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1.
以Co(NO3)3·6H2O为钴源,聚乙二醇(PEG)20000为表面活性剂,与多壁碳纳米管(MWCNTs)混合后通过水热氧化法成功地合成了表面均匀分布纳米絮状Co3O4的MWCNTs复合物,进一步还原Pd的前驱体而制备得到Pd-Co3O4/MWCNTs复合催化剂.利用扫描电镜(SEM)、透射电镜(TEM)及X射线粉末衍射(XRD)等手段对样品的形貌和晶型结构进行了表征,结果表明Pd纳米粒子为面心立方晶体结构,均匀地分布在Co3O4修饰的MWCNTs表面.用循环伏安法和计时电流法表征结果表明:催化剂Pd-Co3O4/MWCNTs具有较大的电化学活性表面积,在碱性介质中对甲醇氧化具有更高的电催化活性和稳定性.研究结果表明,过渡金属氧化物纳米Co3O4颗粒在提高直接甲醇燃料电池(DMFC)催化性能研究中具有十分重要的作用,是一类很有潜力的载体催化剂.  相似文献   

2.
张晶  赵晓  刘长鹏  邢巍 《电化学》2012,18(3):270-274
用聚乙烯吡咯烷酮(PVP)修饰的多壁碳纳米管(MWCNTs)作为Pd纳米粒子的载体,制得了Pd/PVP-MWCNTs催化剂并研究了其对甲酸氧化的电催化性能. 红外光谱仪(FTIR)和透射电镜(TEM)观测结果表明,Pd/PVP-MWCNTs催化剂中的Pd纳米粒子平均粒径小、分散性好. 因此,Pd/PVP-MWCNTs催化剂对甲酸电氧化有很好的电催化性能.  相似文献   

3.
周亚楠  朱宇冉  闫新彤  曹羽宁  李佳  董斌  杨敏  李庆忠  刘晨光  柴永明 《催化学报》2021,42(3):431-438,中插25-中插28
电催化析氢(HER)是清洁制氢的一种有效途径,对于氢经济和氢能产业的发展具有重要意义.金属掺杂是提高电催化剂本征活性的有效方法,导电基底的采用也有利于电荷传输和催化性能的整体提高.尽管已有关于硒化物作为HER催化剂的相关报道,但是合成条件有限、导电性、本征活性的影响,其电催化性能仍有提升的空间.此外,在酸性电解液中的腐蚀和氧化极大限制了催化剂性能的发挥.基于此,本文以氮掺杂碳球为载体,采用金属Nb掺杂、非金属硫硒化物协同以及表面碳包覆的三重策略,将掺杂元素Nb和活性位中心元素Co封装到氮掺杂碳纳米球内并进行连续的硫硒化反应,成功构筑多级纳米结构(Nb-CoSeS@NC)以提高其电催化析氢性能.碳球可为活性位的生长和分散提供足够的空间,同时有效防止活性金属的腐蚀和分解,并阻止金属纳米颗粒的团聚.硫化过程实现了非金属硫元素的掺杂,对于提高硒化物的催化活性和导电性都有重要作用.通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)及电催化性能测试,详细研究了Nb-CoSeS@NC独特的纳米结构和电催化制氢性能,并分析了构效关系.XRD结果发现,引入Nb后Co9Se8和CoSe的特征峰移向更高的角度,表明其晶格体积的减小,有助于电荷传输.同时,氮掺杂碳球(NC)在26°可以观察到无定型碳的峰,而石墨碳的D带和G带强度比约为1.05,均表明NC中缺陷的存在,这可以进一步提高碳材料的导电性.SEM和TEM表征显示,催化剂为直径120 nm的均匀的纳米核壳结构,壳层约为30 nm,无明显的团聚和破碎,这是催化剂具有高稳定性的重要原因.表面的褶皱保证了大的活性比表面积,可以大大增加活性位点的数量.同时,催化剂与NC之间的紧密结合可以降低电子传输的阻抗进而改善其稳定性和析氢性能.分析高分辨率的TEM结果发现,Nb掺杂后,Nb-CoSeS@NC中Co9Se8的(222)晶面由0.301 nm减小至0.184 nm,与XRD结果相符.XPS表征揭示了引入Nb之后的电子效应.与CoSeS@NC相比,Nb的掺杂使Co 2p向更低的结合能移动,而Se 3d则移向高结合能移动,这是由于Nb导致了更强的电子相互作用.在0.5 M的H2SO4中测试催化剂的析氢性能,Nb-CoSeS@NC仅需115 mV的过电位便可以实现10 mA cm-2的电流密度,Tafel斜率为43 mV dec-1,优于CoSeS@NC等其他对比样品,且优于大多数掺杂型硒化物电催化剂.经过12 h稳定性测试,电流密度未见明显降低,表明该多级结构催化剂的优异稳定性.Nb-CoSeS@NC提高活性可归因为Nb的掺杂增强了催化剂的电子相互作用,有助于提高的其本征导电性.Nb、Co正离子可以形成氢化物-受体中心,可能会削弱S-H键和Se-H键,并促进H-H键的形成,因此,多元掺杂产生的协同效应可以有效促进HER过程.此外,坚固的氮掺杂纳米碳壳为活性位点的分散提供了足够的空间和优异的电荷传输性能,同时降低了金属活性位腐蚀的可能性.  相似文献   

4.
使用乙二醇还原法合成了一系列高利用率多壁碳纳米管负载的金铂双金属纳米粒子电催化剂,在碱性溶液中由循环伏安和计时电流法测试该AuPt催化剂对于甲醇氧化反应的电催化活性.透射电子显微镜、X射线衍射与X射线能谱观测催化剂形貌,表征催化剂结构.结果表明,金铂双金属纳米粒子均匀分散在碳纳米管上,催化剂具有良好甲醇电氧化性能.实验表明Au/Pt/MWCNTs比为10∶8∶32(bymass)时,该催化剂具有最高甲醇电氧化峰电流密度与最负起始氧化电位.  相似文献   

5.
电催化析氧反应(OER)是电解水制氢的重要半电池反应。然而,OER的缓慢动力学仍需研究高效的电催化剂。在非贵金属催化剂中,NiFe基材料是OER催化剂研究热点。本文通过食人鱼溶液简单一步浸渍刻蚀法将不同Fe含量的泡沫NiFe合金进行氧化,制备了表面具有纳米片形貌的NiFeOOH自支撑电催化剂,并深入研究其电催化析氧性能。通过SEM、XRD、XPS等对电催化剂的形貌结构及成分进行表征,证实了三维多孔基底上NiFeOOH纳米片结构的形成。由于高价镍、铁物种的存在以及二维纳米片结构的生成,NiFeOOH/NF的析氧性能大幅度提高,在10 mA?cm-2的电流密度下过电位仅155.68 mV,Tafel斜率为 88.2 mV?dec-1。这为研制高效、耐用的自支撑非贵金属电极提供了新思路。  相似文献   

6.
利用小分子电催化氧化反应耦合水解制氢不仅有助于降低阳极反应过电位,提高析氢反应(HER)效率,而且产生高附加值的化学品,是提升电催化水分解性能的有效策略.其关键是开发具有高导电性和低氧化电位的非贵金属电催化剂.以Ni(OH)2纳米片为前驱物,通过退火氮化工艺,制备了具有低氧化电位和高导电性的金属相Ni3N纳米颗粒(Ni3N-NPs).与Ni(OH)2相比,Ni3N-NPs具有较小的法拉第电阻,更低的氧化电位(1.36 V时达到10 mA·cm-2),较小的Tafel斜率(29 mV·dec-1),表现出更好的乙二醇(EG)电催化氧化性能.在1.36 V时,Ni3N-NPs电催化氧化EG生成甲酸盐的法拉第效率高达91.16%.通过X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)对反应前后Ni3N-NPs结构进行详细表征发现,在电催化EG氧化过程中,Ni3  相似文献   

7.
电催化水分解制氢是可以形成闭环的生产过程, 起始原料与副产物均为水、 过程清洁无污染, 是极具希望的产氢策略. 目前制约其发展的瓶颈之一是价格昂贵的Pt基贵金属催化剂. 为推动电催化分解水制氢的普及, 亟待开发低成本非贵金属催化剂. 在众多备选非贵金属催化材料中, 纳米层状结构二硫化钼(MoS2)因催化效果可期、 价格低而获得了广泛关注. 然而, 通常条件下易于获得的层状结构2H相MoS2大面积的基面部分显示惰性, 仅在片层边缘处存在少量活性位点, 且导电性较差, 因而尚不能替代Pt基催化剂, 而如何增加其活性位点数量和提高其导电性成为亟待解决的问题; 另一方面, 1T相MoS2虽然活性高、 导电性好, 但却存在制备困难及稳定性差的问题. 鉴于此, 研究者通过对纳米MoS2进行掺杂改性实现了其活性与稳定性的有效提升. 本文对非贵金属纳米MoS2催化剂掺杂改性的方法、 机理及其电催化水解制氢性能的相关研究进行了总结与讨论. 作为典型的非贵金属电解水析氢催化剂, MoS2具有巨大发展潜力, 本文能够对相关非贵金属催化剂的研发提供有益的参考.  相似文献   

8.
电催化制氢是解决当前能源危机的重要手段之一。 研究高效稳定的非贵金属电催化剂是电催化制氢商业应用的重点。 本文通过直接高温热解双金属沸石咪唑骨架,制备了一种氮掺杂石墨炭(NC)包覆均匀分布的钴纳米颗粒电催化剂(V-Co@NC,这里V是vacancy缩写),前躯体中的Zn元素有效地防止钴纳米颗粒的聚集,并有助于生成均匀分布的钴纳米颗粒。 这种特殊的纳米结构可防止钴与电解液的直接接触,提升了其循环稳定性,同时,氮元素的掺杂提升了导电性,有利于电催化制氢性能的提升。 结果表明,所制备的V-Co@NC催化剂在酸性和碱性电解液中均具有良好的催化性能,且经过5000次循环测试后催化活性基本保持不变,具有良好的应用前景。为高活性和高选择性的电催化制氢催化剂的发展提供一种全新的途径。  相似文献   

9.
钟静萍  黄科薪  许文涛  唐华果  Muhammad Waqas  樊友军  王睿翔  陈卫  王沂轩 《催化学报》2021,42(7):1205-1215,中插71-中插75
有效调控碳纳米材料的几何和电子结构的协同效应和缺陷是获得优良电化学性能的关键.然而,如何设计一种具有优势结构的杂化材料及对其电催化机理的认识尚不清楚.本文提出了一种聚(3,4-乙撑二氧噻吩)/聚苯胺导电共聚物热解策略来制备S和N共掺杂多壁碳纳米管(MWCNTs),发现改变前驱体溶液中两种单体的比例可以调控掺杂MWCNTs中S和N原子的含量与表面活性位结构.S和N的共掺杂明显增大了碳纳米管表面的缺陷程度并暴露出更丰富的活性位点,从而有利于超细Pt和PtCu纳米颗粒的均匀分布和沉积.透射电镜和扫描透射电镜结果表明,所制备S和N共掺杂MWCNTs(SN-MWCNTs)负载的催化剂中Pt和PtCu纳米颗粒以及掺杂的S和N原子都均匀地分布在MWCNTs上,且沉积的Pt和PtCu纳米颗粒的平均尺寸仅分别为2.30和2.87 nm.X射线光电子能谱结果表明,S和N共掺杂MWCNTs与负载的Pt基纳米颗粒之间存在强烈的电荷转移相互作用,明显改变了贵金属Pt的表面电子结构.电化学测试结果表明,与Pt/SN-MWCNTs,Pt/N-MWCNTs,Pt/S-MWCNTs和商业Pt/C催化剂相比,Pt1Cu2/SN-MWCNTs表现出更大的电化学活性表面积(148.85 m2 g?1),更高的甲醇氧化质量活性(1589.9 mA mgPt?1)、电化学稳定性和抗CO毒化能力.密度泛函理论研究表明,S和N共掺杂导致碳纳米管极大地变形,同时极化和激活了相邻的C原子.因此,增强了Pt1Cu2纳米颗粒在SN-MWCNTs上的吸附以及随后甲醇分子的吸附.此外,Pt1Cu2/SN-MWCNTs对甲醇氧化的电催化活性均在热力学和动力学上优于相应的CNTs和N-CNTs基材料.本文提供了一种新颖的在碳基材料上构建高度分散且稳定的Pt基纳米颗粒高性能燃料电池电催化剂的方法.  相似文献   

10.
在众多非贵金属基材料中,金属有机骨架(MOFs)因其高比表面积和丰富的金属活性中心而成为最有前景的氧气析出反应(OER)催化剂之一.但MOFs的本征催化活性、导电性和稳定性较差,从而影响其在OER电催化中的应用.本工作通过电沉积法在泡沫镍支撑的FeNi MOF纳米片表面引入5 nm的CeO2纳米团簇来提高MOFs的催化活性.CeO2纳米团簇与FeNi MOF纳米片之间的固-固界面相互作用以及CeO2纳米团簇的掺杂有效调控了MOF表面金属位点的电子结构,提高了金属位点的本征电催化活性;同时,CeO2团簇良好的导电性促进了FeNi MOF表面的电荷迁移,从而使CeO2/FeNi MOF的OER活性优于FeNi MOF.在1 mol·L-1 KOH溶液中CeO2/FeNi MOF达到50 mA·cm-2和100 mA·cm-2的电流密度所需要的过电位分别只有220 mV和233 mV,同时表现出快速的反应动力学和优异的稳定性.  相似文献   

11.
Water splitting has attracted more and more attention as a promising strategy for the production of clean hydrogen fuel. In this work, a new synthesis strategy was proposed, and Co0.85Se was synthesized on nickel foam as the main matrix. The doping of appropriate Cr amount into the target of Co0.85Se and the Cr‐Co0.85Se resulted in an excellent electrochemical performance. The doping of Cr introduces Cr3+ ions which substitute Co2+ and Co3+ ions in Co0.85Se, so that the lattice parameters of the main matrix were changed. It is worth noting that the Cr0.15‐Co0.85Se/NF material exhibits an excellent performance in the oxygen evolution reaction (OER) test. When the current density reaches 50 mA cm?2 for OER, the overpotential is only 240 mV. For the hydrogen evolution reaction (HER) tests, the overpotential is only 117 mV to drive 10 mA cm?2 of current density. Moreover, when the Cr0.15‐Co0.85Se/NF material is used as a two‐electrode device for whole water splitting, the required cell voltage is only 1.43 V to reach a current density of 10 mA cm?2, which is among the lowest values of the published catalysts up to now. In addition, the Cr0.15‐Co0.85Se/NF catalyst also exhibits excellent stability during a long period of water splitting. The experimental result demonstrates that the change of the lattice structure has an obvious influence on the electrocatalytic activity of the material. When an external electric field is applied, it facilitates the rapid electron transfer rate and enhances the electrocatalytic performance and stability of the material.  相似文献   

12.
Highly methanol-tolerant CoSe nanoparticles supported on different carbon substrates were synthesized by microwave heating of glycerol solutions of cobalt(II) acetate and sodium selenite at different Se/Co mole ratios in the presence of different concentrations of acetic acid and ammonia. The resulting CoSe catalysts were used for the electrochemical oxygen reduction reaction (ORR) in acidic solution in the presence of methanol. The ORR activity of the catalyst was increased by increasing its Se content up to 50?mol%. The presence of acetic acid or ammonia in the synthesis solution significantly affects the electrocatalytic performance of the CoSe catalyst; highest activity was observed when the catalyst was synthesized at NH3/Co(II) mole ratio of 6. Among the catalysts prepared on different supports including carbon black (Vulcan XC-72R), and nanoporous carbons synthesized from resorcinol-formaldehyde and phloroglucinol-formaldehyde resins, the one supported on the carbon prepared from the last resin exhibited highest electrocatalytic activity for ORR.  相似文献   

13.
采用长链聚合物聚二烯丙基二甲基氯化铵(PDDA)对多壁碳纳米管(MWCNTs)进行修饰,并将采用胶体法还原出的铂(Pt)纳米粒子通过静电作用担载于PDDA修饰的多壁碳纳米管上,从而制备出Pt/PDDA/MWCNTs复合电催化剂.透射电镜(TEM)与X射线衍射(XRD)测试结果表明, Pt纳米粒子均匀地分布在MWCNTs的表面,其平均粒径约为3.6 nm.热失重分析显示催化剂的实际负载量为36%(w).旋转圆盘电极测试结果表明, Pt/PDDA/MWCNTs催化剂对碱性条件下的氧气还原反应(ORR)具有优异的催化活性.与负载量为40%(w)的商业Pt/C催化剂相比, Pt/PDDA/MWCNTs催化剂的氧气还原反应的起始电位和半波电位均正移约30 mV,其质量比活性更大.动力学研究结果进一步证实Pt/PDDA/MWCNTs催化剂比负载量为40%(w)的商业Pt/C催化剂在碱性条件下对氧气还原反应具有更优异的催化活性.  相似文献   

14.
Hetero-structure induced high performance catalyst for oxygen evolution reaction(OER)in the water splitting reaction has received increased attention.Herein,we demonstrated a novel catalyst system of NiSe2-CoSe2 consisting of nanorods and nanoparticles for the efficient OER in the alkaline electrolyte.This catalyst system can be easily fabricated via a low-temperature selenization of the solvothermal synthesized NiCo(OH)x precursor and the unique morphology of hybrid nanorods and nanoparticles was found by the electron microscopy analysis.The high valence state of the metal species was indicated by X-ray photoelectron spectroscopy study and a strong electronic effect was found in the NiSe2-CoSe2 catalyst system compared to their counterparts.As a result,NiSe2-CoSe2 exhibited high catalytic performance with a low overpotential of 250 mV to reach 10 mA·cm-2 for OER in the alkaline solution.Furthermore,high catalytic stability and catalytic kinetics were also observed.The superior performance can be attributed to the high valence states of Ni and Co and their strong synergetic coupling effect between the nanorods and nanoparticles,which could accelerate the charge transfer and offer abundant electrocatalytic active sites.The current work offers an efficient hetero-structure catalyst system for OER,and the results are helpful for the catalysis understanding.  相似文献   

15.
Pt/carbon nanofiber (Pt/CNF) nanocomposites were facilely synthesized by the reduction of hexachloroplatinic acid (H(2)PtCl(6)) using formic acid (HCOOH) in aqueous solution containing electrospun carbon nanofibers at room temperature. The obtained Pt/CNF nanocomposites were characterized by TEM and EDX. The Pt nanoparticles could in situ grow on the surface of CNFs with small particle size, high loading density, and uniform dispersion by adjusting the concentration of H(2)PtCl(6) precursor. The electrocatalytic activities of the Pt/CNF nanocomposites were also studied. These Pt/CNF nanocomposites exhibited higher electrocatalytic activity toward methanol oxidation reaction compared with commercial E-TEK Pt/C catalyst. The results presented may offer a new approach to facilely synthesize direct methanol fuel cells (DMFCs) catalyst with enhanced electrocatalytic activity and low cost.  相似文献   

16.
Herein we report a gentle seedless and surfactant‐free method for the preparation of clean‐surface porous platinum nanoparticles. In terms of electrocatalytic CH3OH oxidation, the clean‐surface porous platinum exhibited better performance than platinum nanoparticles and a commercial Pt/C catalyst. The porous nanostructures exhibited 2.26‐fold higher mass activity and 2.8‐fold greater specific activity than the Pt/C catalyst. More importantly, three typical surfactants, cetyltrimethylammonium bromide/chloride (CTAB/C), poly(vinylpyrrolidone), and sodium dodecyl sulfate, were chosen to study the inhibition effect of surfactants on electrocatalytic performance. It was observed that the surfactants led to a clear selective decrease in electrocatalytic performance. CTAB/C inhibited the catalytic activity the most due to the stronger interaction between the OH‐enriched platinum surface and the positively charged molecules. Thus, this work indicates that these clean‐surface porous platinum nanoparticles may be used as efficient catalysts for direct methanol fuel cells and provides a greater understanding of the inhibition effects of surfactants on catalytic activity.  相似文献   

17.
Transition metal phosphides (TMPs) as ever-evolving electrocatalytic materials have attracted increasing attention in water splitting reactions owing to their cost-effective, highly active and stable catalytic properties. This work presents a facile synthetic route to NiCoP nanoparticles with Ru dopants which function as highly efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media. The Ru dopants induced a high content of Ni and Co vacancies in NiCoP nanoparticles, and the more defective Ru doped NiCoP phase than undoped NiCoP ones led to a greater number of catalytically active sites and improved electrical conductivity after undergoing electrochemical activation. The Ru doped NiCoP catalyst exhibited high OER catalytic performance in alkaline media with a low overpotential of 281 mV at 10 mA cm−2 and a Tafel slope of 42.7 mV dec−1.  相似文献   

18.
Structural and morphological behavior under stress–strain of polypropylene/multi‐walled carbon nanotubes (PP/MWCNTs) nanocomposites prepared through ultrasound‐assisted melt extrusion process was studied by means of optical microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, small angle X‐ray scattering (SAXS), and wide angle X‐ray scattering (WAXS). A high ductile behavior was observed in the PP/MWCNT nanocomposites with low concentration of MWCNTs. This was related to an energy‐dissipating mechanism, achieved by the formation of an ordered PP‐CNTs interphase zone and crystal oriented structure in the undeformed samples. Different strain‐induced‐phase transformations were observed by ex situ SAXS/WAXS, characterizing the different stages of structure development during the deformation of PP and PP/MWCNTs nanocomposites. The high concentration of CNTs reduced the strain behavior of PP due to the agglomeration of nanoparticles. A structural pathway relating the deformation‐induced phase transitions and the dissipation energy mechanism in the PP/MWCNTs nanocomposites at low concentration of nanoparticles was proposed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 475–491  相似文献   

19.
Fe3O4 nanoparticles were indirectly implanted onto functionalized multi‐walled carbon nanotubes (MWCNTs) leading to a nanocomposite with stronger magnetic performance. Poly(acrylic acid) (PAA) oligomer was first reacted with hydroxyl‐functionalized MWCNTs (MWCNTs‐OH) forming PAA‐grafted MWCNTs (PAA‐g‐MWCNTs). Subsequently, Fe3O4 nanoparticles were attached onto the surface of PAA‐g‐MWCNTs through an amidation reaction between the amino groups on the surface of Fe3O4 nanoparticles and the carboxyl groups of PAA. Fourier transform infrared spectra confirmed that the Fe3O4 nanoparticles and PAA‐g‐MWCNTs were indeed chemically linked. The morphology of the nanocomposites was characterized using transmission electron microscope (TEM). The surface and bulk structure of the nanocomposites were examined using X‐ray diffraction, X‐ray photoelectron spectrometer (XPS), and thermogravimetric analysis (TGA). The magnetic performance was characterized by vibrating sample magnetometer (VSM) and the magnetic saturation value of the magnetic nanocomposites was 47 emu g?1. The resulting products could be separated from deionized water under an external magnetic field within about 15 s. Finally, the magnetorheological (MR) performances of the synthesized magnetic nanocomposites and pure Fe3O4 nanoparticles were examined using a rotational rheometer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

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