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1.
Silver (Ag) at 0.1–2.0 wt% was incorporated into cathodes for solid oxide fuel cells as a catalyst for oxygen reduction. A novel processing route for Ag incorporation ensuring a very homogeneous Ag ion distribution is presented. From the results of X-ray powder diffraction it can be concluded that the La0.65Sr0.3MnO3– perovskite phase is already formed at 900 °C. The solubility of Ag in the crystal lattice in this type of perovskite was below 1 wt%. The electrochemical tests of these materials show that there is only a slight catalytic effect of Ag. Scanning electron microscopy reveals a low mechanical contact of the cathode grains to the electrolyte due to the low cathode sintering temperature that was chosen. 相似文献
2.
A major impediment to the commercialization of fuel cells is the low activity of electrocatalysts for the oxygen reduction
reaction that involves multiple electron transfer steps. Platinum is considered the best cathode catalyst toward oxygen reduction
to water; however, Pt remains an expensive metal of low abundance, and it is of great importance to find Pt-free metal alternatives.
Among various Pt-free catalysts under development, ruthenium-based compounds show significant catalytic activity and selectivity
for four-electron reduction of oxygen to water in acidic environments. This article provides a short review on the different
classes of Ru-based catalysts focusing on the catalytically active reaction sites and the oxygen reduction mechanism in acidic
media. After a brief discussion of the oxygen reduction kinetics on a pure Ru metal, the paper reviews the catalytic properties
of the selected Ru compounds, including crystalline Chevrel-phase chalcogenides, nanostructured Ru and Ru–Se clusters, and
Ru–N chelate compounds.
This paper is dedicated to Professor Su-Il Pyun, who has pioneered advances in interfacial electrochemistry in the field of
corrosion and materials science in South Korea, on the occasion of his 65th birthday. 相似文献
3.
Chung-Liang Chang Cuo-Ciang Hsu Ta-Jen Huang 《Journal of Solid State Electrochemistry》2003,7(3):125-128
Various copper oxide cathode materials were studied over a YSZ tube at 800 °C and an oxygen partial pressure of 0.21 atm.
It was found that the cathode performance of CuO may be improved by doping Ag metal into it. However, an optimal doping content
exists and is around 50 mol% Ag. It was also found that copper oxide itself possess enough oxygen vacancies needed for the
role of a mixed conductor. The activation energy for the lattice-oxygen reduction and migration has been calculated to be
55.4 kJ/mol. By the use of electrochemical measurements over Ag-YSZ/CuO electrodes, models for the two-layer electrode have
been proposed and justified for oxygen-ion transport mechanisms at low and high overpotentials, respectively; thus, the roles
of CuO on the cathode behavior of the electron and oxygen-ion conductivities were well identified.
Electronic Publication 相似文献
4.
采用氯化法制备石墨烯-无定型碳复合材料(GNS@a-C),并用作质子交换膜燃料电池(PEMFC)氧还原反应Pt催化剂的载体.结果显示,所制Pt/GNS@a-C催化剂与传统商业催化剂Pt/C相比,有较好的活性和较高的稳定性:质量活性(0.121 A/mg)几乎是Pt/C(0.064 A/mg)的两倍.更重要的是,该新型催化剂加速4000圈后其电化学活性面积保留了最初的51%,与Pt/C的33%相比,前者有更好的电化学稳定性,显示它在PEMFC中将具有较好的应用潜力. 相似文献
5.
Carlo Santoro Alexey Serov Kateryna Artyushkova Plamen Atanassov 《Current Opinion in Electrochemistry》2020
The oxygen reduction reaction is one of the limiting steps in microbial fuel cell performance. M–N–C catalysts (M as transition metal) represent the best compromise of optimal cost, electrocatalytic activity and durability. The Fe-based catalysts were shown to be the best compared with Co-, Mn-, Ni-based catalysts. The addition of the second transition metal such as Mn was shown to increase the selectivity of the reaction and reduce peroxide production. The use of different N–C precursors resulted in diverse surface chemistry that directly affects the performance. Generally, surface chemistry plays a critical role in the electrocatalytic activity. Integration of the catalyst in the air-breathing cathode is also discussed with a performance that is enhanced by: (i) increased catalyst loading; (ii) the addition of graphene to structure. 相似文献
6.
Electrochemical reduction of oxygen at the interface between a La0.9Sr0.1MnO3 (LSM)-based electrode and an electrolyte, either yttria-stabilized-zirconia (YSZ) or La0.8Sr0.2Ga0.9Mg0.1O3 (LSGM), has been investigated using DC polarization, impedance spectroscopy, and potential step methods at temperatures from
1053 to 1173 K. Results show that the mechanism of oxygen reduction at an LSM/electrolyte interface changes with the type
of electrolyte. At an LSM/YSZ interface, the apparent cathodic charge transfer coefficient is about 1 at high temperatures,
implying that the rate-determining step (r.d.s.) is the diffusion of partially reduced oxygen species, while at an LSM/LSGM
interface the cathodic charge transfer coefficient is about 0.5, implying that the r.d.s. is the donation of electrons to
atomic oxygen. The relaxation behavior of the LSM/electrolyte interfaces displays an even more dramatic dependence on the
type of electrolyte. Under cathodic polarization, the current passing through an LSM/YSZ interface increases with time whereas
that through an LSM/LSGM interface decreases with time, further confirming that it is the triple phase boundaries (TPBs),
rather than the surface of the LSM or the LSM/gas interface, that dominate the electrode kinetics when LSM is used as an electrode.
Electronic Publication 相似文献
7.
燃料电池具有较高的能量密度和发电效率,以清洁能源为原料,零污染排放,是一种具有发展前景的能量储存和转化装置.阴极氧还原反应(ORR)在燃料电池中起着关键作用.ORR广泛采用贵金属铂基催化剂,但是它们价格昂贵,电子动力学转移速率慢,碱性条件下易团聚,这些亟需解决的问题阻碍了燃料电池商业化进程.近期,一些非贵金属催化剂被广泛研究,例如氮掺杂碳材料、Fe/N/C和Co/N/C材料等,它们有可能在未来替代铂基催化剂.我们的目标是合成新型高催化活性的Co/N/C及其衍生非贵金属材料,用于ORR催化反应.由于石墨烯具有独特的形貌、较大的比表面积和良好的导电性,其表面含有功能化的官能团,所以我们选择石墨烯作为碳载体.首先,用改性休克尔方法合成了氧化石墨烯(GO),为了提高其催化活性,采用聚吡咯作为氮源对其进行了氮掺杂,制备了聚吡咯/氧化石墨烯(Ppy/GO).通过ORR催化性能测试发现,GO对ORR具有一定的催化活性,它的起始电位和阴极电流电位分别为–0.31 V vs SCE和–0.38 V vs SCE;Ppy/GO的起始电位和阴极电流电位分别为–0.20 V vs SCE和–0.38 V vs SCE,氮掺杂对GO的催化活性有所提高.采用水热法沉积氧化钴合成了Co3O4/聚吡咯/氧化石墨烯(Co3O4/Ppy/GO).其形貌为Co3O4分散在氮掺杂GO表面.在KOH电解质(0.1 mol/L)中测试,Co3O4/Ppy/GO的起始电位和阴极电流电位分别为–0.20 V和–0.38 V vs SCE.经过800℃高温煅烧处理后,Co3O4/Ppy/GO-800的催化活性明显提高,起始电位和阴极电流电位分别达到–0.10 V和–0.18 V vs SCE.ORR电子转移数为3.4,接近于4电子反应途径.Co3O4/Ppy/GO对ORR的催化活性及4电子催化选择性较高,可能是由于纳米形态的Co3O4和Ppy/GO之间具有较强的表面作用力,聚吡咯掺杂的氧化石墨烯具有较强的电子储存及释放能力.综上,我们通过水热法制备了钴、氮共掺杂的GO,并研究了其对ORR的催化活性和电子转移选择性.结果表明Co3O4/Ppy/GO是一种高效的非贵金属电催化剂,在碱性电解质中具有很高的ORR催化活性,在燃料电池阴极催化剂方面很有前景. 相似文献
8.
氧还原反应(ORR)是燃料电池和金属空气电池等洁净发电装置中阴极的主要反应,该反应动力学过程慢,电化学极化严重. Pt基电催化剂具有较好的ORR活性,然而Pt资源有限、价格昂贵,研制高活性、低成本的代Pt电催化剂意义重大.经过几十年的探索,研究者发现将含有C, N和Fe等元素的前体进行高温热处理得到的Fe-N-C电催化剂对ORR具有良好的活性,然而在高温热解过程中Fe容易发生聚集而形成大块颗粒,导致Fe的利用率不高,影响了电催化剂的ORR活性.
本文分别以聚吡咯和乙二胺四乙酸二钠(EDTA-2Na)为C和N的前驱体,利用高温热解形成的富含微孔的碳材料对铁前体的吸附及锚定作用,获得了一种Fe高度分散的Fe-N-C电催化剂.采用物理吸脱附技术、高分辨透射电镜(HRTEM)和扫描电镜对Fe-N-C及其制备过程中相关电催化剂的孔结构及表面形貌进行了表征.结果表明,在第一步热解过程中, EDTA-2Na的Na对碳材料起到了活化作用,形成富含微孔的N掺杂碳材料(N-C-1),其BET比表面积达到1227 m2/g,孔径约1.1 nm.在第二步热解过程中, N-C-1有效地抑制了Fe的聚集,产物Fe-N-C中的Fe元素均匀地分布在碳材料中,其比表面积高达1501 m2/g.
电化学测试结果表明,在碱性介质(0.1 mol/L NaOH)中, Fe-N-C电催化剂对ORR具有良好的催化活性, ORR起始电位(Eo)为1.08 V (vs. RHE),半波电位(E1/2)0.88 V,电子转移数n接近4, H2O2产率<3%,与商品20%Pt/C(Johnson Matthey)接近.电化学加速老化测试结果表明, Fe-N-C的E1/2未发生明显变化,而Pt的负移45 mV,表明Fe-N-C具有很好的稳定性;在酸性介质(0.1 mol/L HClO4)中, Fe-N-C的Eo为0.85 V, E1/2为0.75 V,其E1/2比Pt/C负移约0.15 V,表明在酸性介质中Fe-N-C对ORR的催化活性还有待提高.采用TEM、X射线衍射、X射线光电子能谱以及穆斯堡尔谱等方法研究了电催化剂构效关系.结果表明, Fe-N-C较好的ORR活性主要来自于高分散的Fe-N4结构,此外, N(吡啶N和石墨N)掺杂的C也对反应具有一定的催化活性.
与Pt/C相比, Fe-N-C电催化剂具有很好的耐甲醇性能.本文对比了Fe-N-C和Pt/C作为阴极催化剂的直接醇类燃料电池(DMFC)性能,采用质子交换膜的DMFC最大功率密度分别为47(Fe-N-C)和79 mW/cm2(Pt/C),而采用碱性电解质膜的则分别为33(Fe-N-C)和8 mW/cm2(Pt/C).结合半电池结果表明, Fe-N-C电催化剂在碱性介质中具有比Pt更为优秀的催化活性和稳定性,有望用作DMFC阴极代Pt催化剂. 相似文献
本文分别以聚吡咯和乙二胺四乙酸二钠(EDTA-2Na)为C和N的前驱体,利用高温热解形成的富含微孔的碳材料对铁前体的吸附及锚定作用,获得了一种Fe高度分散的Fe-N-C电催化剂.采用物理吸脱附技术、高分辨透射电镜(HRTEM)和扫描电镜对Fe-N-C及其制备过程中相关电催化剂的孔结构及表面形貌进行了表征.结果表明,在第一步热解过程中, EDTA-2Na的Na对碳材料起到了活化作用,形成富含微孔的N掺杂碳材料(N-C-1),其BET比表面积达到1227 m2/g,孔径约1.1 nm.在第二步热解过程中, N-C-1有效地抑制了Fe的聚集,产物Fe-N-C中的Fe元素均匀地分布在碳材料中,其比表面积高达1501 m2/g.
电化学测试结果表明,在碱性介质(0.1 mol/L NaOH)中, Fe-N-C电催化剂对ORR具有良好的催化活性, ORR起始电位(Eo)为1.08 V (vs. RHE),半波电位(E1/2)0.88 V,电子转移数n接近4, H2O2产率<3%,与商品20%Pt/C(Johnson Matthey)接近.电化学加速老化测试结果表明, Fe-N-C的E1/2未发生明显变化,而Pt的负移45 mV,表明Fe-N-C具有很好的稳定性;在酸性介质(0.1 mol/L HClO4)中, Fe-N-C的Eo为0.85 V, E1/2为0.75 V,其E1/2比Pt/C负移约0.15 V,表明在酸性介质中Fe-N-C对ORR的催化活性还有待提高.采用TEM、X射线衍射、X射线光电子能谱以及穆斯堡尔谱等方法研究了电催化剂构效关系.结果表明, Fe-N-C较好的ORR活性主要来自于高分散的Fe-N4结构,此外, N(吡啶N和石墨N)掺杂的C也对反应具有一定的催化活性.
与Pt/C相比, Fe-N-C电催化剂具有很好的耐甲醇性能.本文对比了Fe-N-C和Pt/C作为阴极催化剂的直接醇类燃料电池(DMFC)性能,采用质子交换膜的DMFC最大功率密度分别为47(Fe-N-C)和79 mW/cm2(Pt/C),而采用碱性电解质膜的则分别为33(Fe-N-C)和8 mW/cm2(Pt/C).结合半电池结果表明, Fe-N-C电催化剂在碱性介质中具有比Pt更为优秀的催化活性和稳定性,有望用作DMFC阴极代Pt催化剂. 相似文献
9.
RuxCoySez纳米簇合物对阴极氧还原反应的催化性能 总被引:1,自引:0,他引:1
以Ru3(CO)12、Co4(CO)12和Se为原料,采用低温回流技术在1,6-己二醇中合成了RuxCoySez纳米簇合物.利用SEM和XRD测试表征了催化剂的微观形貌和相结构,催化剂粉末以六方结构的Rux簇为主相,同时形成无定形相,呈现高度均匀聚集的纳米颗粒.利用旋转圆盘电极研究了催化剂对氧还原反应电催化活性.在0.5molL-1H2SO4溶液中,RuxCoySez催化剂对氧还原的催化活性和电化学稳定性明显高于RuxSey,开路电位达到0.91V(vs.NHE). 相似文献
10.
PrGa1-xMgxO3作为燃料电池固体电解质的研究 总被引:6,自引:0,他引:6
用固相反应法合成了具有正交钙钛矿结构的PrGa1-xMgxO3(x=0,0.05,0.10,0.15,0.20,0.25)通过掺杂,样品的电导率显著提高,活化能降低,所有样品均以离子导电为主,其中PrGa0.9Mg0.1O3的氧离子电导率最高,在800℃达到0.05S/cm,PrGa0.8Mg0.2O3的导电活化能量低,为24.19kJ/mol。随着温度的升高,样品的离子迁移数增加,PrGa0.9Mg0.1O3作为电解质的燃料电池在940℃短路电流密度为0.45A/cm^2,最大功率密度达0131W/cm^2,镁掺杂的PrGaO3是一种性能优良的固体电解质。 相似文献
11.
以金属有机骨架为前驱体的高活性氧还原非贵金属催化剂制备 总被引:1,自引:0,他引:1
The development of a non‐precious metal electrocatalyst (NPME) with a performance superior to commercial Pt/C for the oxygen reduction reaction (ORR) is important for the commercialization of fuel cells. We report the synthesis of a NPME by heat‐treating Co‐based metal organic frameworks (ZIF‐67) with a small average size of 44 nm. The electrocatalyst pyrolyzed at 600 °C showed the best performance and the performance was enhanced when it was supported on BP 2000. The resulting electrocatalyst was composed of 10 nm Co nanoparticles coated by 3–12 layers of N doped graphite layers which as a whole was embedded in a carbon matrix. The ORR performance of the electrocatalyst was tested by rotating disk electrode tests in O2‐saturated 0.1 mol/L KOH under ambient conditions. The electrocatalyst (1.0 mg/cm2) showed an onset potential of 1.017 V (vs. RHE) and a half‐wave potential of 0.857 V (vs. RHE), which showed it was as good as the commer‐cial Pt/C (20μgPt/cm2). Furthermore, the electrocatalyst possessed much better stability and re‐sistance to methanol crossover than Pt/C. 相似文献
12.
Transition metal oxide doped lanthanum gallates, La0.9Sr0.1Ga0.8M0.2O3 (where M=Co, Mn, Cr, Fe, or V), are studied as mixed ionic-electronic conductors (MIECs) for electrode applications. The
electrochemical properties of these materials in air and in H2 are characterized using impedance spectroscopy, open cell voltage measurement, and gas permeation measurement. Three single
cells based on La0.9Sr0.1Ga0.8 Mg0.2O3 (LSGM) electrolyte (1.13 to 1.65 mm thick) but with different electrode materials are studied under identical conditions
to characterize the effectiveness of the lanthanum gallate-based MIECs for electrode applications. At 800 °C, a single cell
using La0.9Sr0.1- Ga0.8Co0.2O3 as the cathode and La0.9Sr0.1Ga0.8Mn0.2O3 as the anode shows a maximum power density of 88 mW/cm2, which is better than that of a cell using Pt as both electrodes (20 mW/cm2) and that of a cell using La0.6Sr0.4CoO3 (LSC) as the cathode and CeO2-Ni as the anode (61 mW/cm2) under identical conditions. The performance of LSGM-based fuel cells with MIEC electrodes may be further improved by reducing
the electrolyte thickness and by optimizing the microstructures of the electrodes through processing.
Received: 9 January 1998 / Accepted: 1 May 1998 相似文献
13.
Aneta Kolary-Zurowska Agata Zieleniak Krzysztof Miecznikowski Beata Baranowska Adam Lewera Sebastian Fiechter Peter Bogdanoff Iris Dorbandt Roberto Marassi Pawel J. Kulesza 《Journal of Solid State Electrochemistry》2007,11(7):915-921
An electrocatalytic system that utilizes tungsten oxide modified carbon-supported RuSex nanoparticles is developed and characterized here using transmission electron microscopy and such electrochemical diagnostic
techniques as cyclic voltammetry and rotating ring-disk voltammetry, as well as upon its introduction (as cathode) to the
low-temperature hydrogen–oxygen fuel cell. After the modification of RuSex catalytic centers with ultra-thin films of WO3, the potential of oxygen reduction in 0.5 mol dm−3 H2SO4 (in the absence and presence of methanol) is shifted ca. 70 mV (under rotating disk voltammetric conditions) towards more
positive values, and the percent formation (at ring) of the undesirable hydrogen peroxide has decreased approximately twice
when compared to the WO3-free system. Relative to bare electrocatalyst, an increase of power density from 75 to 100 mW cm−2 (at 300 mA cm−2) has been observed upon utilization of WO3-modified RuSex in polymer electrolyte membrane fuel cell at 80 °C. In comparison to Vulcan-supported Pt nanoparticles, the overall electrocatalytic
performance of tungsten oxide modified carbon-supported RuSex nanoparticles is lower, but the latter system is practically insensitive to the presence of methanol even at 0.5 mol dm−3 level.
Dedicated to Professor Dr. Algirdas Vaskelis on the occassion of his 70th birthday. 相似文献
14.
Dehua Dong Jianfeng Yao Yuzhou Wu Xinyi Zhang Gengsheng Xu Chun-Zhu Li Huanting Wang 《Electrochemistry communications》2011,13(10):1038-1041
A three-dimensional (3D) fibrous cathode of solid oxide fuel cell was fabricated by using eggshell membranes (ESMs) as the template. This cathode possesses high porosity and interconnectivity, and low polarization resistance. A single fuel cell with the 3D fibrous Sm0.5Sr0.5CoO3/Ce0.8Sm0.2O1.9 cathode shows significantly improved performances at low operating temperatures (500–600 °C) as compared with the cell prepared with the ESM-templated cluster cathode in our previous study. 相似文献
15.
质子交换膜燃料电池(PEMFCs)电堆中阴极Pt基催化剂的高用量造成其成本居高不下,成为阻碍燃料电池汽车商业化推进的重要原因,因此开发低Pt、高活性的Pt基催化剂势在必行.Pt合金催化剂能够有效地降低Pt用量,并通过对合金颗粒的元素比例、晶面、粒径等实行精确调控,显著提升氧还原(ORR)催化活性.然而,目前常用的制备方法由于原料与制备成本高昂、过程复杂大都难以适应规模化生产需求.电化学方法通过控制施加的电流或电位控制晶体生长.在水体系中该方法已得到验证,但由于Pt化合物的热力学标准电极电位与过渡金属元素之间相差较大,且对于过渡金属来说,电负性大多小于铂,因此还原电位通常负于析氢电位,使得二者难以实现共沉积.有机体系中电位窗口比水体系大得多,Pt与电位较负的过渡金属可实现共沉积,采用小分子有机溶剂也可避免溶剂清洗问题,具有应用潜力.本文提出了一种简单的一步电沉积方法,选择易溶于水的N,N-二甲基甲酰胺(DMF)作为溶剂,将碳载体滴涂到玻碳电极上作为工作电极,通过电化学方法直接将Pt-Ni合金沉积到碳载体上,并利用物化表征与密度泛函理论(DFT)理论计算来探究共沉积机理.透射电镜表征结果表明,在不同的沉积电位下均可得到分散均匀、粒径适当的催化剂;且随着电位值降低,催化剂颗粒分散得更均匀,颗粒粒径不断减小.元素分布和晶面结果表明,铂镍元素均匀分布于颗粒中.所有样品均表现出优异的ORR性能,最高的面积比活性达到商业催化剂的6.85倍.将材料表征、电化学表征与DFT计算结合,建立起了铂镍合金生长过程的模型,并发现了有机体系中独特的成核-生长机理.将体系中的DMF换成超纯水,用同样的方法进行沉积,得到的催化剂颗粒团聚严重,说明DMF的使用能够避免颗粒团聚.在单独铂的体系中沉积发现,负载量极小,表明体系中镍前驱体的添加对于催化剂的沉积过程起到重要作用.电化学表征结果表明,在所选用的DMF有机体系中,镍的还原电位与铂的十分接近,但还原动力学更慢,趋向于先形成吸附原子后快速还原.由此可以推测,在二者合金的形成过程中,镍在碳载体表面的缓慢还原而形成的吸附原子能够成为铂还原的活性位点,从而降低了铂还原成核所需的能量,使得载体上的成核位点大大增加,这与DFT模拟结果一致.DFT建立了碳上镍的位点和铂的位点,分别在上面进行铂的还原,发现镍位点上比铂位点上更容易实现铂沉积.本文提出了铂镍共沉积的机理:在过电位(即还原能量)下,铂的还原动力学较镍稍快,于是铂先还原形成晶核,但难以达到生长的临界半径,于是单独铂体系中的沉积负载量很少.载体上还原的镍为铂还原提供了大量的活性位点,促进了铂还原,并与镍共沉积.Pt-Ni表面则进一步促进了铂的沉积和颗粒的生长.综上,本文提出了一种用于制备铂合金催化剂的有机电沉积体系,实现了单分散的碳载铂镍合金催化剂的一步制备.随后,本文将材料表征、电化学表征与DFT计算相结合,建立起了有机体系中铂镍合金成核-生长过程的机理模型. 相似文献
16.
质子交换膜燃料电池(PEMFCs)电堆中阴极Pt基催化剂的高用量造成其成本居高不下,成为阻碍燃料电池汽车商业化推进的重要原因,因此开发低Pt、高活性的Pt基催化剂势在必行.Pt合金催化剂能够有效地降低Pt用量,并通过对合金颗粒的元素比例、晶面、粒径等实行精确调控,显著提升氧还原(ORR)催化活性.然而,目前常用的制备方法由于原料与制备成本高昂、过程复杂大都难以适应规模化生产需求.电化学方法通过控制施加的电流或电位控制晶体生长.在水体系中该方法已得到验证,但由于Pt化合物的热力学标准电极电位与过渡金属元素之间相差较大,且对于过渡金属来说,电负性大多小于铂,因此还原电位通常负于析氢电位,使得二者难以实现共沉积.有机体系中电位窗口比水体系大得多,Pt与电位较负的过渡金属可实现共沉积,采用小分子有机溶剂也可避免溶剂清洗问题,具有应用潜力.本文提出了一种简单的一步电沉积方法,选择易溶于水的N,N-二甲基甲酰胺(DMF)作为溶剂,将碳载体滴涂到玻碳电极上作为工作电极,通过电化学方法直接将Pt-Ni合金沉积到碳载体上,并利用物化表征与密度泛函理论(DFT)理论计算来探究共沉积机理.透射电镜表征结果表明,在不同的沉积电位下均可得到分散均匀、粒径适当的催化剂;且随着电位值降低,催化剂颗粒分散得更均匀,颗粒粒径不断减小.元素分布和晶面结果表明,铂镍元素均匀分布于颗粒中.所有样品均表现出优异的ORR性能,最高的面积比活性达到商业催化剂的6.85倍.将材料表征、电化学表征与DFT计算结合,建立起了铂镍合金生长过程的模型,并发现了有机体系中独特的成核-生长机理.将体系中的DMF换成超纯水,用同样的方法进行沉积,得到的催化剂颗粒团聚严重,说明DMF的使用能够避免颗粒团聚.在单独铂的体系中沉积发现,负载量极小,表明体系中镍前驱体的添加对于催化剂的沉积过程起到重要作用.电化学表征结果表明,在所选用的DMF有机体系中,镍的还原电位与铂的十分接近,但还原动力学更慢,趋向于先形成吸附原子后快速还原.由此可以推测,在二者合金的形成过程中,镍在碳载体表面的缓慢还原而形成的吸附原子能够成为铂还原的活性位点,从而降低了铂还原成核所需的能量,使得载体上的成核位点大大增加,这与DFT模拟结果一致.DFT建立了碳上镍的位点和铂的位点,分别在上面进行铂的还原,发现镍位点上比铂位点上更容易实现铂沉积.本文提出了铂镍共沉积的机理:在过电位(即还原能量)下,铂的还原动力学较镍稍快,于是铂先还原形成晶核,但难以达到生长的临界半径,于是单独铂体系中的沉积负载量很少.载体上还原的镍为铂还原提供了大量的活性位点,促进了铂还原,并与镍共沉积.Pt-Ni表面则进一步促进了铂的沉积和颗粒的生长.综上,本文提出了一种用于制备铂合金催化剂的有机电沉积体系,实现了单分散的碳载铂镍合金催化剂的一步制备.随后,本文将材料表征、电化学表征与DFT计算相结合,建立起了有机体系中铂镍合金成核-生长过程的机理模型. 相似文献
17.
Xiaogang Wang Weilin Xu Xiaochun Zhou Tianhong Lu Wei Xing Changpeng Liu Jianhui Liao 《Journal of Solid State Electrochemistry》2009,13(9):1449-1453
A prominent methanol-tolerant characteristic of the PtCeOx/C electrocatalyst was found during oxygen reduction reaction process. The carbon-supported platinum modified with cerium
oxide (PtCeOx/C) as cathode electrocatalyst for direct methanol fuel cells was prepared via a simple and effective route. The synthesized
electrocatalysts were characterized by X-ray diffraction and transmission electron microscopy. It was found that the cerium
oxide within PtCeOx/C present in an amorphous form on the carbon support surface and the PtCeOx/C possesses almost similar disordered morphological structure and slightly smaller particle size compared with the unmodified
Pt/C catalyst. 相似文献
18.
Chemically modified graphenes (CMGs) show great promise for various applications owing to the feasibility of their low-cost mass production and good solution processability. Recently, hetero-atom-doped CMGs have been suggested as good candidate materials for electrochemical catalysts in oxygen reduction reaction (ORR). In this study, we synthesized B, N co-doped graphene nano-platelets (BN-rG-O) using a two-step solution process with sequential reaction of graphene oxide with borane tetrahydrofuran and hydrazine monohydrate. In the ORR measured in a basic medium (0.1 M KOH), BN-rG-O exhibits an onset potential of 0.81 V (vs. reversible hydrogen electrode), follows near four electron pathway, and shows excellent stability against methanol poisoning and during durability tests. 相似文献
19.
20.
Palladium oxide nanoparticles supported on graphene oxide ‐ triethylsilane was found to be an effective reductive system for a broad range of reduction processes, including the reduction of various carbonyl compounds such as aromatic aldehydes to their corresponding alcohols or methyl arene compounds, aromatic ketones to their respective alcohols or saturated compounds, aromatic acyl chlorides to their reduced compounds. The desired products were obtained in good to excellent yields under mild conditions. The heterogeneous environmentally friendly catalyst can be easily separated from the reaction mixture through a simple filtration, facilitating purification of the prepared compounds. 相似文献