碳纳米管表面Pd纳米颗粒对甲醇的电催化氧化研究

采用电化学循环伏安法分别在碳纳米管(CNT)和玻碳(GC)电极表面沉积Pd纳米颗粒。扫描电镜(SEM)和XRD分析显示了Pd纳米颗粒均匀分散于碳纳米管表面,而在GC表面则趋向于堆积形成Pd金属薄膜。比较研究了Pd/CNT和Pd/GC电极在碱液中对甲醇的电催化氧化性能,循环伏安结果发现,Pd/CNT对甲醇的催化活性要高于Pd/GC电极;而交流阻抗谱研究发现,Pd/CNT电极对甲醇具有更快的催化氧化速率。另外,不同Pd载量,不同环境温度以及不同甲醇浓度的研究表明,相对于Pd/GC电极,Pd/CNT电极对甲醇的催化氧化具有更高的灵敏度和电化学稳定性。     

钛基纳米多孔钯电极的制备及对甲酸氧化的电活性

采用水热法,通过改变溶液组成制备了5种不同的钛基纳米多孔钯电极(Pd/PEG、Pd-EDTA/PEG、Pd-EDTA/HCHO、Pd/EG和Pd/HCHO)。扫描电镜图(SEM)分析表明,加入络合剂乙二胺四乙酸(EDTA)后,钯颗粒均匀,粒径明显减小,仅有60 nm左右。利用循环伏安法研究了甲酸在这些电极上的电催化氧化,发现在1.0 mol/L NaOH+0.5 mol/L HCOOH溶液中,加入EDTA且以甲醛作还原剂的电极(Pd-EDTA/HCHO)对甲酸氧化电流密度达132.00 mA/cm2,甲酸氧化的起始电位为-0.85 V,表明电催化活性优于其他电极。同时研究了Pd-EDTA/HCHO电极对不同浓度甲酸电催化氧化,结果表明,在一定甲酸浓度范围内,甲酸氧化的阳极电流密度随浓度的增加而增大。     

纳米晶Pd修饰p-Si电极的制备及其光电析氢性能

在半导体p型Si上化学沉积金属Pd,制备了纳米晶Pd修饰p-Si电极.控制化学沉积的时间,可得到不同沉积量和不同尺度的Pd颗粒,沉积时间为20 min时,Pd颗粒的直径约为80 nm.XRD测试结果表明,Pd颗粒的平均晶粒尺寸为7.37 nm.重点研究了Pd/p-Si电极在光照前后的催化析氢性能.光照下Pd/p-Si电极的析氢过电位较无光照减小约250 mV,比半导体Si减小约450 mV（电流密度为2.5 mA•cm^-2时）.电化学交流阻抗谱（EIS）表明,光照下Pd/p-Si电极的电化学析氢反应电阻由未光照的593.12 Ω•cm2降低至442.20Ω•cm²,光照下的析氢反应速率明显增加.     

Ti/TiO_2/Pd纳米电极的制备和电催化性能

采用阳极氧化法在纯钛表面生成结构高度有序的二氧化钛纳米管阵列,并通过室温固相反应制备了钯纳米颗粒。采用自组装方法将钯纳米颗粒修饰到Ti/TiO2表面制备了Ti/TiO2/Pd纳米电极。利用电子扫描显微镜、X-射线衍射分析二氧化钛纳米管、钯纳米颗粒和纳米电极的微观结构和表面形貌,并研究了Ti/TiO2/Pd纳米电极对甲醇的电催化性能。结果表明,TiO2纳米管排列整齐有序,Ti/TiO2/Pd电极中Pd纳米颗粒均匀分散在TiO2纳米管表面。电化学测试结果表明,Ti/TiO2/Pd纳米电极对甲醇的电催化氧化过程具有很好的电催化活性。     

多壁碳纳米管/PEDOT复合修饰电极的制备及对苯二酚的测定

采用循环伏安法和悬凃法,在玻碳电极表面进行聚(3,4)-乙撑二氧噻吩(PEDOT)和多壁碳纳米管修饰,制备多壁碳纳米管-聚(3,4)-乙撑二氧噻吩复合修饰电极。通过扫描电镜观察复合电极的表面形貌,通过电化学阻抗谱(EIS)和循环伏安(CV)对复合电极进行电化学表征,用差分脉冲法(DPV)研究对苯二酚浓度与峰电流之间的线性关系。实验结果表明,制备的复合修饰电极对对苯二酚有明显的电催化作用,氧化还原峰电流明显增大;在p H为7.0的磷酸缓冲液(PBS)里,对苯二酚的峰电流最大。在1×10^-5～5×10^-4mol/L对苯二酚的浓度范围内,复合修饰电极的氧化峰电流值与浓度呈线性关系,其线性方程为y=47.95+0.097 9x,R²=0.961,检出限为1.9×10^-6mol/L。制备的复合修饰电极能够增强电化学信号,具有较好的稳定性。     

原位合成功能化磁性碳纳米管负载钯的Heck 反应催化性能研究

采用常规化学气相沉积法(CVD)及加水CVD制备磁性碳纳米管(CNTs)。后将其作为催化剂载体以一锅合成法制备负载金属纳米颗粒Pd的催化剂(Pd/CNTs-P,Pd/CNTs-OH)。采用TEM,XRD等手段对其进行表征。结果表明,原位制得的碳纳米管中含有磁性金属Ni颗粒而具有明显的磁性。而以其为载体制得的催化剂中,Pd在CNTs-P和CNTs-OH表面中以Pd(0)的形式分散。在其Heck反应中的催化活性测试发现,当Pd/CNTs-OH催化剂的量为10 mg,反应温度为100℃时是最佳催化碘苯与丙烯酸甲酯的反应条件,产量为99.2%。在催化活性测试中,Pd/CNTs-OH比Pd/CNTs-P有着更优良的催化性能。     

基于离子凝胶电解质的TiO2(B)@C/CNT//AC准固态锂离子电容器

以微波辅助溶剂热法制备多壁碳纳米管负载的碳包覆单斜相二氧化钛纳米复合电极,通过静电纺丝技术制备聚酰亚胺纤维膜,进而制备三元离子凝胶电解质,最后与商业活性炭组装成新型准固态锂离子电容器.结果 表明,TiO2(B)@C/CNT纳米复合电极呈现出高可逆容量(291mAh/g)和高电化学反应动力学特性.PI/[EMIM] [B...     

碳纳米管作为导电添加剂的锂电池阴极材料LiCoO2的性能研究

使用碳纳米管(CNT)作为锂电池阴极材料LiCoO2的导电添加剂,并与传统材料导电碳黑在形貌、循环性能以及电极内阻方面进行了比较。研究结果表明,使用CNT作为导电添加剂,能够在电极颗粒表面形成网状包覆结构,由于这种结构能够提高电极的稳定性,以及CNT材料本身的高电导率,使得LiCoO2/CNT电极表现出较好的电化学性能。     

接枝烯丙基的碳纳米管改性不饱和聚酯树脂的电性能

在碳纳米管(CNT)上接枝烯丙基,将微量接枝后的碳纳米管(ACNT)加入到不饱和聚酯树脂(UPR)中制备出CNT/UPR和ACNT/UPR纳米复合材料。研究了纳米复合材料的电性能,结果表明:ACNT/UPR纳米复合材料的电性能明显优于CNT/UPR纳米复合材料的电性能。ACNT质量分数为0.075%时,ACNT/UPR纳米复合材料相对纯UPR的体积电阻率和耐电弧性有较大的提升,击穿场强略有增加,表面电阻率降低。     

CNT/PAn膜电极的电化学制备及电容性能研究

在含有0.2 mol·L-1苯胺的0.5 mol·L-1硫酸溶液中,采用循环伏安法,以50 mV·s-1的扫描速度,在-0.1~0.9 V的范围内实现了苯胺在碳纳米管修饰的金属钛电极上的电化学聚合,并用循环伏安(CV)法和电化学交流阻抗谱(EIS)对制备的碳纳米管/聚苯胺(CNT/PAn)膜电极的电化学性质进行了表征,同时进一步对该电极的充放电性能进行了研究。实验结果表明此条件下得到的PAn膜电极具有良好的导电性,同时具有疏松、多孔的网络结构,充放电测试研究表明,在电极基体上修饰CNT,不但可以增强PAn的导电性,同时可以使PAn的电容性能得到明显提高。     

Electrocatalytic activity of binary and ternary composite films of Pd, MWCNT, and Ni for ethanol electro-oxidation in alkaline solutions

Binary and ternary composite films of Pd, multiwalled carbon nanotubes (MWCNTs) and Ni are obtained on glassy carbon electrodes and investigated as electrocatalysts for the ethanol oxidation reaction in alkaline medium. The steady-state anodic Tafel polarization study shows that small introduction (1-5%) of MWCNTs to Pd increases the apparent electrocatalytic activity greatly, the magnitude of enhancement, however, being the greatest (∼26 times) with 1%MWCNT. Addition of 1%Ni to the active Pd-1%MWCNT composite improved the apparent electrocatalytic activity (over 50%) further, but its higher additions (2-5%) showed an adverse effect on the apparent catalytic activity. Among the electrodes investigated, the Pd-1%MWCNT-1%Ni composite electrode has the greatest apparent electrocatalytic activity.     

Electrocatalytic Oxidation of Formic Acid at Pt Modified Electrodes: Substrate Effect of Unsintered Au Nano‐Structure

A Pt‐modified Au catalyst featured with novel layered structures and ultra‐low Pt loading has been designed and electrochemically fabricated on a glassy carbon (GC) electrode. SEM characterization suggests that as‐formed Pt/Au/GC electrode grows in a Stranski–Krastanov mode, resulting in a nearly ideal layered structure with Au at the inner layer and Pt at the outer layer. The electrocatalytic activity of the synthesized Pt/Au/GC electrode towards formic acid electrooxidation was studied, and comparative experiments with other modified electrodes (i.e., Pt/GC, Pt/Au, and Pt/Pt) were also conducted. As a result, the electrocatalytic activity of the outer‐layered Pt depends significantly on the intrinsic properties of the substrates. The prepared Pt/Au/GC electrode with Au nanoparticles modified GC as the substrate shows remarkable catalytic activity for the formic acid oxidation, much higher than that of its counterparts, Pt/GC, Pt/Au, and Pt/Pt electrodes. Additionally, the measured electrochemical impedance spectra indicate that the charge‐transfer resistance for formic acid electrooxidation on Pt/Au/GC electrode is smaller than that on other Pt modified electrodes.     

Oxygen reduction at Au nanoparticles electrodeposited on different carbon substrates

The electrocatalytic reduction of molecular oxygen (O₂) has been performed in O₂-saturated 0.5 M KOH solution at Au nanoparticles electrodeposited onto two different carbon substrates, namely glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG). Cyclic voltammetry (CV) technique has been used in this investigation. The electrocatalytic activity of the Au nanoparticle-based electrodes is inherently related to its electrodeposition conditions (i.e., the absence or presence of some additives) as well as the nature of the substrate. For instance, Au nanoparticles electrodeposited onto GC (nano-Au/GC) from K[AuBr₄] in the presence of 25 μM cysteine showed a high electrocatalytic activity towards the oxygen reduction reaction (ORR) as demonstrated by the largest positive shift of the cathodic peak potential (at ca. −0.165 V versus Ag/AgCl/KCl (sat)). On the other hand, two well-separated successive reduction peaks corresponding to the 2-step 4-electron reduction of oxygen were observed at the different nano-Au/HOPG electrodes. The relative ratio of the two peak current heights changed significantly depending on the electrodeposition conditions of the Au nanoparticles. The morphology of the different Au nanoparticles electrodeposited onto the different substrates was depicted by scanning electron microscope (SEM) technique.     

Pt-WO3 supported on carbon nanotubes as possible anodes for direct methanol fuel cells

The carbon nanotube (CNT) synthesised by the template carbonisation of polypyrrole on alumina membrane has been used as the support for Pt-WO₃, Pt-Ru, and Pt. These materials have been used as the electrodes for methanol oxidation in acid medium in comparison with E-TEK 20 wt% Pt and Pt-Ru on Vulcan XC72R carbon. The higher electrochemical surface of the carbon nanotube (as evaluated by cyclic voltammetry) has been effectively used to disperse the catalytic particles. The morphology of the supported and unsupported CNT has been characterised by scanning electron micrograph and high-resolution transmission electron micrograph. The particle size of Pt, Pt-Ru, and Pt-WO₃ loaded CNT was found to be 1.2, 2, and 5 nm, respectively. The X-ray photoelectron spectra indicated that Pt and Ru are in the metallic state and W is in the +VI oxidation state. The electrochemical activity of the methanol oxidation electrode has been evaluated using cyclic voltammetry. The activity and stability (evaluated from chronoamperometric response) of the electrodes for methanol oxidation follows the order: GC/CNT-Pt-WO₃-Nafion>GC/E-TEK 20% Pt-Ru/Vulcan Carbon-Nafion>GC/CNT-Pt-Nafion>GC/E-TEK 20% Pt/Vulcan carbon-Nafion>Bulk Pt. The amount of nitrogen in the CNT plays an important role as observed by the increase in activity and stability of methanol oxidation with N₂ content, probably due to the hydrophilic nature of the CNT.     

Characterization of oxidized reticulated vitreous carbon electrode for oxygen reduction reaction in acid solutions

The oxidation of reticulated vitreous carbon (RVC) and its impact on the oxygen reduction reaction (ORR) in H₂SO₄ solutions has been studied. The results are compared with that of a planar glassy carbon (GC) electrode. The oxidation process was characterized by using different electrode configurations, GC (planar) and RVC electrodes both with flooded (batch process) and flow-through assembly. Cyclic voltammetry, potentiodynamic and rotating ring-disk electrode voltammetry were used for the characterization of the ORR. Anodically oxidized GC and flooded RVC are similar in that the ORR on both electrodes gave a more defined limiting current plateau. For the flow-through porous electrode, the oxidation process caused a distribution of the oxidation extent within the bed thickness, as evident from the SEM images, and only about half of the porous electrode was utilized in the oxidation process. X-ray photoelectron spectroscopy (XPS) measurements confirmed the above distribution and a gradient of the oxygen-to-carbon ratio was obtained within the porous bed. Oxidation of RVC led to an enhancement of its electrocatalytic properties towards ORR. H₂O₂ production was tested at the oxidized RVC from flowing acid solutions. The oxidation of RVC resulted in higher current efficiencies and higher outlet concentrations of the H₂O₂ acid solutions.     

修饰的GC电极上CO2的电催化还原

研究了高压及常压下玻碳电极还原CO2的反应,以及钴酞菁修饰玻碳电极的电还原CO2行为。结果表明,玻碳电极常压下即可还原CO2,但法拉第效率极低。高压下法拉第效率大大提高,可将CO2还原为CO(31%)和HCOOH(15%)。若用钴钛菁修饰玻碳电极常压下即可将CO2还原,法拉第效率可达30%。     

Synthesis and electro-catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes

Template synthesis of various nitrogen containing carbon nanotubes using different nitrogen containing polymers and the variation of nitrogen content in carbon nanotube (CNT) on the behaviour of supported Pt electrodes in the anodic oxidation of methanol in direct methanol fuel cells was investigated. Characterizations of the as-prepared catalysts are investigated by electron microscopy and electrochemical analysis. The catalyst with N-containing CNT as a support exhibits a higher catalytic activity than that carbon supported platinum electrode and CNT supported electrodes. The N-containing CNT supported electrodes with 10.5% nitrogen content show a higher catalytic activity compared to other N-CNT supported electrodes. This could be due to the existence of additional active sites on the surface of the N-containing CNT supported electrodes, which favours better dispersion of Pt particles. Also, the strong metal-support interaction plays a major role in enhancing the catalytic activity for methanol oxidation.     

Electrochemical investigation of Pd nanoparticles and MWCNTs supported Pd nanoparticles-coated electrodes for alcohols (C1–C3) oxidation in fuel cells

Incorporation of palladium nanoparticles (PdNPs) and multi-walled carbon nanotubes (MWCNTs) into chitosan-coated glassy carbon (GC) electrode for alcohols (methanol, ethanol, and isopropanol) electrooxidation has been studied. PdNPs–chitosan and MWCNTs–PdNPs–chitosan nanocomposites are successfully prepared and characterized by transmission electron microscopy images and UV–Vis spectroscopy. Based on the results, PdNPs–chitosan nanocomposite indicates high electrochemical activity and excellent catalytic characteristic for alcohol (C₁–C₃) electrooxidation on a GC electrode in an alkaline medium. The current density of the alcohols oxidation at GC–PdNPs–chitosan electrode is investigated in optimized conditions and compared with that obtained at the GC-modified electrode by Pd with different polymers. Also, our results show that the dispersion of Pd nanoparticles on the MWCNTs significantly improved the performance of the PdNPs/chitosan composite for electrooxidation of the C₁–C₃ alcohols.     

Electrophoretic deposition of network-like carbon nanofibers as a palladium catalyst support for ethanol oxidation in alkaline media

A network-like carbon nanofiber (CNF) film with an open porous structure formed by the open space between entangled CNFs is fabricated by electrophoretic deposition. The performance of the CNF film as an electrocatalyst in the presence of electrodeposited Pd nanoparticles for ethanol oxidation in alkaline media is investigated. Cyclic voltammetric analyses show the electrocatalyst has a good electrocatalytic activity toward ethanol oxidation in KOH solution. This is believed to be due to the high dispersion of Pd on the CNF film with a three-dimensional network structure which can provide a large number of available Pd active sites for ethanol oxidation, and to the structural and electrical properties of the film.