Formic acid oxidation (FAO) on Pd electrode at various temperatures is investigated by cyclic voltammetry, potential step chronoamperometry and electrochemical in situ infrared spectroscopy (IRS). With increasing potential, FAO activity first increases, then decreases at higher potentials, the peak potential increases from 0.65 V to ca. 0.9–1.0 V with increasing temperature from 298 K to 343 K. The Tafel slope for FAO on Pd is found to be ca.260 ± 40mV/dec at around 0.25 V, it increases with the electrode potential and reaches ca. 470 ± 20 mV/dec at around 0.5 V. The apparent activation energies (E_a,app) and pre-exponential factors (A_app) are estimated from the cyclic voltammograms or current transients recorded at different temperatures. E_a,app decreases slightly with increasing reaction potential from 0.25 V to ca. 0.6 V with a slope of ca. 0.27 eV/V. The H/D kinetic isotope effect is found to be ca. 2 in the potential region from 0.2 V to 0.4 V, it increases with potential at E > 0.4 V and reaches ca. 6 at 0.6 V. Only bridge-bonded bicarbonate and formate are detected by IRS during FAO on Pd, the role of these species for FAO on Pd are discussed. Possible origins for the large Tafel slope, and the correlation between the large Tafel slope and the small potential-dependent change of the activation energy are discussed.

通过循环伏安法，电位阶跃计时电流法和电化学原位红外光谱法（IRS）研究了在各种温度下Pd电极上的甲酸氧化（FAO）。随着潜力的增加，粮农组织的活动先增加，然后在较高的潜力下减少，峰值电位从0.65 V增加到大约5V。当温度从298 K升高到343 K时为0.9–1.0V。FAO在Pd上的Tafel斜率在0.25 V左右大约为260±40mV / dec，随着电极电势的增加而上升，达到大约ca。在约0.5 V时为470±20 mV / dec。根据循环伏安图或在不同温度下记录的电流瞬变，估算了表观活化能（E _a，app）和指数前因子（A _app）。E _a，app随着反应电势从0.25 V升高到大约，电压会稍微降低。0.6 V的斜率约为 0.27 eV / V。发现H / D动力学同位素效应为约。2在0.2 V至0.4 V的电势区域中，随着E> 0.4 V的电势而增加，并达到ca。6在0.6 V电压下进行。IRS在Fd期间仅检测到桥键式碳酸氢盐和甲酸盐，并讨论了这些物种对FAO在Pd上的作用。讨论了大Tafel斜率的可能成因，以及大Tafel斜率与活化能的小电位相关变化之间的相关性。