聚苯胺衍生Fe-N-C催化剂在碱性电解质中对氧还原反应的催化性能

经过热解聚苯胺、碳和FeCl₃的混合物制备的Fe-N-C材料在酸性电解质中对氧还原反应表现出高的催化活性;由于材料中不存在任何贵金属, 因而被认为是一类新型非贵金属氧还原催化剂. 然而这类催化剂在碱性电解质中催化氧还原反应的性能如何尚不清楚. 本文使用旋转圆盘电极技术考察了制备的两个Fe-N-C催化剂在KOH水溶液中催化氧还原反应性能, 发现这两个催化剂表现出比无金属的N掺杂碳材料更高的活性. 与商业Pt/C催化剂相比, 它们催化氧还原反应的起始电势和半波电势分别仅低60和40 mV左右, 计时电流测试表明, 它们比Pt/C催化剂显示出更好的稳定性. 此外, 在这两个Fe-N-C催化剂上的氧还原反应主要遵循四电子途径. 本工作显示, Fe-N-C材料有望用于碱性燃料电池氧还原反应催化剂.     

Electrocatalysis of oxygen reduction and small alcohol oxidation in alkaline media

We present here a critical review of several technologically important electrocatalytic systems operating in alkaline electrolytes. These include the oxygen reduction reaction (ORR) occurring on catalysts containing Pt, Pd, Ir, Ru, or Ag, the methanol oxidation reaction (MOR) occurring on Pt-containing catalysts, and the ethanol oxidation reaction (EOR) occurring on Ni-Co-Fe alloy catalysts. Each of these catalytic systems is relevant to alkaline fuel cell (AFC) technology, while the ORR systems are also relevant to chlor-alkali electrolysis and metal-air batteries. The use of alkaline media presents advantages both in electrocatalytic activity and in materials stability and corrosion. Therefore, prospects for the continued development of alkaline electrocatalytic systems, including alkaline fuel cells, seem very promising.     

Electrochemical behaviour of oxygen reduction on polymer carbon electrodes in alkaline media

The preparation of polymer carbon electrocatalysts by the controlled pyrolysis of polyfurfuryl alcohol polymer is described. The potentiostatic method was used to study the electrochemical behaviour of the oxygen reduction reaction on the prepared catalyst electrodes in potassium hydroxide electrolyte. A pure polymer carbon electrode and a cobalt chloride doped polymer carbon electrode were shown to be active in oxygen reduction, but the electrode containing cobalt chloride seemed the most active. The main reaction product at the pure polymer electrode is hydrogen peroxide, involving two electrons, whereas at a poly(CoCl₂) electrode the reduction process reaches partly its ultimate state, and involves at most three electrons.     

Electrocatalytic activity of carbon-supported metallophthalocyanine catalysts toward oxygen reduction reaction in alkaline solution

Carbon-supported metallophthalocyanine catalysts, composed of a transition central metal M (M = Co, Mn, Ni, Fe) in the phthalocyanine ring, were synthesized in this work. As cathodic reaction in a fuel cell, the oxygen reduction reaction (ORR) was investigated in alkaline medium with linear scanning voltammetry at the surface of these electrocatalysts deposited onto a rotating disk electrode (RDE). It was found that the number of electrons transferred depended on the nature of the metallic cation in the catalyst. Evidences provided with Koutecky-Levich approach showed that iron phthalocyanine (FePc) exhibited the better electrocatalytic ability toward the ORR with four electrons exchanged and low activation overpotential. Among these different as-prepared materials, MnPc and FePc led to a four-electron pathway, while CoPc and NiPc proceeded by a two-electron route. The latter reaction process was also determined with a rotating ring-disk electrode (RRDE), which allowed the determination of hydrogen peroxide formed as O₂ reduction intermediate in a small amount, i.e., less than 1.2 %.     

Direct synthesis of platinum group metal-free Fe-N-C catalyst for oxygen reduction reaction in alkaline media

A direct, template-free synthesis of a novel, active Fe-N-C oxygen reduction reaction catalyst by the pyrolysis of ethylenediaminetetraacetic acid ferric sodium salt is demonstrated. Detailed physical characterization of the catalyst is carried out by surface area measurement, X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy in addition to electrochemical analysis using Rotating Ring Disk Electrode measurements. We study the effects of synthesis temperature on graphitization, surface area and their concurrent effects on the catalytic performance of the final products.     

Effect of graphene surface functionalization on the oxygen reduction reaction in alkaline media

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Noble metal-free catalysts for oxygen reduction reaction

Developing noble metal-free catalysts with low cost, high performance and stability for oxygen reduction reaction(ORR) in fuel cells is of great interest to promote sustainable energy devices. In this review, we summarized noble metal-free catalysts for ORR,including non-noble metal-based and heteroatom-doped carbon nanomaterials. Mesoporous structure, homogeneous distribution of nanocrystals and synergistic effect of carbon base and nanocrystals/doped heteroatoms have great effect on the ORR property.The noble metal-free nanomaterials showed comparable catalytic property, better stability and methanol tolerance than commercial platinum(Pt)-based catalysts, showing great potential as substitutes for noble metal-based catalysts. In addition, the challenges and chances of developing noble metal-free ORR catalysts are also discussed.     

Iron phthalocyanine coated on single-walled carbon nanotubes composite for the oxygen reduction reaction in alkaline media

Iron (II) phthalocyanine coated on single-walled carbon nanotubes was synthesized as a non-noble electrocatalyst for the oxygen reduction reaction (ORR). The composite exhibited higher activity than the commercial Pt/C catalyst, and excellent anti-crossover effect for methanol oxidation in the ORR.     

Investigations of the catalytic properties of manganese oxides for the oxygen reduction reaction in alkaline media

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on different manganese oxides, dispersed on a carbon powder (MnO_x/C). The oxides were prepared by different methods, for producing MnO, Mn₃O₄ and MnO₂ as major phases dispersed on the Vulcan XC-72 carbon. The oxides were characterized by XRD (X-ray diffraction) and in situ XANES (X-ray absorption near edge structure). The electrochemical measurements were made using cyclic voltammetry and steady state polarization curves carried out in an ultra-thin layer rotating ring/disk electrode. The results have shown lower activity for the ORR on the MnO_x/C species compared to that on Pt/C, but higher activity compared to that of pure Vulcan carbon. Formation of involving 2e⁻ per O₂ molecule is the main path of the ORR in the studied MnO_x/C catalysts but, at low overpotentials and rotation rates the number of electrons is raised to 4 due to the occurrence of a disproportionation reaction. Large differences of electrocatalytic activity were seen for the different oxide species, and these were related to the presence of a Mn(IV) phase and the occurrence of a mediation processes involving the reduction of Mn(IV) to Mn(III), followed by the electron transfer of Mn(III) to oxygen.     

Platinum nanoparticles supported on nitrobenzene-functionalised graphene nanosheets as electrocatalysts for oxygen reduction reaction in alkaline media

A systematic study on the electrocatalytic properties of Pt nanoparticles supported on nitrobenzene-modified graphene (Pt-NB/G) as catalyst for oxygen reduction reaction (ORR) in alkaline solution was performed. Graphene nanosheets were spontaneously grafted with nitrophenyl groups using 4-nitrobenzenediazonium salt. The electrocatalytic activity towards the ORR and stability of the prepared catalysts in 0.1 M KOH solution have been studied and compared with that of the commercial Pt/C catalyst. The results obtained show that the NB-modified graphene nanosheets can be good Pt catalyst support with high stability and excellent electrocatalytic properties. The specific activity of Pt-NB/G for O₂ reduction was 0.184 mA cm⁻², which is very close to that obtained for commercial 20 wt% Pt/C catalyst (0.214 mA cm⁻²) at 0.9 V vs. RHE. The Pt-NB/G hybrid material promotes a four-electron reduction of oxygen and can be used as a promising cathode catalyst in alkaline fuel cells.     

负载铂的缺陷活性炭作为一种在碱性条件下具有优异氧还原反应性能的催化剂

燃料电池因其高的能量转化效率和无污染的特点而被认为是目前最有发展前景的高效清洁发电技术,然而燃料电池迟缓的阴极氧还原反应(ORR)极大地降低了其整体性能.目前,铂碳(Pt/C)仍然是催化ORR最有效的催化剂.但是,由于Pt的价格很高以及其稳定性差等缺点极大地限制了燃料电池的大规模化应用,因此设计与开发廉价高效稳定的ORR电催化剂对实现燃料电池的大规模商业化应用具有重要的意义.在过去的几十年中,研究发现Pt和其他的非贵金属形成合金,如Pt-Fe,Pt-Ni和Pt-Co等不仅可以降低Pt的用量,而且也可以使所得催化剂具有较高的ORR活性.此外,研究发现核-壳结构也可以提高铂基ORR催化剂的活性与稳定性.但是,这些催化剂的制备一般会使用毒性和危险性较高的有机化学试剂并且其制备过程繁杂,因此并不适用于大规模的实际生产.从这个角度来说,开发一种简易的方法来制备高效廉价的ORR催化剂显得尤为重要.之前的研究表明,Pt的载体对提高所得ORR催化剂来说非常关键.可以发现大部分载体都是经过改进的碳材料,如微孔/介孔材料,杂原子掺杂的石墨烯以及缺陷碳等.尤其是我们课题组最近提出的一种缺陷催化机理表明,在碳材料中特定类型的缺陷(如缺陷活性炭(D-AC)和缺陷石墨烯等)可以使纯的碳材料具有很高的电催化活性.尽管D-AC的ORR催化活性在不含金属的催化剂中位居前列,但是其催化性能仍然比商业化的Pt/C差.鉴于此,如果我们可以通过使用具有较高ORR催化活性的D-AC作为Pt的载体而降低Pt的用量,但并不牺牲其催化活性,这将是一个很具有前景的方法来解决昂贵ORR催化剂的问题,进而有可能实现燃料电池的大规模化生产.在本研究中,我们通过一种简易的液相浸渍法以D-AC作为Pt的载体而制备了一种高效的ORR催化剂.具体来说,我们通过调节合成过程中的还原温度实现了控制所得催化剂中Pt颗粒尺寸的目的,同时我们也对催化剂中的Pt含量对其催化性能的影响进行了探讨.研究表明,所得催化剂中Pt的颗粒尺寸以及其结晶性都可能影响其ORR催化活性.更为重要的是,所得样品D-AC@5.0%Pt中含有约5 wt%的Pt,然而其在碱性条件下的ORR催化活性已经超过了商业化的含有20 wt%Pt的Pt/C,例如其起始电位和半波电位都优于商业化的Pt/C,并且其稳定性也比商业化的Pt/C好.除此之外,D-AC@5.0%Pt在催化ORR的过程中表现出了一种一步四电子的反应路径,而且中间产物过氧化氢的产率很低.所得催化剂D-AC@5.0%Pt优异的ORR反应活性表明D-AC中的特殊缺陷以及负载的Pt纳米颗粒都对提高其催化活性具有很大的贡献,同时也说明选择合适的载体对提高电催化剂的活性至关重要.实验结果还表明,D-AC@5.0%Pt在酸性条件下的ORR催化活性也有一定的提高,虽然比商业化的Pt/C要差一些.更进一步减小Pt的颗粒尺寸到亚纳米甚至原子级别可能会明显地提高其在酸性电解液中的ORR催化活性.     

Electrolyte accessibility of non-precious-metal catalysts with different spherical particle sizes under alkaline conditions for oxygen reduction reaction

Fuel cells are one of the most competitive alternative energy sources because their theoretical efficiency is~15%higher than that of internal combustion engines (ICEs) and they are considered cleaner and safer.When fuel cells are used to replace ICEs in cars and energy conversion systems,the system efficiency increases;furthermore,the process becomes more environmentally-friendly because fuel cells produce electricity by using only hydrogen and oxygen,obtained by purifying atmospheric air by filtering out dust and pollutants.Hence,their final product is only water,instead of pollutants like carboFuel cells are one of the most competitive alternative energy sources because their theoretical efficiency is~15%higher than that of internal combustion engines (ICEs) and they are considered cleaner and safer.When fuel cells are used to replace ICEs in cars and energy conversion systems,the system efficiency increases;furthermore,the process becomes more environmentally-friendly because fuel cells produce electricity by using only hydrogen and oxygen,obtained by purifying atmospheric air by filtering out dust and pollutants.Hence,their final product is only water,instead of pollutants like carbon dioxide.n dioxide.     

Electrocatalysis of oxygen reduction on multi-walled carbon nanotube supported copper and manganese phthalocyanines in alkaline media

Manganese phthalocyanine (MnPc) and copper phthalocyanine (CuPc)-modified electrodes were prepared using multi-walled carbon nanotubes (MWCNTs) as a support material. The catalyst materials were heat treated at four different temperatures to investigate the effect of pyrolysis on the oxygen reduction reaction (ORR) activity of these electrocatalysts. The MWCNT to metal phthalocyanine ratio was varied. Scanning electron microscopy (SEM) was employed to visualise the surface morphology of the electrodes and the x-ray photoelectron spectroscopic (XPS) study was carried out to analyse the surface composition of the most active catalyst materials. The ORR was studied in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. Glassy carbon (GC) electrodes were modified with carbon nanotube-supported metal phthalocyanine catalysts using Tokuyama AS-4 ionomer. The RDE results revealed that the highest electrocatalytic activity for ORR was achieved upon heat treatment at 800 °C. CuPc-derived catalyst demonstrated lower catalytic activity as compared to the MnPc-derived counterpart, which is in good agreement with previous literature, whereas the activity of MnPc-based catalyst was higher than that reported earlier.     

Fabrication of graphene-supported tetraferrocenylporphyrin electrocatalyst for oxygen reduction and its unique electrochemical response in both alkaline and acid media

A novel high-performance non-noble metal electrocatalyst for the oxygen reduction reaction (ORR) was fabricated by anchoring cobalt tetraferrocenylporphyrin (CoFcP) onto poly(sodium-p-styrenesulfonate) modified graphene (PSS-Gr) through solvothermally assisted π–π assembling method. The morphology of the assembled composite was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The interactions between CoFcP moieties and graphene sheets were confirmed by UV–Vis absorption spectroscopy and X-ray photoelectron spectroscopy. The electrocatalytic properties of the CoFcP/PSS-Gr catalyst towards the oxygen reduction reaction were assessed using rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) measurements in both alkaline and acidic media. In addition, cyclic voltammetry and chronoamperometric measurements were utilized to evaluate the catalytic activity and stability of the CoFcP/PSS-Gr composite in alkaline solution. The results showed that CoFcP supported on graphene exhibited an outstanding electrocatalytic performance towards the ORR comparable with commercial Pt/C catalyst in alkaline media, such as high onset potential (0.889 V vs. reversible hydrogen electrode, RHE), half wave potential (0.789 V vs. RHE), better tolerance to methanol, excellent stability (84.1 %, retention after 10000 s), and efficient four-electron pathway. Moreover, the proposed hybrid presented excellent catalytic activity in terms of onset potential (0.72 V vs. RHE) and high-electron transfer number compared with Pt/C in acidic media.     

Oxygen reduction on electrodeposited silver catalysts in alkaline solution

In this study, silver was electrochemically deposited onto glassy carbon (GC) substrate using constant potential regime and tested for oxygen reduction reaction (ORR) in alkaline media. The surface morphology of Ag/GC electrodes was studied by scanning electron microscopy (SEM). It was established that after 10 s of deposition, a number of Ag nanoparticles with the size of 15 nm are produced that grow to about 45 nm after 300 s of electrodeposition. The ORR studies were conducted in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. The Tafel slope at low current densities for electrodeposited silver is in the range from ?70 to ?80 mV. The RDE measurements showed that the electron transfer number (n) is 3.5 for smaller amounts of electrodeposited Ag, and it increases with increasing the loading of Ag on the GC surface. These n values suggest that the electroreduction of oxygen on Ag/GC electrodes proceeds mainly to water.     

Silver supported on Co3O4 modified carbon as electrocatalyst for oxygen reduction reaction in alkaline media

The electroreduction of oxygen was firstly studied on Ag/Co₃O₄–C in alkaline media prepared by depositing Ag on Co₃O₄ modified carbon (Co₃O₄–C). The Ag/Co₃O₄–C composite not only displayed relatively large electrochemical active surface area (ESA), high catalytic activity towards oxygen reduction reaction (ORR), but also exhibited good methanol tolerance and stability in alkaline media. Ag/Co₃O₄–C could be a valuable catalyst for ORR and be applied to alkaline fuel cells and metal–air batteries.     

Transition metal-nitrogen-carbon catalysts for oxygen reduction reaction in neutral electrolyte

Platinum group metal-free (PGM-free) catalysts based on M-N-C types of materials with M as Mn, Fe, Co and Ni and aminoantipyrine (AAPyr) as N-C precursors were synthesized using sacrificial support method. Catalysts kinetics of oxygen reduction reaction (ORR) was studied using rotating ring disk electrode (RRDE) in neutral pH. Results showed that performances were distributed among the catalysts as: Fe-AAPyr > Co-AAPyr > Mn-AAPyr > Ni-AAPyr. Fe-AAPyr had the highest onset potential and half-wave potential. All the materials showed similar limiting current. Fe-AAPyr had an electron transfer involving 4e⁻ with peroxide formed lower than 5%. Considering H₂O₂ produced, it seems that Co-AAPyr, Mn-AAPyr and Ni-AAPyr follow a 2 × 2e⁻ mechanism with peroxide formed during the intermediate step. Durability test was done on Fe-AAPyr for 10,000 cycles. Decrease of activity was observed only after 10,000 cycles.     

Co3O4/聚吡咯/石墨烯碱性溶液中电化学还原氧

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.     

Electrochemical formation and reduction of silver oxides in alkaline media

The anodic oxidation of silver electrodes in NaOH solution and the reduction of the silver oxides formed were studied by potential step chronoamperometry. Oxidation of Ag to Ag₂O is a diffusion-controlled reaction, the diffusion control being established in the solid phase. Oxidation of Ag₂O to AgO proceeds via a nucleation and growth-controlled process. The amount of AgO decreased with increasing step height. The current—time curves for this reaction have been analysed with the Kolmogoroff—Avrami equation. Reduction of AgO to Ag₂O occurs initially on the outside of the electrode, and the rate of the reaction is limited by diffusion of ions across the thickening layer of Ag₂O. Reduction of Ag₂O to Ag proceeds via a nucleation and growth reaction.