusters based on the crystallographically independent molecules in the unit cell allow us to perform specific IR-spectral simulations, by which their distinct hydrogen-bonding environments have been clearly revealed for the first time.

Possible bulk black phosphorus (BP) allotropes are constructed based on single-layer BP with various stacking sequences. Our stacking algorithm shows that there are eight possible allotropes with two stacking layers in their unit cells possessing relatively high symmetries, and six of them are retained after structural relaxation using a van der Waals correction of optB88-vdW. The AF, AG, and AH bulk structures are presented for the first time. The structural relationship of these configurations has been explained via an interlayer slipping process. The total energy of the AF allotrope is closest to the most stable bulk BP structure (AB stacking) among all explored 2-layer stacked bulk structures. The calculated band structure of the AF allotrope using HSE06 shows a direct band gap of 0.48 eV with anisotropic electronic structures. We also presented six possible BP allotropes with three stacking layers in their unit cells. The newly reported AAF and ABC stacked structures show semiconducting and metallic features, respectively. After the bulk structures were explored, we further built the corresponding few-layer phosphorene structures and investigated their electronic properties. The results show that all the few-layer phosphorenes show semiconducting features. The AE, AAE, and AEA phosphorenes have indirect band gaps while the other explored phosphorenes possess direct band gaps located at the Γ point.

Although polymeric graphitic carbon nitride (g-C3N4) has been widely studied as metal-free photocatalyst, the description of its structure still remains a great challenge. Fourier transform infrared (FTIR) spectroscopy can provide complementary structural information. In this paper, we reconsider the representative crystalline melamine and develop a strategic approach to theoretically calculate the IR vibrations of this triazine-based nitrogen-rich system. IR calculations were based on three different models: a single molecule, a 4-molecule unit cell, and a 32-molecule cluster, respectively. By this comparative study the contribution of the intermolecular weak interactions were elucidated in detail. An accurate and visualized description on the experimental FTIR spectrum has been further presented by a combinatorial vibration-mode assignment based on the calculated potential energy distribution of the 32-molecule cluster. The theoretical approach reported in this study opens the way to the facile and accurate assignment for IR vibrational modes of other complex triazine-based compounds, such as g-C3N4.

International audience; This work presents a simple method to generate ordered chromophore/dispersant nanoarrays through a pore-filling process for a nanoporous polymer template to enhance chromophore luminescence. Fluorescence results combining with the morphological evolution examined by scanning probe microscopy reveal that the enhanced luminescence intensity reaches the maximum intensity as the nanopores of the template are completely filled by the chromophore/dispersant mixture. The variation is attributed to nanoscale spatial effect on the enhanced mixing efficiency of chromophore and dispersant, that is, the alleviation of self-quenching problem, as evidenced by the results of attenuated total reflection Fourier transform IR spectroscopy combining with grazing incident wide-angle X-ray diffraction. The enhanced luminescence of the chromophore/dispersant nanoarrays driven by the nanoscale spatial effect is highly promising for use in designing luminescent nanodevices.

International audience; We successfully address the challenge of aligning single-walled carbon nanotubes (SWNTs) and conjugated polymer chains in composite nanofibers for enhancing their opto-electrical properties. A pore-filling template strategy has been developed to prepare such nanocomposites from SWNTs and poly(para-phenylene vinylene) (PPV) chains, with both species well-oriented aligned along the pore axis. Addition of the SWNTs leads to a remarkable increase in photocurrent of four orders of magnitude as compared to equivalent pristine PPV nanofibers. Further analysis indicates that the strong photocurrent enhancement is not simply an effect of alignment, but additionally benefits from alignment-enhanced interaction of polymer chains with SWNTs, as supported by density functional theory (DFT) calculations.

International audience; This work presents a simple method to generate ordered conjugated polymer nanoarrays through a pore-filling process for nanoporous polymer templates so as to enhance the efficiency of photoluminescence (PL). PL results combined with the morphological evolution examined by scanning probe microscopy revealed that the enhanced PL reaches maximum intensity as the template pores are completely filled by conjugated polymers. Polarized PL spectroscopy and grazing incidence Fourier transform infrared spectroscopy were used to determine the chain orientation of templated conjugated polymer; the spectroscopic results indicate a parallel chain orientation along the cylindrical direction of nanopores. The induced alignment of the polymer chains is attributed to a nanoscale spatial effect that increases the PL intensity and the lifetime of the conjugated polymer. The enhanced luminescence of nanostructured conjugated polymers is highly promising for use in designing luminescent nanodevices.

International audience; The radial nanostructure of the binary liquid triethylamine/water confined in 60 nm diameter independent cylindrical pores of anodic aluminium oxide membranes is studied by small angle neutron scattering. It is shown that composition inhomogeneities are present in the confined mixtures well below the bulk critical point. An analysis of the neutron scattering form factor reveals the existence of an adsorbed water layer of a few nanometers at the liquid/alumina interface, coexisting with a TEA-rich phase in the core.