Sputtered electrocatalysts for PEM electrochemical energy converters

The research reports on the electrocatalytic properties of IrO_x, Pt, and composite IrO_x-Pt-IrO_x thin films prepared by physical vacuum deposition technique of dc magnetron sputtering. The efficiency toward the oxygen evolution in aqueous solutions and in a laboratory electrolyser with polymer proton conductive electrolyte has been investigated using the conventional electrochemical methods of cyclic voltammetry and steady state polarisation curves. The sputtered films have demonstrated excellent catalytic properties, mechanical stability, and high corrosion resistance under intensive oxygen evolution. The best performance (anodic current density of 0.84 A cm⁻² at potential of 1.8 V) has shown the IrO_x film with loading of 0.2 mg cm⁻². Some data on the catalytic activity toward oxygen reduction reaction in aerated 0.5 M H₂SO₄ solution and the possibility to use the method of magnetron sputtering for preparation of cost effective composite catalytic films with bifunctional properties are also presented and discussed.     

Preparation, testing and modeling of three-dimensionally ordered catalytic layers for electrocatalysis of fuel cell reactions

The arrays of vertically aligned carbon nano-filaments (VACNF) were synthesized by catalytic chemical vapor deposition on TiO_x substrates, obtained via oxidative treatment of polycrystalline Ti and Ti thin films on Si(1 0 0). VACNF were studied using scanning and transmission electron microscopies. The Pt deposition on VACNF was utilized to prepare a set of model catalysts, which were investigated in two fuel cell related reactions: the oxygen reduction (ORR) and the hydrogen oxidation (HOR) reactions. The experimental data were compared with the results of mathematical modeling performed for a fast (quasi)reversible and a slow irreversible electrochemical reaction. The approach made it possible to study electrochemical reactions (HOR, ORR) on nano-materials under well defined mass transport conditions. The influence of the catalytic layer thickness and the Pt coverage on the penetration depth of the reactive species inside the layer and consequently on the performance and on the Pt effectiveness factor were analyzed.     

Synthesis and characterization of MoOx-Pt/C and TiOx-Pt/C nano-catalysts for oxygen reduction

The oxygen reduction reaction (ORR) was studied at carbon supported MoO_x-Pt/C and TiO_x-Pt nanocatalysts in 0.5 mol dm⁻³ HClO₄ solution, at 25 °C. The MoO_x-Pt/C and TiO_x-Pt/C catalysts were prepared by the polyole method combined by MoO_x or TiO_x post-deposition. Home made catalysts were characterized by TEM and EDX techniques. It was found that catalyst nanoparticles were homogenously distributed over the carbon support with a mean particle size about 2.5 nm. Quite similar distribution and particle size was previously obtained for Pt/C catalyst. Results confirmed that MoO_x and TiO_x post-deposition did not lead to a significant growth of the Pt nanoparticles.The ORR kinetics was investigated by cyclic voltammetry and linear sweep voltammetry at the rotating disc electrode. These results showed the existence of two E − log j regions, usually observed with polycrystalline Pt in acid solution. It was proposed that the main path in the ORR mechanism on MoO_x-Pt/C and TiO_x-Pt/C catalysts was the direct four-electron process with the transfer of the first electron as the rate-determining step. The increase in catalytic activity for ORR on MoO_x-Pt/C and TiO_x-Pt/C catalysts, in comparison with Pt/C catalyst, was explained by synergetic effects due to the formation of the interface between the platinum and oxide materials and by spillover due to the surface diffusion of oxygen reaction intermediates.     

Quantitative study of pH change during LaNi5−xAlx (x = 0, 0.3) discharge process by SECM

Oxygen reduction reaction (ORR) on Pt microelectrode was used for developing a micro pH sensor for scanning electrochemical microscopy (SECM) study in this work. When the potential of Pt microelectrode was held constant in ORR region, the ORR current (cathodic current) increased with decreasing solution pH and vice versa. The response time of the ORR current to pH changes was measured to be ca. 30 ms which implies that the pH response is fast enough for monitoring the temporal pH changes. Furthermore, a fine linear relationship was found to exist between the half wave potential of ORR (E_1/2) and the solution pH value, and the slope is −46 mV/pH. The Pt micro pH sensor was located 1 μm above the LaNi_5−xAl_x (x = 0, 0.3) substrate electrode surface in pH = 9 KOH solution to perform the tip-substrate voltammetry of SECM. In tip voltammogram, the ORR tip current qualitatively reflects the transit solution pH changes during LaNi_5−xAl_x discharge reaction. Also, the minimum values of the solution pH near LaNi₅ and LaNi_4.7Al_0.3 surface during the discharge reaction were quantitatively detected; they were 7.17 and 7.57, respectively. The result indicates that Al partial substitution for Ni degrades the maximum discharge ability of the alloy and decreases the hydrogen diffusion coefficient in alloy bulk.     

A novel nanocomposite catalytic cathode for direct methanol fuel cells

We report a new nanocomposite catalytic cathode composed of iron phthalocyanine, platinum, carbon black and Nafion^® (FePc-Pt/C-Nafion^®) which exhibited enhanced catalytic activity for the oxygen reduction reaction (ORR) in the presence of methanol compared with usual Pt/C based electrodes. The catalytic cathode was prepared by depositing Pt colloidal nanoparticles (d_av = 2.2 nm) on a FePc/C support to form a FePc-Pt/C powder and ultrasonically treating a mixture of Nafion^® and the FePc-Pt/C powder in ethanol, followed by loading the mixture on a glassy carbon electrode and drying at 120 °C. In an O₂-saturated H₂SO₄ solution (0.5 M) with methanol (0.5 M), the onset potential (0.92 V vs RHE) over the FePc-Pt/C-Nafion^® electrode shifted by more than 240 mV toward positive relative to that over an electrode prepared with a commercial Pt/C catalyst and Nafion^®. A new kind of catalytic sites constructed by FePc nanocrystals and Pt nanoparticles was found in the FePc-Pt/C-Nafion^® electrode for the first time, which exhibited higher specific activity for ORR than Pt as calculated based on the hydrogen desorption charge.     

CO tolerance effects of tungsten-based PEMFC anodes

The performance of proton exchange membrane fuel cells (PEMFC) fed with CO-contaminated hydrogen was investigated for anodes with PtWO_x/C and phosphotungstic acid (PTA) impregnated Pt/C electrocatalysts. A quite high performance was achieved for the PEMFC fed with H₂ + 100 ppm CO with anodes containing 0.4 mg PtWO_x cm⁻² and also for those with 0.4 mg Pt cm⁻² impregnated with ca. 1 mg PTA cm⁻². A decay of the single cell performance with time is observed, and this was attributed to an increase of the membrane resistance due to the polymer degradation promoted by the crossover of the tungsten species throughout the membrane.     

Effect of chemisorbed carbon monoxide on Pt/C electrode on the mechanism of the hydrogen oxidation reaction

The influence of poisoning of Pt catalyst by CO on the kinetics and mechanism of H₂ oxidation reaction (HOR) at Pt/C electrode in 0.5 mol dm⁻³ HClO₄, saturated with H₂ containing 100 ppm CO, was examined with rotating disc electrode (RDE) at 22 °C. Commercial carbon black, Vulcan XC-72 was used as support, while Pt/C catalyst was prepared by modified polyol synthesis method in an ethylene glycol (EG) solution. The kinetically controlled current (I_k) for the HOR at Pt/C decreases significantly at CO coverage (Θ_CO) > 0.6. For Θ_CO < 0.6 the HOR takes place through Tafel-Volmer mechanism with Tafel reaction as rate-determining step at the low CO coverage, while Volmer step controls the overall reaction rate at the medium CO coverage. When CO coverage is higher then 0.6, Heyrovsky-Volmer mechanism is operative for the HOR with Heyrovsky as the rate-determining step (rds).     

Study of carbon-supported IrO2 and RuO2 for use in the hydrogen evolution reaction in a solid polymer electrolyte electrolyzer

Carbon-supported IrO₂ and RuO₂ were prepared using an incipient wetness method and were then calcinated at various temperatures. IrO₂/C and RuO₂/C are less expensive than the conventional Pt/C material and more stable than metal Ni in an acidic electrolyte. Moreover, IrO₂/C and RuO₂/C are not influenced by under potential deposition (UPD) and show lower sensitivity to poisoning by Ni or Fe impurities. The physical properties of IrO₂/C and RuO₂/C were investigated via XRD and TEM. Cyclic voltammograms (CV) and Tafel plots were used to provide information regarding surface redox reaction and electrocatalytic activity. The activity and durability of IrO₂/C and RuO₂/C were studied after prolonged potential cycling between −0.3 and 0.3 V_SCE. After comparison of Tafel plots of Pt/C and IrO₂/C after activation, it was observed that they have similar electrocatalytic activities in a hydrogen evolution reaction (HER). A single cell test with solid polymer electrolyte (SPE) proved that the performance of IrO₂/C (0.5 mg cm⁻²) was similar to that of Pt/C (0.5 mg cm⁻²).     

Hydrogen oxidation kinetics on model Pd/C electrodes: Electrochemical impedance spectroscopy and rotating disk electrode study

This work reports on the kinetics of the hydrogen oxidation reaction (HOR) on model Pd nanoparticles supported on a low surface area carbon substrate. Two Pd/C samples, with the average particle size 2.6 and 4.0 nm were used. The structure of the catalysts was characterized with the ex situ (electron microscopy) and in situ (electrochemical) methods. We utilized the electrochemical impedance spectroscopy (EIS) and the rotating disk electrode (RDE) voltammetry to study the kinetics of the HOR on Pd/C. The relevance of these techniques for elucidating the kinetics and the mechanism of the HOR on Pd/C was explored. The experimental results suggest that the catalytic activity of Pd in the HOR is more than 2 orders of magnitude lower than that of Pt, and does not depend on the particle size in the range from 2.6 to 4.0 nm. Computational modeling of the experimental steady-state (RDE) and non-steady-state (EIS) data shows that the reaction kinetics can be adequately described within Heyrovsky-Volmer mechanism, with the rate constants υ_0H = (8.8 ± 1.5) × 10⁻¹⁰ mol cm⁻² s⁻¹ and υ_0V = (1.0 ± 0.3) × 10⁻⁸ mol cm⁻² s⁻¹. The model suggests that underpotentially deposited hydrogen H_UPD is unlikely to be the active intermediate H_ad of the HOR. It is concluded that the surface coverage of H_ad deviates from that of H_UPD with increasing overpotential, and the lateral interactions within H_ad adlayer are weak.     

Sputtered iridium oxide films as electrocatalysts for water splitting via PEM electrolysis

Thin films of iridium oxide deposited by reactive magnetron sputtering have been investigated as catalysts for electrochemical water splitting in a polymer electrolyte membrane (PEM) cell. The sputtered films possess excellent mechanical stability and corrosion resistance at the high anodic potentials where oxygen evolution takes place. Their catalytic activity has been assessed using the conventional electrochemical methods of cyclovoltammetry and steady state polarisation techniques. A morphology factor assessing the catalyst active surface for a series of sputtered samples with varying thickness/loading has been determined and correlated to the catalytic efficiency. It has been proven that iridium oxide is a very efficient catalyst for oxygen evolution reaction (OER). The best performance with anodic current density of 0.3 A cm⁻² at potential of 1.55 V (versus RHE) has shown the 500 nm thick film containing 0.2 mg cm⁻² catalyst. The results obtained have also demonstrated the advantages of the reactive magnetron sputtering as simple and reliable method for deposition of efficient and cost effective catalysts for PEM electrolysis application.     

Rapid rotating-disk-electrode evaluation of catalyst performance and durability during transient conditions: The Pt–Hf binary system

A comprehensive set of rotating disk electrode (RDE) tests has been developed to test the suitability of fuel cell catalyst candidates for use as either anode or cathode catalysts for transient conditions. The activity for Hydrogen Oxidation reaction (HOR), Oxygen Reduction reaction (ORR) and Oxygen Evolution reaction (OER) is tested together in one protocol. A total of 5 Pine Instruments RRDE test stations have been set up with automatic gas flow switching and computer software to control all aspects of the data collection process. The user simply sets up the electrochemical cell with a gas bubbler, reference electrode, counter electrode and sample and then selects a series of tests to be run. The software then switches gas flow, rotation rates and potentiostat set up files automatically. This infrastructure allows the rapid characterization of catalyst candidate materials. The series of tests is described, along with the purpose of each test in the protocol. As an example, the data collected from a Pt_1−xHf_x composition spread is presented. The optimal composition is found to be approximately 30 at.% Hf, when the ORR performance begins to decrease at a faster rate than the HOR performance and the OER current at 1300 mV is also a maximum. However, it was determined that from an applied point of view the drop in ORR performance was insufficient to adequately protect the cathode from the effects of the transient potentials during start-up of the fuel cell.     

Kinetics and PEMFC performance of RuxMoySez nanoparticles as a cathode catalyst

Kinetics of Ru_xMo_ySe_z nanoparticles dispersed on carbon powder was studied in 0.5 M H₂SO₄ electrolyte towards the oxygen reduction reaction (ORR) and as cathode catalysts for a proton exchange membrane fuel cell (PEMFC). Ru_xMo_ySe_z catalyst was synthesized by decarbonylation of transition-metal carbonyl compounds for 3 h in organic solvent. The powder was characterized by X-ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. Catalyst is composed of uniform agglomerates of nanocrystalline particles with an estimated composition of Ru₆Mo₁Se₃, embedded in an amorphous phase. The electrochemical activity was studied by rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. Tafel slopes for the ORR remain invariant with temperature at −0.116 V dec⁻¹ with an increase of the charge transfer coefficient in dα/dT = 1.6 × 10⁻³, attributed to an entropy turnover contribution to the electrocatalytic reaction. The effect of temperature on the ORR kinetics was analyzed resulting in an apparent activation energy of 45.6 ± 0.5 kJ mol⁻¹. The catalyst generates less than 2.5% hydrogen peroxide during oxygen reduction. The Ru_xMo_ySe_z nanoparticles dispersed on a carbon powder were tested as cathode electrocatalyst in a single fuel cell. The membrane-electrode assembly (MEA), included Nafion^® 112 as polymer electrolyte membrane and commercial carbon supported Pt (10 wt%Pt/C-Etek) as anode catalyst. It was found that the maximum performance achieved for the electro-reduction of oxygen was with a loading of 1.0 mg cm⁻² Ru_xMo_ySe_z 20 wt%/C, arriving to a power density of 240 mW cm⁻² at 0.3 V and 80 °C.     

Investigation of the properties of Ti/[IrO2-Nb2O5] electrodes for simultaneous oxygen evolution and electrochemical ozone production, EOP

A systematic investigation of the influence of Ti/[IrO₂-Nb₂O₅] electrode composition ([IrO₂]=40, 45 and 50 mol%) on electrochemical ozone production (EOP), was conducted in 3.0 mol dm⁻³ H₂SO₄ in the presence and absence of 0.03 mol dm⁻³ KPF₆. “In situ” characterisation revealed all oxide layer presented similar structures, except for the 50 mol% IrO₂ nominal composition which showed a higher porosity/roughness. The introduction of KPF₆ in the electrolyte resulted in an inhibition of the oxygen evolution reaction (OER) at high current densities, improving ozone generation efficiency at i > 0.4 A cm⁻², while reducing overpotential for OER. When normalised for the area, the ozone current efficiency presented a good performance of the system. However, improvement of the electrode service life is necessary in order to support the drastic conditions observed during EOP.     

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.     

MnxCu1−xCo2O4 used as bifunctional electrocatalyst in alkaline medium

Composite film electrodes containing mechanically mixed Mn_xCu_1−xCo₂O₄ (0 ≤ x ≤ 1) particles, carbon black Vulcan XC72R and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) were formed on the glassy carbon disk surface of a rotating ring-disk electrode (RRDE) and studied for the oxygen reduction and evolution reactions (ORR and OER, respectively) in 1 M KOH solution. The electrocatalytic activities for both reactions were observed to depend strongly on the Mn content in CuCo₂O₄. An opposite trend was observed for the apparent and intrinsic electrocatalytic activities for the ORR; the simultaneous presence of Cu and Mn was found to be detrimental to the intrinsic charge density, but beneficial to the geometric charge density with a maximum for Mn_0.6Cu_0.4Co₂O₄. The latter was characterized by the highest total number of electrons exchanged per O₂ molecule, n, close to 4, greater k₁ (4e⁻ process)/k₂ (2e⁻ process) ratios, and by a unique and low Tafel slope (−41 mV dec⁻¹). The results obtained for the OER showed that the intrinsic electrocatalytic activity is determined by the number of active sites (Co⁴⁺) electrochemically formed at the oxide surface prior to the OER, from Co³⁺ cations. The partial substitution of Cu by Mn in CuCo₂O₄ was found to decrease the OER activity.     

Hydrogen spillover phenomenon: Enhanced reversible hydrogen adsorption/desorption at Ta2O5-coated Pt electrode in acidic media

The current study is concerned with the preparation and characterization of tantalum oxide-loaded Pt (TaO_x/Pt) electrodes for hydrogen spillover application. XPS, SEM, EDX and XRD techniques are used to characterize the TaO_x/Pt surfaces. TaO_x/Pt electrodes were prepared by galvanostatic electrodeposition of Ta on Pt from LiF-NaF (60:40 mol%) molten salts containing K₂TaF₇ (20 wt%) at 800 °C and then by annealing in air at various temperatures (200, 400 and 600 °C). The thus-fabricated TaO_x/Pt electrodes were compared with the non-annealed Ta/Pt and the unmodified Pt electrodes for the hydrogen adsorption/desorption (H_ads/H_des) reaction. The oxidation of Ta to the stoichiometric oxide (Ta₂O₅) increases with increasing the annealing temperature as revealed from XPS and X-ray diffraction (XRD) measurements. The higher the annealing temperature the larger is the enhancement in the H_ads/H_des reaction at TaO_x/Pt electrode. The extraordinary increase in the hydrogen adsorption/desorption at the electrode annealed at 600 °C is explained on the basis of a hydrogen spillover-reverse spillover mechanism. The hydrogen adsorption at the TaO_x/Pt electrode is a diffusion-controlled process.     

Open-circuit-potentials of gas/electrode/YSZ boundary versus molten carbonate reference electrode at medium temperatures: II. Potential response of Au, Pt and Ni-cermet electrodes in CH4 + O2 and H2 + O2 gas mixtures

Values of open-circuit-potentials (OCP) have been determined for pairs of electrodes: Au and Pt, Ni-Ce_0.8Sm_0.2O_1.9 cermet and Au, Pt and Sm_0.5Sr_0.5CoO₃ composite at the YSZ electrolyte, in the uniform atmospheres of xCH₄ + yO₂ + (1 − x − y)Ar gas mixtures with variable x and y coefficients, at 600 °C. The determined dependencies of OCP values on the initial gas mixture compositions have been compared with the respective dependencies calculated for equilibrium or quasi-equilibrium compositions of these gas mixtures. The OCP values for the pair of Pt and Au electrodes have been measured also in the xH₂ + yO₂ + (1 − x − y)Ar uniform gas mixtures but no distinct difference of the OCP values has been observed in this atmosphere. For some pairs of electrodes investigated in xCH₄ + yO₂ + (1 − x − y)Ar atmospheres the measured OCP values have shown differences up to ca 0.9-1.0 V. These differences were stable within large range of compositions of this gas mixture. Within this gas composition range one of the electrodes conserves the potential of oxygen electrode determined by oxygen partial pressure in the initial gas mixture and is insensitive to reaction occurring in the gas phase. These results are discussed on the basis of equilibria or some quasi-equilibria, that establish in the C-H-O gas mixture and the solid carbon deposition is considered. For a given pair of dissimilar electrodes, their selective sensibility to the electrochemical process of oxygen electrode has been confirmed. Within large range of gas mixture concentrations, in the Pt-Au electrode pair Au has shown behavior of the oxygen electrode, whereas the OCP values of the Pt electrode are within the range of hydrogen electrode, also at gas compositions corresponding to the solid carbon stability. With this pair the OCP differences of ca. 600 mV have been obtained. Among three electrodes studied the cermet Ni-Ce_0.8Sm_0.2O_1.9 electrode shows the best electrocatalytic properties resulting in the OCP values following exactly the respective equilibrium dependence. In the pair Ni-Ce_0.8Sm_0.2O_1.9 and Au a stable potential difference of ca. 900 mV have been established. Unexpectedly, Pt electrode in the pair with the Sm_0.5Sr_0.5CoO₃ composite electrode plays role of the oxygen electrode quite insensitive to other components of the equilibrated initial gas mixture. This surprising fact seems indicate that in conditions of the experiments performed the electrocatalytic behavior of the electrode depends not only of the material of this electrode but also on the properties of the second electrode in the given pairs of electrodes.     

Oxygen reduction behavior of rutile-type iridium oxide in sulfuric acid solution

Two different forms of rutile-type iridium oxide catalysts were prepared: IrO₂-coated titanium plate electrocatalysts prepared by a dip-coating method (IrO₂/Ti) and iridium oxide nanoparticles (IrO₂) prepared by a wet method, the Adams fusion method. The catalytic behavior of the oxygen reduction reaction (ORR) was evaluated by cyclic voltammetry in 0.5 M H₂SO₄ at 60 °C. Both catalysts were found to exhibit considerable activity for the ORR; however, the former oxide electrodes showed higher activity than the latter ones. All the IrO₂/Ti catalyst electrodes heat-treated at a temperature between 400 °C and 550 °C showed ca. 0.84 V (vs. RHE) of the onset potential for the ORR, E_ORR, where the reduction current of oxygen had begun to be observed during the cathodic potential sweep of the test electrodes. It has been confirmed clearly that IrO₂, but neither metallic Ir nor the hydrated IrO₂, behaves as an active catalyst for the ORR in an acidic solution. It was also demonstrated that the enlargement of the surface area of the IrO₂/Ti with the help of lanthanum is effective for the enhancement of the catalytic activity in the reaction.     

Electroreduction of dioxygen (ORR) in alkaline medium on Ag/C and Pt/C nanostructured catalysts—effect of the presence of methanol

Ag/C catalysts with different loading were prepared using a colloidal route to obtain well dispersed catalysts on carbon, with a particle size close to 15 nm. An amount of 20 wt.% Ag on carbon was found to be the best loading in terms of current density and mass activity. The 20 wt.% Ag/C catalyst was then studied and the kinetics towards ORR was determined and compared with that of a 20 wt.% Pt/C catalyst. The number of exchanged electrons for the ORR was found to be close to four with the rotating disk electrode (RDE) as well as with the rotating ring disc electrode (RRDE) techniques. From the RDE results, the Tafel slopes b, the diffusion limiting current density inside the catalytic film (j_l^film) and the exchange current density (j₀) were evaluated. The Tafel slopes b and diffusion limiting current densities inside the catalytic film (j_l^film) were found to be in the same order for both catalysts, whereas the exchange current density (j₀), which is a suitable estimation of the activity of the catalyst, was at least 10 times higher at the Pt/C catalyst than at the Ag/C catalyst. The behavior of both catalysts in methanol containing electrolyte was investigated and it was found that at a low methanol concentration, the Pt/C catalyst was quasi-tolerant to methanol. But, at a high methanol concentration, the ORR at a Pt/C was affected. However, the Pt/C catalyst showed in each case better activity towards ORR than the Ag/C catalyst, even if the latter one was less affected by the presence of methanol than the former one.     

Pd-Co carbon-nitride electrocatalysts for polymer electrolyte fuel cells

In this paper is described the preparation of new platinum-free Pd-Co carbon-nitride electrocatalysts (Pd-Co-CNs) for application in low-temperature fuel cells. Two groups of materials with formula K_n[Pd_xCo_yC_zN_lH_m] were synthesized, which are grouped in two ensembles: the first is characterized by a molar ratio y/x > 1 (I), and the second by y/x < 1 (II). K_n[Pd_xCo_yC_zN_lH_m] materials were prepared through a two-step synthesis protocol. The effect of the Pd/Co molar ratio and of the temperature of the thermal treatments on the structure and properties of the products were studied extensively by thermogravimetry, scanning electron microscopy, and vibrational (FT-IR and micro-Raman) and XPS spectroscopy. Vibrational studies revealed that I and II systems consist of two polymorphs of α- and graphitic-like carbon-nitride nanomaterials. The electrochemical activity towards the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) was measured by cyclic voltammetry measurements with thin-film rotating disk electrode (CV-TF-RDE). The electrochemical performance of Pd-Co-CNs of group I obtained at t_f ≥ 700 °C resulted higher than that measured for a platinum-based commercial electrocatalyst in terms of both the activity towards the ORR and the HOR and of the resistance towards the poisoning effect of methanol towards the ORR.