A microbial fuel cell using manganese oxide oxygen reduction catalysts

Microbial fuel cells (MFCs) are a potential method for enhanced water and waste treatment, which offer the additional benefit of energy generation. Manganese oxide was prepared by a simple chemical oxidation using potassium permanganate. Carbon-supported manganese oxide nanoparticles were successfully characterised as cathode materials for MFCs. The manganese oxide particles when used in a two-chamber MFC, using inoculum from an anaerobically digested sewage sludge, were found to exhibit similar oxygen reduction performance to that in separate electrochemical tests. MFC tests were conducted in a simple two chamber cell using aqueous air-saturated catholytes separated from the anode chamber by a Nafion membrane. MFC peak power densities were ca. 161 mW m^?2 for MnO _x /C compared to 193 mW m^?2 for a benchmark Pt/C, in neutral solution at room temperature. The catalyst materials demonstrated good stability in the 7.0–10.0 pH range. Theoretical (IR free) peak power densities were 937 mW m^?2 for MnO _x /C compared with 1037 mW m^?2 for Pt/C in the same experimental conditions: showing the MFCs performances can easily be improved by using more favourable conditions (more conductive electrolyte, improved cathode catalyst etc.). Our studies indicated that the use of our low cost MnO _x /C catalysts is of potential interest for the future application of MFC systems.     

Non-platinum electrocatalysts: Manganese oxide nanoparticle-cobaltporphyrin binary catalysts for oxygen reduction

This study is concerned with the development of non-platinum electrocatalysts for the efficient 4-electron reduction of molecular oxygen to water in acidic media. A binary catalyst composed of electrodeposited manganese oxide nanoparticles (nano-MnO _x ) and cobalt porphyrin macro complex (CoP) has been proposed in. The modification of glassy carbon (GC) electrode with CoP alone resulted in a significant positive shift of the oxygen reduction reaction (ORR) compared to the unmodified GC electrode while maintining a 2-electron reduction. That is a positive shift of the onset potential of the ORR of ca. 450 mV was achieved at the former electrode. The modification of the GC electrode with nano-MnO _x alone did not affect the ORR peak potential, but caused a remarkable increase in the reduction peak current due to the catalytic disproportionation of the electrogenerated hydrogen peroxide into water and oxygen. The modification of a GC electrode with CoP and nano-MnO _x (utilizing the advantages of the individual catalysts) resulted in the occurrence of the ORR at a significantly positive potential with almost double peak current compared to the unmodified GC electrode, suggesting a promising procedure for developing electrocatalysts for oxygen reduction in replacement of costly Pt. XPS and SEM techniques were employed to probe the structural and morphological characterization of the proposed binary catalysts.     

Electrochemical reduction of cerium oxide into metal

The Fray Farthing and Chen (FFC) and Ono and Suzuki (OS) processes were developed for the reduction of titanium oxide to titanium metal by electrolysis in high temperature molten alkali chloride salts. The possible transposition to CeO₂ reduction is considered in this study. Present work clarifies, by electro-analytical techniques, the reduction pathway leading to the metal. The reduction of CeO₂ into metal was feasible via an indirect mechanism. Electrolyses on 10 g of CeO₂ were carried out to evaluate the electrochemical process efficiency. Ca metal is electrodeposited at the cathode from CaCl₂–KCl solvent and reacts chemically with ceria to form not only metallic cerium, but also cerium oxychloride.     

氮掺杂非贵金属氧还原催化剂研究进展

综述了近几年来用于直接甲醇燃料电池阴极氧还原反应的含氮碳催化材料发展状况,包括催化剂制备过程中热处理条件、金属的种类及负载量、碳载体、新型合成方法等影响催化剂氧还原活性的几个因素。针对当前研究工作的局限展开了评论,指出催化机理和优化制备过程是氮掺杂碳材料负载非贵金属氧还原催化剂深入研究的重点和主要方向。     

Metal-free,carbon-based catalysts for oxygen reduction reactions

Developing metal-free, carbon-based catalysts to replace platinum-based catalysts for oxygen reduction reactions (ORRs) is an emerging area of research. In recent years, different carbon structures including carbon doped with IIIA-VIIA heteroatoms (C−M site-based, where M represents the doped heteroatom) and polynitrogen (PN) compounds encapsulated in carbon nanotubes (CNTs) (N−N site-based) have been synthesized. Compared to metallic catalysts, these materials are highly active, stable, inexpensive, and environmentally friendly. This review discusses the development of these materials, their ORR performances and the mechanisms for how the incorporation of heteroatoms enhances the ORR activity. Strategies for tailoring the structures of the carbon substrates to improve ORR performance are also discussed. Future studies in this area will need to include optimizing synthetic strategies to control the type, amount and distribution of the incorporated heteroatoms, as well as better understanding the ORR mechanisms in these catalysts.     

Electrochemical reduction of graphene oxide in organic solvents

Graphene oxide (GO) cast on conductive substrates was electrochemically reduced in some organic solvents. The amount of electricity required for the almost complete reduction of GO was 2.0 C for 1 mg GO, corresponding to attaching of a one-electron reducible species to each benzene ring in graphene. The electrochemically reduced GO film gave an electrical conductivity of about 3 S cm⁻¹ and exhibited a relatively high specific capacitance of 147.2 F g⁻¹ in propylene carbonate. The electrochemical reduction of GO was feasible on Al foils as well.     

α-硝基萘在介孔结构碳化钨催化剂上的电化学还原行为

以喷雾干燥处理的偏钨酸铵为前驱体，分别采用CH₄/H₂和CO/CO₂为还原碳化气氛，利用固定床气固反应法制备了两种具有介孔结构的碳化钨（WC）粉体.以WC粉末作为电催化材料制成了碳化钨粉末微电极（WC-PME），并采用循环伏安和线性扫描等方法研究了酸性溶液中两种介孔结构WC对α-硝基萘（NP）电还原过程中的电催化行为.结果表明，以CH₄/H₂为还原碳化气氛所制备的WC粉末，其制成的粉末微电极对NP具有更良好的电催化活性，这主要与该WC粉末的结构形貌及其制备后的处理工艺有关，同时该WC-PME具有良好的化学稳定性.     

Production of novel FeOOH/reduced graphene oxide hybrids and their performance as oxygen reduction reaction catalysts

Fe-based hybrid systems have been suggested as promising candidates for oxygen reduction reaction (ORR) catalysts owing to their good catalytic performances and feasibilities for mass production at low cost. In this work, we develop means of producing novel hybrids containing FeOOH particles well-dispersed on graphene-based materials using a one-pot solution process. The hybrid materials show good electrochemical catalytic activity for ORR, such as, an on-set potential of 0.76 V (vs. the reversible hydrogen electrode), a near four electron pathway, and excellent stability against methanol poisoning during durability test. This is the first report of the use of FeOOH/reduced graphene oxide hybrid materials as ORR catalysts.     

Selective reduction of nitric oxide by methanol and dimethyl ether over promoted alumina catalysts in excess oxygen

Selective catalytic reduction (SCR) activity for NO conversion to N₂ over γ-alumina, vanadia/alumina and molybdena/alumina catalysts has been investigated with methanol (MeOH) and dimethyl ether (DME) as reductants under lean conditions. Molybdena/alumina catalysts showed high efficiency for NO reduction with either reductant, especially at low temperature, which may involve surface formyl produced by oxidative dehydrogenation. Sulphated γ-alumina remains active for NO reduction with MeOH, while sulphated 5 wt.% MoO₃/Al₂O₃ remains active with both MeOH and DME over a broad temperature range.     

Effects of methane and oxygen on decomposition of nitrous oxide over metal oxide catalysts

Catalytic activities of various metal oxides for decomposition of nitrous oxide were compared in the presence and absence of methane and oxygen, and the general rule in the effects of the coexisting gases was discussed. The reaction rates of nitrous oxide were well correlated to the heat of formation of metal oxide, i.e., a V-shaped relationship with a minimum at −ΔH_f⁰ around 450 kJ (O mol)⁻¹ was observed in N₂O decomposition in an inert gas. In the case of metal oxides having the heat of formation lower than 450 kJ (O mol)⁻¹, CuO, Co₃O₄, NiO, Fe₂O₃, SnO₂, In₂O₃, Cr₂O₃, the activities were strongly affected by the presence of methane and oxygen. On the other hand, the activities of TiO₂, Al₂O₃, La₂O₃, MgO and CaO were almost independent. The reaction rate of nitrous oxide was significantly enhanced by methane. The promotion effect of methane was attributed to the reduction of nitrous oxide with methane: 4N₂O+CH₄→2N₂+CO₂+2H₂O. The activity was suppressed in the presence of oxygen on the metal oxides having lower heat of formation. On the basis of Langmuir–Hinshelwood mechanism, the effect of oxygen on nitrous oxide decomposition was rationalized with the strength of metal–oxygen bond.     

High-loading Pt-alloy catalysts for boosted oxygen reduction reaction performance

To improve performance of membrane electrode assembly (MEA) at large current density region, efficient mass transfer at the cathode is desired, for which a feasible strategy is to lower catalyst layer thickness by constructing high loading Pt-alloy catalysts on carbon. But the high loading may induce unwanted particle aggregation. In this work, H-PtNi/C with 33% (mass) Pt loading on carbon and monodisperse distribution of 3.55?nm PtNi nanoparticles, was prepared by a bimodal-pore route. In electrocatalytic oxygen reduction reaction (ORR), H-PtNi/C displays an activity inferior to the low Pt loading catalyst L-PtNi/C (13.3% (mass)) in the half-cell. While in H₂-O₂ MEA, H-PtNi/C delivers the peak power density of 1.51?W·cm^?2 and the mass transfer limiting current density of 4.4?A·cm^?2, being 21% and 16% higher than those of L-PtNi/C (1.25?W·cm^?2, 3.8?A·cm^?2) respectively, which can be ascribed to enhanced mass transfer brought by the thinner catalyst layer in the former. In addition, the same method can be used to prepare PtFe alloy catalyst with a high-Pt loading of 36% (mass). This work may lead to a range of catalyst materials for the large current density applications, such as fuel cell vehicles.     

Electrochemical reduction of oxygen on thin-film Pt electrodes in acid solutions

The electrochemical reduction of oxygen on thin-film platinum electrodes in 0.1 M HClO₄ and 0.05 M H₂SO₄ solutions has been investigated using the rotating disk electrode (RDE) method. Thin films of Pt (0.25-20 nm thick) were prepared by vacuum evaporation onto glassy carbon substrate. The surface morphology of Pt films was examined by transmission electron microscopy (TEM). The specific activity of O₂ reduction was higher in HClO₄ and decreased with decreasing film thickness. In H₂SO₄, the specific activity was lower and appeared to be independent of the Pt loading. The values of Tafel slopes close to −120 mV dec⁻¹ in high current density range and −60 mV dec⁻¹ in low current density range were obtained for all electrodes in both solutions, indicating that the mechanism of O₂ reduction is the same for thin-film electrodes as for bulk Pt. The number of electrons transferred per O₂ molecule was close to four for all thin Pt films studied.     

Methanol-resistant cathodic oxygen reduction catalysts for methanol fuel cells

Efforts were made to simplify the structure of Ru-based catalysts, and to tailor industrially practicable methanol insensitive oxygen reduction catalysts both by thermolysis of Ru-carbonyls in organic solvents and by modified preparation techniques of Ru colloids. Selective catalysis was found to be essentially independent of the chalcogene (Se) used which, however, is a crucial factor for facilitating efficient electron transfer. All preparations contained Ru-metal particles of nm size, the surfaces of which were modified by carbonyl and carbido-carbonyl complexes or carbon compounds. The role of carbon as ligand to Ru clusters stabilizing the Ru interface against oxidation and in promoting catalytic electron exchange via nonbonding Ru d-states is theoretically analysed in a model calculation. An analogy is drawn to a biological Fe – only hydrogenase centre in order to discuss projected key experiments for optimizing reduction catalysis: the stabilization of small, inherently unstable catalytic metal clusters by CO or CN and their linking via electron bridges such as S and Se to electron reservoirs (metal colloids).     

金属氧化物催化CO还原NO的研究进展

一氧化碳（CO）广泛存在于烧结/球团/焦化烟气或汽车尾气中,应用CO-选择性催化还原（SCR）技术同时脱除烟气中CO和NO是烟气治理的理想方案之一。目前,在NO-CO反应研究中较多的是贵金属催化剂,但由于其价格昂贵、高温失活、易中毒等问题难以在工业中实现应用。本文将近几年来金属氧化物催化CO还原NO的研究成果进行了系统的梳理与总结,重点介绍Fe基、Ce基、Co基、Cu基这4种金属氧化物催化剂的研究进展,分析催化剂的制备方法、掺杂助剂种类和比例、NO-CO反应条件等因素与催化活性之间的关系,总结催化剂抗水抗硫性能及可能的CO-SCR反应机理,并探讨O₂存在的条件下对催化剂活性的影响,为提高金属氧化物催化剂抗氧性研究提供理论参考。     

Electrocatalysis of oxygen reduction on carbon-supported PtCo catalysts prepared by water-in-oil micro-emulsion

Synthesis of carbon-supported PtCo/C using micro-emulsion method including simultaneous procedure and sequential procedures in both acid and alkaline media was reported. UV-vis and electron microscopy were used to characterize the formation, surface morphology and distribution of PtCo nanoparticles. Crystallite structure of catalysts was analyzed from XRD patterns. Catalytic properties of PtCo/C catalysts synthesized were compared with commercial Pt/C using RDE based on both mass activity (MA) and specific activity (SA). PtCo/C catalysts prepared in both acidic and basic conditions showed better performance than commercial Pt/C catalyst. High-temperature heat treatment was found useful only to PtCo/C by sequential procedure. The peroxide yield was also explored using RRDE technique. The H₂O₂ yield results were correlated with SA and R values (ratio of charge transferred about Co and Pt on the surface of catalyst) obtained from CVs in 1 M KOH solution. A sacrificial Co oxidized effect on impediment of adsorption of OH may cause higher catalytic properties and higher H₂O₂ yield to Pt base alloy catalysts.     

Platinum-alloy nanostructured thin film catalysts for the oxygen reduction reaction

In an effort to study advanced catalytic materials for the oxygen reduction reaction (ORR), a number of metallic alloy nanostructured thin film (NSTF) catalysts have been characterized by rotating disk electrode (RDE). Optimal loadings for the ORR and activity enhancement compared to conventional carbon supported nanoparticles (Pt/C) were established. The most efficient catalyst was found to be PtNi alloy with 55 wt% of Pt. The enhancement in specific activity is more than one order of magnitude, while the improvement factor in mass activity is 2.5 compared to Pt/C. Further lowering of the platinum to nickel ratio in NSTF catalysts did not lead to increased mass activity values.     

Electrochemical reduction of oxygen on palladium nanocubes in acid and alkaline solutions

The electrocatalytic properties of cubic palladium nanoparticles towards the electrochemical reduction of oxygen were studied in acid and alkaline solutions and compared with those of spherical nanoparticles and bulk Pd. The synthesised Pd nanoparticles were characterised by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrooxidation of pre-adsorbed CO was employed for cleaning the palladium catalyst surface. Oxygen reduction was studied using the rotating disk electrode (RDE) method and enhanced electrocatalytic activity of Pd nanocubes was revealed both in acid and alkaline solutions, which was attributed to the prevalence of Pd(1 0 0) facets. The mechanism of oxygen reduction on Pd nanoparticles was similar to that on bulk Pd, the first electron transfer being the rate-limiting step, and the reaction predominantly followed a four-electron pathway in both solutions.     

燃料电池中铁基氧还原催化剂的研究进展

阴极氧还原反应是燃料电池的核心反应之一。目前催化氧还原反应的催化剂通常是贵金属铂,但其普遍存在成本高、对甲醇耐受性差、易CO中毒等缺点,因此开展非贵金属催化剂的研究显得尤为重要。铁基催化剂因催化活性好、稳定性高、甲醇耐受性好、价格低廉等备受青睐,最有希望成为铂基催化剂的替代品。本文主要综述了几类铁基氧还原催化剂的研究现状、催化机理及活性影响因素,并在此基础上阐述了各类催化剂目前尚待解决的问题和发展方向。     

Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts

In this study, new Fe₂O₃ based materials are developed for the selective catalytic reduction (SCR) of NO_x by NH₃ in diesel exhaust. As a result of the catalyst screening, performed in a synthetic model exhaust, ZrO₂ is considered to be the most effective carrier for Fe₂O₃. The modification of the Fe₂O₃/ZrO₂ system with tungsten leads to drastic increase of SCR performance as well as pronounced thermal stability. These results show that tungsten acts as bifunctional component. The highest catalytic activity is observed for ZrO₂ that is coated with 1.4 mol% Fe₂O₃ and 7.0 mol% WO₃ (1.4Fe/7.0W/Zr). By the use of this catalyst quantitative conversion of NO_x is obtained between 285 and 430 °C with selective formation of N₂. Here, the turnover frequency of NO_x per Fe atom is found to be 35 × 10⁻⁵ s⁻¹ that indicates a high catalytic performance. The SCR activity of the 1.4Fe/7.0W/Zr material is decreased in the presence of H₂O and CO₂, whereas it is increased by NO₂.Temperature programmed reduction by H₂ (HTPR) analyses show that the Fe sites of the 1.4Fe/7.0W/Zr catalyst are mainly in the form of crystalline Fe₂O₃, whereby relatively small oxide entities are also present. The strongly aggregated Fe₂O₃ species are associated with the presence of the promoter tungsten. Based upon stationary catalytic examinations as well as diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) studies we postulate an Eley Rideal type mechanism for SCR on 1.4Fe/7.0W/Zr catalyst. The mechanistic model includes a redox cycle of the active Fe sites. As first reaction step, we assume dissociative adsorption of NH₃ that leads to partial reduction of the iron as well as to production of very reactive amide surface species. These amide intermediates are supposed to react with gaseous NO to form N₂ and H₂O. In the final step, the reduced Fe sites be regenerated by oxidation with O₂. As a side reaction of SCR, imide species, originated from decomposition of amide, are oxidized by NO₂ or O₂ into NO.