中科院化学所在金属纳米空心球催化剂方面获突破

最近 ,中科院化学所分子纳米结构与纳米技术研究院重点实验室白春礼院士和万立骏研究领导的研究组 ,在制备金属纳米空心球催化剂方面取得新进展。研究组巧妙地利用钴与贵金属的盐溶液发生置换反应的特点 ,使钴纳米粒子与氯铂酸直接反应制得铂的空心纳米球。该空心球的球壳由纳米级小粒子组成 ,具有高表面积。与具有相近半径的同载量实心铂纳米粒子相比 ,该空心球对甲醇氧化表现出了更好的电催化性能。因此 ,铂的空心球不仅在直接甲醇燃料电池方面有着潜在的应用前景 ,而且还可能应用于与铂催化剂相关的研究领域中科院化学所在金属纳米空心球…     

超声辅助电沉积Ni-Co/ZrO_2复合镀层的性能研究

采用超声辅助电沉积方法将Ni-Co/ZrO_2纳米复合镀层电镀到铜板表面。在不同纳米粒子添加量下,通过线性扫描伏安(LSV)和交流阻抗(EIS)对电沉积过程进行电化学表征,通过SEM、EDS对镀层的组成和表面形貌进行研究,并分别利用显微硬度计和摩擦磨损试验仪对复合镀层的力学性能和摩擦磨损性能进行表征。结果表明,超声的引入能够有效降低镀液中颗粒的团聚量,提高镀层中纳米粒子的复合量,从而改善复合电沉积过程以及镀层性能。在纳米粒子浓度为10g/L时,镀层的表面形貌、摩擦性能和硬度等性能最优。     

纳米ZnO的固相合成及其电化学行为

针对锌电极循环性能差等问题,利用固相配位化学反应制备纳米ZnO粉体,借助XRD、TEM对粉体进行表征,并采用循环伏安法分析6.0 mol/L的KOH溶液中不同粒度与组成的ZnO电极的电化学性能。结果表明,在较慢扫速(1 mV/s)下,不同组成的电极的循环伏安曲线相差较大,具有合适配比的混配电极展示出较好的循环可逆性,而纯纳米粒子组成的电极电化学性能较差。对不同组成的氧化锌电极充放电性能对比测试表明,最佳配比的混配电极循环充放电性能最好。     

水溶液中电沉积Fe-Zr-B纳米合金

在酸性镀液中电沉积了Fe-Zr—B纳米合金。讨论了影响镀层组分的因素。用原子吸收光谱和分光光度法分析了铰层组分，线性扫描和循环伏安法研究了电极过程。实验结果表明，甘氨酸和二甲基甲酰胺(DMF)抑制了铁的沉积，沉积机制可能是诱导共沉积。电镜扫描图像表明镀层粒子是纳米粒子，XRD分析表明镀层含有Fe-Zr合金。     

Au核@Pt壳纳米粒子的光化学还原法合成及表征

在柠檬酸钠-丙酮-乙醇体系中采用光化学还原法同时还原或连续还原Au(III),Pt(IV)离子,合成了Au核@Pt壳复合纳米粒子。采用X射线光电子能谱(XPS),UV-Vis,透射电镜(TEM)等分析手段对两种方法合成的复合粒子的结构、形貌等进行了对比分析,并对复合粒子核壳复合结构的光化学形成机制进行了讨论。研究表明:两种方法均可合成颗粒比较均匀、具有良好单分散性的Au核@Pt壳复合纳米粒子,其平均粒径5.1~10.2 nm;其中,同时还原法制备的复合纳米粒子的平均粒径相对较小是5.1~8.1 nm,而当n(Au)∶n(Pt)=1∶4时,粒径最小,为5.1 nm。同时还原和连续还原法所制备的胶体粒子的UV-Vis吸收光谱与Au,Pt简单混合胶体的有明显不同,双金属复合胶体粒子的UV-Vis吸收光谱中Au的特征共振吸收强度明显下降并且蓝移,下降程度远大于其浓度的降低,且随着粒子中Pt元素含量的进一步增加,Au的特征吸收峰最终消失而只体现Pt的吸收光谱,这表明同时还原和连续还原Au(III),Pt(IV)离子所制备的胶体粒子为双金属复合粒子,复合粒子结构中Au元素存在于粒子内部,Pt元素存在于粒子表面,即两种还原方式所制备的双金属复合粒子具有Au核@Pt壳复合结构。     

一维纳米LiNi1/3Co1/3Mn1/3O2纤维的合成及性能研究

通过静电纺丝法制备出一维纳米LiNi1/3Co1/3Mn1/3O2纤维,根据扫描电子显微镜(SEM)、X射线衍射(XRD)、充放电实验,循环伏安法和交流阻抗法对纳米纤维的形貌、晶体结构和电化学性能进行研究.结果表明,纳米纤维的直径在150～300 nm之间,且具有典型的α-NaFeO2层状结构;所制备的LiNi1/3Co1/3Mn1/3O2纳米纤维在0.5 C(85 mA/g)的倍率下循环30次容量保持率达到了94.1％;在倍率分别为0.1 C、0.2 C、0.5 C、1.0 C、2.0 C和0.2 C的充放电测试中,其比容量分别达到了157 mAh/g、144 mAh/g、134 mAh/g、125 mAh/g、115 mAh/g和141 mAh/g;在CV和EIS测试中,材料表现出优异的可逆性和循环稳定性.由于具有特殊的一维形貌,LiNi1/3Co1/3Mn1/3O2纳米纤维表现出优异的电化学性能.     

一维纳米LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2纤维的合成及性能研究

通过静电纺丝法制备出一维纳米Li Ni1/3Co1/3Mn1/3O2纤维,根据扫描电子显微镜(SEM)、X射线衍射(XRD)、充放电实验,循环伏安法和交流阻抗法对纳米纤维的形貌、晶体结构和电化学性能进行研究.结果表明,纳米纤维的直径在150~300 nm之间,且具有典型的α-Na Fe O2层状结构;所制备的Li Ni1/3Co1/3Mn1/3O2纳米纤维在0.5 C(85 m A/g)的倍率下循环30次容量保持率达到了94.1%;在倍率分别为0.1 C、0.2 C、0.5 C、1.0 C、2.0 C和0.2 C的充放电测试中,其比容量分别达到了157 m Ah/g、144 m Ah/g、134 m Ah/g、125 m Ah/g、115 m Ah/g和141 m Ah/g;在CV和EIS测试中,材料表现出优异的可逆性和循环稳定性.由于具有特殊的一维形貌,Li Ni1/3Co1/3Mn1/3O2纳米纤维表现出优异的电化学性能.     

纳米SiO_2/Au复合粒子的制备及其性质表征

通过改进的方法制备了金壳包覆二氧化硅纳米复合粒子. 二氧化硅和金纳米粒子分别通过Stober法和化学还原法制备. SEM分析表明, 都呈现出单分散的球状分布, 粒径为300和100 nm左右. 制备的纳米复合粒子通过TEM, UV-Vis-Near-IR, FTIR来表征和研究, 结果表明结合柠檬酸钠与硼氢化钾还原法制备所得到的SiO_2/Au复合粒子表层光滑, 完整, 没有团聚现象. SiO_2/Au-3的光学共振峰比SiO_2/Au-1和SiO_2/Au-2有红移. 傅立叶红外光谱研究表明形成SiO_2/Au核-壳结构后, Si-O-Si和Si-OH的键会明显减弱.     

脱碳处理对Pt/WC复合材料催化性能的影响

采用溶胶-凝胶法,以钨酸钠为钨源、酚醛树脂为碳源合成碳化钨前驱体干凝胶,经原位碳化制备纳米碳化钨（WC）粉体,纳米WC粉体中的玻璃碳采用浓硝酸浸渍法脱除。在纳米WC粉料浆中以甲醛（HCHO）作为氯铂酸（H2PtCl6·6H2O）的还原剂,室温合成得到Pt/WC复合催化剂材料;以XRD、SEM、EDS等测试方法对样品的理化特性进行表征,并在酸性介质中采用循环伏安法测试材料的电化学催化活性。结果表明：相较于未经过脱碳处理的WC,经过浓硝酸脱碳处理后的Pt/WC电极催化材料的催化活性更好。经溶胶-凝胶法及原位碳化制备的纳米WC的颗粒径为20-80纳米,其本身具备较好的电催化活性。样品中残留的玻璃碳对WC具有包覆作用,会降低WC的电催化活性。采取浓硝酸脱碳的方式可有效脱除纳米WC粉体中的玻璃碳,发挥WC材料作为电极催化材料的电催化活性。     

凹六面体CuPt纳米粒子的制备及其甲醇电催化性能

凹六面体CuPt合金纳米粒子有比一般八面体,四面体等纳米合金粒子更大的表面积,比纯的Pt纳米粒子更高的性能稳定性。本文用水热法在简单的条件下制备独特的凹六面体CuPt合金纳米粒子。通过STEM、TEM、X射线衍射,X射线光电子谱等研究手段对所制备的CuPt粒子的结构进行表征,结果表明该样品是粒径约为30 nm的均匀凹六面体粒子,由CuPt合金和Pt单质组成。通过对其甲醇电催化氧化性能的研究,发现该凹六面体CuPt合金纳米粒子的质量活性是商业Pt/C催化剂的12倍,且表现出更优异的抗毒化性能,具有潜在的燃料电池阳极催化的应用前景。     

Preparation and application of ZnO doped Pt-CeO2 nanofibers as electrocatalyst for methanol electro-oxidation

ZnO doped Pt/CeO₂ nanocomposites were prepared by electrospinning and reduction impregnation. X-ray diffraction (XRD), transmission electron microscopy (TEM), energy disperse spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the nanocomposites. It is observed that ZnO and CeO₂ form the hexagonal wurtzite phase and cubic fluorite phase in the nanocomposite, respectively, whilst Pt nanoparticles (NPs) with the number-averaged size of ca. 3.1 nm are uniformly distributed on the surface of nanofibers. The mass fraction of Pt NPs in the nanocomposites is about 10 wt%. The doping of ZnO is effective to promote reactive oxygen species, surface reaction sites and the interaction between Pt and oxides. The catalytic performance of nanocomposites was evaluated by the methanol electro-oxidation, indexed with the catalytic activity, stability of catalyst. As a result, it is found that the nanocomposite exhibits much higher activity and stability for methanol oxidation than the undoped Pt/CeO₂ catalyst.     

Effect of CeO_2-ZrO_2 on Pt/C electrocatalysts for alcohols oxidation

The electrocatalytic activity and stability of Pt/C catalyst modified by using CeO_2-ZrO_2 mixed oxides for the alcohols electrochemical oxidation as probes were investigated. The catalyst samples were characterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM). The electrochemical properties were measured by a three electrode system on electrochemical workstation(IVIUM). The results showed that the presence of CeO_2-ZrO_2 might be associated with the presence of Pt, which indicated that possibly there was synergistic effect between CeO_2-ZrO_2 and Pt nanoparticles. The electrocatalytic activity and stability of Pt-MO_x/C(M=Ce, Zr) for methanol and ethanol oxidation was better than that of Pt-CeO_2/C, which was attributed to that CeO_2-ZrO_2 composited oxides enhanced oxygen mobility and promoted oxygen storage capacity(OSC). Furthermore, the best performance was found when the molar ratio of CeO_2 to ZrO_2 was 2:1 for the oxidation of methanol and ethanol. The forward peak current density of Pt-MO_x/C(M=Ce, Zr, Ce:Zr=2:1) towards the methanol electrooxidation was about 3.8 times that of Pt-CeO_2/C. Pt-MO_x/C(M=Ce, Zr) appeared to be a promising and less expensive methanol oxidation anode catalyst.     

Mesoporous CeO_2-C hybrid spheres as efficient support for platinum nanoparticles towards methanol electrocatalytic oxidation

The development of direct methanol fuel cells(DMFCs) is partially limited by the poor kinetics of methanol oxidation reaction(MOR) at the anode side.It was reported that the interaction between Pt and CeO_2 enhances the electrocatalytic performance of Pt catalyst for MOR.In this work,a hybrid material(CeO_2-C) composed of CeO_2 and carbon was successfully prepared by a simple hydrothermal method followed by calcination in inert atmosphere.The hierarchically porous nanostructure and especially good electronic conductivity of CeO_2-C make it an excellent support for Pt particles for application in electrocatalytic process.TEM investigation reveals that triple-phase interface of Pt,carbon and CeO_2 forms in Pt/CeO_2-C catalyst.Performance of the as-prepared catalyst for MOR was studied in alkaline medium.The Pt/CeO_2-C catalyst shows superior catalytic performance for MOR compared with Pt/CeO_2 and the physical mixture of Pt/CeO_2 and acetylene black(Pt/CeO_2+C).The significantly improved performance can be attributed to the synergetic effect between Pt particles and CeO_2-C support,and the better conductivity of CeO_2-C.This study provides a possible method to expand the application potential of CeO_2 materials in MOR,and may also be used in other electrocatalytic process.     

Electrocatalytic enhancement of methanol oxidation by adding CeO2 nanoparticle on porous electrode

The polyaniline/polysulfone(PAN/PSF) composite films were prepared by electropolymerization,and then CeO2-Pt particles were codeposited into this composite film to obtain the CeO2-Pt-modified polyaniline/polysulfone(CeO2-Pt/PAN/PSF) electrodes.Their morphol-ogy and chemical component were characterized by field emission scanning electron microscopy(FESEM) and energy dispersive X-ray spectroscopy(EDS),respectively.The results showed that the composite film had bi-layer structure with asymmetrical pores,and platinum and cerium oxide particles were homogeneously dispersed in the modified film electrodes.The cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) techniques were applied to investigate the electrocatalytic activity of the Pt-CeO2/PAN/PSF electrodes.It was indicated that appropriate amount of CeO2 could enhance the catalytic activity of Pt for methanol electro-oxidation.Chronoamperometry(i-t) measurements revealed that the Pt-CeO2/PAN/PSF electrode was relatively endurable for intermediate production.In addition,different mix-ing amounts of Pt and CeO2 nanoparticles were also investigated in detail.     

Fabrication of copper-ceria hybrid composite electrode for electrocatalytic oxidation of methanol

Copper-ceria hybrid composite electrode prepared by electrochemical co-deposition was examined for their redox process and electrocatalytic activities towards the oxidation of methanol.The structure and morphology of electrodes were characterized by X-ray diffraction(XRD)and scanning electron microscopy(SEM),respectively.XRD pattern of the copper-ceria hybrid composite electrode exhibited some diffraction peaks of CeO2 and SEM micrograph showed that it was composed of grains and flakes.The energy dispersive spectroscopy(EDS)spectrum of this area also showed the presence of cerium.Cyclic voltammetry,CO stripping and chronoamperometry were performed to characterize electrocatalytic property of the prepared samples.In cyclic voltammetry studies and chronoamperometry,copper-ceria hybrid composite electrode towards oxidation of methanol showed a significantly higher response and long term stability.CO stripping results indicated the facile removal of intermediate poisoning species CO in the presence of CeO2,which was helpful for CO and methanol electro-oxidation.     

Ternary PtSmCo NPs electrocatalysts with enhanced oxygen reduction reaction

PtSmCo ternary metal nanoparticles (NPs) were synthesized as electrocatalysts for oxygen reduction reaction (ORR). Firstly, SmCo NPs were prepared by potentiostatic electrodeposition in ionic liquids (ILs), and the average particle diameter of SmCo NPs corresponds to about 238 nm (−0.65 V), 72 nm (−0.75 V) and 45 nm (−0.85 V), respectively. Secondly, displacement and reductions of SmCo NPs occur in the K₂PtCl₄ and l-ascorbic acid sodium with about 3 nm of Pt NPs which grow on the surface of SmCo NPs to form PtSmCo ternary metal NPs. Studies of cycle voltammetry (CV) and line sweep voltammetry (LSV) indicate that the electrocatalytic property for ORR generates a decreasing order of commercial Pt/C > PtSmCo0.85 > PtSmCo0.75 > PtSmCo0.65. Accelerated durability testing (ADT) after 10000 cycles shows that PtSmCo0.85 NPs electrocatalyst decreases by ∼40% in electrochemical active surface areas (ECSA), the half-wave potential (E_1/2) only negatively shifts by 14 mV and decreases by ∼13.6% in mass activity (MA). When compared with JM Pt/C, where it decreases by ∼49% in ECSA, E_1/2 is negatively shifted by 40 mV and decreased by ∼50% in MA. Therefore, PtSmCo0.85 NPs electrocatalyst is more stable than JM Pt/C.     

花状Pt/Bi2WO6微米晶合成、表征及其高可见光催化性能

利用水热-光化学沉积法合成了一系列粒径为1.5~2μm的花状Pt/Bi2WO6微米晶.采用X射线衍射仪（XRD）、N2物理吸附、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、紫外可见漫反射光谱（DRS）、X射线光电子能谱（XPS）和傅里叶变换红外光谱（FT-IR）等手段进行表征.在可见光照射下（λ＞420 nm）,进行了光催化降解染料酸性橙Ⅱ的性能测试.表征和测试结果表明,这些多尺度花状Pt/Bi2WO6复合微米晶,在水溶液中进行光催化降解反应具有优越的性能.此外,沉积1%的Pt 纳米粒子可使光催化活性显著提高,为Bi2WO6的2.8倍.沉积的Pt纳米粒子由于产生表面等离子体的共振吸收,增强对可见光的吸收能力,同时降低了光生电子（e-）和空穴（h+）的复合,促进·OH 自由基的产生,因此能在很大程度上提高光催化活性.此外,这种特殊结构的Pt/Bi2WO6微米晶有利于在水溶液中进行分离和回收,提高催化剂的利用效率.     

Effects of different ligands on luminescence properties of LaF3：Nd nanoparticles

A series of neodymium-doped lanthanum fluoride nanoparticles(NPs) were synthesized with hydrothermal method,and the effects of several ligands on the luminescence properties of the NPs were investigated.The X-ray diffraction(XRD) results indicated that the crystal phases of the modified NPs coincided with the standard spectrum.The transmission electron microscopy(TEM) showed that the samples were of similar size,shape and dispersibility.The infrared spectra suggested that the content of -OH groups as quenchers on the NPs surfaces decreased after modification.Compared with NPs modified by branched paraffin ligands,NPs conjugating ring-contained modifiers had less quenching effect and possessed stronger fluorescence intensity and longer fluorescence lifetime.     

Methanol Oxidation over TiO2-modified Multi-walled Carbon Nanotubes Supported Pt-Mo Electrocatalyst

In order to develop a novel and high-performance catalytic material for direct methanol fuel celIs(DMFC), molybdenum oxide as a co-catalyst with Pt on multi-walled carbon nanotubes which were modified by titanium dio- xide(denoted as CNTs@TiO<,2>) was investigated. The physicochemical characterizations of the catalysts were carried out via X-ray diffraction(XRD), transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS). Cyclic voltammetry(CV) showed that the CO-tolerance performance increased in the sequence of Pt/CNTs< Pt/CNTs@TiO<,2>. The improved CO-tolerance performance of the Pt-Mo/CNTs@TiO<,2> catalyst can be attributed to the combined beneficial effects of highly dispersed Pt nanoparticles on the CNTs, the existence of oxygen holes in the MoO<,3> layer structure and the oxidation capability of TiO<,2>.     

球形氧化镍粉末对乙醇的电催化性能的研究

通过水热-热分解法制备球形介孔氧化镍粉末,并采用X射线衍射、扫描电镜、透射电镜和比表面积仪对氧化镍粉末的形貌和结构进行表征;通过循环伏安法、计时电流法和电化学阻抗谱的测试,系统研究该种粉末在碱性介质中对乙醇的电催化氧化活性.结果表明:所得到的氧化镍粉末为球形,比表面积为35 m2·g-1,平均孔径为15.88 nm;该粉末对乙醇具有良好的催化活性,氧化电流随乙醇浓度和扫描速率的增大而增大,在0.60 V电位下保持1000 s,球形多孔氧化镍对乙醇氧化催化的电流衰减率为0.075%,稳定性比较好.循环伏安法、计时电流法和电化学阻抗谱测试表明,球形介孔NiO/玻碳电极(NiO/GCE)对乙醇的催化氧化反应机理为扩散控制.