Platinum monolayer electrocatalysts for oxygen reduction

We have synthesized a new class of electrocatalysts for the oxygen reduction reaction, consisting of a monolayer of Pt or mixed monolayer of Pt and another late transition metal (Au, Pd, Ir, Ru, Rh, Re or Os) deposited on a Pd(1 1 1) single crystal or on carbon-supported Pd nanoparticles. Several of these electrocatalysts exhibited very high activity, amounting to 20-fold increase in a Pt mass activity, compared with conventional all-Pt electrocatalysts. Their superior activity reflects a low OH coverage on Pt, caused by the lateral repulsion between the OH adsorbed on Pt and the OH or O adsorbed on neighboring, other than Pt, late transition metal atoms. The origin of this effect was identified through a combination of experimental and theoretical methods, employing electrochemical techniques, X-ray absorption spectroscopy, and periodic, self-consistent density functional theory calculations. This new class of electrocatalysts promises to alleviate some major problems of existing fuel cell technology by simultaneously decreasing materials cost and enhancing performance.     

Reductive annealing for generating Se doped 20 wt% Ru/C cathode catalysts for the oxygen reduction reaction

Reductive annealing was chosen as a method for the syntheses of Se modified Ru/C catalysts. Initial preparation of a 20 wt% Ru/C was performed by impregnating RuCl₃·2H₂O on Vulcan XC72 with subsequent conditioning using H₂ at 250 °C for 4 h. Surface treatment of Ru/C by SeO₂ followed by reductive annealing produced Se modified Ru/C catalysts with a pre-determined Ru:Se = 1:0.15 and 1:1 a/o. Structural characterization was carried out using HRTEM while electrochemical characterization was performed using RDE measurements. It is concluded that the presence of Se on Ru has a positive effect on the oxygen reduction reaction of RuSe/C catalyst systems with an optimal loading of Se close to a Ru:Se ratio of 1:0.15 a/o. Overloading of selenium led to neutralization of its promoting effect.     

Pt decorating of PdNi/C as electrocatalysts for oxygen reduction

A low-cost and high performance catalyst consisting of Pt decorating PdNi/C (Pt-PdNi/C) for oxygen reduction is prepared by a two-stage route. The characterization techniques considered are X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX) technique. The results show that the Pt-PdNi/C catalyst has an average diameter of ca. 5 nm. The electrochemical activity for the ORR is evaluated from steady state polarization measurements, which are carried out in an ultra-thin layer rotating disk electrode (RDE). The RDE tests show that the Pt-PdNi/C catalyst has the highest ORR activity compared to pure Pt/C, Pd/C and PdNi/C catalysts. High electrocatalytic activities could be attributed to the synergistic effect between Pt and PdNi.     

The effect of boron doping into Co-C-N and Fe-C-N electrocatalysts on the oxygen reduction reaction

Co-C-N and Fe-C-N thin film catalysts have been modified by controlled doping with boron. Corresponding novel thin film catalysts Co-C-N-B and Fe-C-N-B were synthesized by combinatorial magnetron sputter deposition in an Ar/N₂ gas mixture followed by subsequent heat-treatment between 700 and 1000 °C in an argon atmosphere. The nitrogen content of the as-prepared thin film catalysts could be increased by the addition of boron. Furthermore, the amount of remaining nitrogen in heat-treated catalyst samples was significantly higher in case of boron containing samples. The thin film catalysts were characterized by means of X-ray diffraction (XRD) analysis, electron microprobe and electrochemical measurements. For electrochemical studies the activity as oxygen reduction reaction (ORR) catalyst was investigated using the rotating ring-disk electrode (RRDE) technique in 0.1 M HClO₄ solution at room temperature. The catalytic activity was found to decrease with the boron content in the thin film catalysts even though the N-content increased.     

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.     

Characterization of oxidized reticulated vitreous carbon electrode for oxygen reduction reaction in acid solutions

The oxidation of reticulated vitreous carbon (RVC) and its impact on the oxygen reduction reaction (ORR) in H₂SO₄ solutions has been studied. The results are compared with that of a planar glassy carbon (GC) electrode. The oxidation process was characterized by using different electrode configurations, GC (planar) and RVC electrodes both with flooded (batch process) and flow-through assembly. Cyclic voltammetry, potentiodynamic and rotating ring-disk electrode voltammetry were used for the characterization of the ORR. Anodically oxidized GC and flooded RVC are similar in that the ORR on both electrodes gave a more defined limiting current plateau. For the flow-through porous electrode, the oxidation process caused a distribution of the oxidation extent within the bed thickness, as evident from the SEM images, and only about half of the porous electrode was utilized in the oxidation process. X-ray photoelectron spectroscopy (XPS) measurements confirmed the above distribution and a gradient of the oxygen-to-carbon ratio was obtained within the porous bed. Oxidation of RVC led to an enhancement of its electrocatalytic properties towards ORR. H₂O₂ production was tested at the oxidized RVC from flowing acid solutions. The oxidation of RVC resulted in higher current efficiencies and higher outlet concentrations of the H₂O₂ acid solutions.     

Experimental and theoretical modeling of Fe-, Co-, Cu-, Mn-based electrocatalysts for oxygen reduction

Experience gained during efforts towards optimization of noble-metal-free electrocatalysts for oxygen reduction is simultaneously used to understand the chemical and morphological necessities for inducing efficient multi-electron transfer catalysis. The analysis of many preparative experimental steps between the moderately performing metal porphyrines and the highly efficient transition metal- and sulfur-containing pyrolized catalyst material contributes to the following model of the catalyst: The metals function enclosed in nitrogen or graphitic environment where they are shielded against irreversible oxidation. The metals can be exchanged but are not identical in their efficiency. Higher efficiency is achieved, when the function of a binary reaction center is warranted. The carbonization of the environment is critical and provides intercalated metal centers and attached metal complexes in graphite environment for interaction with the nitrogen-chelated partner center in the simultaneously obtained graphene layers. Three alternatives for the binary catalytic center are presented and their relevance discussed on the basis of EXAFS, RAMAN, EPR, Mössbauer and X-ray spectroscopy. A parallel is drawn with the cytochrome oxidase oxygen reduction catalysis, which is proposed to proceed according to roughly the same mechanism.     

Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO₂ or SO_x forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples.     

Synthesis and characterization of Pd-Ni nanoalloy electrocatalysts for oxygen reduction reaction in fuel cells

Carbon-supported Pd-Ni nanoalloy electrocatalysts with different Pd/Ni atomic ratios have been synthesized by a modified polyol method, followed by heat treatment in a reducing atmosphere at 500-900 °C. The samples have been characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), rotating disk electrode (RDE) measurements, and single-cell proton exchange membrane fuel cell (PEMFC) tests for oxygen reduction reaction (ORR). XRD and TEM data reveal an increase in the degree of alloying and particle size with increasing heat-treatment temperature. XPS data indicate surface segregation with Pd enrichment on the surface of Pd₈₀Ni₂₀ after heat treatment at ≥500 °C, suggesting possible lattice strains in the outermost layers. Electrochemical data based on CV, RDE, and single-cell PEMFC measurement show that Pd₈₀Ni₂₀ heated at 500 °C has the highest mass catalytic activity for ORR among the Pd-Ni samples investigated, with stability and catalytic activity significantly higher than that found with Pd. With a lower cost, the Pd-Ni catalysts exhibit higher tolerance to methanol than Pt, offering an added advantage in direct methanol fuel cells (DMFC).     

Nitrogen-doped carbon coated palygorskite as an efficient electrocatalyst support for oxygen reduction reaction

An electrocatalyst support, nitrogen-doped graphitic layer (CN_x) coated palygorskite (PLS) (donated as PLS@CN_x), is synthesized by carbonizing the polypyrrole (PPy) coated PLS and is explored for the first time as a cathode electrocatalyst support in proton exchange membrane fuel cell. The structural and chemical properties of the PLS@CN_x are investigated by Fourier-Transform infrared spectrometer, thermogravimetric analysis, X-ray diffraction and transmission electron microscopy. The electrocatalytic activity and stability of Pt/PLS@CN_x toward oxygen reduction reaction (ORR) are studied by cyclic voltammetry (CV) and steady state polarization measurements. Upon loading Pt (20 wt%), the catalysts exhibit superior catalytic performance during ORR, surpassing the conventional Pt/C (Vulcan XC-72) catalysts. High electrocatalytic activity and good stability can be attributed to the nitrogen atom incorporation and SiO₂ component in PLS.     

Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells

A non-precious nitrogen-modified carbon composite (NMCC) catalyst is synthesized by the pyrolysis of cobalt, iron-ethylenediamine-chelate complexes on silica followed by chemical and pyrolysis treatments. Pyrolysis temperature and time have a remarkable impact on the content and the type of the nitrogen-containing functional groups in the NMCC catalysts, which affect their catalytic activity and stability. Based on the analysis of the nitrogen functional groups before and after the stability tests, the ORR active sites of the NMCC catalysts are proposed to be pyridinic-N and quaternary-N functional groups. However the pyridinic-N group is not stable in the acidic environment due to the protonation reaction.     

Cobalt based non-precious electrocatalysts for oxygen reduction reaction in proton exchange membrane fuel cells

Cobalt based non-precious metal catalysts were synthesized using chelation of cobalt (II) by imidazole followed by heat-treatment process and investigated as a promising alternative of platinum (Pt)-based electrocatalysts in proton exchange membrane fuel cells (PEMFCs). Transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements were used to characterize the synthesized CoN_x/C catalysts. The activities of the catalysts towards oxygen reduction reaction (ORR) were investigated by electrochemical measurements and single cell tests, respectively. Optimization of the heat-treatment temperature was also explored. The results indicate that the as-prepared catalyst presents a promising electrochemical activity for the ORR with an approximate four-electron process. The maximum power density obtained in a H₂/O₂ PEMFC is as high as 200 mW cm⁻² with CoN_x/C loading of 2.0 mg cm⁻².     

Carbon-supported manganese oxide nanoparticles as electrocatalysts for oxygen reduction reaction (orr) in neutral solution

Manganese oxides (MnO _x ) catalysts were chemically deposited onto various high specific surface area carbons. The MnO _x /C electrocatalysts were characterised using a rotating disk electrode and found to be promising as alternative, non-platinised, catalysts for the oxygen reduction reaction (ORR) in neutral pH solution. As such they were considered suitable as cathode materials for microbial fuel cells (MFCs). Metal [Ni, Mg] ion doped MnO _x /C, exhibited greater activity towards the ORR than the un-doped MnO _x /C. Divalent metals favour oxygen bond splitting and thus orientate the ORR mechanism towards the 4-electron reduction, yielding less peroxide as an intermediate.     

CoPdx oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm² single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 °C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd_x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd₃, exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd₃ has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd₃ catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd₃ catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt.     

Porous nitrogen doped carbon foam with excellent resilience for self-supported oxygen reduction catalyst

Fabrication of graphitized carbon materials (e.g. carbon nanotubes and graphene) normally entails the assistance of transition metal catalyst. In this paper, a nitrogen doped carbon foam (NCF) with both graphitized and porous carbon structure was fabricated by direct pyrolysis of melamine foam (MF) without using any transition metal catalyst. The graphitized carbon structure was possibly attributed to the triazine moieties in the MF precursor. The introduction of oxygen groups in the oxidation step resulted in the formation of large amount of micro- and mesopores and therefore high specific surface area. The NCF exhibited a three-dimensional cellular network consisting of carbon microfiber with abundant micro- and mesopores and giving rise to a specific surface area over 980 m² g⁻¹. Due to such graphitized porous structure, the NCF was demonstrated to have superior resilience, excellent electrocatalytic activity and good durability for oxygen reduction.     

Oxalate supported pyrolysis of CoTMPP as electrocatalysts for the oxygen reduction reaction

The utilisation of different metal oxalates in the pyrolysis of cobalt-tetramethoxyphenylporphyrin (CoTMPP) has been investigated as a structure forming agent to obtain highly active electrocatalysts for the oxygen reduction reaction (ORR). Decomposition products of the metal oxalates provide a nano-scaled template for the carbonisation of CoTMPP. After the pyrolysis this template is removed by an etching step so that highly porous carbon-based particles with different morphologies are attained. Thermogravimetric measurements, gas sorption isotherms (BET and pore size distribution), neutron activation analysis (NAA), SEM and XRD analysis examine the pyrolysis process of CoTMPP in the presence of the metal oxalates and the subsequent conditioning step. Thereby, the degree of graphitisation and the morphology of the formed carbon matrix are influenced by the decomposition products of the metal oxalates. Furthermore, the solubility of the decomposition products in the etching step is a crucial factor for the porosity of the final obtained product. Electrochemical analysis (CV and RDE) shows that the catalysts exhibit high kinetic current densities towards the ORR in acidic electrolyte, which is correlated with the contribution of mesopores within the catalyst. Among the investigated metal oxalates, the utilisation of tin oxalate reveals the most beneficial characteristics for the preparation.     

Hexagonal boron nitride nanosheets as metal-free electrochemical catalysts for oxygen reduction reactions

A high-performance ball milling technique was developed for synthesizing hexagonal boron nitride (h-BN) carbon paper (CP) electrodes as metal-free catalyst for the oxygen reduction reaction (ORR) and hydrogen storage (electrochemically) in acidic media. The h-BN nanosheets were functionalized with glycine to enhance the number of active sites and to boost the catalytic activity. The ball-milled h-BN catalytic electrodes demonstrated ultra-high catalytic activity toward electrochemical hydrogen adsorption/desorption (～3.5 times higher than pristine electrodes) as well as ORR in acidic electrolytes. Furthermore, in-situ durability analysis of the h-BN electrodes was performed via conducting a long-duration cycling experiment (>200 cycles). A mechanistic reaction pathway (sequential) including chemisorption and charge transfer reactions (four-electron and two-electron pathways) was also proposed for the ORR. Considering superior catalytic activity of as-prepared h-BN/CP electrodes, this class of metal-free nanostructured materials can be employed as inexpensive catalysts for the electrochemical H-storage and ORR within various energy storage/conversion devices (e.g., batteries, electrolyzers, and fuel cells).     

Fe-based catalysts for oxygen reduction in proton exchange membrane fuel cells with cyanamide as nitrogen precursor and/or pore-filler

Fe/N/C catalysts for oxygen reduction reaction were synthesized via impregnation or ballmilling. The role of cyanamide (CM) as nitrogen precursor and/or pore-filler for a highly microporous carbon (Black Pearls 2000) was investigated. The use of CM in this work resulted in two main differences compared with phenanthroline from our previous work; (i) ballmilling the precursors did not result in improved activity of the resulting catalysts, and (ii) the activity after the first pyrolysis in argon was relatively high, but did not increase after a second pyrolysis in NH₃. These differences may be explained by TGA measurements of both pore-fillers, where complete gasification of CM is observed at temperatures above 750 °C in Ar, while pyrolysis of phenanthroline in Ar results in 20 wt% residual carbon-based material. Consequently, when using CM as pore-filler with a highly microporous carbon support, the maximum microporous surface area and nitrogen content is reached after only a single pyrolysis in Ar. The most active catalyst prepared with CM was obtained by pyrolysing in Ar at 950 °C a catalyst precursor containing 1 wt% Fe, 80 wt% CM and Black Pearls 2000. This catalyst possessed about 1/6th the catalytic activity of best reported using phenanthroline as a pore-filler. Changing the carbon support had effects on the activity and stability of the catalysts. The catalysts made with a non-porous furnace black (N330) or carbon nanotubes as a carbon support were more stable but less performing than those using carbon supports having high microporous surface area like Black Pearls 2000 or Ketjenblack. The desirable properties for a pore-filler molecule used in the synthesis of Fe/N/C-catalysts by the pore-filling method are discussed.     

Activity-stability relationships of ordered and disordered alloy phases of Pt3Co electrocatalysts for the oxygen reduction reaction (ORR)

We report on synthesis-structure-activity-stability relationships of Pt₃Co nanoparticle electrocatalysts for the oxygen reduction reaction (ORR). We have synthesized Pt₃Co alloy electrocatalysts using liquid impregnation techniques followed by reductive annealing at high and low temperatures. We have performed detailed structural X-ray diffraction (XRD)-based structural characterization (symmetry, lattice parameters and composition) of individual Pt-Co alloy phases before and, importantly, after electrochemical rotating disk electrode (RDE) measurements. This enables us to directly evaluate the corrosion stability of various Pt-Co alloy phases under typical fuel cell cathode conditions.Pt₃Co prepared at low annealing temperatures (600 °C) resulted in multiple phases including (i) a disordered face-centered cubic (fcc) Pt₉₅Co₅ phase and (ii) an ordered face-centered tetragonal (L1₀) Pt₅₀Co₅₀ phase; high temperature annealing (950 C) resulted in a single ordered primitive cubic (L1₂) Pt₃Co phase. The ordered alloy phases in both catalysts were not stable under electrochemical treatment: The ordered face-centered tetragonal (fct) phase showed corrosion and dissolution, while the ordered primitive cubic (L1₂) Pt₃Co phase transformed into a disordered structure. The ordered primitive cubic structure exhibited higher resistance to sintering.Low annealing temperatures resulted in higher Pt surface-area specific activities for ORR. Kinetic Tafel analysis confirmed a general shift in the formation potential of oxygenated surface species, such as Pt-OH, for both alloy catalysts. Reduced OH coverage alone proved insufficient to account for the observed activity trends of the two alloy catalysts.     

Heat treatment effect of Pt-V/C and Pt/C on the kinetics of the oxygen reduction reaction in acid media

This work studies the heat treatment effect of carbon-dispersed platinum and platinum-vanadium alloys on the kinetics of the oxygen reduction reaction (ORR) in acid medium. The catalyst powders were subjected to heat treatments at three temperatures for 1 h. The electronic and structural features of the materials were characterized by X-ray diffraction (XRD) and in situ X-ray absorption near edge structure (XANES). The XANES results for the oxidized state composites showed an increase of the Pt 5d band occupancy with increased heat treatment temperature for the Pt/C catalyst, while no changes were noted for Pt-V/C for the same treatments. The electrochemical characteristics for the ORR were investigated by cyclic voltammetry and state-state polarization measurements. The results showed that the ORR takes place by the multi-electronic charge transfer process, following a four electron mechanism. The kinetics of the ORR was evaluated using Tafel diagrams. It was observed that the ORR activity of the Pt/C and Pt-V/C is enhanced with the increase of the heat treatment temperature. The catalytic activity of the materials was analyzed in terms of the electronic and structural properties of Pt in the metallic particles.