Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilita...Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.展开更多
Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst onl...Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2) product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.展开更多
GaAs-based nanomaterials are essential for near-infrared nano-photoelectronic devices due to their exceptional optoelectronic properties.However,as the dimensions of GaAs materials decrease,the development of GaAs nan...GaAs-based nanomaterials are essential for near-infrared nano-photoelectronic devices due to their exceptional optoelectronic properties.However,as the dimensions of GaAs materials decrease,the development of GaAs nanowires(NWs)is hindered by type-Ⅱquantum well structures arising from the mixture of zinc blende(ZB)and wurtzite(WZ)phases and surface defects due to the large surface-to-volume ratio.Achieving GaAs-based NWs with high emission efficiency has become a key research focus.In this study,pre-etched silicon substrates were combined with GaAs/AlGaAs core-shell heterostructure to achieve GaAs-based NWs with good perpendicularity,excellent crystal structures,and high emission efficiency by leveraging the shadowing effect and surface passivation.The primary evidence for this includes the prominent free-exciton emission in the variable-temperature spectra and the low thermal activation energy indicated by the variable-power spectra.The findings of this study suggest that the growth method described herein can be employed to enhance the crystal structure and optical properties of otherⅢ-Ⅴlow-dimensional materials,potentially paving the way for future NW devices.展开更多
CdS/ZnS core-shell microparticles were prepared by a simple two-step method combining ultrasonic spray pyrolysis and chemical bath deposition.The core-shell structures showed enhanced photocatalytic properties compare...CdS/ZnS core-shell microparticles were prepared by a simple two-step method combining ultrasonic spray pyrolysis and chemical bath deposition.The core-shell structures showed enhanced photocatalytic properties compared with those of CdS or ZnS spherical particles.CdS/ZnS photocatalysts with different amount of ZnS loaded as shells were prepared by adjusting the concentrations of Zn and S precursors during synthesis.The optical properties and photocatalytic activity for hydrogen production were investigated and the amount of ZnS loaded as shell was optimized.Thermal annealing and hydrothermal sulfurization treatments were applied to the core-shell structure and both treatments enhanced the material＇s photocatalytic activity and stability by eliminating crystalline defects and surface states.The result showed that thermal annealing treatment improved the bulk crystallinity and hydrothermal sulfurization improved the surface properties.The sample subjected to both treatments showed the highest photocatalytic activity.These results indicate that CdS/ZnS core-shell microspheres are a simple structure that can be used as efficient photocatalysts.The hydrothermal sulfurization treatment may also be a useful surface treatment for metal sulfide photocatalysts.The simple two-step method provides a promising approach to the large-scale synthesis of core-shell microsphere catalysts.展开更多
The hollow α-MnO2 nanoneedle-based microspheres coated with Pd nanoparticles were reported as a novel catalyst for rechargeable lithium-air batteries. The hollow microspheres are composed ofα-MnO2 nanoneedles. Pd na...The hollow α-MnO2 nanoneedle-based microspheres coated with Pd nanoparticles were reported as a novel catalyst for rechargeable lithium-air batteries. The hollow microspheres are composed ofα-MnO2 nanoneedles. Pd nanoparticles are deposited on the hollow microspheres through an aqueous-solution reduction of PdCl2 with NaBH4 at room temperature. The results of TEM, XRD, and EDS show that the Pd nanoparticles are coated on the surface ofα-MnO2 nanoneedles uniformly and the mass fraction of Pd in the Pd-coated α-MnO2 catalyst is about 8.88%. Compared with the counterpart of the hollow α-MnO2 catalyst, the hollow Pd-coated α-MnO2 catalyst improves the energy conversion efficiency and the charge-discharge cycling performance of the air electrode. The initial specific discharge capacity of an air electrode composed of Super P carbon and the as-prepared Pd-coatedα-MnO2 catalyst is 1220 mA＆#183;h/g （based on the total electrode mass） at a current density of 0.1 mA/cm2, and the capacity retention rate is about 47.3% after 13 charge-discharge cycles. The results of charge-discharge cycling tests demonstrate that this novel Pd-coatedα-MnO2 catalyst with a hierarchical core-shell structure is a promising catalyst for the lithium-air battery.展开更多
Cu2O@Cu2O core-shell nanoparticles (NPs) were prepared by using solution phase strategy. It was found that Cu2O@Cu2O NPs were easily converted to Cu2O@Cu NPs with the help of polyvinylpyrrolidine (PVP) and excessive a...Cu2O@Cu2O core-shell nanoparticles (NPs) were prepared by using solution phase strategy. It was found that Cu2O@Cu2O NPs were easily converted to Cu2O@Cu NPs with the help of polyvinylpyrrolidine (PVP) and excessive ascorbic acid (AA) in air at room temperature, which was an interesting phenomenon. The features of the two kinds of NPs were characterized by XRD, TEM and extinction spectra. Cu2O@Cu NPs with different shell thicknesses showed wide tunable optical properties for the localized surface plasmon (LSP) in metallic Cu. But Cu2O@Cu2O NPs did not indicate this feature. FTIR results reveal that Cu+ ions on the surface of Cu2O shell coordinate with N and O atoms in PVP and are further reduced to metallic Cu by excessive AA and then form a nucleation site on the surface of Cu2O nanocrystalline. PVP binds onto different sites to proceed with the reduction utill all the Cu sources in Cu2O shell are completely assumed.展开更多
The spray-dried spheres within a W/Pt multi-separation can be used to prepare discrete core-shell WC@C/Pt catalysts through a typical carburization production mechanism at 800 ℃. In contrast with previous studies of ...The spray-dried spheres within a W/Pt multi-separation can be used to prepare discrete core-shell WC@C/Pt catalysts through a typical carburization production mechanism at 800 ℃. In contrast with previous studies of the WC/Pt synthesis, the reaction observed here proceeds through an indirect annealing thereby resulting in core-shell structure, and mechanism at 600℃ wherein species diffuse, Pt nanoparticles were successfully dispersed in size/shape and randomly scattered across the in situ produced C spheres. Through direct carburization or at higher initial hydrochloroplatiuic acid concentrations, however, complete reaction with core-shell spheres was not observed. Indirect carburization reduces the strain felt by the bonds featuring the larger WC WC and Pt nanoparticles to be reserved, stability toward methanol oxidation. particles and allows the motion of carbon around influencing the eleetrocatalytic performance and展开更多
Al-1.0%Sc-1.0%Zr （mass fraction） master alloy was prepared at different cooling rates. The morphology and thermodynamics data of the primary particles of the master alloy were investigated by X-ray diffraction （XRD...Al-1.0%Sc-1.0%Zr （mass fraction） master alloy was prepared at different cooling rates. The morphology and thermodynamics data of the primary particles of the master alloy were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and differential scanning calorimetry （DSC）. It shows that the primary particles are dendrite-shaped particles comprised of several attached small cubic, cusped-cubic or crucifer shape particles at slow cooling rate. However, the primary particles are separated with crucifer shape at intermediate cooling rate, and they are cubic with cusped-cubic shape at high cooling rate. Meanwhile, the separated and attached particles present AlaSc/AlaZr1-xScx core-shell structure. The formation mechanism of the structure was systematically investigated by a mathematical model.展开更多
We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by twostep electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide （AAO） membr...We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by twostep electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide （AAO） membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes＇ tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO2 nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.展开更多
A range of poly（ε-caprolactone）/poly（N-vinyl-2-pyrrolidone） amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chai...A range of poly（ε-caprolactone）/poly（N-vinyl-2-pyrrolidone） amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and struc- ture of the targeted resultants were characterized with 1H NMR, 13C NMR, FT-IR spec- troscopy and gel permeation chromatography. The various block copolymers were success- fully employed to fabricate the spherical micelle with core-shell morphological structure. The poly（N-vinyl-2-pyrrolidone） block-dependent characteristics of the copolymeric micelles were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.展开更多
A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorob...A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.展开更多
Willow branch-shaped MoS2/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectr...Willow branch-shaped MoS2/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS2/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS2. In particular, the optimized MC-5 (5 at.% MoS2/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h–1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS2/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS2 nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H2 evolution by MoS2/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.展开更多
Magnetically separable bismuth ferrite(BiFeO3)nanoparticles were fabricated by a citrate self‐combustion method and coated with titanium dioxide(TiO2)by hydrolysis of titanium butoxide(Ti(OBu)4)to form BiFeO3@TiO2cor...Magnetically separable bismuth ferrite(BiFeO3)nanoparticles were fabricated by a citrate self‐combustion method and coated with titanium dioxide(TiO2)by hydrolysis of titanium butoxide(Ti(OBu)4)to form BiFeO3@TiO2core-shell nanocomposites with different mass ratios of TiO2to BiFeO3.The photocatalytic performance of the catalysts was comprehensively investigated via photocatalytic oxidation of methyl violet(MV)under both ultraviolet and visible‐light irradiation.The BiFeO3@TiO2samples exhibited better photocatalytic performance than either BiFeO3or TiO2alone,and a BiFeO3@TiO2sample with a mass ratio of1:1and TiO2shell thickness of50-100nm showed the highest photo‐oxidation activity of the catalysts.The enhanced photocatalytic activity was ascribed to the formation of a p‐n junction of BiFeO3and TiO2with high charge separation efficiency as well as strong light absorption ability.Photoelectrochemical Mott-Schottky(MS)measurements revealed that both the charge carrier transportation and donor density of BiFeO3were markedly enhanced after introduction of TiO2.The mechanism of MV degradation is mainly attributed to hydroxyl radicals and photogenerated electrons based on energy band theory and the formation of an internal electrostatic field.In addition,the unique core-shell structure of BiFeO3@TiO2also promotes charge transfer at the BiFeO3/TiO2interface by increasing the contact area between BiFeO3and TiO2.Finally,the photocatalytic activity of BiFeO3@TiO2was further confirmed by degradation of other industrial dyes under visible‐light irradiation.展开更多
In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and exce...In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and excellent N2 selectivity.Furthermore,it displays better SO2 and H2O tolerance than its MnOx,TiO2,and MnOx/TiO2 counterparts.The prepared catalyst was characterized systematically by transmission electron microscopy,high‐resolution transmission electron microscopy,X‐ray diffraction,Raman,BET,X‐ray photoelectron spectroscopy,NH3 temperature‐programmed desorption and H2 temperature‐programmed reduction analyses.The optimized MnOx@TiO2 catalyst exhibits an obvious core‐shell structure,where the TiO2 shell is evenly distributed over the MnOx nanorod core.The catalyst also presents abundant mesopores,Lewis‐acid sites,and high redox capability,all of which enhance its catalytic performance.According to the XPS results,the decrease in the number of Mn4+active centers after SO2 poisoning is significantly lower in MnOx@TiO2 than in MnOx/TiO2.The core‐shell structure is hence able to protect the catalytic active sites from H2O and SO2 poisoning.展开更多
In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respective...In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respectively.The introduction of Cr^3+and Cr2O3/C,which were derived from the calcination of MIL-101,in the composite enhanced its visible light absorbing ability and lowered the recombination rate of the photogenerated electrons and holes.The large surface area of the Cr2O3/C@TiO2 composite provided numerous active sites for the photoreduction reaction.Consequently,the photocatalytic performance of the composite for the production of H2 was better than that of pure TiO2.Under the irradiation of a 300 W Xe arc lamp,the H2 production rate of the Cr2O3/C@TiO2 composite that was calcined at 500°C was 446μmol h−1 g−1,which was approximately four times higher than that of pristine TiO2 nanoparticles.Moreover,the composite exhibited the high H2 production rate of 25.5μmol h−1 g−1 under visible light irradiation(λ>420 nm).The high photocatalytic performance of Cr2O3/C@TiO2 could be attributed to its wide visible light photoresponse range and efficient separation of photogenerated electrons and holes.This paper offers some insights into the design of a novel efficient photocatalyst for water-splitting applications.展开更多
The purpose of this study is to explore the adsorption performance of meso-2,3-dimercaptosuccinic acid(DMSA)modified Fe3O4@SiO2 magnetic nanocomposite(Fe3O4@SiO2@DMSA)for Pb2+ions removal from aqueous solutions.The ef...The purpose of this study is to explore the adsorption performance of meso-2,3-dimercaptosuccinic acid(DMSA)modified Fe3O4@SiO2 magnetic nanocomposite(Fe3O4@SiO2@DMSA)for Pb2+ions removal from aqueous solutions.The effects of solution pH,initial concentration of Pb2+ions,contact time,and temperature on the amount of Pb2+adsorbed were investigated.Adsorption isotherms,adsorption kinetics,and thermodynamic analysis were also studied.The results showed that the maximum adsorption capacity of the Fe3O4@SiO2@DMSA composite is 50.5 mg/g at 298 K,which is higher than that of Fe3O4 and Fe3O4@SiO2 magnetic nanoparticles.The adsorption process agreed well with Langmuir adsorption isotherm models and pseudo second-order kinetics.The thermodynamic analysis revealed that the adsorption was spontaneous,endothermic and energetically driven in nature.展开更多
The design of efficient Ru-based electrocatalysts with high intrinsic activities for acidic water oxidation is highly desirable and challenging for water splitting in proton exchange membrane electrolyzers.Here,for th...The design of efficient Ru-based electrocatalysts with high intrinsic activities for acidic water oxidation is highly desirable and challenging for water splitting in proton exchange membrane electrolyzers.Here,for the first time,we engineer the charge density of Ru(IV)by creating tensile strains in the RuO2 shell of Ru@RuO2 core-shell nanoparticles,viz.Ru@RuO2-L.High-resolution spectroscopic characterizations confirm the presence of av.6%tensile strain in Ru-O bonds,which results in an effective reduction of the Ru(IV)charge density.The resultant Ru^X+(4<X<5)active sites greatly accelerate the oxygen evolution reaction(OER)in an acidic electrolyte,leading to a remarkably low overpotential of 191 mV at 10 mA cm^-2.These values are lower than those for the benchmark RuO2 catalyst and are also among the lowest for efficient Ru-based electrocatalysts reported thus far.The specific activity and mass activity are also greatly enhanced 4.2-fold and 17.7-fold compared to those of RuO2,respectively.The acidic OER activity improvement is ascribed to the lowered adsorption energy of*OOH,owing to the reduced charge density of Ru(IV),and the rapid charge transport owing to the Ru core.Ru@RuO2-L also demonstrates high feasibility as the anode catalyst for the overall water splitting in acidic media.展开更多
Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction(ORR).However,the application of Pt-transition metal alloys in fuel cells is largely limited by po...Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction(ORR).However,the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach.In this study,we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR.Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell(denoted as PtPx@Pt/C)were synthesized via heat-treatment phosphorization of commercial Pt/C,followed by acid etching.Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region(approximately 1 nm)of the carbon-supported core-shell nanoparticles.Owning to P doping,the ORR specific activity and mass activity of the PtP_(1.4)@Pt/C catalyst were as high as 0.62 mA cm^(–2)and 0.31 mAμgPt–^(1),respectively,at 0.90 V,and they were enhanced by 2.8 and 2.1 times,respectively,in comparison with the Pt/C catalyst.More importantly,PtP_(1.4)@Pt/C exhibited superior stability with negligible mass activity loss(6%after 30000 potential cycles and 25%after 90000 potential cycles),while Pt/C lost 46%mass activity after 30000 potential cycles.The high ORR activity and durability were mainly attributed to the core-shell nanostructure,the electronic structure effect,and the resistance of Pt nanoparticles against aggregation,which originated from the enhanced ability of the PtP_(1.4)@Pt to anchor to the carbon support.This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.展开更多
Novel hydrophilic NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+double-jacket microtubes(DJMTs)with upconversion/downconversion dual-mode luminescence were designed and prepared through epitaxial growth of NaGdF4:Ce^3+,Eu^3+she...Novel hydrophilic NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+double-jacket microtubes(DJMTs)with upconversion/downconversion dual-mode luminescence were designed and prepared through epitaxial growth of NaGdF4:Ce^3+,Eu^3+shell onto the NaYF4:Yb^3+,Tm^3+microtube via poly(acrylic acid)(PAA)mediated hydrothermal method.It is demonstrated that PAA ligand played an important role in guiding the direct growth of NaGdF4:Ce^3+,Eu^3+shell onto the surface of NaYF4:Yb^3+,Tm^3+parent microtubes.The growth of NaGdF4:Ce^3+,Eu^3+shell experienced a crystal phase transition fromβ-NaGdF4 andβ-NaYF4 mixture toβ-NaYF4@NaGdF4 composite crystal,and morphology evolution from mixture ofβ-NaGdF4:Ce^3+,Eu^3+nanorods andβ-NaYF4:Yb^3+,Tm^3+microtubes to NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+DJMTs.The formation mechanism of DJMTs was the dissolution−renucleation ofβ-NaGdF4:Ce^3+,Eu^3+nanorods and the growth ofβ-NaGdF4:Ce^3+,Eu^3+shell via the classical Ostwald ripening mechanism.The as-prepared DJMTs could exhibit blue upconversion and red downconversion luminescence,which was further made into environmentally benign luminescent inks for creating highly secured and fluorescent-based anti-counterfeiting patterns via inkjet printing.展开更多
The hydrogenation of CO_(2) into methanol has attracted much attention and In_(2)O_(3) is a promising catalyst.Introducing metal elements into In_(2)O_(3)(M/In_(2)O_(3))is one of the main strategies to improve its per...The hydrogenation of CO_(2) into methanol has attracted much attention and In_(2)O_(3) is a promising catalyst.Introducing metal elements into In_(2)O_(3)(M/In_(2)O_(3))is one of the main strategies to improve its performance.However,its mechanism and active sites remain unclear and need to be further elucidated.Here,the noble‐metal‐free In_(x)‐Co_(y) oxides catalysts were prepared.Much‐improved performance and obvious product selectivity shift were observed.The optimized catalyst(In_(1)‐Co_(4))(9.7 mmol g_(cat)^(–1) h^(–1))showed five times methanol yields than pure In_(2)O_(3)(2.2 mmol g_(cat)^(–1) h^(–1))(P=4.0 MPa,T=300°C,GHSV=24000 cm^(3)_(STP) g_(cat)^(–1) h^(–1),H_(2):CO_(2)=3).And the cobalt‐catalyzed CO_(2) methanation activity was suppressed,although cobalt was most of the metal element.To unravel this selectivity shift,detailed catalysts performance evaluation,together with several in‐situ and ex‐situ characterizations,were employed on cobalt and In‐Co for comparative study.The results indicated CO_(2) hydrogenation on cobalt and In‐Co catalyst both followed the formate pathway,and In‐Co reconstructed and generated a surface In_(2)O_(3)‐enriched core‐shell‐like structure under a reductive atmosphere.The enriched In_(2)O_(3) at the surface significantly enhanced CO_(2) adsorption capacity and well stabilized the intermediates of CO_(2) hydrogenation.CO_(2) and carbon‐containing intermediates adsorbed much stronger on In‐Co than cobalt led to a feasible surface C/H ratio,thus allowing the*CH_(3)O to desorb to produce CH_(3)OH instead of being over‐hydrogenated to CH_(4).展开更多
文摘Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.
文摘Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2) product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.
文摘GaAs-based nanomaterials are essential for near-infrared nano-photoelectronic devices due to their exceptional optoelectronic properties.However,as the dimensions of GaAs materials decrease,the development of GaAs nanowires(NWs)is hindered by type-Ⅱquantum well structures arising from the mixture of zinc blende(ZB)and wurtzite(WZ)phases and surface defects due to the large surface-to-volume ratio.Achieving GaAs-based NWs with high emission efficiency has become a key research focus.In this study,pre-etched silicon substrates were combined with GaAs/AlGaAs core-shell heterostructure to achieve GaAs-based NWs with good perpendicularity,excellent crystal structures,and high emission efficiency by leveraging the shadowing effect and surface passivation.The primary evidence for this includes the prominent free-exciton emission in the variable-temperature spectra and the low thermal activation energy indicated by the variable-power spectra.The findings of this study suggest that the growth method described herein can be employed to enhance the crystal structure and optical properties of otherⅢ-Ⅴlow-dimensional materials,potentially paving the way for future NW devices.
基金supported by the National Natural Science Foundation of China(51202186,51323011)the Fundamental Research Funds for the Central University(xjj2016039)~~
文摘CdS/ZnS core-shell microparticles were prepared by a simple two-step method combining ultrasonic spray pyrolysis and chemical bath deposition.The core-shell structures showed enhanced photocatalytic properties compared with those of CdS or ZnS spherical particles.CdS/ZnS photocatalysts with different amount of ZnS loaded as shells were prepared by adjusting the concentrations of Zn and S precursors during synthesis.The optical properties and photocatalytic activity for hydrogen production were investigated and the amount of ZnS loaded as shell was optimized.Thermal annealing and hydrothermal sulfurization treatments were applied to the core-shell structure and both treatments enhanced the material＇s photocatalytic activity and stability by eliminating crystalline defects and surface states.The result showed that thermal annealing treatment improved the bulk crystallinity and hydrothermal sulfurization improved the surface properties.The sample subjected to both treatments showed the highest photocatalytic activity.These results indicate that CdS/ZnS core-shell microspheres are a simple structure that can be used as efficient photocatalysts.The hydrothermal sulfurization treatment may also be a useful surface treatment for metal sulfide photocatalysts.The simple two-step method provides a promising approach to the large-scale synthesis of core-shell microsphere catalysts.
基金Project(20973124)supported by the National Natural Science Foundation of ChinaProject(KLAEMC-OP201101)supported by the Open Project of Key Laboratory of Advanced Energy Materials Chemistry of Ministry of Education(Nankai University),China
文摘The hollow α-MnO2 nanoneedle-based microspheres coated with Pd nanoparticles were reported as a novel catalyst for rechargeable lithium-air batteries. The hollow microspheres are composed ofα-MnO2 nanoneedles. Pd nanoparticles are deposited on the hollow microspheres through an aqueous-solution reduction of PdCl2 with NaBH4 at room temperature. The results of TEM, XRD, and EDS show that the Pd nanoparticles are coated on the surface ofα-MnO2 nanoneedles uniformly and the mass fraction of Pd in the Pd-coated α-MnO2 catalyst is about 8.88%. Compared with the counterpart of the hollow α-MnO2 catalyst, the hollow Pd-coated α-MnO2 catalyst improves the energy conversion efficiency and the charge-discharge cycling performance of the air electrode. The initial specific discharge capacity of an air electrode composed of Super P carbon and the as-prepared Pd-coatedα-MnO2 catalyst is 1220 mA＆#183;h/g （based on the total electrode mass） at a current density of 0.1 mA/cm2, and the capacity retention rate is about 47.3% after 13 charge-discharge cycles. The results of charge-discharge cycling tests demonstrate that this novel Pd-coatedα-MnO2 catalyst with a hierarchical core-shell structure is a promising catalyst for the lithium-air battery.
基金Projects(41172110,61107090)supported by the National Natural Science Foundation of China
文摘Cu2O@Cu2O core-shell nanoparticles (NPs) were prepared by using solution phase strategy. It was found that Cu2O@Cu2O NPs were easily converted to Cu2O@Cu NPs with the help of polyvinylpyrrolidine (PVP) and excessive ascorbic acid (AA) in air at room temperature, which was an interesting phenomenon. The features of the two kinds of NPs were characterized by XRD, TEM and extinction spectra. Cu2O@Cu NPs with different shell thicknesses showed wide tunable optical properties for the localized surface plasmon (LSP) in metallic Cu. But Cu2O@Cu2O NPs did not indicate this feature. FTIR results reveal that Cu+ ions on the surface of Cu2O shell coordinate with N and O atoms in PVP and are further reduced to metallic Cu by excessive AA and then form a nucleation site on the surface of Cu2O nanocrystalline. PVP binds onto different sites to proceed with the reduction utill all the Cu sources in Cu2O shell are completely assumed.
基金This work is supported by the International Science ＆ Technology Cooperation Program of China（No.2010DFB63680）, the Natural Science Foundation of Zhejiang Province （LQ15B030004） and Loughborough University and the EPSRC （EP/1013229/1）.
文摘The spray-dried spheres within a W/Pt multi-separation can be used to prepare discrete core-shell WC@C/Pt catalysts through a typical carburization production mechanism at 800 ℃. In contrast with previous studies of the WC/Pt synthesis, the reaction observed here proceeds through an indirect annealing thereby resulting in core-shell structure, and mechanism at 600℃ wherein species diffuse, Pt nanoparticles were successfully dispersed in size/shape and randomly scattered across the in situ produced C spheres. Through direct carburization or at higher initial hydrochloroplatiuic acid concentrations, however, complete reaction with core-shell spheres was not observed. Indirect carburization reduces the strain felt by the bonds featuring the larger WC WC and Pt nanoparticles to be reserved, stability toward methanol oxidation. particles and allows the motion of carbon around influencing the eleetrocatalytic performance and
基金Project(2012CB619503)supported by the National Basic Research Program of ChinaProject(2013AA031001)supported by the National High-tech Research and Development Program of ChinaProject(2012DFA50630)supported by the International Science and Technology Cooperation Program of China
文摘Al-1.0%Sc-1.0%Zr （mass fraction） master alloy was prepared at different cooling rates. The morphology and thermodynamics data of the primary particles of the master alloy were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and differential scanning calorimetry （DSC）. It shows that the primary particles are dendrite-shaped particles comprised of several attached small cubic, cusped-cubic or crucifer shape particles at slow cooling rate. However, the primary particles are separated with crucifer shape at intermediate cooling rate, and they are cubic with cusped-cubic shape at high cooling rate. Meanwhile, the separated and attached particles present AlaSc/AlaZr1-xScx core-shell structure. The formation mechanism of the structure was systematically investigated by a mathematical model.
基金This work is supported by the National Natural Science Foundation of China （No.10574122, No.50772110, No.50721091） and the National Basic Research Program of China （No.2011CB921400, No.2007CB925202, No.2009CB939901）.
文摘We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by twostep electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide （AAO） membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes＇ tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO2 nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.
文摘A range of poly（ε-caprolactone）/poly（N-vinyl-2-pyrrolidone） amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and struc- ture of the targeted resultants were characterized with 1H NMR, 13C NMR, FT-IR spec- troscopy and gel permeation chromatography. The various block copolymers were success- fully employed to fabricate the spherical micelle with core-shell morphological structure. The poly（N-vinyl-2-pyrrolidone） block-dependent characteristics of the copolymeric micelles were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.
基金Supported by the National Natural Science Foundation of China （20476035, 20846003）.
文摘A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.
基金supported by the National Natural Science Foundation of China(51502155,51572152,21673127,21671119)the Research Project of Hubei Provincial Department of Education(D20151203)the State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(20170020)~~
文摘Willow branch-shaped MoS2/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS2/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS2. In particular, the optimized MC-5 (5 at.% MoS2/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h–1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS2/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS2 nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H2 evolution by MoS2/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.
基金supported by the Australian Research Council(ARC DP150103026)the National Natural Science Foundation of China(51278242)~~
文摘Magnetically separable bismuth ferrite(BiFeO3)nanoparticles were fabricated by a citrate self‐combustion method and coated with titanium dioxide(TiO2)by hydrolysis of titanium butoxide(Ti(OBu)4)to form BiFeO3@TiO2core-shell nanocomposites with different mass ratios of TiO2to BiFeO3.The photocatalytic performance of the catalysts was comprehensively investigated via photocatalytic oxidation of methyl violet(MV)under both ultraviolet and visible‐light irradiation.The BiFeO3@TiO2samples exhibited better photocatalytic performance than either BiFeO3or TiO2alone,and a BiFeO3@TiO2sample with a mass ratio of1:1and TiO2shell thickness of50-100nm showed the highest photo‐oxidation activity of the catalysts.The enhanced photocatalytic activity was ascribed to the formation of a p‐n junction of BiFeO3and TiO2with high charge separation efficiency as well as strong light absorption ability.Photoelectrochemical Mott-Schottky(MS)measurements revealed that both the charge carrier transportation and donor density of BiFeO3were markedly enhanced after introduction of TiO2.The mechanism of MV degradation is mainly attributed to hydroxyl radicals and photogenerated electrons based on energy band theory and the formation of an internal electrostatic field.In addition,the unique core-shell structure of BiFeO3@TiO2also promotes charge transfer at the BiFeO3/TiO2interface by increasing the contact area between BiFeO3and TiO2.Finally,the photocatalytic activity of BiFeO3@TiO2was further confirmed by degradation of other industrial dyes under visible‐light irradiation.
文摘In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and excellent N2 selectivity.Furthermore,it displays better SO2 and H2O tolerance than its MnOx,TiO2,and MnOx/TiO2 counterparts.The prepared catalyst was characterized systematically by transmission electron microscopy,high‐resolution transmission electron microscopy,X‐ray diffraction,Raman,BET,X‐ray photoelectron spectroscopy,NH3 temperature‐programmed desorption and H2 temperature‐programmed reduction analyses.The optimized MnOx@TiO2 catalyst exhibits an obvious core‐shell structure,where the TiO2 shell is evenly distributed over the MnOx nanorod core.The catalyst also presents abundant mesopores,Lewis‐acid sites,and high redox capability,all of which enhance its catalytic performance.According to the XPS results,the decrease in the number of Mn4+active centers after SO2 poisoning is significantly lower in MnOx@TiO2 than in MnOx/TiO2.The core‐shell structure is hence able to protect the catalytic active sites from H2O and SO2 poisoning.
文摘In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respectively.The introduction of Cr^3+and Cr2O3/C,which were derived from the calcination of MIL-101,in the composite enhanced its visible light absorbing ability and lowered the recombination rate of the photogenerated electrons and holes.The large surface area of the Cr2O3/C@TiO2 composite provided numerous active sites for the photoreduction reaction.Consequently,the photocatalytic performance of the composite for the production of H2 was better than that of pure TiO2.Under the irradiation of a 300 W Xe arc lamp,the H2 production rate of the Cr2O3/C@TiO2 composite that was calcined at 500°C was 446μmol h−1 g−1,which was approximately four times higher than that of pristine TiO2 nanoparticles.Moreover,the composite exhibited the high H2 production rate of 25.5μmol h−1 g−1 under visible light irradiation(λ>420 nm).The high photocatalytic performance of Cr2O3/C@TiO2 could be attributed to its wide visible light photoresponse range and efficient separation of photogenerated electrons and holes.This paper offers some insights into the design of a novel efficient photocatalyst for water-splitting applications.
基金Project(2013DFA51290)supported by International S&T Cooperation Program of China
文摘The purpose of this study is to explore the adsorption performance of meso-2,3-dimercaptosuccinic acid(DMSA)modified Fe3O4@SiO2 magnetic nanocomposite(Fe3O4@SiO2@DMSA)for Pb2+ions removal from aqueous solutions.The effects of solution pH,initial concentration of Pb2+ions,contact time,and temperature on the amount of Pb2+adsorbed were investigated.Adsorption isotherms,adsorption kinetics,and thermodynamic analysis were also studied.The results showed that the maximum adsorption capacity of the Fe3O4@SiO2@DMSA composite is 50.5 mg/g at 298 K,which is higher than that of Fe3O4 and Fe3O4@SiO2 magnetic nanoparticles.The adsorption process agreed well with Langmuir adsorption isotherm models and pseudo second-order kinetics.The thermodynamic analysis revealed that the adsorption was spontaneous,endothermic and energetically driven in nature.
文摘The design of efficient Ru-based electrocatalysts with high intrinsic activities for acidic water oxidation is highly desirable and challenging for water splitting in proton exchange membrane electrolyzers.Here,for the first time,we engineer the charge density of Ru(IV)by creating tensile strains in the RuO2 shell of Ru@RuO2 core-shell nanoparticles,viz.Ru@RuO2-L.High-resolution spectroscopic characterizations confirm the presence of av.6%tensile strain in Ru-O bonds,which results in an effective reduction of the Ru(IV)charge density.The resultant Ru^X+(4<X<5)active sites greatly accelerate the oxygen evolution reaction(OER)in an acidic electrolyte,leading to a remarkably low overpotential of 191 mV at 10 mA cm^-2.These values are lower than those for the benchmark RuO2 catalyst and are also among the lowest for efficient Ru-based electrocatalysts reported thus far.The specific activity and mass activity are also greatly enhanced 4.2-fold and 17.7-fold compared to those of RuO2,respectively.The acidic OER activity improvement is ascribed to the lowered adsorption energy of*OOH,owing to the reduced charge density of Ru(IV),and the rapid charge transport owing to the Ru core.Ru@RuO2-L also demonstrates high feasibility as the anode catalyst for the overall water splitting in acidic media.
文摘Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction(ORR).However,the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach.In this study,we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR.Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell(denoted as PtPx@Pt/C)were synthesized via heat-treatment phosphorization of commercial Pt/C,followed by acid etching.Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region(approximately 1 nm)of the carbon-supported core-shell nanoparticles.Owning to P doping,the ORR specific activity and mass activity of the PtP_(1.4)@Pt/C catalyst were as high as 0.62 mA cm^(–2)and 0.31 mAμgPt–^(1),respectively,at 0.90 V,and they were enhanced by 2.8 and 2.1 times,respectively,in comparison with the Pt/C catalyst.More importantly,PtP_(1.4)@Pt/C exhibited superior stability with negligible mass activity loss(6%after 30000 potential cycles and 25%after 90000 potential cycles),while Pt/C lost 46%mass activity after 30000 potential cycles.The high ORR activity and durability were mainly attributed to the core-shell nanostructure,the electronic structure effect,and the resistance of Pt nanoparticles against aggregation,which originated from the enhanced ability of the PtP_(1.4)@Pt to anchor to the carbon support.This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.
基金Project(51874129)supported by the National Natural Science Foundation of ChinaProjects(2018JJ3115,2019JJ60049)supported by the Science Foundation of Hunan Province,ChinaProjects(19B153,19B158)supported by the Scientific Research Fund of Hunan Provincial Education Department,China。
文摘Novel hydrophilic NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+double-jacket microtubes(DJMTs)with upconversion/downconversion dual-mode luminescence were designed and prepared through epitaxial growth of NaGdF4:Ce^3+,Eu^3+shell onto the NaYF4:Yb^3+,Tm^3+microtube via poly(acrylic acid)(PAA)mediated hydrothermal method.It is demonstrated that PAA ligand played an important role in guiding the direct growth of NaGdF4:Ce^3+,Eu^3+shell onto the surface of NaYF4:Yb^3+,Tm^3+parent microtubes.The growth of NaGdF4:Ce^3+,Eu^3+shell experienced a crystal phase transition fromβ-NaGdF4 andβ-NaYF4 mixture toβ-NaYF4@NaGdF4 composite crystal,and morphology evolution from mixture ofβ-NaGdF4:Ce^3+,Eu^3+nanorods andβ-NaYF4:Yb^3+,Tm^3+microtubes to NaYF4:Yb^3+,Tm^3+@NaGdF4:Ce^3+,Eu^3+DJMTs.The formation mechanism of DJMTs was the dissolution−renucleation ofβ-NaGdF4:Ce^3+,Eu^3+nanorods and the growth ofβ-NaGdF4:Ce^3+,Eu^3+shell via the classical Ostwald ripening mechanism.The as-prepared DJMTs could exhibit blue upconversion and red downconversion luminescence,which was further made into environmentally benign luminescent inks for creating highly secured and fluorescent-based anti-counterfeiting patterns via inkjet printing.
文摘The hydrogenation of CO_(2) into methanol has attracted much attention and In_(2)O_(3) is a promising catalyst.Introducing metal elements into In_(2)O_(3)(M/In_(2)O_(3))is one of the main strategies to improve its performance.However,its mechanism and active sites remain unclear and need to be further elucidated.Here,the noble‐metal‐free In_(x)‐Co_(y) oxides catalysts were prepared.Much‐improved performance and obvious product selectivity shift were observed.The optimized catalyst(In_(1)‐Co_(4))(9.7 mmol g_(cat)^(–1) h^(–1))showed five times methanol yields than pure In_(2)O_(3)(2.2 mmol g_(cat)^(–1) h^(–1))(P=4.0 MPa,T=300°C,GHSV=24000 cm^(3)_(STP) g_(cat)^(–1) h^(–1),H_(2):CO_(2)=3).And the cobalt‐catalyzed CO_(2) methanation activity was suppressed,although cobalt was most of the metal element.To unravel this selectivity shift,detailed catalysts performance evaluation,together with several in‐situ and ex‐situ characterizations,were employed on cobalt and In‐Co for comparative study.The results indicated CO_(2) hydrogenation on cobalt and In‐Co catalyst both followed the formate pathway,and In‐Co reconstructed and generated a surface In_(2)O_(3)‐enriched core‐shell‐like structure under a reductive atmosphere.The enriched In_(2)O_(3) at the surface significantly enhanced CO_(2) adsorption capacity and well stabilized the intermediates of CO_(2) hydrogenation.CO_(2) and carbon‐containing intermediates adsorbed much stronger on In‐Co than cobalt led to a feasible surface C/H ratio,thus allowing the*CH_(3)O to desorb to produce CH_(3)OH instead of being over‐hydrogenated to CH_(4).
