甲醇在欠电位沉积Ru修饰Pt电极上的催化氧化

采用欠电位沉积(upd)方法在Pt 表面沉积亚单层的Ru制备出upd-Ru/Pt 电极. 通过欠电位沉积前后电极在0.5 mol·L-1 H2SO4溶液中循环伏安图-152 - 128 mV(vs Ag/AgCl)电位范围内对氢区的数值积分确定Pt表面Ru 的覆盖度. 用电化学方法测试了甲醇在upd-Ru/Pt电极上的催化氧化, 并讨论分析了欠电位沉积电位和Ru的表面覆盖度对甲醇氧化的影响. 结果表明, Ru能够欠电位沉积到Pt表面. Pt表面欠电位沉积少量的Ru 即能大大促进甲醇的氧化.只要控制upd-Ru的沉积量, upd-Ru原子就能大大促进甲醇氧化而与沉积电位无关. Ru原子对甲醇氧化的促进作用与Ru和Pt是否形成合金无关, 而取决于Ru 在Pt表面的百分含量.     

Pd/Pt二元合金电极的制备及氧还原性能

本文利用欠电位沉积亚单层的Cu及Pt置换取代Cu的方法, 制备了具有不同表面元素组成的Pd/Pt二元合金电极(用Pd/Ptx表示, x指欠电位沉积Cu-Pt置换取代Cu过程的次数),并对其表面元素组成、氧还原性能进行了表征. 在控制欠电位沉积Cu的下限电位恒定(0.34 V)的前提下, 表面Pt/Pd的元素组成比通过重复欠电位沉积Cu及Pt置换取代Cu的次数(1~5次)来可控地调变. 光电子能谱(XPS) 以及红外光谱实验表明,Pd/Ptx电极表层区的Pt：Pd元素组成比随着Pt沉积次数增加而增加, 对Pd/Pt4电极, 在电极表层区约2~3 nm内的Pt/Pd的原子比大约是1:4,而最表层裸露Pd原子的比例仍在20%以上。循环伏安结果显示, 随着Pt沉积次数的增加(1-5次), Pd/Ptx电极表面越不易被氧化。氧还原测试结果显示随着Pt沉积次数的增加(1~4次), Pd/Ptx二元金属电极的氧还原活性依次增加, 经过第3次沉积后其氧还原活性已优于纯Pt,而经4次以上沉积,其氧还原活性基本不变。在其它反应条件相同条件的前提下, Pd/Pt4电极上氧还原的半波电位与纯Pt相比右移约25 mV。结合本文与文献的实验结果,我们初步认为Pd/Ptx二元金属体系氧还原性能改善主要源自表层Pd原子导致其邻近的Pt原子上含氧物种吸附能的降低.     

离子液体中Au(111)和Pt(111)表面Ge欠电位沉积的现场STM研究

本文研究BMIPF₆离子液体中Au(111)和Pt(111)表面Ge的电沉积行为. 循环伏安法测试结果表明,在含0.1 mol·L^-1 GeCl₄的BMIPF₆溶液Au(111)和Pt(111)表面均有两个与Ge沉积过程相关的还原峰. 第一个还原峰包含了Ge⁴⁺还原成Ge²⁺及Ge的欠电位沉积,第二个还原峰对应Ge的本体沉积. 现场扫描隧道显微镜研究结果表明,Ge在Au(111)和Pt(111)表面均有两层欠电位沉积. 第一层欠电位沉积厚度约为0.25 nm、形貌平整、带有缝隙的亚单层结构. 第二层欠电位沉积形貌相对粗糙的点状团簇结构. 该欠电位沉积过程伴随表面合金化.     

铂电极上锑吸附原子对1,2-丙二醇电催化氧化性能的影响

运用电化学循环伏安(CV)和电化学原位石英晶体微天平(EQCM)研究了Pt电极表面不可逆吸附Sb原子的电化学特性以及Pt电极上Sb吸附原子对0.1mol·L-1H2SO4溶液中1,2 丙二醇电催化氧化性能的影响.研究发现,当扫描电位的上限Eu≤0.50V(SCE)时,Sb可以稳定地吸附在Pt电极表面,饱和覆盖度为0.34;通过控制电位扫描上限和扫描圈数剥离部份Sb可方便地得到Sbad的不同覆盖度;Pt电极表面Sb吸附原子能在较低的电位下吸附氧,可显著提高1,2 丙二醇电催化氧化活性.与Pt电极相比较,Sb饱和吸附原子修饰的Pt电极使1,2 丙二醇氧化的峰电流增加了近2倍.作者还从表面质量变化提供了吸附原子电催化作用的新数据.     

Ru膜上Pt层的自发沉积及其在电化学表面增强红外光谱中的应用

采用自发沉积法在Ru膜上生成超薄Pt层(简称Ru/Pt膜), 即在开路状态下将电化学还原后的Ru膜浸于除去氧的H2PtCl6溶液中进行自发沉积. 电化学伏安法测量表明, 随着电还原-自发沉积循环次数的增加, 该Ru/Pt膜电极所含Pt组分增加, 且CO吸附层的电氧化峰电位较Pt膜电极上的明显负移. 应用现场衰减全反射表面增强红外光谱法(ATR-SEIRAS)可轻易检测到在该膜电极Pt和Ru位上吸附CO的振动谱峰. 所制Ru/Pt膜电极不仅对CO的电催化氧化具有协同效应, 还可应用于现场ATR-SEIRAS的研究中.     

Au/Si 载体负载单层Pt 催化剂的制备及其电催化性能的研究

以Si 纳米粉为载体, 通过化学镀的方法在其表面部分沉积纳米Au 颗粒后, 再通过欠电位的方法在Au 颗粒表面沉积了单层及亚单层的Pt. 通过透射电子显微镜(TEM), 循环伏安(CV)等方法对所制备的Pt/Au/Si 催化剂进行了形貌及电化学性能的表征. 结果表明, 该单层Pt 覆盖的Au/Si 催化剂对于甲醇的质量电催化活性是商业E-TEK(Pt/C)的8 倍,相比于不同层数的Pt, 单层覆盖时Pt 的利用率最高, 该单层Pt 负载Au/Si 催化剂对于抑制CO 的中毒的性能也比商业E-TEK(Pt/C)有明显的提高.     

Au@Pt纳米粒子催化O2还原反应的电化学研究

以100 nm的Au粒子为核,抗坏血酸为还原剂,H2PtCl6·6H2O为前驱体,合成了Pt包Au核壳结构纳米粒子( Au@ Pt)及其修饰的玻碳(GC)电极(Au@ Pt/GC).采用旋转圆盘电极等常规电化学方法,比较了Au@ Pt/GC和商用碳载铂(Pt/C)修饰的玻碳电极(Pt/C/GC)催化O2还原反应活性及耐甲醇性能,发现Au@ Pt纳米粒子在铂用量很低的情况下,其催化O2还原反应活性仍与商用Pt/C相当,而且还具有优良的耐甲醇性能;其催化O2还原反应机理按O2直接还原成H2O的四电子历程进行.     

H2S气体在不同催化剂表面的电化学氧化行为

1　引　　言H2 S气体能对人体产生严重伤害。在环保、生产等领域对其进行检测 ,具有重要意义。本实验通过循环伏安、线性扫描、XPS等手段 ,研究H2 S、Pd、Pt、Rh和Au电极上的电化学氧化行为。实验表明 :Au在特定条件对H2 S具有良好的电催化活性 ,以Au为工作电极并选择合适工作条件 ,可以解决催化剂中毒问题 ,传感器灵敏度可达 0 .76 μA·m3 /mg。2　实验部分2 .1　仪器设备　三电极电化学池 ;CHI6 0 2电化学系统 (美国CHI公司 ) ;恒电位仪 (长春市环保分析仪器厂 )。2 .2　样品准备与测试条件　工作电极是将Pd、Pt、Rh和Au用树…     

“三明治式”多层Au/Pt复合薄膜的制备及其对甲醇的电氧化

采用界面组装、欠电位沉积和氧化还原置换反应组合方法制备了单层Pt/Au复合薄膜, 并且不需要任何有机偶联剂; 组装单层Pt/Au复合薄膜为三类多层Pt/Au复合薄膜: (Pt/Au)_n、Pt_m/Au和(Pt₃/Au)_k (n、m和k分别为Pt/Au、Pt和Pt₃/Au的层数). 采用电子显微镜研究了Au纳米粒子单层膜和Pt/Au复合多层膜的形貌. 对于所有的多层膜电极而言, 其电化学活性面积随着层数的增加而增加. 通过研究甲醇在每一类Pt/Au复合薄膜上的氧化电流密度, 考察了其对甲醇的电催化和抗毒化性能. 对于同一类复合薄膜而言, 甲醇分别在(Pt/Au)₃、Pt₃/Au和(Pt₃/Au)₂电极上均具有最大的氧化电流密度, 且优于本体Pt电极. 在这三种电极中, (Pt/Au)₃电极无论从电流密度上还是从抗毒化能力上讲, 其性能是最好的, 而且其抗毒化能力也优于商业Pt/C催化剂. 这种良好的催化性能源于Au和Pt之间最大化的协同效应, 这取决于Pt和Au原子比率以及Pt纳米层和Au纳米层之间的排布方式.     

Au,Pb对Cr^3＋／Cr^2＋氧化还原反应催化性能的XPS研究

本文研究玻碳电极(GCE)表面Cr~(3+)/Cr~(2+)氧化还原反应产物和沉积的Au、Pb催化剂的价态以及它们对Cr~(3+)/Cr~(2+)反应的催化作用。XPS研究结果表明,Cr~(3+)/Cr~(2+)氧化还原反应产物无Cr~0或其它价态的化合物生成。Au、Pb作为催化剂以金属零价形式沉积在GCE表面。随Au、Pb光电子峰强度的变化,它们对Cr~(3+)/Cr~(2+)氧化还原反应呈现不同的催化作用。     

Electrochemical quartz crystal microbalance study on Au-supported Pt adlayers for electrocatalytic oxidation of methanol in alkaline solution

Underpotential deposition (UPD) of Cu on an Au electrode followed by redox replacement reaction (RRR) of Cu_UPD with a Pt source (H₂PtCl₆ or K₂PtCl₄) yielded Au-supported Pt adlayers (for short, Pt(CuUPD-Pt⁴⁺)n/Au for H₂PtCl₆, or Pt(CuUPD-Pt²⁺)n/Au for K₂PtCl₄, where n denotes the number of UPD-redox replacement cycles). The electrochemical quartz crystal microbalance (EQCM) technique was used for the first time to quantitatively study the fabricated electrodes and estimate their mass-normalized specific electrocatalytic activity (SECA) for methanol oxidation in alkaline solution. In comparison with Pt(CuUPD-Pt²⁺)n/Au, Pt(CuUPD-Pt⁴⁺)n/Au exhibited a higher electrocatalytic activity, and the maximum SECA was obtained to be as high as 35.7 mA μg^?1 at Pt(CuUPD-Pt⁴⁺)3/Au. The layer-by-layer architecture of Pt atoms on Au is briefly discussed based on the EQCM-revealed redox replacement efficiency, and the calculated distribution percentages of bare Au sites agree with the experimental results deduced from the charge under the AuO _x -reduction peaks. The EQCM is highly recommended as an efficient technique to quantitatively examine various electrode-supported catalyst adlayers, and the highly efficient catalyst adlayers of noble metals are promising in electrocatalysis relevant to biological, energy and environmental sciences and technologies.     

Mechanistic Study on the Monofunctional Binding of Hydrolysis Products of Non-planar Heterocyclic Complexes Trans-[PtCl_2NH_3（piperidine）] and Trans-[PtCl_2（piperidine）_2] to DNA Purine Bases

The monofunctional substitution reactions between trans-[PtCl(H2O)(NH3)(pip)]+,trans-[Pt(H2O)2(NH3)(pip)]2+,trans-[PtCl(H2O)(pip)2]+,trans-[Pt(H2O)2(pip)2]2+ (pip = piperidine) and adenine/guanine nucleotides are explored by using B3LYP hybrid functional and IEF-PCM salvation models. For the trans-[Pt(H2O)2(NH3)(pip)]2+ and trans-[PtCl(H2O)(NH3)(pip)]+ complexes,the computed barrier heights in aqueous solution are 13.5/13.5 and 11.6/11.6 kcal/mol from trans-Pt-chloroaqua complex to trans/cis-monoadduct for adenine and guanine,and the corresponding values are 20.7/20.7 and 18.8/18.8 kcal/mol from trans-Pt-diaqua complex to trans/cis-monoadduct for adenine and guanine,respectively. For trans-[PtCl(H2O)(pip)2]+ and trans-[Pt(H2O)2(pip)2]2+,the corresponding values are 21.5/21.3 and 19.4/19.4 kcal/mol,and 26.0/26.0 and 20.7/20.8 kal/mol for adenine and guanine,respectively. Our calculations demonstrate that the barrier heights of chloroaqua are lower than the corresponding values of diaqua for adenine and guanine. In addition,the free energies of activation for guanine in aqueous solution are all smaller than that for adenine,which predicts a preference of 1.9 kcal/mol when trans-[PtCl(H2O)(NH3)(pip)]+ and trans-[Pt(H2O)2(NH3)(pip)]2+ are the active agents and ～1.9 and ～ 5.3 kcal/mol when trans-[PtCl(H2O)(pip)2]+ and trans-[Pt(H2O)2(pip)2]2+ are the active agents,respectively. For the reaction of trans-Pt-chloroaqua (or diaqua) to cis-monoadduct,we obtain the same transition-state structure as from the reaction of trans-Pt-chloroaqua (or diaqua) to trans-monoadduct,which seems that the trans-Pt-chloroaqua (or diaqua) complex can generate trans-or cis-monoadduct via the same transition-state.     

195Pt NMR study of the speciation and preferential extraction of Pt(IV)-mixed halide complexes by diethylenetriamine-modified silica-based anion exchangers

A detailed 195Pt NMR study of the distribution of Pt(IV) complex species resulting from the aquation of H2PtCl6, H2PtBr6, and mixtures of H2PtCl6/H2PtBr6 in water/dilute HClO4 has been carried out to obtain an understanding of the speciation in these solutions as relevant to the recovery of Pt(IV) complexes from process solutions. A species distribution plot of the [PtCl6]2-, [PtCl5(H2O)]-, and [PtCl4(H2O)2] shows that in equilibrated, relatively concentrated H2PtCl6 solutions ([Pt]t > 0.12 M), the [PtCl4(H2O)2] species is below the 195Pt NMR detection limit; for [Pt]t concentrations < 0.1 M, the relative concentrations of the [PtCl5(H2O)]- and [PtCl4(H2O)2] species increase significantly, as a result of relatively rapid aquation of the [PtCl6]2- and [PtCl5(H2O)]- complexes under these conditions. From this (195)Pt NMR data the aquation constants of [PtCl6]2- and [PtBr6]2- of log K6 approximately 1.75 +/- 0.05 and log K6 approximately 2.71 +/- 0.15, respectively, have been determined at 30 degrees C. In mixtures of H2PtCl6/H2PtBr6 in water, a number of previously unidentified aquated complexes of the general formula [PtCl(5-n)Br(n)(H2O)]- (n = 0-5) could be identified, including the possible geometrical isomers of these complexes. These 195Pt NMR assignments were confirmed by remarkably systematic, linear relationships between the 195Pt chemical shift increments induced by substitution of Cl- ions by n Br- ions in [PtCl(6-n)Br(n)]2- and [PtCl(5-n)Br(n)(H2O)]- complexes. Preferential extraction of the [PtX6]2- (X = Cl, Br, or a mixture of the two halides) species over their corresponding aquated [PtX5(H2O)]- counterparts by silica-based diethylenetriamine anion exchangers could be demonstrated by means of 195Pt NMR spectroscopy.     

Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction

Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.     

手性修饰的介孔碳材料MPC-61负载铂催化剂上α-酮酸酯的不对称氢化反应

采用氯铂酸乙醇溶液和氯铂酸水溶液为前体,通过浸渍法制备了介孔碳材料MPC-61负载Pt质量分数分别为4%和10%的Pt/MPC-61催化剂,并利用XRD,TEM,N2吸附-脱附和CO化学吸附等手段对催化剂进行了表征.考察了经过手性分子辛可尼定修饰后的Pt/MPC-61催化剂在丙酮酸乙酯不对称氢化反应中的催化性能.以氯铂...     

金属间化合物电催化剂Pt1Te1/XC-72的制备及其电催化氧化甲醇性能

以氯铂酸和亚碲酸钠为前驱体,采用两步法在醇水体系下得到负载型Pt1Te1金属间化合物前驱体,通过热处理得到负载型金属间化合物电催化剂Pt1Te1/XC-72.采用X射线衍射（XRD）、透射电子显微镜（TEM）、选区电子衍射（SAED）、电子能谱（EDS）和循环伏安方法（CV）对催化剂进行表征.结果表明：所得产物呈有序金属间化合物Pt1Te1结构,平均粒径4.5nm,在碳载体上具有很好的分散性;负载型金属间化合物电催化剂Pt1Te1/XC-72具有较高的电催化氧化甲醇活性,其优秀的催化氧化甲醇活性与Pt形成金属间化合物后所带来的几何及电子结构改变密切相关.     

Pt/CeO_2催化剂上甲醛催化氧化

以CeO2为载体,采用浸渍法制备了负载型Pt催化剂用于低温甲醛氧化反应,考察了Pt前驱体及Pt负载量等因素对催化性能的影响。XRD,TEM和CO化学吸附表征结果表明Pt粒子在载体上高度分散。反应结果表明,以Pt(NO3)2为前驱体比H2PtC l6为前驱体制备的催化剂表现出更好的反应性能,C l-离子的存在降低了催化剂的氧化还原能力,从而抑制了催化活性。此外,催化剂的活性随着Pt负载量的增加而增强,其中Pt负载量为3%时催化剂在30℃时甲醛转化率仍在80%以上。     

浸渍溶剂对Pt/炭-氧化铝催化氢化2-氧-4-苯基丁酸乙酯的影响

螯合辅助溶剂挥发共组装法制备的炭-氧化铝复合材料为载体,分别使用水、乙醇或二者混合物为氯铂酸的分散介质,浸渍制备炭-氧化铝复合材料负载Pt催化剂.通过XRD,N2物理吸附以及TEM表征可知,乙醇作为浸渍溶剂时,最有利于Pt的分散,而混合溶剂浸渍制备的催化剂Pt颗粒最大.2-氧-4-苯基丁酸乙酯不对称加氢反应结果表明,氯铂酸水溶液浸渍得到的催化剂Pt纳米粒子的粒径有利于获得高的光学选择性,催化剂经辛可尼丁修饰后,以乙酸为反应溶剂,可获得最高84.8%的光学选择性.此外,该催化剂重复利用性能优异,可以重复利用22次,活性没有下降.     

(195)Pt NMR isotopologue and isotopomer distributions of [PtCl(n)(H(2)O)(6 - n)](4 - n) (n = 6,5,4) species as a fingerprint for unambiguous assignment of isotopic stereoisomers

A detailed analysis of the (35)Cl/(37)Cl isotope shifts induced in the 128.8 MHz (195)Pt NMR resonances of [PtCl(n)(H(2)O)(6 - n)](4 - n) complexes (n = 6,5,4) in acidic solution at 293 K, shows that the unique isotopologue and isotopomer distribution displayed by the resolved (195)Pt resonances, serve as a fingerprint for the unambiguous identification and assignment of the isotopic stereoisomers of [PtCl(5)(H(2)O)](-) and cis/trans-[PtCl(4)(H(2)O)(2)].     

二十四面体Pt纳米晶电极上甲酸解离吸附反应动力学研究

研究了甲酸在二十四面体Pt纳米晶（THHPtNCs）电极表面解离吸附反应过程.电化学原位红外反射光谱结果显示,甲酸在低电位（-0.20V（SCE））即可在THHPtNCs电极上氧化到CO2,同时发生分子内化学键断裂生成吸附态CO物种.运用程序电位阶跃暂态方法定量研究甲酸解离吸附反应动力学,测得5×10^-3mol·L^-1 HCOOH＋0.1mol·L^-1 H2SO4溶液中甲酸在THHPtNCs电极上解离吸附的最大平均速率υamax为13.19×10^-10mol·cm^-2·s^-1,是商品Pt/C催化剂电极上υamax的1.5倍.研究结果揭示了THHPtNCs的反应活性显著高于Pt/C催化剂.