Au催化剂对于碱性电解质中氧气电化学还原反应的纳米尺寸效应

使用旋转电极技术考察了一系列碳载金纳米颗粒(颗粒平均尺寸处在3~14 nm)在碱性电解质(0.5 mol/L KOH)中对氧还原反应的催化行为.随着金纳米颗粒尺寸由14 nm下降至3 nm,其对氧还原反应的本征活性和质量比活性均呈现持续走高趋势; 但金颗粒的纳米尺寸对氧还原反应的机理及分子氧还原过程中的电子转移数目并无显著影响.使用高分辨透射电镜技术表征了金纳米颗粒的形貌,通过对金颗粒表面不同位置原子的比例进行估算,发现金颗粒表面高能原子所占比例与金对氧还原反应的本征活性密切相关,表明高能表面原子决定着金催化剂对氧还原反应的本征活性.此外,还将金纳米颗粒对氧还原反应的本征催化活性与其表面电子结构进行了关联.     

Pt monolayer electrocatalysts for O2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle’s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O₂ reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O₂ reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate. Dedicated to Professor Oleg Petrii on the occasion of his 70th birthday on August 24, 2007.     

Electrocatalytic activity of non-precious metal catalyst Co-N/C toward oxygen reduction reaction

<正>Metallic cobalt was deposited on acetylene black to synthesize a composite Co/C by chemical reduction method.A platinumfree electrocatalyst Co-N/C(800) for oxygen reduction reaction(ORR) was synthesized by mixing the composite Co/C with urea and heat-treating at 800℃.The results from linear sweep voltammograms indicated that the Co-N/C(800) is active to ORR.Theβ-Co and cobalt oxides are not the active site of the catalyst Co-N/C.However,the existence of cobalt facilitated the modification of nitrogen to carbon black and led to the formation of active site of catalyst Co-N/C(800).     

Catalytic dechlorination of aromatic chlorides with Pd/C catalyst in alkaline 2-propanol: activity enhancement by the addition of methanol

Summary p- and o-Chloroanisole were catalytically dechlorinated with Pd/C at 30°C in a solution of NaOH in mixtures of 2-propanol and methanol. The dechlorination rate of p-chloroanisole in the mixture containing 1% methanol was 12 times as high as that in 2-propanol alone. The dechlorination rate of o-chloroanisole was also enhanced by the addition of a small amount of methanol.     

高活性和高稳定性的核壳结构PtPx@Pt/C催化氧还原

在质子交换膜燃料电池中,金属铂是最高效的阴极氧还原催化剂之一,但是铂昂贵的价格严重阻碍了其在燃料电池领域中的大规模商业化应用.通过铂与3d过渡金属(Fe、Co和Ni)合金化可以有效提高催化剂的氧还原活性,然而在实际的高腐蚀性、高电压和高温的燃料电池运行环境中,铂合金纳米粒子易发生溶解、迁移和团聚,从而导致催化剂耐久性差.同时过渡金属离子的溶出会影响质子交换膜的质子传导,并且一些过渡金属离子会催化芬顿反应,产生高腐蚀性?OH自由基,加快Nafion和催化剂的劣化.与过渡金属掺杂相比,非金属掺杂具有明显优势:一方面,非金属溶出产生的阴离子不会取代Nafion中的质子,也不会催化芬顿反应;另一方面,与3d过渡金属相比,非金属具有更高的电负性,其掺杂很容易调节Pt的电子结构.因此,本文通过非金属磷掺杂合成具有优异稳定性的核壳结构PtPx@Pt/C氧还原催化剂.通过热处理磷化商业碳载铂形成磷化铂(PtP2),经由酸洗处理产生富铂壳层,即PtPx@Pt/C.X射线粉末多晶衍射结果证明了PtP2相的存在,并且进一步通过电子能量损失谱对纳米粒子进行微区面扫描分析以及X射线光电子能谱分析证实了富铂壳层的存在,壳层厚度约1 nm.得益于核壳结构及磷掺杂引起的电子结构效应,PtP1.4@Pt/C催化剂在0.90 V(RHE)时的面积活性(0.62 mA cm–2)与质量活性(0.31 mAμgPt–1)分别是商业Pt/C的2.8倍和2.1倍.更重要的是,在加速耐久性测试中,PtP1.4@Pt/C催化剂在30000圈电位循环后质量活性仅衰减6％,在90000圈电位循环后仅衰减25％;而商业Pt/C催化剂在30000圈电位循环后就衰减46％.PtP1.4@Pt/C催化剂高活性与高稳定性主要归功于核壳结构、磷掺杂引起的电子结构效应以及磷掺杂增加了碳载体对催化剂粒子的锚定作用进而阻止了其迁移团聚.综上所述,本文为设计同时具有优异活性与稳定性非金属掺杂Pt基氧还原催化剂提供新的思路.     

SO_2-tolerant Pt-MoO_3/C catalyst for oxygen reduction reaction

A Pt-MoO_3/C catalyst,aimed to eliminate the harmful effect of sulfur dioxide(SCb) on the performance of Pt nanoparticles(NPs) for catalysis of oxygen reduction reaction(ORR) in proton exchange membrane fuel cells(PEMFC),is developed and characterized by TEM,XRD and XPS.The results reveal that Pt-MoO_3/C catalyst exhibits not only a higher catalytic activity,but also a better SO_2 poisoning resistance and a better recovery performance than the commercial Pt/C catalyst does.     

SO2-tolerant Pt-MoO3/C catalyst for oxygen reduction reaction

A Pt-MoO3/C catalyst,aimed to eliminate the harmful effect of sulfur dioxide（SCb） on the performance of Pt nanoparticles（NPs） for catalysis of oxygen reduction reaction（ORR） in proton exchange membrane fuel cells（PEMFC）,is developed and characterized by TEM,XRD and XPS.The results reveal that Pt-MoO3/C catalyst exhibits not only a higher catalytic activity,but also a better SO2 poisoning resistance and a better recovery performance than the commercial Pt/C catalyst does.     

Cathodic reduction of oxygen on PdCo/C catalyst synthesized based on commercial Pd/C catalyst

The data on the cathodic PdCo/C catalyst prepared by high-temperature synthesis from 20 wt % Pd/C (E-TEK) are shown. According to XRD data, the catalyst represents an alloy with the preferential composition of Pd₂Co. The kinetics and mechanism of oxygen reduction on the PdCo/C catalyst are studied by the methods of rotating disk electrode, rotating ring-disk electrode, and electrochemical impedance. It is shown that oxygen is reduced preferentially to water (k ₁) but in the potential range more negative than 0.6 V, the ratio of constants k ₁/k ₂ decreases, which suggests that the contribution of the reaction that proceeds through the formation of H₂O₂ (k ₂) increases. The activity of PdCo/C catalyst under model conditions in 0.5 M H₂SO₄ was assessed to be 15 mA/mg_cat at a potential of 0.7 V.     

Biomass derived Fe-N/C catalyst for efficiently catalyzing oxygen reduction reaction in both alkaline and neutral pH conditions

Fe-N/C is a promising oxygen reduction reaction (ORR) catalyst to substitute the current widely used precious metal platinum. Cost-effectively fabricating the Fe-N/C material with high catalytic activity and getting in-depth insight into the responsible catalytic site are of great significance. In this work, we proposed to use biomass, tea leaves waste, as the precursor to prepare ORR catalyst. By adding 5% FeCl₃ (wt%) into tea precursor, the pyrolysis product (i.e., 5%Fe-N/C) exhibited an excellent four-electron ORR activity, whose onset potential was only 10 mV lower than that of commercial Pt/C. The limiting current density of 5%Fe-N/C (5.75 mA/cm²) was even higher than Pt/C (5.44 mA/cm²). Compared with other biomass or metal organic frameworks derived catalysts, 5%Fe-N/C showed similar ORR activity. Also, both the methanol tolerance and material stability performances of as-prepared 5%Fe-N/C catalyst were superior to that of Pt/C. X-ray adsorption fine structure characterization revealed that the FeN₄O₂ might be the possible catalytic site. An appropriate amount of iron chloride addition not only facilitated catalytic site formation, but also enhanced material conductivity and reaction kinetics. The results of this work may be useful for the Fe based transition metal ORR catalyst design and application.     

Rational catalyst design and interface engineering for electrochemical CO2 reduction to high-valued alcohols

Electrochemical CO₂ reduction(eCO₂RR) is an emerging strategy to address the global carbon balance issues and fulfill the carbon-neutral goal through converting CO₂ to value-added chemicals/fuels driven by renewable energy sources. The production of highly reduced carbon compounds beyond CO and formate, especially oxygenate alcohol products with high energy densities and large global market capacities, is particularly desirable for practical applications. However...     

Graphyne-oxide supported Pd catalyst with ten times higher nitrobenzenes reduction activity than Pd/C

Research on Chemical Intermediates - Upon oxidation, a graphyne-like porous carbon-rich network (GYLPC), which is a two-dimensional carbon material consisting of sp- and sp2-hybridized carbon atoms...     

Mn-N-C催化剂的制备及其在碱性介质中对氧还原反应的电催化性能

选用壳聚糖(CS)为原料制备了壳聚糖水杨醛席夫碱锰配合物(Mn-CS-sal)。将Mn-CS-sal配合物负载于石墨碳上得到碳载配合物(Mn-CS-sal/C),后经高温热处理得到Mn-N-C目标催化剂(Mn-N-C-t,t=200、400、600、800、1 000℃)。采用FT-IR、XRD、XPS和电化学等方法对催化剂的组成和结构进行了表征,对其在氧还原反应中的电催化性能进行了研究。结果表明,所得到的Mn-N-C催化剂对氧还原反应(ORR)具有很好的催化作用,但以600℃热处理制备的催化剂其活性最好。催化剂中Mn-N-C结构是催化ORR的活性位。采用循环伏安法获得了Mn-N-C-t催化ORR的动力学参数,即总的转移电子数n和电子传递系数αnα;具有最佳活性的Mn-N-C-600催化剂的总转移电子数为3.63,说明在此条件下,Mn-N-C-600催化ORR主要以4e转移途径为主,由此提出了可能的氧还原反应的机理。     

Synthesis of carbon-supported Pd/SnO_2 catalyst for highly selective hydrogenation of 2,4-difluoronitrobenzene

Halogenated anilines have a wide range of applications in the production of pharmaceuticals and agrochemical substances, and thus it is of great importance to develop highly active and selective catalysts for the hydrogenation of halogenated nitrobenzenes. We approach this challenge by probing noble metal/non-noble metal oxide nanoparticles(NPs) catalysts. Carbon-supported Pd/SnO2catalysts were synthesized by the chemical reduction method, and their catalytic activity was evaluated by the hydrogenation reaction of 2,4-difluoronitrobenzene(DFNB) to the corresponding 2,4-difluoroaniline(DFAN), showing a remarkable synergistic effect of the Pd and SnO2 NPs. The as-prepared Pd/SnO2/C catalysts were characterized using TEM, XRD, H2 TPD and XPS techniques. Modifications to the electronic structure of the Pd atoms through the use of SnO2 led to the suppression of the hydrogenolysis of the C–F bond and the acceleration of nitrosobenzene(DFNSB) conversion and consequently, resulted in the inhibition of the formation of reactive by-products and may be responsible for the enhancements observed in selectivity.     

Toward highly active electrochemical CO2 reduction to C2H4 by copper hydroxyphosphate

Journal of Solid State Electrochemistry - Electrocatalytic carbon dioxide reduction reaction (CO2RR) is a promising method to deal with the greenhouse effect and the energy crisis. In a...     

Using a Fe-doping MOFs strategy to effectively improve the electrochemical activity of N-doped C materials for oxygen reduction reaction in alkaline medium

Journal of Solid State Electrochemistry - For the rational design of heteroatom-doping carbon catalysts toward the oxygen reduction reaction (ORR), various structure-wise and porous...     

The mechanism of asymmetric reduction catalyzed by a C2 symmetric bis-amino alcohol catalyst

By means of¹H,¹³C,¹¹B NMR, polar transfer DEPT135, DEPT90 and 2D NMR experiments, IR, etc, the structure of the diaminodihydroxyl ligand and its derivatives used in the asym-metric reduction of prochiral ketones were detected. The catalysts derived from the ligand and borane formedin situ were also studied and the structure transformations in solution were monitored. The structure of the catalyst was proved to be a new type of dual-centered catalyst — bisoxazaborolidine.     

直接甲醇燃料电池阳极催化剂PtRu/MWCNTs的水热合成及其电催化行为

采用水热法合成了PtRu/MWCNTs阳极催化剂,并以循环伏安、线性扫描、计时电流和交流阻抗等电化学测试研究了其对甲醇的电催化氧化,结果表明,水热合成的PtRu/MWCNTs较之同样条件下合成的PtRu/Vu lcan XC-72有更好的对甲醇氧化的催化活性和更强的抗毒化能力。     

Catalytic activity and stability toward methanol oxidation of PtRu/CNTs prepared by adsorption in aqueous solution and reduction in ethylene glycol

In this paper, we reported an improved process for the preparation of PtRu/CNTs, which involves the adsorption of Pt and Ru ions on CNTs in aqueous solution and the reduction of the adsorbed Pt and Ru ions on CNTs in ethylene glycol. The surface morphology, structure, and compositions of the prepared catalyst were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy-dispersive spectrometer. TEM observation showed that the particles size of the prepared PtRu alloy was in the range of 2–5 nm, XRD patterns confirmed a face-centered cubic crystal structure. The activity and stability of the prepared catalyst toward methanol oxidation were studied in 0.5 M H₂SO₄ + 1 M CH₃OH solution by cyclic voltammetry, chronoamperometry, and chronopotentiometry. The electrochemical results showed that the prepared catalyst exhibited higher activity and stability toward methanol oxidation than commercial PtRu/C with the same loading amount of Pt and Ru.     

甲醇电氧化催化剂Pt/CeO2-CNTs与PtRu/C的比较研究

为认识合成催化剂Pt/CeO2-CNTs与商用催化剂PtRu/C(E-TEK)的催化性能和结构特点, 用CO溶出法和恒电位氧化法比较了这两种催化剂对CO的电氧化活性, 运用循环伏安法和恒电位氧化法比较了这两种催化剂对甲醇的电氧化活性. CO电氧化实验结果表明, PtRu/C上CO的电氧化活性明显优于Pt/CeO2-CNTs; 甲醇电氧化实验结果却表明, Pt/CeO2-CNTs与PtRu/C上甲醇电氧化表观活性相当. 为从结构特点上解释PtRu/C上CO电氧化和甲醇电氧化活性的不一致, 对PtRu/C进行了循环伏安扫描和CO溶出实验. 结果表明, PtRu/C的甲醇电氧化电流之所以没有预期高, 一是由于Pt比表面积不够大, 同时Pt-Ru之间协同作用有待提高. 本研究结果表明, 尽管Ru对Pt上CO电氧化有显著助催化作用, 但要充分发挥其对Pt上甲醇电氧化的助催化作用, 需同时提高Pt表面积和Pt-Ru接触界面. 该结论对设计甲醇电氧化催化剂具有普适意义.