Ultralow-weight loading Ni catalyst supported on two-dimensional vermiculite for carbon monoxide methanation

Nickel-based catalysts represent the most commonly used systems for CO methanation.We have successfully prepared a Ni catalyst system supported on two-dimensional plasma-treated vermiculite(2D-PVMT)with a very low Ni loading(0.5 wt%).The catalyst precursor was subjected to heat treatment via either conventional heat treatment(CHT)or the plasma irradiation method(PIM).The as-obtained CHT-Ni/PVMT and PIM-Ni/PVMT catalysts were characterized with scanning electron microscopy(SEM),energy dispersive X-ray(EDX),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),inductively coupled plasma-atomic emission spectroscopy(ICP-AES)and high-angle annular dark field scanning transmission electron microscopy(HAADF-STEM).Additionally,CHT-NiO/PVMT and PIM-NiO/PVMT catalysts were characterized with hydrogen temperature programmed reduction(H_2-TPR).Compared with CHT-Ni/PVMT,PIM-Ni/PVMT exhibited superior catalytic performance.The plasma treated catalyst PIM-Ni/PVMT achieved a CO conversion of93.5%and a turnover frequency(TOF)of 0.8537 s^(-1),at a temperature of 450°C,a gas hourly space velocity of 6000 ml·g^(-1)·h^(-1),a synthesis gas flow rate of 65 ml·min^(-1),and a pressure of 1.5 MPa.Plasma irradiation may provide a successful strategy for the preparation of catalysts with very low metal loadings which exhibit excellent properties.

A Green Strategy to Synthesize Ag/Ag3PO4/Chitosan Composite Photocatalysts and Their Photocatalytic Degradation Performance under Visible Light Irradiation

In this work, the plasmonic Ag/Ag3PO4/chitosan(Ag/Ag3PO4/CS) composite photocatalyst was prepared by a low-temperature strategy. Environmentally friendly CS plays triple vital roles in this composite. First, it was devoted to in situ reducing metallic silver from silver ions of Ag3PO4. Also, as the carrier of Ag/Ag3PO4 nanoparticles,CS can effectively prevent aggregation. Furthermore, benefitting from the settlement of hydrophilic CS, the prepared composite could be easily separated and recovered from the solution system. X-ray diffraction(XRD), the scanning electron microscope, energy-dispersive X-ray spectroscopy(EDS), ultraviolet-visible(UV-vis) diffused reflectance spectroscopy, and X-ray photoelectron spectroscopy(XPS) were employed to characterize the properties of materials. The results of photo-decomposition testing showed that the Ag/Ag3PO4/CS composite possessed good activity for the decomposition of Rhodamine B(Rh B) under visible light.

High-efficiency removal of NO_x using dielectric barrier discharge nonthermal plasma with water as an outer electrode

With the rapid increase in the number of cars and the development of industry, nitrogen oxide （NOx） emissions have become a serious and pressing problem. This work reports on the development of a water-cooled dielectric barrier discharge reactor for gaseous NOx removal at low temperature. The characteristics of the reactor are evaluated with and without packing of the reaction tube with 2 mm diameter dielectric beads composed of glass, ZnO, MnO2, ZrO2, or Fe203. It is found that the use of a water-cooled tube reduces the temperature, which stabilizes the reaction, and provides a much greater NO conversion efficiency （28.8%） than that obtained using quartz tube （14.1%） at a frequency of 8 kHz with an input voltage of 6.8 kV. Furthermore, under equivalent conditions, packing the reactor tube with glass beads greatly increases the NO conversion efficiency to 95.85%. This is because the dielectric beads alter the distribution of the electric field due to the influence of polarization at the glass bead surfaces, which ultimately enhances the plasma discharge intensity. The presence of the dielectric beads increases the gas residence time within the reactor. Experimental verification and a theoretical basis are provided for the industrial application of the proposed plasma NO removal process employing dielectric bead packing.

A novel black TiO2/ZnO nanocone arrays heterojunction on carbon cloth for highly efficient photoelectrochemical performance

ZnO nanocone arrays(NCAs)decorated with black TiO2 nanoparticles(BTiO2 NPs)were uniformly anchored on the surface of carbon cloth(CC)directly by a simply electrochemical deposition method.Thus a novel B-TiO2 NPs/ZnO NCAs-CC hierarchical heterostructure was formed.It displayed superior performance and achieved a higher photocurrent over 0.4 mA·cm^-2 before the onset of the dark current,attributed to the separation of the photogenerated electron-hole pair.Based on the B-TiO2 NPs/ZnO NCAs-CC heterostructure,the catalyst was fabricated for promoting the separation of charge carriers.Moreover,the introduction of Ti^3+ and oxygen vacancies on the surface of TiO2 NPs expanded the absorption band edge and enhanced the electrical conductivity as well as the charge transportation on the catalytic surface.It indicates that the B-TiO2 NPs/ZnO NCAs-CC composite is beneficial to the improvement of the photoelectrochemical(PEC)activity.

3D printed modular Bouligand dissipative structures with adjustable mechanical properties for gradient energy absorbing

Three-dimensional(3D)printing allows for the creation of complex,layered structures with precise micro and macro architectures that are not achievable through traditional methods.By designing 3D structures with geometric precision,it is possible to achieve selective regulation of mechanical properties,enabling efficient dissipation of mechanical energy.In this study,a series of modular samples inspired by the Bouligand structure were designed and produced using a direct ink writing system,along with a classical printable polydimethylsiloxane ink.By altering the angles of filaments in adjacent layers(from 30◦to 90◦)and the filament spacing during printing(from 0.8 mm to 2.4 mm),the mechanical properties of these modular samples can be adjusted.Compression mechanical testing revealed that the 3D printed modular Bouligand structures exhibit stress-strain responses that enable multiple adjustments of the elastic modulus from 0.06 MPa to over 0.8 MPa.The mechanical properties were adjusted more than 10 times in printed samples prepared using uniform materials.The gradient control mechanism of mechanical properties during this process was analyzed using finite element analysis.Finally,3D printed customized modular Bouligand structures can be assembled to create an array with Bouligand structures displaying various orientations and interlayer details tailored to specific requirements.By decomposing the original Bouligand structure and then assembling the modular samples into a specialized array,this research aims to provide parameters for achieving gradient energy absorption structures through modular 3D printing.

A novel 3D printed technology to construct a monolithic ultrathin nanosheets Co_(3)O_(4)/SiO_(2) catalyst for benzene catalytic combustion

In this study,a novel three-dimensional(3D)-OMm-Co_(3)O_(4)/SiO_(2)-0.5AP(OMm=ordered macro–meso porous,AP=aluminum phosphate)monolithic catalyst was for the first time constructed successfully with the hierarchical Co-phyllosilicate ultrathin nanosheets growth on the surface of 3D printed ordered macropore–mesoporous SiO_(2)support.On the one hand,we discovered that the construction of ordered macropore–mesoporous structures is beneficial to the diffusion and adsorption of reactants,intermediates,and products.On the other hand,the formation of hierarchical Co-phyllosilicate ultrathin nanosheets could provide more active Co&+species,abundant acid sites,and active oxygen.The above factors are in favor of improving the catalytic performance of benzene oxidation,and then a 3D-OMm-Co_(3)O_(4)/SiO_(2)-0.5AP catalyst exhibited the superior catalytic activity.To explore the effect of catalysts structure and morphology,various Co-based catalysts were also constructed.Simultaneously,the 3D-OMm-Co_(3)O_(4)/SiO_(2)-0.5AP catalyst has excellent catalytic performance,water resistance,and thermal stability in the catalytic combustion of benzene due to the strong interactions between Co&+species and SiO_(2)in the phyllosilicate.Therefore,this study proposes a new catalyst synthesis method through 3D printing,and presents considerable prospects for the removal of VOCs from industrial applications.

Facile preparation of low swelling,high strength,self-healing and pH-responsive hydrogels based on the triple-network structure

A polyacrylic acid(PAA)/gelatin(Gela)/polyvinyl alcohol(PVA)hydrogel was prepared by copolymerization,cooling,and freezing/thawing methods.This triplenetwork(TN)structure hydrogel displayed superior mechanical properties,low swelling ratio and self-healing properties,The superior mechanical properties are attributed to the triple helix association of Gela and PVA crystallites by reversible hydrogen bonding.The characterization results indicated that the fracture stress and the strain were 808 kPa and 370% respectively,while the compression strength could reach 4443 kPa and the compressive modulus was up to 39 MPa under the deformation of 90%.The hydrogen bonding in PVA contributed to maintain and improve the self-healing ability of hydrogels.Every type of hydrogels exhibited a higher swelling ratio under alkaline conditions,and the swelling ratios of PAA,PAA/PVA and PAA/Gela hydrogels were 27.71,12.30 and 9.09,respectively.The PAA/Gela/PVA TN hydrogel showed the lowest swelling ratio(6.57)among these hydrogels.These results indicate that the novel TN hydrogels possess good environmental adaptability and have potential applications in the biomedical engineering and sensor field.

Environmentally benign chitosan as reductant and supporter for synthesis of Ag/AgCI/chitosan composites by one-step and their photocatalytic degradation performance under visible-light irradiation

A novel Ag/AgCl/chitosan composite photocatalyst was successfully prepared by a simple one-step method. During this progress, environmentally benign chitosan not only served as reductant to reduce Ag＋ to Ag0 species, but also acted as supporter for Ag/AgCI nanoparticles. XRD, SEM, EDX, UV-vis DRS and XPS were employed to characterize the as-prepared simples. SEM images of Ag/AgCI/chitosan composites revealed that Ag/AgCI nanoparticles were successfully loaded onto chitosan without obvious aggregation. All Ag/AgCI/chitosan composites exhibited efficient photocatalytic activity for the degradation of rhodamine B （RhB） under visible-light irradiation. The result of photocatalytic degradation experiment indicated that 20% of the mass ratio of AgCI to chitosan was the optimum, and after 40 min photocatalytic reaction, the degradation rate reached about 96%.

Novel robust cellulose-based foam with pH and light dual-response for oil recovery

We fabricated pH and light dual-responsive adsorption materials which could induce the transition of surface wettability between hydrophobicity and hydrophilicity by using ATRPo The structure and morphology of adsorption materials were confirmed by ATR-FTIR, XPS, TGA and SEM. It showed that the modified cellulose （CE）- based foam was hydrophobic, which can adsorb a range of oils and organic solvents in water under pH = 7.0 or visible light irradiation （λ〉500 nm）. Meanwhile, the wettability of robust CE-based foam can convert hydrophobicity into hydrophilicity and underwater oleophobicity under pH = 3.0 or UV irradiation （λ = 365 nm）, giving rise to release oils and organic solvents. Most important of all, the adsorption and desorption processes of the modified CE-based foam could be switched by external stimuli. Furthermore, the modified CE-based foam was not damaged and still retained original performance after reversible cycle repeated for many times with variation of surface wettability. In short, it indicates that CE-based foam materials with switchable surface wettability are new responsive absorbent materials and have owned potential application in the treatment of oil recovery.

Sprayable and rapidly bondable phenolic-metal coating for versatile oil/water separation

Phenolic-metal complexation coatings have been discovered to be a universal route for the deposition of multifunctional coatings. However, most complexation coatings have been prepared by the immersion method, which limits their practical large-scale application. Herein, we describe a facile and green engineering strategy that involves spraying phenolic compound and metal ions on substrate to form in-situ complexation coating with different coordination states. The coating is formed within minutes and it can be achieved in large scale by the spray method. The pyrogallol-Fem complexation coating is prepared at pH 7.5, which consists predominantly of biscoordination complexation with a small amount of tris-coordination complexation. It displays that the water contact angle is near zero due to the generation of rough hierarchical structures and massive hydroxyl groups. The superhydrophilic cotton resulting from the deposition of the pyrogallol-Fe^Ⅲ complexation can separate oil/water mixtures and surfactant-stabilized oil-in-water emulsions with high separation efficiency. The formation of the phenolic-metal complexation coating by using spray technique constitutes a cost-effective and environmentally friendly, strategy with potential to be applied for large-scale surface engineering processes and green oil/water separation.

Hydrochlorination of acetylene using expanded multilayered vermiculite(EML-VMT)-supported catalysts

Catalyst supports have very important effects on catalyst performance.A novel expanded multilayered vermiculite（EML-VMT） is successfully used as the catalyst support for the acetylene hydrochlorination.By mixing carbon on the surface of EML-VMT[i.e.,EML-VMT-C）,the HgCl2/EML-VMT-C achieved a high acetylene conversion of 97.3%,a vinyl chloride selectivity of 100%and a turn over frequency（TOF） value of 8.83 × 10^-3s^-1 at a temperature of 140 C,an acetylene gas hourly space velocity（GHSV） of 108 h^-1,and a feed volume ratio V（HC1）/V（C2H2） of 1.15.Moreover,the HgCl2/EML-VMT-C shows good stability.The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.

锚定在W_(18)O_(49)纳米线上高度分散的Pt催化剂促进酸性溶液中高效稳定的析氢反应

铂(Pt)基材料是酸性电解质中析氢反应活性最高、稳定性最强的电催化剂;但是它的低丰度以及昂贵的价格限制了其在质子交换膜电解水(PEMWE)技术中的应用.因此,最小化Pt的使用量并且保持其高活性成为研究热点.在本文中我们利用低温抑制成核反应冷冻干燥合成法,促使Pt组分高度分散地锚定在富含缺陷的W_(18)O_(49)纳米线上(Pt-W_(18)O_(49)),进而实现了酸性电解质中高效稳定的析氢过程.第一性原理计算证明了Pt组分与W_(18)O_(49)载体之间的强电荷相互作用可以提升析氢性能.Pt-W_(18)O_(49)催化剂中Pt用量仅为商业化20 wt%Pt/C催化剂的1/10,该催化剂在0.5 mol L^(−1)H_(2)SO_(4)电解质中达到100和1000 mA cm^(−2)电流密度时的过电位分别为116和743 mV,超过了商业化的Pt/C催化剂.该催化剂可以在500 mA cm^(−2)的高电流密度条件下持续析氢超过38 h,没有明显的性能衰减.本工作为PEMWE技术的实际应用中降低Pt用量却保持高活性开创了新的研究思路.

Synthesis of Self-assemble pH-responsive Cyclodextrin Block Copolymer for Sustained Anticancer Drug Delivery

Well-defined pH-responsive poly（e-caprolactone）-graft-β-cyclodextrin-graft-poly（2-（dimethylamino）ethyl- methacrylate）-co-poly（ethylene glycol） methacrylate amphiphilic copolymers （PCL-g-β-CD-g-P（DMAEMA-co-PEGMA）） were synthesized using a combination of atom transfer radical polymerization （ATRP）, ring opening polymerization （ROP） and ＂click＂ chemistry. Successful synthesis of polymers was confirmed by Fourier transform infrared spectroscopy （FTIR）, proton nuclear magnetic resonance （^1H-NMR）, and gel permeation chromatography （GPC）. Then, the polymers could self- assemble into micelles in aqueous solution, which was demonstrated by dynamic light scattering （DLS） and transmission electron microscopy （TEM）. The pH-responsive self-assembly behavior of these copolymers in water was investigated at different pH values of 7.4 and 5.0 for controlled doxorubicin （DOX） release, and these results revealed that the release rate of DOX could be effectively controlled by altering the pH, and the release of drug loading efficiency （DLE） was up to 88% （W/W）. CCK-8 assays showed that the copolymers had low toxicity and possessed good biodegradability and biocompatibility, whereas the DOX-loaded micelles remained with high cytotoxicity for HeLa cells. Moreover, confocal laser scanning microscopy （CLSM） images revealed that polymeric micelles could actively target the tumor site and the efficient intracellular DOX release from polymeric micelles toward the tumor cells further confirmed the anti-tumor effect. The DOX-loaded micelles could easily enter the cells and produce the desired pharmacological action and minimize the side effect of free DOX. These results successfully indicated that pH-responsive polymeric micelles could be potential hydrophobic drug delivery carriers for cancer targeting therapy with sustained release.

One-step synthesis and self-assembly behavior of thermo-responsive star-shaped β-cyclodextrin-（P（M EO2MA-co-PEGMA））21 copolymers

A novel β-cyclodextrin-poly（2-（2-methoxyethoxy）ethyl methacrylate）-co- poly（ethylene glycol） methacrylate （abbreviated as： β-CD-（P（MEO2MA-co-PEGMA））21） was prepared by using the one-step strategy, and then the star-shaped copolymers were used in the atom transfer radical polymerization （ATRP）. The structure of star-shaped β- CD-（P（MEO2MA-co-PEGMA））21 copolymers were studied by FTIR, 1H NMR and gel permeation chromatography （GPC）. The star-shaped copolymers could self-assembled into micelles in aqueous solution owing to the outer amphiphilic β-CD as a core and the hydrophilic P（MEO2MA-co-PEGMA） segments as a shell. These thermo-responsive starshaped copolymers micelles exhibited lower critical solution temperature （LCST） in water, which could be finely tuned by changing the feed ratio of MEO2MA to PEGMA. The LCST of star-shaped β-CD-（P（MEO2MA-co-PEGMA））21 copolymer micelles were increased from 35℃ to 58℃ with the increasing content of PEGMA. The results were investigated by DLS and TEM. When the temperature was higher than corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, β- CD-（P（MEO2MA-co-PEGMA））21 star-shaped copolymer micelles could be potentially applied in nano-carrier, nano-reactor, smart materials and biomedical fields.

Folate-conjugated pH-responsive nanocarrier designed for active tumor targeting and controlled release of doxorubicin

A novel type of amphiphilic pH-responsive folate-poly（ε-caprolactone）- block-poly（ 2-hydroxyethylmethacrylate ）-co-poly（ 2-（ dimethylamino ）-ethylmethacrylate ） （FA-PCL-b-P（HEMA-co-DMAEMA）） （MFP） block copolymers were designed and synthe- sized via atom transfer radical polymerization （ATRP） and ring opening polymerization （ROP） techniques. The molecular structures of the copolymers were confirmed with IH NMR, FTIR and GPC measurements. The critical micelle concentration （CMC） of MFP in aqueous solution was extremely low （about 6.54 mglL）. The in vitro release behavior of DOX-Ioaded micelles was significantly accelerated when the pH value of solution decreased from 7.4 to 5.0. In vitro antitumor efficiency was evaluated by incubating DOX- loaded micelles with Hela cells. The results demonstrated that this copolymer possessed excellent biocompatibility, and FA-decorated micelles MFP showed higher cellular uptake than those micelles without the FA moiety, indicating their unique targetability. These folate-conjugated biodegradable micelles are highly promising for targeted cancer chemothe-rapy.

Preparation of few-layer reduced graphene oxide-wrapped mesoporous Li4Ti5O12 spheres and its application as an anode material for lithium-ion batteries

A three-dimensional few-layer reduced graphene oxide-wrapped mesoporous Li4TisO12 （m-LTO@FL- RGO） electrode is produced using a simple solution fabrication process. When tested as an anode for Li- ion batteries, the m-LTO@FL-RGO composite exhibits excellent rate capability and superior cycle life. The capacity of m-LTO@FL-RGO reaches 165.4 mA h g 1 after 100 cycles between I and 2.5 V at a rate of 1 C. Even at a rate of 30 C, a high discharge capacity of 115.1 mA h g 1 is still obtained, which is three times higher than the pristine mesoporous Li4TisO12 （m-LTO）. The graphene nanosheets are incorporated into the m-LTO microspheres homogenously, which provide a high conductive network for electron transportation.

The fabrication of hollow magnetite microspheres with a nearly 100% morphological yield and their applications in lithium ion batteries

Hollow Fe3O4（H-Fe3O4） microspheres were fabricated through a facile one-step solvothermal synthesis,which was performed in an ethylene glycol（EG）–diethylene glycol（DEG） mixed solvent using polyethylene glycol（PEG） as the stabilizer. The addition of DEG increased the viscosity of the system,which caused the Fe3O4 primary crystal to aggregate slower and the morphological yield to approach nearly 100%. The as-prepared hollow Fe3O4 microspheres show promise for application in lithium ion battery anodes and showed a reversible specific capacity of 453.3 mAh g^-1 after 50 cycles at 100 mA g^-1.