Formic Acid Electrooxidation Reaction Research Articles

Methanol, Ethanol, and Formic Acid Oxidation on New Platinum-Containing Catalysts

Electrooxidation of methanol, ethanol, and formic acid was studied on three platinum-containing electrocatalysts: PtCu/C, Pt/(SnO2/C), and Pt/C, Pt content being about 20 wt%. In all reactions, the integral specific activity of the catalysts, estimated from the results of cyclic voltammetry, grows in the Pt/C < Pt/(SnO2/C) < PtCu/C row. The influence of the reagent nature subjected to electrooxidation is manifested both in the difference of the absolute rate values of the corresponding reactions, decreasing in the order CH3OH > HCOOH > C2H5OH, and in the different ratio of these rates on different catalysts and at different potentials. Pt/(SnO2/C) catalyst containing SnO2 nanoparticles is the most active among the studied catalysts in methanol and formic acid electrooxidation reactions under potentiostatic conditions at the E = 0.60 V. Moreover, in formic acid electrooxidation reaction it is significantly superior to even the PtRu/C commercial catalyst. The reasons for the positive influence of Cu atoms and SnO2 nanoparticles on the catalytic activity of platinum are presumably associated with different effects: Interaction of the d-orbitals of copper and platinum atoms in bimetallic nanoparticles and implementation of the bifunctional catalysis mechanism on the adjacent platinum and tin dioxide nanoparticles.

Synthesis of carbon-supported bimetallic palladium\u2013iridium catalysts by microemulsion: characterization and electrocatalytic properties

Carbon (Vulcan XC-72)-supported bimetallic Pd–Ir catalysts with different Pd/Ir proportions (5–50 mol% Ir, 2 wt% Pd) were prepared by “water-in-oil” microemulsion method (w/o) using solutions of low (0.02 M, L series) and high concentration (0.2 M, H series) of the metals precursors (PdCl2 and IrCl3). The bimetallic particles were examined in terms of nanoscale phase properties (extent of Pd–Ir alloying, phase separation), surface composition (Pd and Ir fractions) and electrocatalytic performance for the formic acid oxidation reaction. Structural characterization was performed using XRD, SEM and HRTEM techniques. Electrochemical characterization allowed estimating the PdH formation ability and the surface composition of Pd–Ir particles what was confirmed by XPS data. The Pd–Ir nanoparticles of similar average size (ca. 4 nm), close to that of Ir (3.8 nm) and below that of Pd (6.2 nm) were formed regardless of the Pd/Ir proportion and the concentration of the metals precursors in the w/o. In contrast to the largely alloyed PdIr nanoparticles with the Pd-rich surface formed at low concentration of the metals precursors (0.02 M), the particles of almost closed surface and bulk Pd/Ir ratios composed mostly of randomly distributed single-phase domains were formed at high concentration (0.2 M). At the lowest bulk Ir content, 5 mol%, the particles have Ir-rich surface regardless of the preparation method. The catalytic studies involving formic acid electrooxidation reaction showed the activity enhancement for the L series catalysts with respect to monometallic Pd/C (twofold TOF increase) and H series counterparts. The Pd85Ir15/C catalyst of the Pd–Ir alloyed and the surface composition expressed by the Pd/Ir atomic ratio near to 6 displayed the highest activity which was 2.9-times higher relative to that of Pd.Graphic abstract

High Active PdSn Binary Alloyed Catalysts Supported on B and N Codoped Graphene for Formic Acid Electro-Oxidation

A series of PdSn binary catalysts with varied molar ratios of Pd to Sn are synthesized on B and N dual-doped graphene supporting materials. The catalysts are characterized by X-ray diffraction (XRD) and Transmission electron microscopy (TEM). Formic acid electro-oxidation reaction is performed on these catalysts, and the results reveal that the optimal proportion of Pd:Sn is 3:1. X-ray photoelectron spectroscopy (XPS) measurements show that when compared with 3Pd1Sn/graphene, B and N co-doping into the graphene sheet can tune the electronic structure of graphene, favoring the formation of small-sized metallic nanoparticles with good dispersion. On the other hand, when compared with the monometallic counterparts, the incorporation of Sn can generate oxygenated species that help to remove the intermediates, exposing more active Pd sites. Moreover, the electrochemical tests illustrate that 3Pd1Sn/BN-G catalyst with a moderate amount of Sn exhibits the best catalytic activity and stability on formic acid electro-oxidation, owing to the synergistic effect of the Sn doping and the B, N co-doping graphene substrate.

Highly Active and Durable Ordered Intermetallic PdFe Electrocatalyst for Formic Acid Electrooxidation Reaction

In this paper, we report the preparation of highly active and durable ordered intermetallic PdFe catalyst supported on carbon black for formic acid oxidation reaction (FAOR) by high-temperature hea...

Effect of Carbon Support on the Electrocatalytic Performance of the Pt Nanoparticles Toward Oxidation of Formic Acid

Nowadays, fuel cells (FCs) attracted a great deal of attention due to their many applications and advantages: Higher efficiency than diesel or gas engines, less pollution than fossil fuels, no using fuels such as oil and gas and reducing economic dependence on fossil fuel producing countries and easy maintenance are the advantages of FCs. However, the obstacles encountered FCs commercialization’s are mainly expensive electrocatalyst materials such as platinum (Pt), it’s poisoning by intermediates like as CO and sluggish electrooxidation kinetics of fuels. For this reasons, in order to minimize the amount of Pt and accordingly total cost of FCs and also decreasing the poisoning effects, Pt particles are deposited on/in different conductive supports. Herein we investigated the effect of carbon nanoparticles (CNPs) and reduced graphene oxide (RGO) nanosheets on the carbon-ceramic electrode (CCE) as support for Pt nanoparticles (PtNPs) toward formic acid electro-oxidation. PtNPs were successfully deposited on the CNPs and RGO with electrochemical method. The fabricated nanocomposites were characterized by the field emission scanning electron microscopy, energy-dispersive X-ray and X-ray powder diffraction spectroscopy. The electrocatalytic activities of the prepared electrocatalysts for oxidation of formic acid were investigated in 0.1 M H2SO4 solution by electrochemical techniques including cyclic voltammetry (CV) and chronoamperometry (CA). The results of the experiments revealed that the PtNPs on the CNPs, PtNPs/CNPs/CCE, shows more electrocatalytic activity than the RGO nanosheets support. This high electrocatalytic efficiency of the PtNPs/CNPs/CCE can be attributed to large specific surface area and unique structure of CNPs that is being used as support. The influence of some experimental agents on the electrocatalytic activity of the PtNPs/CNPs/CCE was investigated and the optimal conditions were suggested. The present investigation reveals that the PtNPs/CNPs/CCE is a promising electrocatalyst for the formic acid electro-oxidation reaction in FCs. Preparation and electrocatalytic performance of carbon support and alone PtNPs toward oxidation of formic acid.

Polyol assisted formaldehyde reduction of bi-metallic Pt-Pd supported agro-waste derived carbon spheres as an efficient electrocatalyst for formic acid and ethylene glycol oxidation

This report explains, (i) the preparation of carbon spheres (CS) from agro-waste through hydrothermal carbonization (HTC) followed by high temperature carbonization, (ii) the decoration of bi-metallic Pt-Pd nanoparticles (Pt-Pd NPs) with different compositions (Pt/C, Pt0.5Pd1/C, Pt1Pd1/C and Pt1Pd0.5/C, Pd/C) on the carbon by ethylene glycol solvated polyol assisted formaldehyde reduction method and (iii) subsequently used as the electrocatalyst for formic acid (FA) and ethylene glycol (EG) electro-oxidation. The structural and morphological properties of the electrocatalysts were studied using advanced physicochemical characterization techniques. The obtained results well evidence the homogeneous dispersion of Pt-Pd NPs on the surface of the carbon. Especially, Pt0.5Pd1/C exhibited excellent electrocatalytic property towards formic acid electro-oxidation reaction (FAOR) with a higher current density (256 mA cm−2) and stability due to “third body effect”. On the other hand, Pt1Pd0.5/C expressed superior electrochemical performance towards ethylene glycol electro-oxidation reaction (EGOR) due to the strong interaction between high Pt content and Pd. Hence, this work reveals the improved electrocatalytic performance of bi-metallic Pt-Pd NPs supported biomass-derived carbon as a promising anodic electrocatalyst towards FAOR and EGOR.

Electrocatalytic properties of a Pd0(Pb) composite synthesized by galvanic displacement: activity towards formic acid oxidation

Galvanic displacement of electrodeposited lead by palladium fails to produce Pd shells. The anomalous ratio between formic acid electrooxidation reaction (FAOR) rates on Pd0(Pb) observed in HClO4 and H2SO4 solutions is associated with the reduction of ClO4− anions to chloride ones which inhibit the FAOR.

Evidences of CO spillover at a Pt/Pd bimetallic interface during the formic acid oxidation reaction

The surface diffusion (spillover) through the intermetallic Pt/Pd junction of adsorbed CO (COad) during the formic acid electrooxidation reaction (FAO) was analyzed on a bimetallic Pt/Pd electrode by chronoamperometry followed by stripping voltammetry. An ordered matrix of equally spaced square palladium islands on a platinum substrate was prepared by the Mask-Assisted E-Beam (MAEB) method in order to have a large interface length/area relationship. Potential steps were applied in 0.5 M HCOOH + 0.5 M H2SO4 solution (0.2 V ≤ Es vs. RHE ≤ 0.5 V) during times t ≤ 500 s in a flow cell. After changing solution to 0.5 M H2SO4, the amount of COad on Pt and Pd were measured by voltammetric stripping. Under these experimental conditions, the pure metals show the presence of COad on Pt but not on Pd. The results obtained on the bimetallic electrode demonstrate the COad spillover from Pt towards Pd through the heterometallic junction.

Specific features of galvanic displacement of electrodeposited copper by palladium. Activity of Pd0(Cu) composite in FAOR

Galvanic displacement (GD) of electrodeposited (e.d.) copper by palladium in PdSO4+H2SO4 solutions in the absence (solution I) and in the presence (solution II) of copper ions Cu2+ is carried out. The resulting samples are characterized by several methods (SEM, XPS, AES-ICP, etc.). In is found that on freshly formed Pd0(Cu)-I and Pd0(Cu)-II composites, no Pd shell is formed. The copper content is shown to be 10at.% and higher in the surface layer and 22–27% in the bulk (Pd+Cu=100%). Voltammetric and XPS data allow assuming that the surface layer contains mixed oxides (such as PdCuOx) and copper ions which prevent the formation of the Pd shell. Both freshly formed Pd0(Cu) samples and those subjected to potential cycling (0.3–1.2V, RHE) demonstrate the high specific activity in formic acid electrooxidation reaction (FAOR, 1M HCOOH+0.5M H2SO4) which exceeds the activity of e.d. Pd by a factor of 3–4 at 150mV and 8–10 at 300mV. The possible reasons for the higher FAOR activity of Pd in Pd0(Cu) composites are discussed.

Enhanced catalytic activity and stability of palladium decorated iridium-copper nanoparticles for formic acid electro-oxidation reaction

Enhanced catalytic activity and stability of palladium decorated iridium-copper nanoparticles for formic acid electro-oxidation reaction

A complementary study on novel PdAuCo catalysts: Synthesis, characterization, direct formic acid fuel cell application, and exergy analysis

At present, Pd containing (10–40 wt%) multiwall carbon nanotube (MWCNT) supported Pd monometallic, Pd:Au bimetallic, and PdAuCo trimetallic catalysts are prepared via NaBH4 reduction method to examine their formic acid electrooxidation activities and direct formic acid fuel cell performances (DFAFCs) when used as anode catalysts. These catalysts are characterized by advanced analytical techniques as N2 adsorption and desorption, XRD, SAXS, SEM-EDX, and TEM. Electronic state of Pd changes by the addition of Au and Co. Moreover, formic acid electrooxidation activities of these catalysts measured by CV indicates that particle size changes in wide range play a major role in the formic acid electrochemical oxidation activity, ascribed the strong structure sensitivity of formic acid electrooxidation reaction. PdAuCo (80:10:10)/MWCNT catalyst displays the most significant current density increase. On the other hand, lower CO stripping peak potential obtained for PdAuCo (80:10:10)/MWCNT catalyst, attributed to the awakening of the Pd-adsorbate bond strength down to its optimum value, which favors higher electrochemical activity. DFAFCs performance tests and exergy analysis reveal that fuel cell performances increase with the addition of Au and Co which can be attributed to synergetic effect. Furthermore, temperature strongly influences the performance of formic acid fuel cell.

Enhanced formic acid electrooxidation reaction enabled by 3D PtCo nanodendrites electrocatalyst

The lack of high-performance anodic electrocatalysts for the electrooxidation of liquid fuel remains a prohibited challenge in realizing the large-scale application fuel cells technique. To this end, we herein demonstrated a simple wet-chemical approach for preparing the composition-tunable PtCo nanocatalysts with the three-dimensional (3D) dendrites structure and active surface composition. These unique properties have enabled them to exhibit superior electrocatalytic activity towards formic acid electrooxidation with the mass/specific activities of 1216.9 mA mg−1Pt and 3.36 mA cm−2, 4.3 and 8.2 times higher than that of the commercial Pt/C catalyst. Moreover, the Pt4Co1 nanodendrites can endure the durability test for at least 500 cycles with less decay, showing an advanced class of electrocatalysts for fuel cells. This work paves up a new avenue to promote the electrocatalytic performances of catalyst by designing their morphologies and pushes Pt-based nanocatalysts system much stronger for commercial application in fuel cells and beyond.

Effect of treatment at high temperatures on morphology of a carbon supported Pd catalyst investigated by X-ray diffraction and photoelectron spectroscopy aided with QUASES

The 20 wt% Pd supported on carbon Vulcan XC-72 (Pd/C) anode catalyst, used to formic acid (FA) electro-oxidation reaction, submitted to different high temperature treatment (HTT) procedures in the temperature range 200–400 °C was studied using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) aided with Quantitative Analysis of Surfaces by Electron Spectroscopy (QUASES).The HTT procedures increased the diameter of Pd crystallites influencing their electronic properties, led to formation of surface PdO and PdO2 from the respective bulk Pd oxides, decreased Pd oxide content and PdOx overlayer thickness. Carbon incorporation into Pd with PdCx composition of x < 0.01 (200 °C), x ∼ 0.015 (300 °C) and x ∼ 0.04 (400 °C) was observed (XRD). The XRD confirmed that FA reduces the surface PdOx to Pd increasing Pd metallic nanoparticle diameter. The values of Pd nanoparticle diameter and PdOx overlayer thickness obtained from QUASES and corrected for elastic electron scattering effects are in better agreement with the values resulting from XRD and Stohmeier equation, respectively. Due to this correction the root-mean-square (RMS) deviations between Pd nanoparticle diameter determined by QUASES and XRD decrease from 21.5% to 19.8%, whereas deviations between the PdOx overlayer thickness evaluated by QUASES and Stohmeier equation decrease from 54.8% to 22.8%.

A high stability AuPd-ZrO2-multiwall carbon nanotubes supported-catalyst in a formic acid electro-oxidation reaction

Catalytic activity and stability in a formic acid electro-oxidation, chemical and structural properties of AuPd nanoparticles deposited (a polyol method) on ZrO2 decorated functionalised multiwall carbon nanotubes (f-MWCNTs) (a hydrothermal method) were investigated using a fuel cell test, scanning transmission electron microscopy (STEM), high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).Non-stoichiometric ZrOx nanoparticles of a cubic phase (C-phase) and average size of 5–10 nm (STEM, HR-TEM), 4.5–5.0 nm (XRD) are anchored by f-MWCNTs carboxylic group through Zr-O-C bonds. Decoration by AuPd nanoparticles leads to ternary Pd/AuPd/Au phase of 6.9 nm crystallite size (XRD) with metallic Pd, oxidised (PdO, PdO2) and Pd-O-Zr phases (XPS). Oxidation/reduction at 300 °C/200 °C leads to nanoparticles sintering, increasing/decreasing Pd surface coverage, oxides/oxygen groups content and ZrOx stoichiometry. Catalysts after oxidation (the largest nanoparticle size, Pd oxides content, ZrOx stoichiometry) showed the highest activity and stability. Activity of AuPd-ZrO2/f-MWCNTs catalysts is smaller than that of these catalysts without ZrO2, however, the stability is remarkably larger, i.e. AuPd-ZrO2/f-MWCNTs > Pd-ZrO2/f-MWCNTs > AuPd/f-MWCNTs > Pd/f-MWCNTs, what is attributed to electronic properties of AuPd and role of ZrOx and oxygen functional groups in COad desorption and oxidation to CO2 releasing catalyst active sites.

Extraordinary electrocatalytic performance for formic acid oxidation by the synergistic effect of Pt and Au on carbon black

Improving catalyst performance and understanding reaction mechanism of formic acid electrooxidation (FAO), a typical anodic reaction in fuel cells, are of technological and scientific importance. Here, Pt-Au/C catalysts were designed and synthesized for catalyzing the FAO reaction. An ultrasound-assisted method was developed to enable the uniform and dense loading of Pt and Au on carbon black without any surfactant. The Pt-Au/C sample with a Pt/Au atomic ratio of 32:68 exhibits an FAO catalytic activity of 14.5 A mgPt−1, which is 153 times higher than that of Pt/C. The extraordinary performance is attributed to the optimized synergistic effect of Pt and Au. Density functional theory calculations disclose that the neighboring Au decreases the reaction energy barriers of the direct pathway on Pt. This work demonstrates a promising FAO catalyst and an effective strategy to obtain supported catalysts.

Kinetic Study of Formic Acid Electrochemical Oxidation on Supported Pd Based Electrocatalysts

Developing high performance catalyst based on Pd/C catalyst is critical in investigating and commercializing direct formic acid fuel cell. The improvement of the electron-transfer rate of novel catalysts could solve the sluggish reaction kinetics of formic acid electro-oxidation reaction in some extent. We have demonstrated that phosphotungstic acid (PWA) modified Pd/C catalyst could improve the electro-oxidation activity toward formic acid. In this paper, the electrochemical oxidation reaction kinetics of PWA modified Pd/C catalyst were studied by cyclic voltammetry (CV), Tafel polarization, electrochemical impedance spectroscopy (EIS) and rotating disc voltammetry (RDV) at different scanning rates and temperatures. The results showed that smaller apparent activation energy, charge transfer resistance and Tafel slope of formic acid electro-oxidation from Pd/PWA–C electrode catalyst was obtained, which indicated better electrocatalytic kinetics by PWA modification. The rate-determining step of formic acid electro-oxidation is diffusion process and reaction paths are different with potential. The larger diffusion coefficients of Pd/PWA–C electrode catalyst was verified by CV, EIS and RDV, respectively. With the help of electrochemical measurements, it is concluded that PWA modified Pd/C catalyst has better electrocatalytic activity and faster kinetic performance for formic acid electro-oxidation.

Pd/C CATALYSTS SYNTHESIZED BY MICROWAVE ASSISTED POLYOL METHOD FOR FORMIC ACID ELECTRO-OXIDATION

Synthesis of carbon supported palladium particles based on a polyol process was investigated. The activity of Pd catalysts, synthesized by microwave assisted polyol method on carbon support, has been examined for formic acid electro-oxidation reaction. The catalysts were characterized with XRD to identify their nanostructure properties. The effect of catalyst preparation parameters on electrocatalytic performance of catalysts was examined. The electrocatalytic properties of Pd/C catalysts for the oxidation of formic acid were investigated by cyclic voltammetry (CV). The electrocatalytic activity of Pd/C synthesized at 30 s and 130 oC are higher than the other Pd/C catalysts synthesized at different temperature and reaction time. It is proposed that the longer reaction time and higher temperature increased the particle size.

Nitrogen-doped carbon black supported Pd nanoparticles as an effective catalyst for formic acid electro-oxidation reaction

Pd nanoparticles supported on nitrogen doped carbon black (Vulcan XC-72R) with two different levels of doping were prepared by the microwave-assisted ethylene glycol reduction process and used as catalyst for the formic acid electro-oxidation (FAEO). The results indicate that the different nitrogen doping contents in Pd/N-C catalysts have a significant effect on the performance of FAEO. A higher N content facilitates the uniform dispersion of Pd nanoparticles on carbon black with narrow particle size distribution. Furthermore, the electrochemical results show that the catalyst with a higher N-doping content possesses a higher catalytic activity and a long-term stability for FAEO. The peak current density of the Pd/N-C (high) catalyst is 1.27 and 2.31 times that of the Pd/N-C (low) and homemade Pd/C-H catalyst. The present paper may provide a simple method for preparation of high-performance anode catalyst for direct formic acid fuel cells (DFAFCs).

La2O3 Promoted Pd/rGO Electro-catalysts for Formic Acid Oxidation.

High activity, a low rate of CO poisoning, and long-term stability of Pd electro-catalysts are necessary for practical use as an anode material in direct formic acid fuel cells. Achieving a high degree of Pd nanoparticle dispersion on a carbon support, without agglomeration, while maintaining a facile electron transfer through the catalyst surface are two challenging tasks to be overcome in fulfilling this aim. Herein, we report the effect of addition of La/La-oxides on the efficiency of Pd nanoparticles supported on reduced graphene oxide (rGO) for formic acid electro-oxidation reaction. A series of electro-catalysts with different Pd-La molar ratios were successfully synthesized and characterized using a range of techniques including PXRD, XPS, TEM, FTIR, and Raman spectroscopy and then tested as anode materials for direct formic acid fuel cells. We explore that the lanthanum species (La/La-oxide) significantly promote the activity and stability of Pd catalyst toward electrocatalytic oxidation of formic acid. The metallic ratio is found to be critical, and the activity order of various catalysts is observed as follows; Pd30La70/rGO > Pd80La20/rGO > Pd70La30 rGO. The obtained mass specific activity for Pd30La70/rGO (986.42 A/g) is 2.18 times higher than that for Pd/rGO (451 A/g) and 16 times higher than that for Pd/C (61.5 A/g) at given onset peak potentials. The high activity and stability of the electro-catalysts are attributed to the uniform dispersion of Pd nanoparticles over the rGO support, as evidenced from TEM images. It is believed that the role of La species in promoting the catalyst activity is to disperse the catalyst particles during synthesis and to facilitate the electron transfer via providing a suitable pathway during electrochemical testing.

Experimentally Determined Correlation Between Electronic and Electrocatalytic Properties in Oxidation of Small Organic Molecules for Systems Consisting of Noble Metal

It is widely accepted that catalytic and electronic properties of catalyst‘s surface are strongly related. It has been postulated that the catalyst’s center of the d-band (εd) can be used to predict the adsorption strength and dissociation energy of simple molecules adsorbed on it. However there are not many studies correlating electronic properties of catalysts determined experimentally to the catalytic activity, because usually the electronic properties of catalysts surface are calculated using DFT. In this presentation we will focus on experimental verification of the role of electronic properties on the electrocatalytic activity of selected systems containing Pt, Pd and Rh, with purposefully modified electronic properties, in electrooxidation of small organic molecules, such as ethanol and formic acid. Model systems with purposely modified electronic properties were obtained by alloying and by forming of pseudomorfic layers of one metal on the surface of other metal. As a result in the investigated catalysts the lattice parameter was modified which, together with the possible partial charge transfer, induced the changes in their electronic properties. Modification of the lattice parameter changes the degree of overlapping of band forming orbitals and, according to the d-band center theory, it can be expected that when metal lattice is contracted, the valence band becomes broader, and when metal lattice is expanded the valence band (d-band) shrinks. The changes in d-band width causes the shift of the d-band: the broadening of the valence band leads to shift of the d-band center away from Fermi level and when the d-band shrinks, the d-band center shifts in the opposite direction. The changes in electronic properties can be observed using X-ray Photoelectron Spectroscopy (XPS) and UV Photoelectron Spectroscopy (UPS), and for the same material the catalytic properties can be monitored using electrochemical methods. We used this approach to investigate how the changed electronic properties influence the catalytic activity. We focused on CO, formic acid and ethanol electrooxidation reaction. Electrooxidation of small organic molecules, such as ethanol and formic acid, on noble metals is of particular interest due to its potential application in low temperature direct ethanol/formic acid fuel cells (DEFCs/DFAFCs), and for better understanding the mechanisms of electrode reactions. In particular CO and formic acid oxidation are considered model electrode reaction, where oxidation of ethanol, albeit more complicated, is of particular interest due to its importance in DEFCs. Despite the significant work already devoted to find a good low temperature catalyst for electrooxidation of ethanol, there is no known ethanol electrooxidation reaction (EOR) catalyst, allowing for complete electrooxidation of ethanol to CO2. Even for the most active systems, incomplete and slow EOR renders the DEFCs not economically viable. Better understanding of the factors influencing the catalytic activity should allow for development of novel, more active and selective electrocatalysts, and for further development of direct, liquid fuel feed, low temperature fuel cells. This project was funded from Polish National Science Centre budget based on decision number DEC-2013/09/B/ST4/00099