Nanoscale compositional changes and modification of the surface reactivity of Pt3Co/C nanoparticles during proton-exchange membrane fuel cell operation

This study bridges the structure/composition of Pt-Co/C nanoparticles with their surface reactivity and their electrocatalytic activity. We show that Pt₃Co/C nanoparticles are not stable during PEMFC operation (H₂/air; j = 0.6 A cm⁻², T = 70 °C) but suffer compositional changes at the nanoscale. In the first hours of operation, the dissolution of Co atoms at their surface yields to the formation of a Pt-enriched shell covering a Pt-Co alloy core (“Pt-skeleton”) and increases the affinity of the surface to oxygenated and hydrogenated species. This structure does not ensure stability in PEMFC conditions but is rather a first step towards the formation of “Pt-shell/Pt-Co alloy core” structures with depleted Co content. In these operating conditions, the Pt-Co/C specific activity for the ORR varies linearly with the fraction of Co alloyed to Pt present in the core and is severely depreciated (ca. −50%) after 1124 h of operation. This is attributed to: (i) the decrease of both the strain and the ligand effect of Co atoms contained in the core (ii) the changes in the surface structure of the electrocatalyst (formation of a multilayer-thick Pt shell) and (iii) the relaxation of the Pt surface atoms.     

Preparation of cost-effective Pt–Co electrodes by pulse electrodeposition for PEMFC electrocatalysts

Low loading platinum–cobalt (Pt–Co) cathode catalyst on a Nafion(Na⁺)-bonded carbon layer is fabricated by using galvanostatic pulse technique to show the advantage of electrodeposition for high utilization of catalyst in proton exchange membrane fuel cell (PEMFC). We observed that Pt–Co catalysts evenly exist on the surface of carbon electrode and its thickness is about 5.8 μm, which is four times thinner than conventional Pt/C. Improved single cell power performance of Pt–Co cathode catalysts with a ratio of 3.2:1 compared with Pt/C is clearly presented.     

Phosphate adsorption and its effect on oxygen reduction reaction for PtxCoy alloy and Aucore–Ptshell electrocatalysts

The phosphate adsorption characteristics and its effect on oxygen reduction reaction (ORR) were examined for various carbon-supported catalysts (Pt/C, Pt₃Co/C, PtCo/C, and Au_core–Pt_shell/C). Using cyclic voltammetry (CV) and the addition of phosphoric acid, the degree of phosphate adsorption for each catalyst was evaluated based on the intensity of the phosphate adsorption peaks (0.25–0.3 V and 0.5–0.65 V) and on the decrease in the platinum oxidation current (0.9 V). In the N₂O reduction technique, the surface structures were analyzed using N₂O as an electrochemical probe, which showed that as the Co content increased, (i) steps or defects were introduced by surface reconstruction, (ii) the phosphate adsorbed more strongly compared to Pt/C with a preference for the terrace sites, and (iii) the potential of zero total charge (PZTC) shifted to negative potentials. In the case of the Au_core–Pt_shell/C, the phosphate adsorption was found to be weaker than other catalysts, including Pt/C catalyst. The relative ORR activity with PA addition, normalized by that with no phosphate adsorption, was significantly smaller for Co containing alloy catalysts (PtCo/C: 18.2%) and larger for Au_core–Pt_shell (30.2%) compared with the Pt/C catalyst (27.8%), confirming the phosphate adsorption characteristics of each catalyst, as measured by CV and N₂O reduction analysis.     

Stability characteristics of Pt1Ni1/C as cathode catalysts in membrane electrode assembly of polymer electrolyte membrane fuel cell

To understand the difference in degradation characteristics between carbon-supported platinum (Pt/C) and platinum–nickel alloy (Pt₁Ni₁/C) cathode catalysts in membrane electrode assemblies (MEAs) of a polymer electrolyte membrane fuel cell (PEMFC), constant current operation of MEA in a single cell was conducted for 1100 h. A significant change in cell potential for the Pt₁Ni₁/C MEA was observed throughout the test. High-resolution transmission electron microscopy showed that sintering and detachment of metal particles in the Pt₁Ni₁/C catalyst occurred more sparingly than in the Pt/C catalyst. Instead, X-ray photoelectron spectroscopy element mapping revealed dissolution of Ni atoms in the Pt₁Ni₁ catalysts even when the Pt₁Ni₁/C catalyst used in the MEA was well synthesized.     

Insights on the SO2 poisoning of Pt3Co/VC and Pt/VC fuel cell catalysts

SO₂ poisoning of carbon-supported Pt₃Co (Pt₃Co/VC) catalyst is performed at the cathode of proton exchange membrane fuel cells (PEMFCs) in order to link previously reported results at the electrode/solution interface to the FC environment.First, the surface area of Pt₃Co/VC catalyst is rigorously characterized by hydrogen adsorption, CO stripping voltammetry and underpotential deposition (upd) of copper adatoms. Then the performance of PEMFC cathodes employing 30 wt.% Pt₃Co/VC and 50 wt.% Pt/VC catalysts is compared after exposure to 1 ppm SO₂ in air for 3 h at constant cell voltage of 0.6 V. In agreement with results reported for the electrode/solution interface, the Pt₃Co/VC is more susceptive to SO₂ poisoning than Pt/VC at a given platinum loading.Both catalysts can be recovered from adsorbed sulfur species by running successive polarization curves in air or cyclic voltammetry (CV) in inert atmosphere. However, the activity of Pt₃Co/VC having ∼3 times higher sulfur coverage is recovered more easily than Pt/VC. To understand the difference between the two catalysts in terms of activity recovery, platinum-sulfur interaction is probed by thermal programmed desorption at the catalyst/inert gas interface and CV at the electrode/solution interface and in the FC environment.     

Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations

A simple procedure is introduced to use periodic Density Functional Theory calculations to estimate trends in the thermodynamics of surface alloy dissolution in acidic media. With this approach, the dissolution potentials for solute metal atoms embedded in the surface layer of various host metals (referenced to the dissolution potential of the solute in its pure, metallic form) are calculated. Periodic trends in the calculated potentials are found to be related to trends in surface segregation energies of the various solute/host pairs. The effects of water splitting and concomitant hydroxyl adsorption on the dissolution potentials are also considered; these effects do not change the potentials for highly oxophilic solutes embedded in less active hosts, but they do decrease the dissolution potential for more inert solutes on oxophilic hosts. Finally, the dissolution of Pt “skin” layers from Pt₃X (X = Fe, Co, and Ni) bulk alloys is analyzed; the Pt skins are found to be stabilized compared to pure Pt.     

Partial oxidation of methane to synthesis gas over α-Al2O3-supported bimetallic Pt–Co catalysts

The partial oxidation of methane to synthesis gas was studied at atmospheric pressure and in the temperature range of 550–800°C over -Al₂O₃-supported bimetallic Pt–Co, and monometallic Pt and Co catalysts, respectively. Both methane conversion and CO selectivity over a bimetallic Pt_0.5Co₁ catalyst were higher than those over monometallic Pt_0.5 and Co₁ catalysts. Furthermore, the addition of platinum in Pt–Co bimetallic catalysts effectively improved their resistance to carbon deposition with no coking occurring on Pt_0.5Co₁ during 80 h reaction. The FTIR study of CO adsorption observed only linearly bonded CO on bimetallic Pt–Co catalysts. TPR and XPS showed enhanced formation of a cobalt surface phase (CSP) in bimetallic Pt–Co catalysts. The origins of the good coking resistivity of bimetallic Pt–Co catalysts were discussed.     

Synthesis and electrocatalytic oxygen reduction activity of graphene-supported Pt3Co and Pt3Cr alloy nanoparticles

Graphene-supported Pt and Pt₃M (M = Co and Cr) alloy nanoparticles are prepared by ethylene glycol reduction method and characterized with X-ray diffraction and transmission electron microscopy. X-ray diffraction depicted the face-centered cubic structure of Pt in the prepared materials. Electron microscopic images show the high dispersion of metallic nanoparticles on graphene sheets. Electrocatalytic activity and stability of the materials is investigated by rotating-disk electrode voltammetry. Oxygen reduction activity of the Pt₃M/graphene is found to be 3–4 times higher than that of Pt/graphene. In addition, Pt₃M/graphene electrodes exhibited overpotential 45–70 mV lower than that of Pt/graphene. The high catalytic performance of Pt₃M alloys is ascribed to the inhibition of formation of (hydr) oxy species on Pt surface by the alloying elements. The fuel cell performance of the catalysts is tested at 353 K and 1 atm. Maximum power densities of 790, 875, and 985 mW/cm² are observed with graphene-supported Pt, Pt₃Co, and Pt₃Cr cathodes, respectively. The enhanced electrocatalytic performance of the Pt₃M/graphene (M = Co and Cr) compared to that of Pt/graphene makes them a viable alternative to the extant cathodes for energy conversion device applications.     

Optimum Pt and Ru atomic composition of carbon-supported Pt–Ru alloy electrocatalyst for methanol oxidation studied by the polygonal barrel-sputtering method

The optimum Pt and Ru atomic composition of a carbon-supported Pt–Ru alloy (Pt–Ru/C) used in a practical direct methanol fuel cell (DMFC) anode was investigated. The samples were prepared by the polygonal barrel-sputtering method. Based on the physical properties of the prepared Pt–Ru/C samples, the Pt–Ru alloy was found to be deposited on a carbon support. The microscopic characterization showed that the deposited alloy forms nanoparticles, of which the atomic ratios of Pt and Ru (Pt:Ru ratios) are uniform and are in accordance with the overall Pt:Ru ratios of the samples. The formation of the Pt–Ru alloy is also supported by the electrochemical characterization. Based on these results, methanol oxidation on the Pt–Ru/C samples was measured by cyclic voltammetry and chronoamperometry. The results indicated that the methanol oxidation activities of the prepared samples depended on the Pt:Ru ratios, of which the optimum Pt:Ru ratio is 58:42 at.% at 25 °C and 50:50 at.% at 40 and 60 °C. This temperature dependence of the optimum Pt:Ru ratio is well explained by the relationship between the methanol oxidation reaction process and the temperature, which is reflected in the rate-determining steps considered from the activation energies. It should be noted that at 25–60 °C, the Pt–Ru/C with Pt:Ru = 50:50 at.% prepared by our sputtering method has the higher methanol oxidation activity than that of a commercially available sample with the identical overall Pt:Ru ratio. Consequently, the polygonal barrel-sputtering method is useful to prepare the practical DMFC anode catalysts with the high methanol oxidation activity.     

Palladium-based electrodes: A way to reduce platinum content in polymer electrolyte membrane fuel cells

To decrease the Pt content, a polymer electrolyte membrane fuel cell (PEMFC) was formed using a carbon supported Pd₉₆Pt₄ catalyst as the anode material, and a carbon supported Pd₄₉Pt₄₇Co₄ catalyst as the cathode material. The as-obtained Pd-based PEMFC with an overall Pd:Pt:Co atomic composition of electrodes (anode + cathode) = 72:26:2 exhibited a performance not too far from that of the fuel cell with the conventional 100% Pt electrodes. With a Pt content of 35 wt% of that of the cell with full Pt electrodes, at a current density of 1 A cm⁻² the performance loss of the cell with the Pd-based catalysts was only 11%, with 6% ascribed to the anode catalyst and 5% to the cathode catalyst. The maximum power density of the Pd-based cell was 76% of that of the cell with Pt catalysts.     

Preparation of Pt–Co alloy catalysts by electrodeposition for oxygen reduction in PEMFC

Direct current (DC) and pulse current (PC) electrodeposition of Pt–Co alloy onto pretreated electrodes has been conducted to fabricate catalyst electrodes for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). The effect of plating mode and pulse plating parameters on the Pt–Co alloy catalyst structure, composition and electroactivity for the ORR in PEMFC has been investigated. The electrodeposited Pt–Co alloy catalyst indicates higher electrocatalytic activity towards the ORR than the electrodeposited Pt catalyst. The activity of the electrodeposited Pt–Co catalysts is further improved by applying the current in a pulse waveform pattern. The electrodeposition mode and the pulse plating parameters do not have the significant effect on the Pt:Co composition of deposited catalysts, but show the substantial effect on the deposit structures produced. The Pt–Co catalysts prepared by PC electrodeposition have finer structures and contain smaller Pt–Co catalyst particles compared to that produced by DC electrodeposition. By varying the Pt concentration in deposition solution, the Pt:Co composition of the electrodeposited catalyst that exhibits the highest activity is found. The Pt–Co alloy catalyst with the Pt:Co composition of 82:18 obtained at the charge density of 2 C cm⁻², the pulse current density of 200 mA cm⁻², 5% duty cycle and 1 Hz was found to yield the best electrocatalytic activity towards the ORR in PEMFC.     

Activity,selectivity, and methanol tolerance of novel carbon-supported Pt and Pt<Subscript>3</Subscript>Me (Me = Ni,Co) cathode catalysts

The activity, selectivity, and methanol tolerance of novel, carbon supported high-metal loading (40 wt.%) Pt/C and Pt₃Me/C (Me = Ni, Co) catalysts for the O₂ reduction reaction (ORR) were evaluated in model studies under defined mass transport and diffusion conditions, by rotating (ring) disk and by differential electrochemical mass spectrometry. The catalysts were synthesized by the organometallic route, via deposition of pre-formed Pt and Pt₃Me pre-cursors followed by their decomposition into metal nanoparticles. Characteristic properties such as particle sizes, particle composition and phase formation, and active surface area, were determined by transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. For comparison, commercial Pt/C catalysts (20 and 40 wt.%, E-Tek, Somerset, NJ, USA) were investigated as well, allowing to evaluate Pt loading effects and, by comparison with the pre-cursor-based catalyst with their much smaller particle sizes (1.7 nm diameter), also particle size effects. Kinetic parameters for the ORR were evaluated; the ORR activities of the bimetallic catalysts and of the synthesized Pt/C catalyst were comparable and similar to that of the high-loading commercial Pt/C catalyst; at typical cathode operation potentials H₂O₂ formation is negligible for the synthesized catalysts. Due to their lower methanol oxidation activity the bimetallic catalysts show an improved methanol tolerance compared to the commercial Pt/C catalysts. The results indicate that the use of very small particle sizes is a possible way to achieve reasonably good ORR activities at an improved methanol tolerance at DMFC cathode relevant conditions.     

Synthesis of Pt3Co Alloy Nanocatalyst via Reverse Micelle for Oxygen Reduction Reaction in PEMFCs

Monodispersed, uniformly alloyed Pt₃Co alloy nanoparticle electrocatalysts were synthesized via reduction of metallic precursors by sodium borohydride in heptane/polyethylene glycol dodecylether (Brij)/water reverse micelles. These particles were further adsorbed on XC-72R carbon powder, separated from micelles, and characterized using X-ray diffraction (XRD), transmission electronic microscopy (TEM). The electrochemical activity for the oxygen reduction reaction (ORR) was characterized using a Rotating Disk Electrode (RDE) technique. Even though residual surfactants on the metallic nanoparticle reduced the active surface area of the electrocatalytic particles, the catalytic activity of the prepared Pt₃Co nanoparticles exhibited higher Pt mass and Pt surface area specific activities compared to pure Pt. The impact of heat treatment on the mean particle size, the electrochemical surface area (ESA), and on the activity was investigated and correlated to the residual surfactant coverage. Intermediate annealing temperatures resulted in larger ESA, despite particle growth pointing to lower surfactant coverage. Higher annealing temperatures caused large particle growth and reduced ESA, yet significant activity gains. A surface segregation mechanism resulting in a catalytically active Pt skin structure is hypothesized.     

Dissolution of Pt–M (M: Cu, Co, Ni, Fe) binary alloys in sulfuric acid solution

The dissolution behavior of equimolar Pt–M (M: Cu, Co, Ni, Fe) alloys has been studied under conditions of immersion, potentiostatic polarization, and potential cycling in 0.5 M H₂SO₄ solution at 25 °C. The quantity of dissolved ions under these conditions has been determined with inductively coupled plasma mass spectrometry (ICP-MS). In 3-h immersion tests, selective dissolution of M atoms occurs immediately after immersion and is quickly suppressed. The rest potential shifts rapidly in the noble direction and approaches that for pure Pt. The general features of cyclic voltammograms of the alloys are very similar to those for pure Pt, although the current is considerably larger for the Pt–Fe alloy. These results indicate that the surfaces of these alloys are covered with a Pt-enriched layer because of preferential dissolution of M atoms. The resulting suppression of dissolution is reversed by potentiostatic polarization at 1.4 V. The enhancement at 1.4 V is more remarkable under the condition of potential cycling.     

Scanning electrochemical microscopy characterization of bimetallic Pt–M (M = Pd, Ru, Ir) catalysts for hydrogen oxidation

A combinatorial screening method, combined with scanning electrochemical microscopy (SECM) in a tip-generation–substrate-collection (TG–SC) mode, was applied to systematically and rapidly identify potential bimetallic catalysts (Pt–M, M = Pd, Ru, Ir) for the hydrogen oxidation reaction (HOR). The catalytic oxidation of hydrogen on the candidate catalysts was further examined during cyclic voltammetric scans of the substrate with a tip close to the substrate. The quantitative rate of hydrogen oxidation on the candidate substrates was determined for different substrate potentials from SECM approach curves by fitting to a theoretical model. SECM screening results revealed that Pt₄Pd₆, Pt₉Ru₁ and Pt₃Ir₇ were the optimum composition of the catalysts from the Pt–Pd, Pt–Ru and Pt–Ir bimetallic systems for hydrogen sensors. The catalytic activity of the candidate catalysts in HOR was highly dependent on the substrate potential. The kinetic parameters for HOR were obtained on Pt₄Pd₆ (Tafel slope = 124 mV, k° = 0.19 cm/s, α = 0.52), Pt₉Ru₁ (Tafel slope = 140 mV, k° = 0.08 cm/s, α = 0.58) and Pt₃Ir₇ (Tafel slope = 114 mV, k° = 0.11 cm/s, α = 0.48) and compared with Pt (Tafel slope = 118 mV, k° = 0.17 cm/s, α = 0.5). Among the bimetallic catalysts studied, Pt₄Pd₆ exhibited the highest activity toward HOR with a high standard rate constant value in a wide range of applied potentials.     

Study of the kinetics and the influence of Biirr on formic acid oxidation at Pt2Ru3/C

Electrochemical oxidation of HCOOH in H₂SO₄ and HClO₄ solutions was examined on thin film Pt₂Ru₃/C electrode. XRD pattern revealed that Pt₂Ru₃ alloy consisted of the solid solution of Ru in Pt and the small amount of Ru or solid solution of Pt in Ru. According to STM images, Pt₂Ru₃ particles size was between 2 and 6 nm. It was established that electrochemical oxidation of HCOOH commenced at −0.1 V versus SCE at Pt sites in the catalyst. Kinetic parameters indicated that dehydrogenation path was predominant. Dehydration occurs in parallel, but without significant poisoning by CO_ad owing to oxidative removal by OH species on Ru atoms. The coverage of Pt₂Ru₃ surface by CO preadsorbed from the solution was found to be 24% lower when the surface was modified by irreversibly adsorbed Bi. Modification by Bi also shifted the onset potential for HCOOH oxidation for about 50 mV towards more negative values and consequently, increased the reaction rate for a factor of two. It was proposed that Ru acts through bifunctional mechanism, i.e. OH species adsorbed on Ru oxidizes CO_ad from Pt sites, while Bi hinders the adsorption of CO on Pt sites via electronic and/or ensemble effects.     

CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC

The performance of H₂/O₂ proton exchange membrane fuel cells (PEMFCs) fed with CO-contaminated hydrogen was investigated for anodes with PdPt/C and PdPtRu/C electrocatalysts. The physicochemical properties of the catalysts were characterized by energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and “in situ” X-ray absorption near edge structure (XANES). Experiments were conducted in electrochemical half and single cells by cyclic voltammetry (CV) and I-V polarization measurements, while DEMS was employed to verify the formation of CO₂ at the PEMFC anode outlet. A quite high performance was achieved for the PEMFC fed with H₂ + 100 ppm CO with the PdPt/C and PdPtRu/C anodes containing 0.4 mg metal cm⁻², with the cell presenting potential losses below 200 mV at 1 A cm⁻², with respect to the system fed with pure H₂. For the PdPt/C catalysts no CO₂ formation was seen at the PEMFC anode outlet, indicating that the CO tolerance is improved due to the existence of more free surface sites for H₂ electrooxidation, probably due to a lower Pd-CO interaction compared to pure Pd or Pt. For PdPtRu/C the CO tolerance may also have a contribution from the bifunctional mechanism, as shown by the presence of CO₂ in the PEMFC anode outlet.     

Degradation of proton exchange membrane by Pt dissolved/deposited in fuel cells

An accelerated single cell test and single electrode cell test were carried out to investigate membrane degradation by Pt dissolved/deposited on the membrane. For a cell operating under accelerated conditions (OCV, 90°C, anode RH 0%, cathode O₂ supply), MEA analyses revealed that Pt particles were deposited in the membrane at the anode side, with a decrease in F, O, and C content near the anode side of the membrane. Dissolved Pt from the cathode showed that Pt existed mainly in the form of Pt²⁺ ionic species. Oxygen and hydrogen helped Pt dissolution from the cathode and Pt deposition in the membrane, respectively. Radical formation on deposited Pt in the membrane was detected by electron spin resonance (ESR). Fluoride emission rate (FER, an indicator of membrane degradation rate) increased with an increase in the amount of Pt in the membrane.     

The effectiveness of platinum/carbon electrocatalysts: Dependence on catalyst layer thickness and Pt alloy catalytic effects

In our previous work, we have proposed a new method to estimate the effective Pt utilization or “effectiveness” (Ef_Pt) using the ratio of the mass activity (MA) for the oxygen reduction reaction in the membrane-electrode assembly (MEA) in the polymer electrolyte fuel cell to that in the channel flow double electrode measurement, MA_max, under similar conditions. In the present research, applying this method, we have focused on elucidating the effect of the thickness of the catalyst layer (CL), the effect of Pt-based alloy catalysts, and effect of the state of dispersion of the Pt/C catalysts in the CL in measurements carried out at 80 °C and various relative humidities (RH), in either O₂ or air. The effect of a thin CL (0.04 mg cm⁻², Pt/C) has improved Ef_Pt by a factor of four, going from 3% to 12%, and the integrated effect of a thin CL and alloying (0.05 mg cm⁻² Pt₃Co) has improved Ef_Pt by a factor of six, going from 3% to 17% for air at 0.85 V, T_cell = 80 °C, and 30% RH. Furthermore, we found that the Ef_Pt values were dependent upon the state of Pt dispersion in the CL. The highest Ef_Pt value obtained thus far for air at 0.85 V, T_cell = 80 °C, and 100% RH was ca. 22%, shown by a low Pt loading CL diluted with added uncatalyzed carbon black (0.04 mg cm⁻², overall average 30 wt%-Pt).     

Performance and stability of Pt-based ternary alloy catalysts for PEMFC

Carbon-supported Pt-based ternary alloy electrocatalysts were prepared by incipient wetness method in order to elucidate the origin of the enhanced activity of oxygen reduction reaction in PEMFC. To measure the catalytic activity and stability of the cathode alloy catalysts (electrodes containing Pt loading of 0.3 mg/cm², 20 wt.% Pt/C, E-TEK), the I-V polarization curves were obtained. All alloy catalysts showed higher performances than Pt/C. It can be concluded that as platinum formed alloys with transition metals, the electronic state of Pt and the nearest neighbor Pt-Pt distance changes, which significantly influence the electrocatalytic activity for oxygen reduction.Long-term stability test was performed with the Pt₆Co₁Cr₁/C alloy catalyst for 500 h. According to XPS analysis, the lower oxide component with Pt₆Co₁Cr₁/C electrocatalyst provides a large portion of platinum in metallic species in the electrocatalyst and it seems to be mainly responsible for its enhanced activity towards oxygen reduction.