Co3O4/C催化氧还原反应的活性及机理

采用液相控制沉淀法制备了平均粒径约为10nm的C03O4/C催化剂,运用X射线衍射和透射电镜对催化剂进行了表征,通过循环伏安法和线性扫描伏安法测试了催化剂催化氧还原反应的性能.结果表明,在酸性条件下,C03O4/C对氧还原反应具有电催化活性.利用Koutecky-Levich理论计算得到了交换电流密度为1.1×10-9...     

Pt纳米颗粒在氮掺杂空心碳微球上的高分散负载及其氧还原性能

通过热解自聚合多巴胺法制备了氮掺杂空心碳微球(N-HCMS), 并采用微波辅助乙二醇还原方法把Pt纳米粒子负载于N-HCMS上制得了Pt/N-HCMS催化剂. 催化剂的表面形貌、晶体结构及其比表面积和孔径分布等分别采用扫描电子显微镜、透射电子显微镜、X射线衍射仪及比表面分析仪等进行表征. 采用循环伏安法和线性扫描伏安法研究了Pt/N-HCMS 催化剂在酸性条件下的电催化氧还原性能. Pt/N-HCMS 催化剂由于Pt纳米粒子的均匀分散、N-HCMS载体的快速电子传递及其独特的微孔和中空结构而具有很高的电催化氧还原活性, 其质量比活性是E-TEK Pt/C 催化剂的近两倍. Pt/N-HCMS 催化剂还具有优良的稳定性. 本工作对于开发高性能的燃料电池阴极催化剂具有重要意义.     

Ir0.08Ti0.92O2及其载Pt催化剂的制备与电催化性能

采用TiN浸渍热分解法制备了低铱含量Ir0.08Ti0.92O2纳米粉体,再通过微波辅助制备Pt/Ir0.08Ti0.92O2催化剂,并与采用传统亚当斯法制备的IrO2和商品化Pt/C进行对比研究.利用X射线衍射(XRD)、透射电子显微镜(SEM)、X射线能量散射谱(EDS)和X射线光电子能谱(XPS)对产物进行了分析.结果表明,Ir0.08Ti0.92O2是一种纳米棒状金红石相固溶体,直径约15 nm,担载Pt粒度5~7 nm,其中本体Ir/Ti原子比为0.084∶0.916,表面Ir/Ti原子比为0.296∶0.704,表明Ir在表面发生富集.经稳态极化曲线和线性扫描伏安测试得到析氧反应的本征催化活性由高到低为Ir0.08Ti0.92O2>Pt/Ir0.08Ti0.92O2>IrO2,前两者性能相近;Pt/Ir0.08Ti0.92O2的氧还原反应活性低于Pt/C,需进一步优化载Pt粒度.研究结果表明,Ir0.08Ti0.92O2既是高效、低成本的析氧反应催化剂,也是高性能载体材料,这使Pt/Ir0.08Ti0.92O2作为双效催化剂在成本、催化性能和稳定性上具有更大优势,也可作为优异的析氢反应催化剂.     

三维多孔结构Pt-Ag气凝胶的制备及电催化氧还原反应性能

采用化学还原法及水热法制备了具有树枝状结构的铂-银气凝胶,并对其进行酸碱刻蚀再处理获得刻蚀后的铂-银气凝胶催化剂.利用X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等表征了铂-银气凝胶的结构、组成及微观形貌.利用循环伏安法(CV)和线性扫描伏安法(LSV)测试了催化剂对氧还原反应(ORR)的电催化活性和稳定性.结果表明,刻蚀后的Pt-Ag气凝胶具有优异的ORR活性,在0.9 V处,刻蚀后Pt-Ag气凝胶的质量比活性和面积比活性分别为166.3 m A/mgPt和0.295 m A/cm~2,分别是商业铂/碳催化剂(20%Pt/C)的2.0倍和1.8倍.该催化剂还具有优异的稳定性,循环5000周后,动力学催化质量比活性和面积比活性分别只降低了6.1%和9.1%,远小于商业Pt/C的35%和52.1%.     

Fe-N/C-TsOH催化剂应用碱性介质催化氧还原的电催化活性(英文)

通过溶剂分散热处理方法制备了一种吡咯和对甲苯磺酸(TsOH)共同修饰的碳载非贵金属复合催化剂(Fe-N/C-TsOH),并采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对催化剂的形貌和组成成分进行表征.借助循环伏安法(CV)和旋转圆盘技术研究了TsOH对催化剂在0.1 mol·L-1KOH介质中催化氧还原性能的影响.结果表明:TsOH的存在对催化剂催化氧还原反应(ORR)的活性影响很大.以其制备的气体扩散电极在碱性电解质溶液中催化氧还原过程时转移的电子数为3.899,远比不含TsOH修饰的催化剂催化氧还原的电子数(3.098)高.此外,研究发现600°C热处理过的Fe-N/C-TsOH催化剂表现出最佳的氧还原催化性能.相比未经热处理过的Fe-N/C-TsOH催化剂,起峰电位和-1.5 mA·cm-2电流密度对应的电压分别向正方向移动30和170 mV.XPS研究结果表明吡咯氮是催化剂主要活性中心,提供氧还原活性位,而TsOH加入形成的C―Sn―C和―SOn―有利于催化剂催化氧还原活性的提高,从而使该催化剂对氧还原表现出很好的电催化性能和选择性.     

用于燃料电池Co@Pt/C核壳结构催化剂的制备及表征

采用两步化学还原法制备了Co@Pt/C电催化剂, 并在还原气氛下对催化剂进行热处理. 通过高分辨透射电镜(HR-TEM)和X射线光电子能谱(XPS)等技术对催化剂的微观结构和形貌进行表征. 结果表明: 形成的Co@Pt/C催化剂具有核壳结构, 金属纳米颗粒均匀负载于碳上, 其粒径分布范围较窄; 热处理对催化剂的结构和形貌有较大影响. 利用循环伏安(CV)法和线性伏安扫描(LSV)法表征催化剂的电化学活性、氧还原反应(ORR)动力学特性及耐久性. 制备的Co@Pt/C催化剂在电解质溶液中表现出良好的电化学性能, 核壳结构的形成有助于提高Pt 的利用率. 动力学性能测试表明催化剂的ORR反应以四电子路线进行. 相比于合金催化剂,核壳结构催化剂的耐久性和稳定性有很大程度的改善.     

Fe-N/C-TsOH催化剂应用碱性介质催化氧还原的电催化活性

通过溶剂分散热处理方法制备了一种吡咯和对甲苯磺酸(TsOH)共同修饰的碳载非贵金属复合催化剂(Fe-N/C-TsOH),并采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对催化剂的形貌和组成成分进行表征. 借助循环伏安法(CV)和旋转圆盘技术研究了TsOH对催化剂在0.1 mol·L^-1 KOH介质中催化氧还原性能的影响. 结果表明：TsOH的存在对催化剂催化氧还原反应(ORR)的活性影响很大. 以其制备的气体扩散电极在碱性电解质溶液中催化氧还原过程时转移的电子数为3.899,远比不含TsOH修饰的催化剂催化氧还原的电子数(3.098)高. 此外,研究发现600 ℃热处理过的Fe-N/C-TsOH催化剂表现出最佳的氧还原催化性能. 相比未经热处理过的Fe-N/C-TsOH催化剂,起峰电位和-1.5 mA·cm^-2电流密度对应的电压分别向正方向移动30 和170 mV. XPS研究结果表明吡咯氮是催化剂主要活性中心,提供氧还原活性位,而TsOH加入形成的C―S_n―C和―SO_n―有利于催化剂催化氧还原活性的提高,从而使该催化剂对氧还原表现出很好的电催化性能和选择性.     

不同晶型TiO_2负载镍催化剂催化顺酐液相加氢

分别以锐钛矿相Ti O2和金红石相Ti O2为载体,采用等体积浸渍法制备了Ni/Ti O2催化剂,考察了其催化顺酐液相加氢性能.采用氮气吸附-脱附、氢气程序升温还原(H2-TPR)、X射线衍射(XRD)、氢气程序升温脱附(H2-TPD)及X射线光电子能谱(XPS)等技术对催化剂进行了表征.催化剂评价结果表明,以锐钛矿型Ti O2为载体催化剂的C O加氢活性明显高于以金红石型Ti O2为载体的催化剂.这主要是由于在还原过程中锐钛矿型Ti O2较易被还原,产生了较高浓度的氧缺陷位,该氧缺陷位可通过接受C O中O的孤对电子来活化C O,促使其与H2发生加氢反应,进而使催化剂表现出较高的C O加氢活性.     

还原热处理条件对Pt-Fe/C 合金催化剂性能的影响

采用脉冲微波辅助化学还原-含氢气体热处理法制备了质子交换膜燃料电池(PEMFC)用Pt-Fe/C合金催化剂.通过电感耦合等离子体(ICP)检测了金属元素含量,用透射电镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等技术对催化剂的微观结构和形貌进行了表征,并利用循环伏安(CV)法评价了催化剂催化氧还原性能.结果表明,脉冲微波辅助化学还原法是一种快速制备粒径较小、分布均匀的Pt-Fe/C催化剂的有效方法,含氢气体热处理对提高催化剂活性有重要作用.还原热处理温度和时间对催化剂活性也有很大影响.经过500°C还原热处理后的催化剂活性比还原热处理之前的催化剂性能有很大提高.TEM和XRD结果显示,Pt-Fe/C-500-3h的纳米粒子均匀地分散在碳载体上,平均粒径为1.8nm,500°C下热处理3h的催化剂有最大的电化学表面积(ESA),为55.14m2·g-1.     

Fe-Nx/C电催化剂的氧还原性能及配体结构对催化活性的影响

以2,6-二氨基嘌呤(Hdap)为配体合成了Fe-Nx/C氧还原催化剂, 并优化了热处理温度和Fe含量. 对催化剂组成和结构进行了表征, 分析了配体Hdap在热处理过程中随温度的变化情况, 通过循环伏安法和线性扫描伏安法测试了催化剂的氧还原催化性能. 结果表明, 热处理温度为800℃, Fe质量分数为5%时, 催化剂活性最高. 吡啶N含量较高的配体有利于提高催化剂的活性, 配体中含S元素会增加催化剂的活性.     

Synthesis and Electrochemical Investigation of Tetra Amino Cobalt (II) Phthalocyanine Functionalized Polyaniline Nanofiber for the Selective Detection of Dopamine

A new electrochemical sensing platform based on tetra‐amino cobalt (II) phthalocyanine (TACoPc) ingrained polyaniline (PANI) nanofiber composite (TACoPc/PANI hybrid) has been developed for the selective detection of dopamine. The uniform fibrous network of PANI/TACoPc hybrid was synthesized by a one‐step oxidative polymerization at room temperature. The synthesized nanocomposite was characterized using field emission scanning electron microscopy (FESEM), energy dispersive X‐ray (EDX), fourier transmission infrared spectroscopy (FTIR), raman spectroscopy, X‐ray diffraction (XRD) and UV‐Visible spectroscopy. The electrochemical behavior of the TACoPc/PANI hybrid material was studied by using different electrochemical techniques, including cyclic voltammetry (CV) and chronoamperometry in 0.1 M phosphate buffer solution (PBS) of pH 7 by modifying the glassy carbon electrode (GCE). Due to the synergistic impact of PANI and TACoPc, the suggested altered electrode provided superior catalytic performance for dopamine even in the presence of ascorbic acid. It exhibited a linear reaction with a high sensitivity of 1.212 μA/μM cm^?2 and a low detection limit of 0.064 μM over the 20–200 μM concentration range in 0.1 M PBS. One of the commonly faced problems of interference of ascorbic acid and uric acid in the electrochemical detection of dopamine was completely excluded from this modified electrode which led to an increase in the catalytic activity of the material for the detection of dopamine in the presence of ascorbic acid.     

碳电极上电沉积的Ni-MgO纳米复合物催化甲醇和乙醇电氧化反应

在细小MgO增强颗粒的存在下,采用电沉积法在碳阳极上经瓦特镍制得Ni–MgO纳米复合物,考察了它在碱性介质中电催化氧化甲醇和乙醇反应性能,并与碳涂覆的纯Ni催化剂(Ni/C)性能进行了比较。运用能量散射谱、X射线衍射和扫描电镜分别表征了沉积的纳米复合物的化学组成、相结构和表面形貌,并采用循环伏安法(CV)、计时电流法和电化学阻抗谱(EIS)等电化学技术考察了所制电催化剂阳极的催化活性。结果表明, Ni/C催化剂在电氧化反应中表现出很低的催化活性和稳定性,而MgO的引入显著增加了Ni催化剂在醇氧化反应中的催化活性和抗中毒性能。 EIS和CV结果证实Ni–MgO/C纳米复合物电极具有比Ni/C更低的电荷转移阻力和更高的抗中毒性能。     

贫燃条件 In-Ag/TiO2-γ-Al2O3催化 CO选择性还原NO

汽车尾气中主要污染成分 CO和 NOx可导致酸雨、光化学烟雾和臭氧空洞效应,对生物、环境及生态系统造成重大危害。污染源中 CO是性能优良的还原剂,如能不添加还原剂实现 CO催化还原 NOx,将成为最具经济技术优势的 NOx脱除技术。在富氧、低温条件下,利用 CO选择性催化还原 NOx为 N2,是目前选择性催化还原研究中的热点和难点。催化 CO还原 NOx常用的贵金属 Ir, Rh, Pt和Pd矿藏稀少,价格昂贵,有氧条件下活性急降,而分子筛催化剂和一些金属氧化物催化剂普遍存在反应温度高,尤其对 N2选择性差等问题。为解决上述问题,需寻找新的适合我国矿产资源的催化体系。研究发现,稀散金属基催化剂对氮氧化物的净化具有一定效果,因而可将我国的稀散金属资源优势转化为技术优势和经济优势。因此,本文以 TiO2-γ-Al2O3(TA)为载体, In/Ag为活性组分,采用等体积浸渍法制备了 InAg/TA以及 In/TA, Ag/TA和InAg/Al (γ-Al2O3为载体)催化剂,考察了贫燃条件下 CO选择性还原NO的催化活性。研究表明,双金属催化剂InAg/Al和 InAg/TA的活性比单金属催化剂In/TA和 Ag/TA高, In/TA催化剂中引入 Ag物种能降低起燃温度;另外,相比于InAg/Al催化剂, InAg/TA催化剂具有较高的催化活性,550?600°C时 N2产率超过60%,说明载体中引入TiO2可以提高催化剂活性。为了深入研究 InAg/TA催化剂中 Ag物种和TiO2对 In物种的作用,通过比表面测定、X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱、紫外-可见光吸收光谱、氢气程序升温还原、傅立叶变换红外线光谱等方法分析了催化剂结构和表面形态。结果表明, Ag物种可以提高 In物种的分散性, In和 Ag物种在 TA载体表面可以很好地分散,从而有利于提高催化活性。 In和 Ag物种在 TA载体表面以氧化态形式存在,并且 Ag物种可以提高 In物种表面含量,表面 In和 Ag物种含量越高,吸附活性位越多,催化活性越高;同时, TiO2也可以促进 NO吸附,从而提高 InAg/TA催化剂活性。 InAg/TA催化剂在450°C连续反应72 h进行稳定性测试,测试前后分别在50?600°C进行活性测试,并用 XRD和 TEM对反应后的催化剂进行表征测试。结果表明, InAg/TA催化剂具有较好的稳定性,连续反应前后催化剂活性基本保持不变,推测可能由于在有 CO和O2存在的体系中, Ag物种利用自身 Ag+与 Ag0之间的氧化还原反应抑制了活性组分 In2O3的还原和聚集,稳定了 In物种乃至催化剂活性。 InAg/TA催化剂用于贫燃条件下CO还原NO具有较好的催化效果,主要归因于催化剂活性组分分散性好,稳定性高,对NO吸附能力强。 Ag物种可以稳定In物种并提高其分散性, TiO2可以改善In物种和Ag物种的分散性并促进NO吸附。     

High‐Performance Electrocatalytic Activity of Palladium‐Copper Nanoalloy towards Methanol Electro‐oxidation in an Alkaline Medium

Nanoalloy of PdCu were synthesized with three different stoichiometry ratio (3 : 1, 1 : 1, 1 : 3) by simple co‐reduction process at 5 °C with Triton X‐100 as surface modifier. Morphology and composition of the synthesized catalyst were characterized by X‐ray diffraction (XRD), X‐ray photo electron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X‐ray analysis (EDAX) with selected area electron diffraction (SAED) techniques. Electrocatalytic activity and stability of the catalysts towards methanol oxidation reaction were verified in alkaline medium by cyclic voltammetry (CV) and chronoamperometry (CA). Observed results emphasis that PdCu nanoalloy in the 3 : 1 stoichiometric ratio shows better catalytic activity (778.98 mA mg⁻¹) and stability not only in the initial state (93.73 mA mg⁻¹) but also after 1800 s (8.61 mA mg⁻¹) among all other prepared catalysts.     

高能机械球磨法制备V-Ti-O超细微粒催化剂

负载型V2O5/TiO2氧化物催化剂因具有优良的催化性能而广泛地用于烃类选择性氧化[1,2]和氮氧化物选择性催化还原(SCR)[3]. 迄今,所研究的负载型V2O5/TiO2氧化物催化剂大多是采用浸渍法制备的[2,4～6],通过调整催化剂的组成[2,5]、引入适当的助剂组分[2,6]和选择适宜的反应操作条件[2,5]可进一步优化其催化性能.     

A composite polyaniline/graphene–coated polyamide6 nanofiber mat for electrochemical applications

In this study, polyamide6 (PA6) nanofiber mats were fabricated through the electrospinning process. The nanofibers were coated by polyaniline (PANI) using the in situ polymerization of aniline in the presence of graphene oxide. The composite of the PANI/graphene oxide–coated nanofiber mat was treated with hydrazine monohydrate to reduce graphene oxide to graphene, and this was followed by the reoxidation of PANI. Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), wide angle X‐ray diffraction (WAXD), thermal gravimetric analysis (TGA), tensile strength tests, electrical conductivity measurements, cyclic voltammetry (CV), and charge/discharge measurements were conducted on the composite PA6/graphene nanofiber mats. It was found that the surface of the PA6 nanofibers was coated uniformly with the granular PANI and graphene oxide. Besides, the composite nanofibers showed good tensile and thermal properties. Their electrical conductivity and specific capacitance, when used as a separator in the cell, were 1.02 × 10^?4 S/cm and 423.28 F/g, respectively. Therefore, the composite PANI/reduced graphene oxide–coated PA6 nanofiber mats could be regarded as suitable candidates for application in energy storage devices.     

Immersion Deposition of Pt Nanoparticles on Porous Silicon for Methanol Oxidation

Porous silicon (PS) was chosen as the substrate for supporting the Pt particles because of great surface area, good conductivity and stability. Pt nanoparticles have been successfully prepared on the substrate by immersion deposition, which is convenient. The component and morphological properties of the films have been investigated by means of X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDX) and scanning electron microscopy (SEM), which shows that the Pt particles have small size and big specific surface. Cyclic voltammetry (CV) research showed that the Pt nanoparticles had novel catalytic activity for methanol when the immersion deposition time was past 24 min.     

Synthesis of Carbon Quantum Dots Nanoparticles by Cyclic Voltammetry and Its Application as Methanol Tolerant Oxygen Reduction Reaction Electrocatalyst

Carbon quantum dot (CQD) nanoparticles are synthesized by one‐step electrochemical method, cyclic voltammetry (CV), at different potentials using graphite rods and NaOH/EtOH as electrolyte. The electro‐chemically manufactured CQD is characterized by Transmission electron microscopy, Ultra violet absorption, X‐ray diffraction and Fourier transform infrared spectrometry. The morphology and microstructure methods confirm the formation of high quality CQD. Finally, we design a new gas diffusion electrode (GDE) based on CQD pasted on carbon paper for the oxygen reduction reaction at cathode side as methanol tolerance in direct methanol fuel cell and compared it with standard Pt‐C catalysts using cyclic voltammetry and linear sweep voltammetry. The ORR results in presence of methanol indicate that the GDE prepared from CQD exhibits methanol tolerance compared to the GDE prepared from Pt/C (Electrochem).     

Free‐standing Graphene/Poly(methylene blue)/AgNPs Composite Paper for Electrochemical Sensing of NADH

Highly flexible graphene/poly(methylene blue)/AgNPs composite paper was successfully prepared for amperometric biosensing of NADH. For this purpose, a dispersion including graphene oxide (GO), methylene blue (MB) and silver nanoparticles (AgNPs) was prepared and GO/MB/AgNPs paper was acquired by vacuum‐filtration of this dispersion through a suitable membrane. After peeling it off from membrane, it was transformed to rGO/MB/AgNPs paper by performing reduction with hydriodic acid. In a three‐electrode cell, which is containing 0.1 M phosphate buffer solution (pH: 9.0), rGO/MB/AgNPs paper was used as working electrode and rGO/poly(MB)/AgNPs composite paper was generated by surface‐confined electropolymerization of MB using successive cyclic voltammetry approach in a suitable potential window. Characterization of this composite paper was carried out by using scanning electron microscopy, scanning tunneling microscopy, X‐ray photoelectron spectroscopy, powder X‐ray diffraction spectroscopy, Raman spectroscopy, four‐point probe conductivity measurement and cyclic voltammetry techniques. Flexible rGO/poly(MB)/AgNPs composite paper has demonstrated high sensitivity, wide linear range and low detection limit for amperometric quantification of NADH.     

Synthesis and Characterization of Core‐Shell Selenium/Carbon Colloids and Hollow Carbon Capsules

A novel Se/C nanocomposite with core‐shell structures has been prepared through a facile one‐pot microwave‐induced hydrothermal process. The new material consists of a trigonal‐Se (t‐Se) core and an amorphous‐C (a‐C) shell. The Se/C composite can be converted to hollow carbon capsules by thermal treatment. These products were characterized by transmission electron microscopy (TEM), powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), energy‐dispersive X‐ray (EDX) spectroscopy, and X‐ray photoelectron spectroscopy (XPS).