Photoreduction of Aqueous Protons Coupling with Alcohol Oxidation on a S-Scheme Heterojunction Photocatalyst MnO/Carbon Nitride.

Crystalline carbon nitride (CCN), derived from amorphous polymeric CN, is considered as a new generation of metal-free photocatalyst because of its high crystallinity. In order to further promote the photocatalytic performance of CCN, p-type MnO nanoparticles are in situ synthesized and merged with n-type CCN through a one-pot process to form p-n heterojunction. The formed interfacial electric field between the semiconductors with different work functions efficiently breaks the coulomb interaction between MnO and CCN. The prepared catalysts exhibit drastically increased photocatalytic hydrogen evolution (PHE) activity integrated with oxidation of alkyl and aryl alcohols under irradiation of visible light. In the aqueous solution of benzyl alcohol (BzOH), the hydrogen generation rate over MnO/CCN (39.58 µmol h-1) is nearly 7 times and 37 times that of pure CCN (5.76 µmol h-1) and CN (1.06 µmol h-1), respectively, combining with oxidation of BzOH to benzaldehyde. This work proposes an avenue for in situ construction of a novel 2D material-based S-scheme heterojunction and extends its application in solar energy conservation and utilization.

Preparation of Flexible Carbon Fiber Fabrics with Adjustable Surface Wettability for High-Efficiency Electromagnetic Interference Shielding.

In the 5G era, for portable electronics to operate at high performance and low power levels, the incorporation of superior electromagnetic interference (EMI) shielding materials within the packages is of critical importance. A desirable wearable EMI shielding material is one that is lightweight, structurally flexible, air-permeable, and able to self-clean. To this end, a bioinspired electroless silver plating strategy and a one-step electrodeposition method are utilized to prepare an EMI shielding fabric (CEF-NF/PDA/Ag/50-30) that possesses these desirable properties. Porous CEF-NF mats with a spatially distributed silver coating create efficient pathways for electron movement and enable a remarkable conductivity of 370 S mm-1. When tested within a frequency range of 8.2-12.4 GHz, this highly conductive fabric not only achieves an EMI shielding effectiveness (EMI SE of 101.27 dB at 5028 dB cm2 g-1) comparable to a very thin and light metal but also retains the unique properties of fabrics-being light, structurally flexible, and breathable. In addition, it exhibits a high contact angle (CA) of 156.4° with reversible surface wettability. After having been subjected to 1000 cycles of bending, the performance of the fabric only decreases minimally. This strategy potentially provides a novel way to design and manufacture an easily integrated EMI shielding fabric for flexible wearable devices.

Effect of hydroxypropyl methylcellulose molecular weight on supramolecular structures and properties of HPMC/sodium citrate photophobic films.

Photophobic (white) films were prepared by mixing hydroxypropyl methylcellulose (HPMC) of different molecular weights with sodium citrate (SC). Wide angle X-ray diffractometry, small angle X-ray scattering, scanning electron microscopy, dynamic mechanical analysis, whiteness determination and texture analysis were used to investigate the effect of HPMC molecular weight on the aggregation structures and properties of HPMC film. The crystalline integrity decreased with the increased molecular weight of HPMC for these HPMC/SC films. Similar crystallinity was observed for 6HPMC/SC and 15HPMC/SC, which was larger than that of 50HPMC/SC. All the three HPMC/SC film showed surface fractal structure with similar Ds. With the increasing molecular weight of HPMC, the HPMC/SC film showed honeycomb structures with smaller holes and more compact porous structure, Tg first increased and then decreased a little, the tensile strength and elongation increased with the increasing HPMC molecular weight. 50HPMC/SC films with the smallest pores showed the largest whiteness. A new Tg' peak was observed for HPMC/SC film.

Noble Metal-Free Photocatalysts Consisting of Graphitic Carbon Nitride, Nickel Complex, and Nickel Oxide Nanoparticles for Efficient Hydrogen Generation.

A facile and simple synthetic route is developed to prepare earth-abundant and noble metal-free hybrid photocatalysts, which are composed of graphitic carbon nitride (CN), nickel complex, and NiO x nanoparticles. Bimolecular nucleophilic substitution reaction was employed to attach a nickel complex onto a graphitic CN framework through covalent bonds to support its high loading and dispersion. NiO x nanoparticles were further incorporated into the catalysts to serve as a hole-transporting medium to improve the separation of photogenerated carriers for higher photocatalytic activity. Both yNiL/CN and yNiL/NiO x/CN exhibit superb H2 evolution activity. The optimum H2 evolution rate of the binary photocatalysts yNiL/CN reaches 303.3 µmol·h-1·g-1, whereas that of the ternary photocatalysts yNiL/NiO x/CN reaches 524.1 µmol·h-1·g-1, and the apparent quantum efficiency reaches 1.46% at 450 nm. This finding reveals that coordination of a nickel complex is significant in promoting photocatalytic performance, and the incorporation of NiO x nanoparticles as a hole-transporting medium is beneficial for separation of the photogenerated charge carriers. The novel hybrid system offers a new horizon for designing transition-metal complex-modified graphitic CN as noble metal-free and highly active photocatalysts for efficient visible light-driven hydrogen generation.

Microstructures and properties of photophobic films composed of hydroxypropyl methylcellulose and different salts.

Monosodium phosphate (MP), sodium citrate (SC), sodium lactate (SL) and magnesium citrate (MC) can be blended with hydroxypropyl methylcellulose (HPMC) to make photophobic (white) films at lower drying temperatures. Small angle X-ray scattering (SAXS), wide angle X-ray diffraction (XRD), scanning electron microscopy (SEM), whiteness determination, dynamic mechanical analysis (DMA) and texture analysis were adopted to study the variation of microstructures and properties. These four kinds of HPMC/salt films showed decreased crystallinity and increased compactness and smoothness of the self-similar structures in larger scale ranges. HPMC/MP, HPMC/SC and HPMC/SL film showed coarser and porous morphologies, lower mechanical parameters and higher whiteness than pure HPMC film. HPMC/MC film showed smoother morphologies, higher tensile strength, elongation and whiteness than pure HPMC film. Porous structures and more compact self-similar structures might contribute to the photophobic property of these films, and relatively smooth morphology might dominate the increasing mechanical parameters of HPMC/MC film.

Triamterene-Grafted Graphitic Carbon Nitride with Electronic Potential Redistribution for Efficient Photocatalytic Hydrogen Evolution.

In this study, a photocatalyst with a distorted skeleton and synthesized by grafting triamterene onto graphitic carbon nitride (g-C3 N4 ) frameworks was prepared. The pteridine ring of the triamterene-based nitrogen-enriched organic structure functions as a trapped electron site owing to its inductive effect. The benzene ring in triamterene plays an important role in the even dispersion of electrons by a conjugative effect. Redistribution of the intramolecular electronic potential is caused by a synergistic effect between the pteridine and benzene rings of triamterene and promotes separation and migration of the photoinduced charge carriers. After coupling with triamterene, the π electrons of g-C3 N4 are relocated; that is, the intrinsic electronic and band structures of g-C3 N4 are effectively modulated. The modified polymeric photocatalyst shows a high photocatalytic H2 evolution rate of 157.5 µmol h-1 , a value that is 4.3 times higher than the H2 evolution rate of pristine g-C3 N4 (36.8 µmol h-1 ), with an apparent quantum efficiency of 9.7 % at λ=450 nm. The incorporation of triamterene into the g-C3 N4 frameworks significantly expands its π-delocalized system by redistribution of the electronic potential, expands the visible-light absorption range, and effectively promotes the separation and migration of photoinduced charge carriers. This strategy may provide a reference for promoting charge separation of g-C3 N4 through redistribution of the electronic potential and for synthesizing novel carbon nitride based semiconductors for efficient solar energy conversion into hydrogen.

Carbon nanotubes-modified graphitic carbon nitride photocatalysts with synergistic effect of nickel(II) sulfide and molybdenum(II) disulfide co-catalysts for more efficient H2 evolution.

This work reports effective photocatalysts which are composed of carbon nitride (CN), carbon nanotubes (CNTs), MoS2 and NiS, for hydrogen evolution aiming at energy crises and environmental pollutions. The morphologies and optical properties of the photocatalysts were carefully characterized and their photocatalytic performance towards water reduction was studied afterwards. MoS2 and NiS exhibit a significant synergistic effect working as co-catalysts. Compared to MoS2/CN nanohybrid, carbon nanotubes and NiS improved the absorption of visible light and the separation of charge carriers effectively. NiS-MoS2/CNTs/CN catalyst exhibits high performance for H2 evolution and the optimized rate is 309.9 µmol·h-1·g-1 with no noble metals under visible light irradiation. The study demonstrates a non-noble metal photocatalyst system for effective generation of hydrogen with low cost.

Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis.

The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin.

High and stable photoelectrochemical activity of ZnO/ZnSe/CdSe/Cu(x)S core-shell nanowire arrays: nanoporous surface with Cu(x)S as a hole mediator.

Advanced materials for electrocatalytic and photoelectrochemical water splitting are key for taking advantage of renewable energy. In this study, ZnO/ZnSe/CdSe/Cu(x)S core-shell nanowire arrays with a nanoporous surface were fabricated via ion exchange and successive ionic layer adsorption and reaction (SILAR) processes. The ZnO/ZnSe/CdSe/Cu(x)S sample displays a high photocurrent density of 12.0 mA cm(-2) under AM 1.5G illumination, achieves the highest IPCE value of 89.5% at 500 nm at a bias potential of 0.2 V versus Ag/AgCl, and exhibits greatly improved photostability. The functions of the ZnSe, CdSe, and Cu(x)S layers in the ZnO/ZnSe/CdSe/Cu(x)S heterostructure were clarified. ZnSe is used as a passivation layer to reduce the trapping and recombination of charge carriers at the interfaces of the semiconductors. CdSe functions as a highly efficient visible light absorber and builds heterojunctions with the other components to improve the separation and transportation of the photoinduced electrons and holes. Cu(x)S serves as a passivation layer and an effective p-type hole mediator, which passivates the defects and surface states of the semiconductors and forms p-n junctions with CdSe to promote the hole transportation at the semiconductor-electrolyte interface. The nanoporous surface of the ZnO/ZnSe/CdSe/Cu(x)S core-shell nanowire arrays, together with the tunnel transportation of the charge carriers in the thin films of ZnSe and CdSe, also facilitates the kinetics of photoelectrochemical reactions and improves the optical absorption as well.

Construction of ZnO/ZnS/CdS/CuInS2 core-shell nanowire arrays via ion exchange: p-n junction photoanode with enhanced photoelectrochemical activity under visible light.

ZnO/ZnS/CdS/CuInS2 core-shell nanowire arrays with enhanced photoelectrochemical activity under visible light were successfully prepared via ion exchange and hydrothermal methods. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-vis absorption, X-ray photoemission spectroscopy, and photoelectrochemical response. As a p-n junction photoanode, ZnO/ZnS/CdS/CuInS2 heterostructure shows much higher visible light photoelectrocatalytic activity toward water splitting than ZnO/ZnS/CdS and ZnO/ZnS films. The ZnO/ZnS/CdS/CuInS2 film with optimal constitution exhibits the highest photocurrent of 10.5 mA/cm(2) and the highest IPCE of approximately 57.7% at 480 nm and a bias potential of 0 V versus Ag/AgCl. The critical roles of CdS and ZnS in ZnO/ZnS/CdS/CuInS2 heterostructure were investigated. ZnS, as a passivation layer, suppresses the recombination of the photogenerated charge carriers at the interface of the oxide and CuInS2. CdS enhances the absorption of visible light and forms p-n junctions with CuInS2, which promotes the transport of charge carriers and retards the recombination of electrons and holes in CuInS2 to improve the photoelectrochemical performance of ZnO/ZnS/CdS/CuInS2 heterostructure.

Wide bandgap Bi2O2CO3-coupled Bi2MoO6 heterostructured hollow microspheres: one-pot synthesis and enhanced visible-light photocatalytic activity.

Hierarchical Bi2O2CO3/Bi2MoO6 heterostructured photocatalysts composed of nanoplatelets of Bi2O2CO3 and Bi2MoO6 were successfully prepared by a facile template-free solvothermal process. The microsphere-like Bi2O2CO3/Bi2MoO6 composites exhibited superior visible light photocatalytic activity towards degradation of rhodamine B. The highest degradation efficiency was observed on the material with the Bi/Mo molar ratio of 2.88/1, which can degrade 99% rhodamine B within 90 min, while only 44% rhodamine B was degraded over the pure Bi2MoO6 microspheres and 2% over the Bi2O2CO3 nanoplatelets. The dramatic enhancement in their photocatalytic performance of the Bi2O2CO3/Bi2MoO6 photocatalysts can be attributed to the high surface area and the effective separation of the photoinduced carriers at the interfaces and in the semiconductors. The photo-generated h+(VB) in the Bi2O2CO3/Bi2MoO6 photocatalysts turn out to be the dominant active species in the photocatalytic reaction. Importantly, Bi2O2CO3/Bi2MoO6 displayed visible-light photocatalytic activity for the destruction of E. coli (the percent kill is 99.09 in 60 min). In addition, the Bi2O2CO3/Bi2MoO6 composite was very stable during the reaction and can be used repeatedly. These features mean the present heterostructured photocatalyst can be applied in environmental remediation, and waste water disinfection.

Electrodeposition of polyaniline onto TiO2 nanoparticles/multiwalled carbon nanotubes for visible light photoelectrocatalysis.

In this study, polyaniline (PANI) was coated onto TiO2 nanoparticles/multiwalled carbon nanotubes (TiO2/MWCNTs) hybrid by electrochemical polymerization. Modification of TiO2/MWCNTs with PANI endows the resulted hybrid with visible light activity. The PANI/TiO2/MWCNTs hybrid shows remarkable photoelectrocatalytic activity for the degradation of RhB under visible light irradiation. The enhanced photocatalytic activity of the PANI/TiO2/MWCNTs hybrid originates from the effective charge transfer properties of the heterojunctions of PANI-TiO2 and TiO2-MWCNTs. The efficient charge transportation and high photoelectrocatalytic activity towards degradation of rhodamine B make this novel hybrid material promising for photocatalysis and for the development of photoelectrical devices.

Preparation and antibacterial property of waterborne polyurethane/Zn-Al layered double hydroxides/ZnO nanocomposites.

In this work, a novel environmental-friendly waterborne polyurethane/ZnAl-layered double hydroxides/ZnO nanoparticles composite (WPU/ZnAl-LDHs/ZnO) was synthesized via in-situ polymerization. ZnAl-LDHs and ZnAl-LDHs/ZnO were synthesized by refluxing in an oil bath. In order to disperse ZnAl-LDHs/ZnO homogeneously into WPU matrix, ZnAl-LDHs/ZnO was firstly functionalized by isophorone diisocyanate. The incorporated content of ZnAl-LDHs/ZnO in the composite has profound effect on such physical properties as mechanical strength, thermal stability and water swelling. It is demonstrated that appropriate amount of ZnAl-LDHs/ZnO with good dispersion in the WPU matrix significantly improves the physical performance of the composites. Finally, the antibacterial activity of the composite was tested against G(-) Escherichia coli and G(+) Staphylococcus aureus. The results indicate that WPU incorporated with ZnAl-LDHs/ZnO shows strong antibacterial activity upon contact.

A facile hydrothermal strategy for synthesis of SnO2 nanorods-graphene nanocomposites for high performance photocatalysis.

In this study, we report a facilely hydrothermal process for synthesizing SnO2 nanorods-graphene (SnO2 nanorods-GR) composite using graphite oxide and SnCl4 as raw materials. The SnO2 nanorods-GR composite was characterized by X-ray diffraction, electron microscopy, Xray photoelectron spectroscopy, and thermogravimetric analysis. Compared to commercial TiO2 nanoparticles P25 and neat SnO2 nanorods, the SnO2 nanorods-GR composite exhibits higher photocatalytic activity under UV light irradiation. The mechanism of its high photocatalytic activity is mainly ascribed to the synergy effect between SnO2 and graphene, in which graphene acts as an adsorbent and electron acceptor due to its large structure of pi-pi conjugation from sp2 hybrid carbon atoms. The results demonstrated in this study provide a promising way to enhance the photocatalytic activity by compounding semiconductive nanocrystals with graphene.

A highly sensitive hydrogen peroxide amperometric sensor based on MnO2-modified vertically aligned multiwalled carbon nanotubes.

In this report, a highly sensitive amperometric sensor based on MnO(2)-modified vertically aligned multiwalled carbon nanotubes (MnO(2)/VACNTs) for determination of hydrogen peroxide (H(2)O(2)) was fabricated by electrodeposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, energy-dispersive X-ray spectrometer and X-ray diffraction. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were applied to investigate the electrochemical properties of the MnO(2)/VACNTs nanocomposite electrode. The mechanism for the electrochemical reaction of H(2)O(2) at the MnO(2)/VACNTs nanocomposite electrode was also discussed. In borate buffer (pH 7.8, 0.20 M), the MnO(2)/VACNTs nanocomposite electrode exhibits a linear dependence (R=0.998) on the concentration of H(2)O(2) from 1.2 x 10(-6)M to 1.8 x 10(-3)M, a high sensitivity of 1.08 x 10(6) microA M(-1) cm(-2) and a detection limit of 8.0 x 10(-7) M (signal/noise=3). Meanwhile, the MnO(2)/VACNTs nanocomposite electrode is also highly resistant towards typical inorganic salts and some biomolecules such as acetic acid, citric acid, uric acid and D-(+)-glucose, etc. In addition, the sensor based on the MnO(2)/VACNTs nanocomposite electrode was applied for the determination of trace of H(2)O(2) in milk with high accuracy, demonstrating its potential for practical application.