Towards More Active and Stable Pdagcr Electrocatalysts for Formic Acid Electrooxidation: the Role of Optimization Via Response Surface Methodology

Abstract

In this study, multiwall carbon nanotube (MCNT)-supported Pd (Pd/MWCNT) catalysts are prepared by using NaBH4 reduction method. In order to maximize the oxidation and reduction of H2SO4, synthesis conditions (Pd ratio, molar ratio of NaBH4/K2PdCl4, volume of deionized water, and duration of agitation) are optimized by using response surface methodology (RSM). The optimum synthesis conditions are determined as 58.2% of Pd by weight, 154.6 molar ratio of NaBH4 to K2PdCl4, 19.48 mL of deionized water, and 186.16 min of agitation duration. The effect of electrochemical measurement conditions on the oxidation kinetics of Pd/MWCNT is also investigated by RSM. The optimum electrochemical measurement conditions are found as 10 mu L of catalyst mixture, 90 degrees C of H2SO4 solution, and 5.5 M H2SO4. The Pd/MWCNT, Pd50Ag50/MWCNT, and Pd65.6Ag33.6Cr0.80/MWCNT catalysts prepared under optimized conditions are characterized by using X-ray diffraction, transmission electron microscopy, N-2 adsorption-desorption, and inductively coupled plasma mass spectrometry. The crystallite sizes of these catalysts are found as 4.85, 5.66, and 5.26 nm for Pd/MWCNT, Pd50Ag50/MWCNT, and Pd65.6Ag33.6Cr0.80/MWCNT catalysts, respectively. Isotherms of all these catalysts are found to be similar to Type V isotherms with H3 hysteresis loop. The average particle size of Pd50Ag50/MWCNT and Pd65.6Ag33.6Cr0.80/MWCNT catalysts are determined as 5.2 and 9.2 nm, respectively. Electrochemical performance of as-prepared catalysts is evaluated by using cyclic voltammetry and chronoamperometry. The formic acid electrooxidation (FAEO) activities are found as 18.9, 27.8, and 51.6 mA/cm(2) for Pd/MWCNT, Pd50Ag50/MWCNT, and Pd65.6Ag33.6Cr0.80/MWCNT, respectively. Pd65.6Ag33.6Cr0.80/MWCNT shows the highest activity and stability. Optimization of synthesis conditions and electrochemical measurement parameters allow us to obtain very good electrochemical activity and stability for FAEO reaction compared with anode catalysts in the literature.