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Nanomaterials 2021, 11, 1017 for Pd/Co3O4@MWCNT were recorded in O2-saturated 1.0 M KOH at various rotation speeds [29–31]. As shown in Figure 5, the polarization curves suggest that the measured current in- tensity increased with the high-speed rotation rate due to enhanced diffusion. Based on the diffusion in the kinetically limited regions, the Koutecky-Levich (K-L) plot was8uosfe1d2 to determine the electron transfer number. The K-L equation is as follows: 1=1+1= 1 +1 (1) 1𝑎/2 𝐽 𝐽𝐿 𝐽𝑘 𝐵2/𝑤3−1/6𝐽𝑘 B = 0.62nFCoDo ν (2) B = 0.62nFCoDo2/3 ν−1/6 (2) where J is the measured current density, Jk and JL are the kinetic- and diffusion-limiting current density, ω is the electrode rotation rate, F is Faraday’s constant (96,485 C mol−1), ν where J is the measured current density, Jk and JL are the kinetic- and diffusion-limiting isthekineticviscosityintheelectrolyte(0.01cm2s−1),C istheconcentrationofoxy−g1en o current density, ω is the electrode rotation rate, F is Faraday’s constant (96,485 C mol ), ν in the electrolyte (7.8 × 10−7 mol cm−1), and D 2is −t1he diffusion coefficient O (1.8 × 10−5 o2 is the kinetic viscosity in the electrolyte (0.01 cm s ), Co is the concentration of oxygen in m2s−1).Thenumber−o7felectro−n1stransferred,determinedusingEquations(1)−5and2 (−21), the electrolyte (7.8 × 10 mol cm ), and Do is the diffusion coefficient O2 (1.8 × 10 m s ). was approximately 3.67 electrons on average, indicating a four-electron oxygen reduction The number of electrons transferred, determined using Equations (1) and (2), was approx- pathway. imately 3.67 electrons on average, indicating a four-electron oxygen reduction pathway. Figure 5. (a) LSV curves of Pd/Co O @MWCNT at different rotation rates. (b) K−L plots for synthesized catalysts from Figure 5. (a) LSV curves of Pd/Co3O4@MWCNT at different rotation rates. (b) K−L plots for synthesized catalysts from RDE measurements. (c) RRDE curves for the ORR using diifferenttelleccttrroccaattaalylyssttssaatt220000rrppmininO2−saturated 1.0 M KOH 2 aqueous solution. Figure 5c shows the RRDE curves of Pd/Co3O4@MWCNT at a rotating speed of 2000 rpm in O2-saturated 1.0 M KOH. The ORR is under mixed kinetic-diffusion control in the potential range between 0.5 V and 1.1 V, followed by a region where diffusion limiting currents can be observed. The ring and disk currents both increased dramatically because of the saturated oxygen environment, which is supplied to the working electrode surface area. This could result in an enhancement of the oxygen reduction reaction [32,33]. Figure 6 presents the durability test results for the commercial Pd/C catalyst and Pd/Co3O4@MWCNT composites. Fuel tolerance and stability are vital characteristics of high-performance ORR catalysts. The current density of commercial Pd/C decreased by 57%, whereas that of the Pd/Co3O4@MWCNT composite catalyst decreased to a lesser extent and retained 68% of its initial value. With regard to the long-time durability of the catalysts, the voltammograms showed high stability of the Pd/Co3O4@MWCNT composite, with no distinct current change; the initial limiting current density was 0.67 V (vs. RHE). All chronoamperometric responses demonstrate that the Pd/Co3O4@MWCNT composite possesses high durability and favorable kinetics. Therefore, the composite can be used effectively as a cathode catalyst in alkaline fuel cells.PDF Image | Effect of Co3O4 Nanoparticles on Improving Catalytic Behavior
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