Ti基纳米TiO_2-CNT-Pt复合电极制备、表征及电化学性能

以电合成前驱体Ti(OEt)4直接水解法和电化学扫描电沉积法制备Ti基纳米TiO2-CNT-Pt(Ti/nanoTiO2-CNT-Pt)复合电极.透射电镜(TEM)和X射线衍射(XRD)测试表明,锐钛矿型纳米TiO2粒子(粒径5～10nm)和碳纳米管(CNT)结合形成网状结构,Pt纳米粒子(平均粒径9nm)均匀地分散在纳米TiO2-CNT复合膜表面.循环伏安及计时电流测试表明,Ti/nanoTiO2-CNT-Pt复合电极具有高活性表面,对甲醇的电化学氧化具有高催化活性和稳定性,Pt载量为0.32mg/cm2时,常温常压下甲醇氧化峰电流达到480mA/cm2.     

乙二醛在Ti/纳米TiO2-Pt修饰电极上的电催化氧化

采用溶胶.凝胶和电沉积法制备Ti基纳米TiO2-Pt(Ti/纳米TiO2-Pt)修饰电极.X射线衍射(XRD)表明纳米TiO2为锐钛矿型,扫描电镜(SEM)显示Pt纳米粒子在纳米TiO2多孔膜的表面呈现簇分散状态,平均粒径约25nm.通过循环伏安(CV)和计时电流法研究了Ti/纳米TiO2-Pt修饰电极对乙二醛直接电氧化的电催化活性,结果表明,修饰电极对乙二醛的直接电氧化呈现良好的催化活性,在0.60和1.23 V(vs SCE)出现两个氧化峰,二者电流密度分别为16和42 mA·cm2,约为纯Pt电极的2倍和1.5倍,反应过程受浓差扩散控制.     

乙二醛在Ti/纳米TiO2-Pt修饰电极上的电催化氧化

采用溶胶-凝胶和电沉积法制备Ti基纳米TiO2-Pt(Ti/纳米TiO2-Pt)修饰电极. X射线衍射(XRD)表明纳米TiO2为锐钛矿型, 扫描电镜(SEM)显示Pt纳米粒子在纳米TiO2多孔膜的表面呈现簇分散状态, 平均粒径约25 nm. 通过循环伏安(CV)和计时电流法研究了Ti/纳米TiO2-Pt修饰电极对乙二醛直接电氧化的电催化活性, 结果表明, 修饰电极对乙二醛的直接电氧化呈现良好的催化活性, 在0.60和1.23 V(vs SCE)出现两个氧化峰, 二者电流密度分别为16 和42 mA·cm-2, 约为纯Pt电极的2倍和1.5倍, 反应过程受浓差扩散控制.     

Pt/PMo12/PEDOT/GC电极的制备及其甲醇电氧化性能

将磷钼酸(PMo12)修饰到电化学聚合制得的聚3,4-乙烯二氧噻吩(PEDOT)(PEDOT/GC)膜表面(PMo12/PEDOT/GC),随后电沉积Pt得Pt/PMo12/PEDOT/GC电极.研究了PMo12和PEDOT对电极氧化甲醇性能的影响.结果表明,PMo12改变了电极上负载Pt的形态和结构,导致Pt纳米结构边缘产生尖锐的刺状结构.Pt/PMo12/PEDOT/GC和Pt/PEDOT/GC电极有较好的甲醇氧化电催化活性,而前者尤佳.PEDOT不仅提高甲醇氧化的电流,还使甲醇的起始氧化电位负移.进一步修饰PMo12后,可明显增大甲醇氧化的电流.     

甲酸在纳米金承载铂(Pt^Au)电催化剂上的电化学氧化

采用循环伏安扫描测试对不同浓度的甲酸在纳米Au颗粒((10.0±1.2)nm)承载Pt电催化剂(记为Ptm^Au,其中m为Pt/Au原子比)上的电化学氧化过程进行了研究.结果表明,Pt在纳米Au颗粒表面的形态对甲酸的电化学氧化行为影响显著.当Pt对Au颗粒形成壳层覆盖(m>0.2)时,甲酸电氧化反应主要发生在高电势(相对SCE电极为0.6~1.0 V)范围,与常规Pt/C电催化剂上甲酸的电氧化行为类似;当Au表面Pt的形态由单原子壳层(m=0.2)递变为不大于1.0 nm的Pt原子簇或原子筏(m<0.2)时,在低电势(-0.2~0.6 V)范围也能明显检测到甲酸的电氧化反应,而且随着m的减小,Pt的质量比活性显著提高.Pt呈现100%暴露(电化学活性面积EAS=236 m2/g-Pt)的Pt0.05^Au/C电催化剂在甲酸电氧化峰(0.38 V)处的质量比活性是通常Pt/C电催化剂(Pt分散度为30%或EAS为74 m2/g-Pt)的40倍,表明随着Au颗粒上Pt尺寸的减小或分散度的提高,Ptm^Au/C电催化剂对甲酸电氧化反应的催化活性也显著提高.在甲酸浓度由0.2 mol/L渐提高至3.2 mol/L时,Ptm^Au/C和Pt/C催化剂上甲酸电氧化反应的比电流均呈先增大后减小的火山形变化,表明适宜的甲酸工作浓度也是在Pt基催化剂上实现高功率直接甲酸燃料电池的关键因素之一.     

三种碳材料上原位电沉积AuPt合金的催化性能

在碳纸(CP)及涂覆了碳粉科琴黑(KB)或石墨烯纳米片(GNs)的碳纸上,原位电沉积了Au Pt合金,制备成CP/Au Pt、CP/KB/Au Pt、CP/GNs/Au Pt三种空气电极。对比研究发现,以石墨烯纳米片为载体的CP/GNs/Au Pt空气电极上,Au Pt合金载量高,颗粒分散均匀,粒径约为100 nm,Au和Pt的含量分别为78.84%(n/n)和21.16%(n/n)。在0.1 mol·L-1 KOH溶液中氧还原反应的起峰电势为0.93 V,催化活性和稳定性优于其他两种空气电极。分析认为,石墨烯纳米片具有高导电性、高比表面积以及较多的缺陷活性位点,有利于Au Pt合金在其上均匀电沉积且沉积载量较高,同时GNs本身具有一定的催化活性,两者能够产生协同催化作用,提高了CP/GNs/Au Pt电极的催化性能。     

电化学制备二维“花状”Pt纳米结构及其对甲醇的电催化氧化

采用恒电流电化学技术在玻碳基底上制得二维"花状"Pt纳米结构(2D FPNs)样品,所用的电解液为HAuCl4+HClO4溶液,无需添加任何表面结构诱导的有机试剂,Pt纳米结构表面更"洁净",有较高的反应活性.扫描电子显微镜测试显示,2D FPNs样品是由球状纳米花构成,纳米叶子是构筑纳米花的最小单元.通过控制电沉积时间可调控球状Pt纳米花数的密度.高倍透射电子显微镜测试表明每个叶状纳米片沿着Pt(111)晶面定向生长.甲醇电催化氧化活性与电沉积时间有关.2D FPNs电极的甲醇的电催化活性稍高于商业Pt/C电极,却有更好的抗毒化能力,这可能归因于其特定的暴露晶面及表面的"洁净性".     

Pt微粒修饰纳米纤维聚苯胺电极对甲醇氧化电催化

以脉冲电流法制备的纳米纤维状聚苯胺(PANI)为Pt催化剂载体，用它制备了甲醇阳极氧化的催化电极Pt/（nano-fibular PANI）.研究结果表明, Pt/（nano-fibular PANI）电极对甲醇氧化具有很好的电催化活性,并有协同催化作用.在相同的Pt载量条件下， Pt/（nano-fibular PANI）电极比Pt微粒修饰的颗粒状聚苯胺电极Pt/(granular PANI)具有更好的电催化活性.此外， Pt的电沉积修饰方法同样影响Pt/（nano-fibular PANI）电极对甲醇氧化的催化活性.脉冲电流法沉积Pt形成的复合电极较循环伏安法电沉积得到的Pt复合电极具有更优异的催化活性.     

Pt及其修饰电极上甲醇吸附和氧化的CV和EQCM研究

运用电化学循环伏安和石英晶体微天平 (EQCM )研究了 0 .1mol·L- 1H2 SO4 溶液中甲醇在Pt电极和以Sb ,S不可逆吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的吸附和氧化过程 .结果表明甲醇的氧化与电极表面氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子能在较低的电位下吸附氧 ,可显著提高甲醇电催化氧化活性 .与Pt电极相比较 ,Sb吸附原子修饰的Pt电极使甲醇氧化的峰电位负移了 0 .13V .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制了甲醇的电氧化 .本文从表面质量变化提供了吸附原子电催化作用的新数据     

Pt纳米粒子修饰的多孔硅电极的制备及其电催化性能

通过循环伏安法电沉积使直径约为7 nm的Pt纳米粒子均匀地分散于多孔硅表面, 拟用作微型质子交换膜燃料电池的催化电极. 与刷涂法相比较, 电沉积Pt纳米粒子的多孔硅电极(Pt/Si)呈现出高的Pt利用率和增强的电催化活性. 当Pt载量为0.38 mg•cm−2时, 其电化学活性比表面积高达148 cm2•mg−1, 是刷涂相近质量的纳米Pt/C催化剂的多孔硅电极Pt-C/Si的2倍多；该修饰电极对甲醇氧化也呈现了增强的催化性能和好的稳定性, 在0.5 V(vs SCE)极化1 h后电流密度为4.52 mA•cm−2, 而刷涂了相近Pt量的Pt-C/Si电极的电流密度只有0.36 mA•cm−2.     

电化学石英晶体微天平研究碱性介质中单层级铂原子修饰的金电极上甲醇的电催化氧化

通过在Au电极表面欠电位沉积(UPD)Cu、再与Pt源(H2PtCl6或K2PtCl4)进行置换反应,制得单层级Pt原子修饰的金电极(对H2PtCl6或K2PtCl4,所制电极分别记为Pt(CuUPD-Pt4+)n/Au或Pt(CuUPD-Pt2+)n/Au,n表示欠电位沉积-置换过程的重复次数).用电化学石英晶体微天平(EQCM)技术定量研究了所制电极,评估了其在碱性环境中催化甲醇氧化的质量比活性(SECA).结果表明,以H2PtCl6为Pt源所制电极(Pt(CuUPD-Pt4+)3/Au)的活性更高,最大SECA高达35.7mAμg-1.根据EQCM结果计算了置换效率,籍此讨论了Pt原子在Au电极表面的层层组装结构,发现所制电极表面的裸Au位点分布百分数与实验结果(由AuOx还原峰电量测算)吻合.我们认为,EQCM技术是一种定量研究电极支撑的超薄催化剂的有效手段,这种高效的单层级贵金属催化剂有望在生物、能源、环境相关的电催化研究中进一步应用.     

Enhanced Photocurrent Generation in Self-Assembled Monolayers Formed at Plasmonic Gold Nanostructures

The effect of localized surface plasmon resonance (SPR) appearing at the surfaces of gold nanoparticles (AuPs) was successfully applied for the enhancement of photocurrents from porphyrin ( Po ) immobilized on AuPs. The electrode consisting of AuPs with different sizes (∼15 or ∼35 nm) was prepared using the AuP film formed at the liquid/liquid interface, and then Po was self-assembled on the gold surface. The SPR effect for the AuP film was verified from the attenuated total reflection SPR and absorption measurements. Photocurrents from the modified electrodes were compared with the corresponding planar electrode. Appreciable enhancement of photocurrents was observed.     

Electrooxidation of carbon monoxide and methanol on platinum-overlayer-coated gold nanoparticles: effects of film thickness

The electrooxidation of carbon monoxide and methanol on Pt-coated Au nanoparticles attached to 3-aminopropyl trimethoxysilane-modified indium tin oxide electrodes was examined as a function of Pt film thickness and Au particle coverage. For the electrodes with medium and high Au particle coverages, the CO stripping peak position shifts to more negative values with increasing Pt film thickness, from ca. 0.8 V (vs Ag/AgCl) at 1 ML to 0.45 V at 10 ML. Accompanying this peak potential shift is the sharpening of the peak width from more than 150 to 65 mV. For the electrode with low Au particle coverage, similar peak width narrowing was also observed, but the peak potential shift is much smaller, from 0.85 V at 1 ML of Pt to 0.65 V at 10 ML. These observations are compared with the CO oxidation on bulk Pt electrodes and on Pt films deposited on bulk Au electrodes. The film-thickness-dependent CO oxidation is explained by d band theory in terms of strain and ligand effects, the particle size effect, and the particle aggregation induced by Pt film growth. Corresponding to the increasing CO oxidation activity, the current density of methanol oxidation grows with the Pt film thickness. The peak potential and current density reach the same values as those obtained on a polycrystalline bulk Pt electrode when more than 4 ML of Pt is deposited on the Au particle electrodes with a particle coverage higher than 0.25. These results suggest that it is feasible to reduce Pt loading in methanol fuel cells by using Pt thin films as the anode catalyst.     

脉冲电沉积法制备Pt-TiO2 纳米管电极及其电催化性能

采用阳极氧化法在高纯钛片上原位组装TiO2纳米管阵列, 然后用脉冲电沉积方法将Pt沉积到TiO2纳米管阵列上, 制备出Pt-TiO2纳米管电极. 利用XRD和SEM对所获电极的微观结构和形貌进行表征, 结果表明, Pt纳米颗粒以花簇状分散在TiO2纳米管上, 晶粒大小约为25.6 nm. 对甲醇的电催化性能的研究结果表明, 脉冲电沉积制得的Pt-TiO2纳米管电极比TiO2纳米管电极和纯Pt片电极具有更高的电催化活性, 是Pt电极的40多倍.     

Self‐Assembly of Platinum Nanoparticle/Multiwalled Carbon Nanotube Multilayer Film on Au Substrate Electrode

A novel approach to assemble multilayer films of Pt nanoparticle/multiwalled carbon nanotube (MWNTs) composites on Au substrate has been developed for the purpose of improving the methanol oxidation efficiency by providing high catalytic surface area. MWNTs were firstly functionalized with 4‐mercaptobenzene and then assembled on an Au substrate electrode. Pt nanoparticles were fabricated and attached to the surface of the functionalized MWNTs subsequently. Thus a layer of Pt/MWNT composites were assembled on the Au substrate electrode. Repeating above process can assemble different layers of film of Pt/MWNTs composites on the Au electrode. Cyclic voltammetry shows that the Au electrode modified with two layers of film of Pt/MWNT composites exhibits high catalytic ability and long‐term stability for methanol oxidation. The layer‐by‐layer self‐assembly technique provides an efficient strategy to construct complex nanostructure for improving the methanol oxidation efficiency by providing high catalytic surface area.     

Multispectral Plasmon of Anisotropic Core-shell Gold Nanorods@SiO2: Dual-band Absorption Enhancement with Coupling Dye Molecules

Direct evidence of effects of surface plasmon resonance(SPR) of gold nanorods(GNRs) on dual-band light absorption enhancement with coupling dye molecules was reported by introducing gold nanorod@SiO₂(GNR@SiO₂) core-shell nanoparticles into a photoelectric conversion system. GNR with asymmetric shape had unusual anisotropic SPR[transversal surface plasmon resonance(TSPR) and longitudinal surface plasmon resonance(LSPR)]. The excellent SPR of GNR made it a promising candidate as enhancing light absorption material to increase power conversion efficiency(PCE). The PCE was improved nearly 17.2% upon incorporating GNRs, mostly due to the increase in J_sc, while V_oc and FF were unchanged. The improvement was mostly contributed by the SPR of the GNRs with coupling of N719. And there was also a complementary to N719 in visible light range. Therefore, SPR is an effective tool in improving the photocurrent and consequently enhancement of PCE. The TSPR and LSPR effects of GNRs on light harvesting were reflected in the increased monochromatic incident photon-to-electron conversion efficiency(IPCE). We also utilized finite-difference time-domain(FDTD) to investigate the light coupling of GNRs with TiO₂. Compare to the base anode, the IPCE of optimized electrode showed significant improvement and peaks broadening at 500-600 nm and 610-710 nm. We got an increase in overall conversion efficiency from 6.4% to 7.5%.     

Platinum monolayers stabilized on dealloyed AuCu core-shell nanoparticles for improved activity and stability on methanol oxidation reaction

Deposition of platinum(Pt)monolayers(PtML)on Au substrate represents a robust strategy to maximally utilize the Pt atoms and meanwhile achieve high catalytic activity towards methanol oxidation reaction for direct methanol fuel cells owing to a substrate-induced tensile strain effect.However,recent studies showed that Pt(ML)on Au substrate are far from perfect smooth monoatomic layer,but actually exhibited three-dimensional nanoclusters.Moreover,the Pt(ML)suffered from severe structural instability and thus activity degradation during long-term electrocatalysis.To regulate the growth of Pt(ML)Au surface and also to improve its structural stability,we exploit dealloyed AuCu core-shell nanoparticles as a new substrate for depositing Pt(ML).By using high-resolution scanning transmission electron microscopy and energy dispersive X-ray elemental mapping combined with electrochemical characte rizations,we reveal that the dealloyed AuCu core-shell nanoparticles can effectively promote the deposition of Pt(ML)closer to a smooth monolayer structure,thus leading to a higher utilization efficiency of Pt and higher intrinsic activity towards methanol oxidation compared to those on pure Au nanoparticles.Moreover,the Pt(ML)deposited on the AuCu core-shell NPs showed substa ntially enhanced stability compared to those on pure Au NPs during long-term electrocatalysis over several hours,during which segregation of Cu to the Au/Pt interface was revealed and suggested to play an important role in stabilizing the Pt(ML)catalysts.     

Pt纳米空球壳厚的可控制备及对甲酸的电催化氧化

本文以约120nm的α-Se球为模板,抗坏血酸为还原剂,H2PtCl6为前驱体,通过改变氯铂酸的用量可控合成了不同壳厚的纳米铂空球（Pthollow）及其修饰玻碳（GC）电极（Pthollow／GC）;采用扫描电子显微镜（SEM）、高分辨透射电子显微镜（HR-TEM）、能量色散X射线（EDX）谱、X射线衍射（X-ray diffraction,XRD）谱和选区电子衍射（SAED）图等表征其形貌、组成与结构;以甲酸为探针分子,采用循环伏安和计时电流法研究了甲酸在Pthollow／GC电极上的电催化氧化行为．结果表明,所制备的Pthollow分散性好、粒径比较均匀,其多孔球壳是由多维多级的铂原子团簇所构建,呈现多晶铂的结构与性质;当RPt/Se=1．2时,所合成Pthollow。对甲酸的电催化氧化活性最高,且明显优于电沉积铂（Ptnano）修饰GC电极（Ptnano／GC）,为直接甲酸燃料电池（DFAFC）阳极材料的优化制备提供了一定的实验与理论依据,有潜在的应用推广价值．     

Gold particles supported on self-organized nanotubular TiO2 matrix as highly active catalysts for electrochemical oxidation of glucose

Au/TiO₂/Ti electrode was prepared by a two-step process of anodic oxidation of titanium followed by cathodic electrodeposition of gold on resulted TiO₂. The morphology and surface analysis of Au/TiO₂/Ti electrodes was investigated using scanning electron microscopy and EDAX, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm in diameter, and the electrode surface was covered by gold particles with a diameter of about 100–200 nm which are distributed evenly on the titanium dioxide nanotubes. This nanotubular TiO₂ support provides a high surface area and therefore enhances the electrocatalytic activity of Au/TiO₂/Ti electrode. The electrocatalytic behavior of Au/TiO₂/Ti electrodes in the glucose electro-oxidation was studied by cyclic voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the glucose oxidation than that of gold electrode.