Department of Chemical & Biochemical Engineering, College of Chemistry & Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
Nanoscale. 2019 Feb 14;11(7):3311-3317. doi: 10.1039/c8nr08935c.
Self-recoverable Pd-Ru/TiO2 nanocatalysts have been prepared by electrochemical stripping of Pd-Ru/TiO2 precursors. For the ethanol oxidation reaction (EOR), these Pd-Ru/TiO2 nanocatalysts are used as an anode catalyst. The characterization of catalysts via chronoamperometry has been repeated 15 times. After 15 stability tests, the Pd1Ru0.69/TiO2 nanocatalysts still achieve a factor of 9.4 enhancement at the residual current density (309.42 mA mgPd-1) for the EOR over commercial Pd/C catalysts (33.01 mA mgPd-1). From the 5th to 15th test, when each 10 000 s stability test is performed in a fresh ethanol electrolyte, the initial and residual current density of the catalysts could recover to the original or even better value in a few hours before performing another 10 000 s stability test. Herein, these Pd-Ru/TiO2 nanocatalysts with ultrastability towards ethanol electrooxidation are self-recoverable. Density functional theory calculations reveal that the introduction of oxophilic metal Ru and a TiO2 support into Pd-based catalysts and the synergistic effects between Ru and TiO2 have led to the ultrastability towards the EOR. The introduction of oxophilic metal Ru and a TiO2 support into catalysts can reduce the adsorption energy of OHads on the Pd-Ru/TiO2 nanocatalysts, and it will inhibit the COads produced and adsorbed on the Pd surface.
通过电化学剥离 Pd-Ru/TiO2 前驱体制备了自修复 Pd-Ru/TiO2 纳米催化剂。对于乙醇氧化反应 (EOR),这些 Pd-Ru/TiO2 纳米催化剂被用作阳极催化剂。通过计时安培法对催化剂进行了 15 次重复表征。经过 15 次稳定性测试,Pd1Ru0.69/TiO2 纳米催化剂在 EOR 中的剩余电流密度(309.42 mA mgPd-1)仍比商业 Pd/C 催化剂(33.01 mA mgPd-1)高 9.4 倍。从第 5 次到第 15 次测试,在新鲜的乙醇电解质中每次进行 10,000 s 的稳定性测试时,催化剂的初始和剩余电流密度可以在几个小时内恢复到原始值甚至更好的值,然后再进行另一个 10,000 s 的稳定性测试。在此,这些具有超稳定性的 Pd-Ru/TiO2 纳米催化剂可自行修复。密度泛函理论计算表明,将亲氧金属 Ru 和 TiO2 载体引入 Pd 基催化剂中和 Ru 和 TiO2 之间的协同效应导致了对 EOR 的超稳定性。将亲氧金属 Ru 和 TiO2 载体引入催化剂可以降低 Pd-Ru/TiO2 纳米催化剂上 OHads 的吸附能,并抑制在 Pd 表面上产生和吸附的 COads。