炭载Ir金属催化剂的制备及其对氨氧化的电催化性能

利用乙醇-水二元体系制备含质量分数为30%Ir的碳载Ir(Ir/C)催化剂.X射线衍射(XRD)谱和电化学测试分别表明,该催化剂Ir粒子的平均粒径约为2.2 nm.在NaC lO4电解液中,Ir/C催化剂对氨氧化的电催化活性与纯Ir催化剂的相似,但稳定性有明显增加.同时,NH3氧化的电流密度与NH3浓度呈现良好的线性关系,有望在定电位电解型NH3传感器中得到应用.     

不同载量Ir/C催化剂对氨氧化的电催化性能

研究电流型电化学氨气传感器阳极碳载Ir(Ir/C)催化剂电催化NH3氧化性能.实验表明,在NaC lO4中性电解液中,Ir/C催化剂对NH3氧化的电催化性能与Ir载量有关.其中以Ir载量为10%(by m ass)的Ir/C催化剂的电催化性能最好,稳定性和灵敏度也最高.此外,NH3在不同载量的Ir/C催化剂上电催化氧化的电流密度与NH3浓度均呈现出良好的线性关系,此类Ir/C催化剂在电流型电化学氨气传感器中可望有良好的应用前景.     

炭载Ir-Co催化剂的制备及其对氨氧化的电催化性能

通过液相化学还原法制备了炭载Ir-Co(Ir-Co/C)催化剂。 X射线衍射测试表明,Co原子进入了金属Ir的晶格中,形成了Ir-Co合金,并导致了Ir晶格收缩。 透射电子显微镜观察表明,Ir-Co纳米颗粒均匀分散在炭载体表面,没有出现Ir/C催化剂中金属Ir严重团聚的现象。 电化学测试表明,与炭载Ir(Ir/C)催化剂相比,NH3在Ir-Co/C催化剂电极上氧化的起始电位负移,峰电流密度增大,增加了检测灵敏度和降低了检出限,表明Ir-Co/C催化剂对NH3氧化的电催化性能明显优于Ir/C催化剂。 Ir-Co/C催化剂在电化学氨气传感器中有良好的应用前景。     

石墨烯载Ir催化剂对氨氧化的电催化性能

用石墨烯(G)代替Vulcan XC-72炭(XC)作Ir的载体制备石墨烯载Ir(Ir/G)催化剂. 电化学的测量结果表明, Ir/G催化剂对氨氧化的电催化性能优于XC炭载Ir(Ir/XC)催化剂. X射线衍射(XRD)谱测量结果表明, Ir/G和Ir/XC催化剂的Ir粒子平均粒径相似. 拉曼光谱的测量结果表明, G的石墨化程度和电导率高于XC. 因此, Ir/G催化剂对氨氧化的电催化性能优于Ir/XC催化剂. 氨在Ir/G催化剂电极上氧化的电流密度与氨浓度呈很好的线性关系曲线, 相关系数R为0.99557. 因此, Ir/G催化剂电极可作为电流型电化学氨传感器的工作电极.     

碳化钨和Vulcan XC-72炭混合载Ir催化剂对氨氧化的电催化性能

以碳化钨(WC)和Vulcan XC-72炭黑(XC)为载体制备了XC载Ir(Ir/XC)和WC/XC载Ir(Ir-WC/XC)催化剂,在用X射线能量色散谱、X射线衍射谱对催化剂表征的基础上,用电化学方法研究了2种载体Ir催化剂对氨氧化的电催化性能,发现氨在Ir-WC/XC催化剂电极上的氧化峰峰电流密度比在Ir/XC催化剂电极上大31.26%,而且电催化稳定性明显好于Ir/XC催化剂。     

IrO_2改性钛网对固体聚合物电解质电解器集电极层电化学性能的影响

采用亚当斯熔融法(Adams fusion method)在钛网上包覆Ir O2催化剂,并将其用作固体聚合物电解质(SPE)电解器的阳极集电极,发现其可以显著降低电解过电位.通过X射线多晶衍射(XRD)和透射电子显微镜(TEM)分析发现,包裹在钛网上的Ir O2催化剂晶粒为2.0~3.0 nm,结晶度良好;交流阻抗谱(EIS)和循环伏安(CV)分析结果表明,改性的钛网集电极层可增加三相反应活性点,使三相反应通道由催化层延伸到集电极层,活性催化剂表面积增大,从而大幅度降低了活化阻抗,电解性能获得提升.通过对不同Ir O2催化剂负载量改性的钛网进行研究发现,随着钛网负载Ir O2量的增加,在相同电流密度下,极化曲线的过电位先减小后增加,当Ir O2负载量为1.38%(质量分数)时,电解池的过电位最低,在1 A/cm2电流密度下,过电位为2.028 V.     

超细Ir催化剂对氨氧化的电催化性能

报道了一种新型的、用NH4F作络合剂的络合还原法制备的Ir催化剂及其对氨氧化的电催化性能. 结果表明, 由于溶液中的Ir3+和NH4F形成络合物, 因此用这种络合法制得Ir催化剂中Ir粒子的平均粒径为2.8 nm, 要比不加络合剂时制得的Ir催化剂中Ir粒子的平均粒径(7.5 nm)小很多. 所以, 用络合还原法制得的Ir催化剂对氨氧化的电催化活性和稳定性都比不加络合剂时制得的Ir催化剂好很多. 且该制备方法简单、实用, 适用于催化剂的实际生产.     

Pt-Ir/Al2O3催化剂催化2-氧-4-苯基丁酸乙酯不对称加氢

用浸渍法制备了一系列γ-Al2O3负载的Pt、Ir单金属及不同Pt/Ir比例的双金属催化剂,在辛可尼定修饰下用于对2-氧-4-苯基丁酸乙酯不对称加氢合成(R)-2-羟基-4-苯基丁酸乙酯反应.运用XRD、TEM、TPR、XPS、UV-Vis等表征手段,对催化剂的物化性质进行了研究,并对Pt、Ir金属表面辛可尼定手性诱导机理进行了初步探讨.结果表明,金属组分在催化剂上分散均匀,无团聚现象,平均粒径为3～4 nm;Pt-Ir/γ-Al2O3上Pt、Ir组分以单质形式存在;Ir作为低活性物种,在Pt/γ-Al2O3催化剂掺杂Ir组分遮盖和稀释了催化剂表面总体Pt活性位点数目,降低了Pt-Ir/γ-Al2O3催化剂加氢性能.辛可尼定在Pt、Ir表面的不同吸附行为(吸附方式、吸附强度、吸附构象)影响EOPB不对称加氢活性和对映选择性.     

Electrochemical Oxidation of Ammonia on Ir Anode in Potential Fixed Electrochemical Sensor

Ir catalyst possesses a good electrocatalytic activity and selectivity for the oxidation of NH3 and/or NH4OH at Ir anode in the potential fixed electrochemical sensor with the neutral solution. Owing to the same electrochemical behavior of NH3 and NH4OH in a NaClO4 solution, NH4OH can be used instead of NH3 for the experimental convenience. It was found that the potential of the oxidation peak of NH4OH at the Ir/GC electrode in NaClO4 solutions is at about 0.85 V, and the current density of the oxidation peak of NH4OH is linearly proportional to the concentration of NHaOH. The electrocatalytic oxidation of NH4OH is diffusion-controlled. Especially, Ir has no electrocatalytic activity for the CO oxidation, illustrating that CO does not interfere in the measurement of NH4OH and the potential fixed electrochemical NH3 sensor with the neutral solution, and the anodic Ir catalyst possesses a good selectivity. Therefore, Ir may have practical application in the potential fixed electrochemical NH3 sensor with the neutral solution.     

大孔碳载Ir催化剂对氨氧化的电催化性能

分别以大孔炭(MC)和Vulcan XC-72炭黑(XC)为载体,制备了Ir/MC和Ir/XC催化剂。 在用X射线能量色散谱(EDS)、X射线衍射(XRD)谱、拉曼光谱对催化剂表征的基础上,用电化学技术研究了2种炭载Ir催化剂对氨氧化的电催化性能,发现氨在Ir/MC催化剂电极上,氧化峰峰电流密度比在Ir/XC催化剂电极上大38.7%左右,而且电催化稳定性明显好于Ir/XC催化剂。 由于Ir/MC和Ir/XC催化剂的Ir粒子平均粒径和相对结晶度相似,因此,这只能归结于MC有大的孔径和孔率及高的石墨化程度引起的高电导率。 所以MC是一种比XC更好的催化剂的炭载体。     

二氧化硫的电化学氧化过程：Ⅰ.电极材料的影响

采用循环伏安法研究了SO_2在多种电极(催化剂)上的电化学氧化过程。根据催化剂上是否存在表面氧化物以及SO_2吸附形态的不同,可将所研究的催化剂分为三种类型。第一类以Au、Pt、Pd为代表,第二类以Ru、Rh、Ir为代表,第三类以聚钴卟啉类N_4大环配合物为代表。并对SO_2在三类催化剂上反应的特点进行了讨论。     

Platinum nanocube catalysts for methanol and ethanol electrooxidation

We prepared Pt nanocube catalyst with about 3.6 nm in size by a polyol process in the presence of PVP as a stabilizer and Fe ion as a kinetic controller. The crystal structure of Pt nanocube with {1 0 0} faces was confirmed by field-emission transmission electron microscopy. In a cyclic voltammogram, we found that the Pt nanocube catalyst showed relatively high ratio of the forward anodic peak current to the reverse anodic peak current resulting in less accumulation of residues on the catalyst. The Pt nanocube catalyst with the edge of stepped {1 0 0} faces was preferable to breakage of CH₃OH and CH₃CH₂OH compared to polycrystalline Pt nanocatalyst. In an electrochemical measurement for methanol and ethanol electrooxidation, the Pt nanocube catalyst showed an excellent catalytic activity, i.e., lower onset potential and higher current density, compared to the polycrystalline Pt nanocatalyst.     

钒(V)化合物在硫酸中的电化学行为研究

应用循环伏安法和旋转环盘电极法研究了H2 SO4 溶液中五价钒化合物 (NH4 VO3和V2 O5)的电化学行为 .由光滑Pt电极测得其CV图 ,两者的基本峰位和峰形都很相似 ,通常出现三个还原峰和三个氧化峰 ,但NH4 VO3多一个氧化峰 ,RRDE测定也出现了四个氧化峰 ,本文分析了这些对应峰的反应 ,并给予初步解释     

Ru(bpy)^2^+~3-C2O^2^-~4-PtE体系的两条电致化学发光通道

运用电位分辨电致化学发光(PRECL)手段发现Ru(bpy)^2^+~3-C2O^2^-~4-PtE体系在预氧化的多晶铂电极上存在两个发光通道,这两个通道分别位于1.22V和1.44V处,对影响两发光通道的条件进行了研究,比较了几种经过不同预处理方式(直接抛光、阳极极化和阴极极化的电极以及S吸附电极)以及体系中不同C2O^2^-~4浓度,pH,溶解氧和溶解二氧化碳对两PRECL峰形、峰强度的影响。提出第二个ECL发光峰的机制为C2O^2^-~4直接电极氧化产物CO^-^.~2(或C2O^-^.~4)的催化发光。     

Ir/CNTs催化剂的制备及对氨的电催化氧化

分别以碳纳米管(CNTs)和XC-72活性碳为载体制备了Ir/CNTs和Ir/C催化剂. X射线衍射(XRD)结果显示, CNTs拥有更高的石墨化程度. 电化学研究结果表明, 与Ir/C催化剂相比, Ir/CNTs对氨氧化具有更高的电流密度、更低的起始氧化电位和更好的稳定性. 同时, Ir/CNTs催化剂对氨检测的线性范围更宽, 灵敏度更高, 检出限更低.     

Investigation of the Pt–Ni–Pb/C ternary alloy catalysts for methanol electrooxidation

This research is aimed to increase the activity of anodic catalysts and thus to lower noble metal loading in anodes for methanol electrooxidation. The Pt–Ni–Pb/C catalysts with different molar compositions were prepared. Their performance were tested by using a glassy carbon disk electrode through cyclic voltammetric curves in a solution of 0.5 mol L⁻¹ CH₃OH and 0.5 mol L⁻¹ H₂SO₄. The performances of Pt–Ni–Pb/C catalyst with optimum composition (the molar ratio of Pt/Ni/Pb is 5:4:1) and Pt/C (E-Tek) were also compared. Their particle sizes and structures were determined by means of X-ray diffraction (XRD). The XRD results show, compared with that of Pt/C, the lattice parameter of Pt–Ni–Pb (5:4:1)/C catalyst decreases, its diffraction peaks are shifted slightly to a higher 2θ values. This indicates the formation of an alloy involving the incorporation of Ni and Pb atoms into the fcc structure of Pt. The electrochemical measurement shows the activity of Pt–Ni–Pb/C catalyst with an atomic ratio of 5:4:1 for methanol electrooxidation is the best among all different compositions. The activity of Pt–Ni–Pb (5:4:1)/C catalyst is much higher than that of Pt/C (E-Tek).     

Carbon-supported IrSn catalysts for a direct ethanol fuel cell

Carbon-supported Ir₃Sn/C and Ir/C catalysts were simply prepared with NaBH₄ as a reducing agent under the protection of ethylene glycol at room temperature. TEM and X-ray diffraction (XRD) data showed that the catalysts with small particle size exhibited the typical characteristic of a crystalline Ir fcc structure. Their electro-catalytic activities in comparison with Pt/C and Pt₃Sn/C catalysts also prepared by the NaBH₄ reduction process were characterized by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperometry (CA) techniques. The results indicated that Ir-based catalysts showed superior electro-catalytic activity towards ethanol oxidation to Pt/C and Pt₃Sn/C catalysts, mainly at low potential region. During single-cell tests at 90 °C, better performances of Ir-based catalysts as anodes were obtained compared to that of Pt/C catalyst. The comparable overall performance of Ir₃Sn/C to Pt₃Sn/C makes it a promising alternative choice of anode catalyst for direct ethanol fuel cells.     

Microwave-assisted polyol synthesis of carbon-supported platinum-based bimetallic catalysts for ethanol oxidation

High surface area carbon-supported Pt, PtRh, and PtSn catalysts were synthesized by microwave-assisted polyol procedure and tested for ethanol oxidation in perchloric acid. The catalysts were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning tunnelling microscopy (STM), TEM, and EDX techniques. STM analysis of unsupported catalysts shows that small particles (～2?nm) with a narrow size distribution are obtained. TEM and XRD examinations of supported catalysts revealed an increase in particle size upon deposition on carbon support (diameter?～?3?nm). The diffraction peaks of the bimetallic catalysts in X-ray diffraction patterns are slightly shifted to lower (PtSn/C) or higher (PtRh/C) 2θ values with respect to the corresponding peaks at Pt/C catalyst as a consequence of alloy formation. Oxidation of ethanol is significantly improved at PtSn/C with the onset potential shifted for?～?150?mV to more negative values and the increase of activity for approximately three times in comparison to Pt/C catalyst. This is the lowest onset potential found for ethanol oxidation at PtSn catalysts with a similar composition. Chronoamperometric measurements confirmed that PtSn/C is notably less poisoned than Pt/C catalyst. PtRh/C catalyst exhibited mild enhancement of overall electrochemical reaction in comparison to Pt/C.