Ni2P@CoP3核壳纳米球的制备、表征及其用于超级电容器性能

利用水热技术先后获得Ni纳米球和Ni@Co(OH)_2海胆状核壳纳米球前驱体,通过高温煅烧法获得NiO@CoO核壳纳米球,再以次磷酸钠为原料,通过高温磷化法最终获得Ni_2P@CoP_3核壳纳米球。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高角度环形暗场像扫描透射电子显微镜(HAADF-STEM)、X射线粉末衍射仪(XRD)、能谱仪(EDS)及X射线光电子能谱(XPS)对产物的形貌、结构和组成进行表征。采用循环伏安(CV)、恒电流充放电(GCD)以及循环稳定性实验探索了电极材料的电化学性能。结果表明,Ni_2P@CoP_3核壳纳米球的直径约为400 nm,由六方系Ni_2P纳米核和立方相CoP_3纳米壳构成。相比单纯的Ni_2P或CoP_3纳米球,Ni_2P@CoP_3核壳纳米球发挥了复合结构的协同效应,更加有利于电解液的质子传递,促进了赝电容反应,表现出更高的比容量、稳定性和更长的循环寿命。     

Structural and oxidation-state changes at its nonstandard Ni-Fe site during activation of the NAD-reducing hydrogenase from Ralstonia eutropha detected by X-ray absorption, EPR, and FTIR spectroscopy

Structure and oxidation state of the Ni-Fe cofactor of the NAD-reducing soluble hydrogenase (SH) from Ralstonia eutropha were studied employing X-ray absorption spectroscopy (XAS) at the Ni K-edge, EPR, and FTIR spectroscopy. The SH comprises a nonstandard (CN)Ni-Fe(CN)(3)(CO) site; its hydrogen-cleavage reaction is resistant against inhibition by dioxygen and carbon monoxide. Simulations of the XANES and EXAFS regions of XAS spectra revealed that, in the oxidized SH, the Ni(II) is six-coordinated ((CN)O(3)S(2)); only two of the four conserved cysteines, which bind the Ni in standard Ni-Fe hydrogenases, provide thiol ligands to the Ni. Upon the exceptionally rapid reductive activation of the SH by NADH, an oxygen species is detached from the Ni; hydrogen may subsequently bind to the vacant coordination site. Prolonged reducing conditions cause the two thiols that are remote from the Ni in the native SH to become direct Ni ligands, creating a standardlike Ni(II)(CysS)(4) site, which could be further reduced to form the Ni-C (Ni(III)-H(-)) state. The Ni-C state does not seem to be involved in hydrogen cleavage. Two site-directed mutants (HoxH-I64A, HoxH-L118F) revealed structural changes at their Ni sites and were employed to further dissect the role of the extra CN ligand at the Ni. It is proposed that the predominant coordination by (CN),O ligands stabilizes the Ni(II) oxidation state throughout the catalytic cycle and is a prerequisite for the rapid activation of the SH in the presence of oxygen.     

Superparamagnetic Ag@Fe3O4 core-shell nanospheres: fabrication, characterization and application as reusable nanocatalysts

Superparamagnetic Ag@Fe(3)O(4) nanospheres with core-shell nanostructures have been prepared by a facile one-pot method. The diameter of the as-synthesized nanospheres was about 200 nm and the core sizes were between 50 and 100 nm. By varying the concentrations, particles with tunable core size and total size are successfully achieved. Time dependent experiments were constructed to investigate the synthesis mechanism, which indicated that the present method corresponded to an Ostwald ripening progress. The BET area of the core-shell nanospheres is about 22.6 m(2)/g and this result indicates that the product shows a porous character. The saturated magnetization of the superparamagnetic Ag@Fe(3)O(4) nanospheres is 27.4 emu g(-1) at room temperature, which enables them to be recycled from the solution by simply applying a small magnet. Due to the unique nanostructure, these particles show high performance in catalytic reduction of 4-nitrophenol and can be used as reusable nanocatalysts.     

Facile fabrication of AgCl@polypyrrole-chitosan core-shell nanoparticles and polymeric hollow nanospheres

A one-step sequential method for preparing AgCl@polypyrrole-chitosan core-shell nanoparticles and subsequently the formation of polypyrrole-chitosan hollow nanospheres is reported. The formation of the core and the shell is performed in one reaction medium almost simultaneously. Transmission electron microscopy (TEM) images show the presence of core-shell nanoparticles and hollow nanospheres. Ultraviolet-visible (UV-vis) studies reveal that AgCl was formed first followed by polypyrrole. X-ray diffration (XRD) and UV-vis studies show that AgCl was present in the core-shell nanoparticles and could be removed completely from the core.     

Nanocomposite ta-C films prepared by the filtered vacuum arc process using nanosized Ni dots on a Si substrate

Recently, structural manipulation of tetrahedral amorphous carbon (ta-C) film at the nanometer scale has attracted much attention. We demonstrate a novel method to obtain a nanocomposite film where nanoscale columns of graphitic phase are embedded in a tetrahedral amorphous carbon matrix. When using a Si substrate with nanosized Ni dots on the surface, graphitic columns grew selectively on the Ni dots, while a dense ta-C film was deposited on the bare Si surface. The growth of the graphitic columns is closely related to the nanosized Ni dots that catalyze the graphitic-carbon formation in a filtered vacuum arc deposition condition.     

Nickel-promoted Electrocatalytic Graphitization of Biochars for Energy Storage: Mechanistic Understanding using Multi-scale Approaches

Owing to high-efficiency and scalable advantages of electrolysis in molten salts, electrochemical conversion of carbonaceous resources into graphitic products is a sustainable route for achieving high value-added carbon. To understand the complicated kinetics of converting amorphous carbon (e.g. carbonized lignin-biochar) into highly graphitic carbon, herein this study reports the key processing parameters (addition of Ni, temperature and time) and multi-scale approach of nickel-boosted electrochemical graphitization-catalysis processes in molten calcium chloride. Upon both experiments and modellings, multi-scale analysis that ranges from nanoscale atomic reaction to macroscale cell reveal the multi-field evolution in the electrolysis cell, mechanism of electrochemical reaction kinetics as well as pathway of nickel-boosted graphitization and tubulization. The results of as-achieved controllable processing regions and multi-scale approaches provide a rational strategy of manipulating electrochemical graphitization processes and utilizing the converted biomass resources for high value-added use.     

In-situ self-templated preparation of porous core-shell Fe1-xS@N,S co-doped carbon architecture for highly efficient oxygen reduction reaction

Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_1-xS@N,S co-doped carbon(Fe_1-xS@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe³⁺released through the etching of Fe₃O₄ by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_1-xS@NSC-t.Based on the cha racterizations,we find Fe_1-xS@NSC-24 can realize effective and balanced combination of Fe_1-xS and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.     

Controlled synthesis, characterization, and crystallization of Ni-P nanospheres

The size- and composition-controlled synthesis of Ni-P nanospheres from nickel chloride and sodium hypophosphite has been systematically investigated by changing the conditions, such as the ratio of the starting materials, pH value, and reduction temperature. It was found that when the starting ratio of H2PO2(-)/Ni2+ was changed the size and chemical composition of the nanoparticles changed simultaneously. Within a suitable pH range, the phosphorus content was altered without affecting the particle size. Increasing the reduction temperature resulted in smaller Ni-P nanospheres but invariable phosphorus content. The Ni-P nanospheres were amorphous when the phosphorus content was higher than 10.0 mol %, while lower phosphorus content led to a composite of amorphous Ni-P and face-centered cubic (fcc) Ni. During postsynthesis calcinations, amorphous Ni-P nanospheres with a low phosphorus content directly crystallized to Ni3P and fcc Ni. However, the specimens with high phosphorus content crystallized via some intermediate phases such as Ni5P2 and Ni12P5. In the latter, an amorphous P-rich shell was developed simultaneously. A preliminary catalytic test of growth of carbon nanofibers on the Ni-P nanospheres has been carried out.     

Effects of surface states over core-shell Ni@SiO_2 catalysts on catalytic partial oxidation of methane to synthesis gas

In the present work, core-shell Ni@Si O2 catalysts were investigated in order to evaluate the relevance of catalytic activity and surface states of Ni core as well as Ni nanoparticles size to catalytic partial oxidation of methane(POM). The catalysts were characterized by N2 adsorption,H2-TPR, XRD, TEM and XPS techniques. The catalytic performance of the core-shell catalysts was found to be dependent on the surface states of catalyst, which influenced the formation of products. It was considered that carbon dioxide formed on the oxidized nickel sites(Ni O)and carbon monoxide produced on the reduced sites(Ni). The surface states of active metal in the dynamic were influenced both by the size of Ni core and the porosity of silica shell. However, the catalytic activity would be debased when the size of Ni core was under a certain extent,which can be ascribed to the fact the carbon deposition increased with the increasing content of Ni O. The effects of surface states of Ni@Si O2 catalyst on the catalytic performance were discussed and the reaction pathway over Ni core encapsulated inside silica shell was proposed.     

Enhancement of oxygen evolution reaction by X-doped (X = Se,S, P) holey graphitic carbon shell encapsulating NiCoFe nanoparticles: a combined experimental and theoretical study

Among the two half-reactions of the electrochemical water splitting, the anodic oxygen evolution reaction (OER) is a kinetically sluggish process and usually requires noble metal oxide catalysts. Therefore, the development of highly active, noble metal-free, and durable catalysts for OER is an urgent need for sustainable applications. The encapsulation of transition-metal alloyed nanoparticles in graphitic carbon layers, with core-shell features, is a viable approach for establishing an undegradable and highly efficient catalyst toward OER. Furthermore, the reactivity of the carbon shell surface can be further improved by the electron transfers between the core alloy and carbon shell, through a control of the alloyed nanoparticle compositions, or through a chemical doping. Nevertheless, it is still not clear whether the incorporation of a chemical dopant directly into the carbon shells systematically promotes the catalytic activities toward OER. To clarify this point, we synthetize trimetallic (CoNiFe) nanoparticles encapsulated in graphitic carbon shells by pyrolysis of metal?organic frameworks. We then investigate the effect of a doped graphitic carbon shell by incorporating non-metallic elements such as sulfur, phosphorus, and selenium. The main finding is that all doped CoNiFe@C core-shell catalysts exhibit an enhanced catalytic activity toward OER in the alkaline electrolyte with a low overpotential, a small Tafel slope, and long stability, which are all being comparable to those of RuO₂ benchmark. Electrochemical impedance spectroscopy, X-ray photoelectron spectroscopic, and Raman measurements collected at different applied potentials during the OER process indicate that the doping of graphitic carbon shell significantly improves the interfacial electron-transfer kinetics and facilitates the adsorption of OH^? ion as well as promotes the formation of metal oxyhydroxide, which positively affect the OER performances. Moreover, this improvement in OER efficiency upon incorporating of a chemical doping is rationalized by the optimization of the Gibbs free energy of OER intermediates, thereby remarkably reducing the required energy input of rate-determining step, as elucidated by the density functional theory calculations.     

Graphitic carbon nanostructures via a facile microwave-induced solid-state process

A novel approach to fabricate highly graphitic carbon nanostructures such as carbon nanotubes (CNTs), metal/graphitic-shell nanocrystals and hollow carbon nanospheres (HCNSs) in a very short time is demonstrated.     

A bis(p-sulfonatophenyl)phenylphosphine-based synthesis of hollow Pt nanospheres

We report herewith the synthesis of hollow Pt nanospheres by using bis(p-sulfonatophenyl)phenylphosphine to selectively remove the Ag cores of Ag-Pt core-shell nanoparticles. Core-shell Ag-Pt nanoparticles were first obtained by the successive reduction method with a discontinuous Pt shell to allow the BSPP passage. Transmission electron microscopy imaging of the core-shell Ag-Pt nanoparticles before and after BSPP dissolution showed little changes in the particle size, indicating that the removal of the Ag cores had occurred isomorphously. The hollow Pt nanospheres, together with the predecessor Ag-Pt core-shell particles of the same size, were transferred from water to toluene and surface modified by dodecylamine in toluene. This allows the catalytic activities of solid and hollow Pt particles in room temperature methanol oxidation reaction to be compared under conditions of identical particle size and the same surface environment. The measured higher specific activity of the Pt hollow nanospheres could then be attributed unambiguously to the larger specific surface area prevalent in the porous hollow structure.     

High electrocatalytic activity of non-noble Ni-Co/graphene catalyst for direct ethanol fuel cells

The electrocatalytic oxidation of ethanol is studied on the non-noble catalysts Ni-Co/graphene and Ni/graphene supported on glass carbon electrode (GCE) in alkaline medium. The synthesized materials are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning transmission electron microscopy. The elements of Ni-Co/graphene and Ni/graphene catalysts are characterized using energy-dispersive X-ray spectroscopy. The electrocatalytic properties of Ni-Co/graphene and Ni/graphene for ethanol oxidation are investigated by cyclic voltammetry, chronoamperometry, and Tafel plot. Compared with Ni/graphene catalyst, Ni-Co/graphene has the higher electroactivity and better stability for ethanol oxidation. The rate constant (k _s) and charge-transfer coefficient (α) are calculated for the electron exchange reaction of the modified GCE. The results indicate that Co addition could promote the oxidation reaction at the Ni/graphene catalyst. Our study demonstrates that the low-cost electrocatalyst Ni-Co/graphene has a great potential for real direct ethanol fuel cells’ application.     

Preparation of phosphorus-doped carbon nanospheres and their electrocatalytic performance for O2 reduction

Phosphorus-doped carbon nanospheres without any metal residues were synthesized and characterized.The results revealed that the doping phosphorus atoms could significantly improve the electrocatalytic activity of graphitic carbon for the oxygen-reduction reaction(ORR) both in acidic and alkaline media,and the materials exhibited high electrocatalytic activity,long-term stability,and excellent tolerance to crossover effects especially in alkaline media.Quantum mechanics calculations with the density functional theory demonstrated that the changes in charge density and energetic characteristics of frontier orbitals for the P-doped graphene sheet could facilitate the ORR.     

制备核-壳结构聚合物纳米微球和空心球的原位聚合方法的普适性研究

采用原位聚合制备核-壳结构聚合物纳米微球和空心球的新方法, 利用甲基丙烯酸2-羟丙酯(HPMA)和乙酸乙烯酯(VAc)两种单体, 在类似的反应条件下, 成功地制备了以聚(ε-己内酯)(PCL)为核, 分别以交联PHPMA和PVAc为壳的纳米微球; 将微球的核酶解后, 分别得到了对应的交联PMAA空心球和交联PVA空心球. 结果表明, 原位聚合制备核-壳结构聚合物微球的新方法具有一定的普适性, 适用于单体可溶于水而生成的聚合物不溶于水的体系.     

甲烷干重整催化剂Ni/Al2O3表面积炭表征与分析

用蒸发法制备了Ni/Al2O3催化剂及浸渍法制备了Ni/α-Al2O3和Ni/γ-Al2O3催化剂, 并与商品天然气水蒸气重整催化剂Z118Y一起进行了甲烷干重整实验, 考察了各催化剂上表面积炭行为. 通过H2程序升温还原(H2-TPR)、BET(Brunauer-Emmett-Teller)比表面积分析、X射线衍射(XRD)、透射电镜(TEM)、热重-差式扫描量热(TG-DSC)、程序升温氢化(TPH)等表征手段对催化剂表面沉积炭的特性进行了表征. 结果表明, 各催化剂上至少存在三种形式的碳物种: 无定形碳、丝状碳及石墨碳. 由于载体性质不同, 各催化剂上沉积炭的种类及其含量有所差别. Z118Y、Ni/Al2O3及Ni/α-Al2O3催化剂上主要沉积丝状炭, 而Ni/γ-Al2O3催化剂上则主要是石墨碳. Ni/γ-Al2O3催化剂中金属Ni颗粒较小(小于15 nm)、粒径分布范围较窄、分散性较好, 能减少催化剂表面炭的沉积, 有效地抑制丝状碳的生长.     

Growth of filamentous carbon from the surface of Ni/SiO2 doped with alkali metal bromides

The growth of ordered filamentous carbon, catalytically generated from the decomposition of ethylene, has been studied over the temperature range 673-898 K using an 11% w/w Ni/SiO2 catalyst doped to varying degrees (0.1-9.3% w/w) with a range of alkali metal bromides. The effect of these alkali metal/halogen adatoms in promoting/inhibiting carbon growth has been assessed and variations in the associated carbon structural characteristics have been examined. The introduction of Li consistently promoted filamentous carbon growth (where 723 K相似文献   

原位聚合法制备具有温敏PNIPAM壳的核-壳结构聚合物纳米微球的研究

结合大分子自组装和原位自由基聚合方法,采用油溶性引发剂偶氮二异丁腈(AIBN),在聚(ε-已内酯)(PCL)纳米粒子表面引发聚合单体N-异丙基丙烯酰胺(NIPAM)和交联剂亚甲基双(丙烯酰胺)(MBA),制备得到了核-壳结构的PCL/PNIPAM聚合物纳米微球.系统研究了单体和交联剂用量、壳层目标交联度、初始PCL/DMF溶液的浓度及引发剂AIBN含量4个反应参数对核-壳结构PCL/PNIPAM纳米微球的PNIPAM壳层得率、微球尺寸、温敏性能及电镜形貌的影响.结果表明,在制备核-壳结构PCL/PNIPAM纳米微球的反应过程中,PCL粒子表面的聚合和水中的聚合二者之间相互竞争.适当增加引发剂AIBN的添加量,有利于制备得到核/壳比例可控的PCL/PNIPAM纳米微球;交联剂MBA较高的反应活性导致形成了非均匀交联的PNIPAM壳层.     

A novel method for the templated synthesis of homogeneous samples of hollow carbon nanospheres from cellulose chars

A novel method for the production of homogeneous samples of hollow carbon nanospheres is reported from cellulose, an inexpensive and renewable precursor. The nanospheres are of diameter 50 nm, graphitic wall thickness 5-10 nm, and can easily be produced in several hundred milligram batches. The nanospheres are derived from the laser pyrolysis of a nickel chloride templated cellulose char via open Ni-core shells.     

Formation Mechanism and Structure of Monatomic Carbon Films in Ethylene Decomposition on the Pt(111) Surface According to XPS Data

The interaction of ethylene with a Pt(111) single-crystal surface was studied using X-ray photoelectron spectroscopy. It was found that both two-dimensional flat graphite islands and curved fullerene-like carbon structures or nanotubes can be formed depending on the reaction temperature of ethylene and the presence of dissolved carbon in the bulk of the crystal. It was assumed that the size and curvature of the islands depend on the size of terraces on the single-crystal surface.