Oxygen reduction reaction (ORR) in acidic media is investigated at various potentials in a thin-film rotating disk electrode (TF-RDE) configuration using electrochemical impedance spectroscopy (EIS). The ionomer-free and ionomer-containing thin-film catalyst layers are composed of Pt black and carbon-supported Pt catalysts of different metal loadings (5 and 20 wt%). The simplest EI spectrum consisting of an arc or a semi-circle is obtained at high potentials with ionomer-free Pt catalyst layers. The most complex spectrum consisting of a high frequency (HF) arc and two semi-circles is observed in the mixed diffusion-controlled region of the ionomer-containing catalyst layer with high loading of carbon-supported Pt. The nature of the EI spectrum is decided by the constituents of the thin-film catalyst layer and by the operating potential. The evolution of the EI spectra with ionomer and carbon contents is underlined. The effect of rotation rate (rpm) of the electrode on the impedance spectrum is also investigated. A series of equivalent circuits is required to completely describe the EI spectra of ORR. The kinetic parameters and the electrochemical surface area of the catalysts are derived from the impedance spectrum. Oxygen reduction reaction (ORR) is one of the most important reactions at the cathode side in low-temperature fuel cells (e.g., polymer electrolyte fuel cells (PEFCs) and direct methanol fuel cells (DMFCs)) and metal-air batteries.1-14 Because of the sluggish ORR kinetics and the stability issues of the catalyst in the electrochemical environment, expensive precious metal catalysts are often used in these electrochemical devices to catalyze the ORR. 15 Conventionally, the performance of the catalyst is evaluated in an operating fuel cell mode using the DC methods. [16][17][18] The information gathered from a DC analysis usually provides the sum of various polarizations of the electrode, which is difficult to separate into individual contributions. 19 On the other hand, electrochemical impedance spectroscopy (EIS), one of the AC methods, is a sensitive tool to investigate electrode-electrolyte interface and it allows the simultaneous resolution of various charge-transfer and mass-transfer processes (kinetic, ohmic, and diffusion). It involves a small sinusoidal electrical perturbation around a steady-state value and measures the impedance along with the phase angle. However, the interpretation of the EI spectra is difficult. Often, simple fitting models based on equivalent circuit analogues and physical models are used to extract the parameters those represent the underlying cell processes. [20][21][22][23][24][25][26] Springer et al. proposed the theoretical impedance spectrum of ORR on porous gas-diffusion electrode using the flooded-agglomerate electrode model in series with a thin electrolyte film. 20,25 The model predicted by Raistrick shows three semi-circles in the spectrum attributed to the charge-transfer process (ORR); agglomerate diffusion (depletion of the oxygen concentration in the pores...
Shape-controlled Pt nanoparticles (cubic, tetrahedral, and cuboctahedral) are synthesized using stabilizers and capping agents. The nanoparticles are cleaned thoroughly and electrochemically characterized in acidic (0.5 M H2SO4 and 0.1 M HClO4) and alkaline (0.1 M NaOH) electrolytes, and their features are compared to that of polycrystalline Pt. Even with less than 100% shape-selectivity and with the truncation at the edges and corners as shown by the ex-situ TEM analysis, the voltammetric features of the shape-controlled nanoparticles correlate very well with that of the respective single-crystal surfaces, particularly the voltammograms of shape-controlled nanoparticles of relatively larger size. Shape-controlled nanoparticles of smaller size show somewhat higher contributions from the other orientations as well because of the unavoidable contribution from the truncation at the edges and corners. The Cu stripping voltammograms qualitatively correlate with the TEM analysis and the voltammograms. The fractions of low-index crystallographic orientations are estimated through the irreversible adsorption of Ge and Bi. Pt-nanocubes with dominant {100} facets are the most active toward oxygen reduction reaction (ORR) in strongly adsorbing H2SO4 electrolytes, while Pt-tetrahedral with dominant {111} facets is the most active in 0.1 M HClO4 and 0.1 M NaOH electrolytes. The difference in ORR activity is attributed to both the structure-sensitivity of the catalyst and the inhibiting effect of the anions present in the electrolytes. Moreover, the percentage of peroxide generation is 1.5-5% in weakly adsorbing (0.1 M HClO4) electrolytes and 5-12% in strongly adsorbing (0.5 M H2SO4 and 0.1 M NaOH) electrolytes.
Oxygen reduction reaction (ORR) is investigated on bulk PdO-based catalysts (oxides of Pd and Pd3Co) in oxygen-saturated 0.1 M HClO4 to establish the role of surface oxides and adsorbed hydrogen in the activity and product selectivity (H2O/H2O2). The initial voltammetric features suggest that the oxides are inactive toward ORR. The evolution of the ORR voltammograms and potential-dependent H2O2 generation features on the PdO catalyst suggest gradual and parallel in situ reduction of the bulk PdO phase below ∼0.4 V in the hydrogen underpotential deposition (Hupd) region; the reduction of the bulk PdO catalyst is confirmed from the X-ray photoelectron spectra (XPS) and X-ray diffraction (XRD) patterns. The potential-dependent H2O2 generation features originate due to the presence of surface oxides and adsorbed hydrogen; this is further confirmed using halide ions (Cl(-) and Br(-)) and peroxide as the external impurities.
Carbon is heat-treated with a nitrogen-containing precursor (ammonia) to obtain nitrogen-doped carbon and the composition is estimated using CHN and XPS analysis. The active site density of the carbon and nitrogen-doped carbon is quantified using 1,2-dihydroxybenzene (catechol) molecules as an adsorbate in phosphate buffer (pH 7) solution. The features of the voltammograms of the catechol-adsorbed high surface area carbon and nitrogen-doped carbon are similar to that of the polished nitrogen-grafted glassy carbon electrode (GCE) reported in the literature. At the same time, the polished GCE does not show any well-defined catechol adsorption features. It is found that the adsorption charge (obtained by integrating the peak area, after subtracting the background) is in the order of N/C 900 > N/C 1000 > N/C 800 > N/C 700 > C. A similar trend is observed in their oxygen reduction reaction (ORR) activity in 0.1 M KOH. Moreover, the turnover frequency (ToF) of the catalysts is calculated and it is comparable to that reported in the literature using other methods for non-precious catalysts. Therefore, the adsorption charge can be correlated with the active site density of the carbon and nitrogen-doped carbon samples.
Shape-controlled nanoparticles are of utmost scientific and technological importance because of their facet-dependent physical and chemical properties. Under long-term electrochemical conditions, little is known about the stability and fate of these nanoparticles with selected exposed crystallographic orientations (facets) of high surface energy, while it is generally accepted that the surface area decreases. Therefore, the reconstruction and dissolution of platinum nanocubes (Pt-NCs), platinum cuboctahedral (Pt-CO) and platinum polycrystalline (Pt-PC) nanoparticles are investigated using voltammetry and in situ irreversible adsorption of Bi and Ge; the cleanliness of the Pt nanoparticles and the purity of the electrolyte solution are established with systematic voltammetric analysis in a H2SO4 electrolyte of different concentrations (0.01, 0.05, 0.5 and 1 M). The voltammetric results suggest that the {100} terrace sites undergo reconstruction/dissolution at a much higher rate relative to that of the {111} ordered bi-dimensional terrace sites and the reconstruction leads to the formation of {110}/{100} step sites. Therefore, the stability of the Pt-NCs is lower than that of the Pt-CO nanoparticles. The gradual decrease in the Hupd area on prolonged cycling in the lower potential range (0.06-0.6 and 0.06-0.8 V) is attributed to the accumulation of oxy-anions from the electrolyte on the Pt surface. Moreover, dissolution of highly energetic Pt sites also contributes to the reduction in the Hupd area, unlike that observed with low index Pt single crystal surfaces. On cycling to higher potential limits (1.0 and 1.2 V), the adsorbed anions are replaced with the oxygenated species or oxide; the protective oxide layer helps to stabilize the electrochemical surface area (ESA) of the Pt nanoparticles. With cycling, both Pt-NCs and Pt-CO eventually get converted to Pt-PC. These results are supported with cyclic voltammograms, irreversible adsorption of Bi and Ge, and HR-TEM.
Shape-controlled precious metal nanoparticles have attracted significant research interest in the recent past due to their fundamental and scientific importance. Because of their crystallographic-orientation-dependent properties, these metal nanoparticles have tremendous implications in electrocatalysis. This review aims to discuss the strategies for synthesis of shape-controlled platinum (Pt) and palladium (Pd) nanoparticles and procedures for the surfactant removal, without compromising their surface structural integrity. In particular, the electrocatalysis of oxygen reduction reaction (ORR) on shape-controlled nanoparticles (Pt and Pd) is discussed and the results are analyzed in the context of that reported with single crystal electrodes. Accepted theories on the stability of precious metal nanoparticle surfaces under electrochemical conditions are revisited. Dissolution, reconstruction, and comprehensive views on the factors that contribute to the loss of electrochemically active surface area (ESA) of nanoparticles leading to an inevitable decrease in ORR activity are presented. The contribution of adsorbed electrolyte anions, in-situ generated adsorbates and contaminants toward the ESA reduction are also discussed. Methods for the revival of activity of surfaces contaminated with adsorbed impurities without perturbing the surface structure and its implications to electrocatalysis are reviewed.
Electrochemical characterization to investigate the extent of reduction and the nature of reminiscent oxygen moieties in GO-based materials.
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