铅修饰的纳米多孔铂催化剂对甲酸氧化的电活性
收稿日期: 2017-07-07
修回日期: 2017-12-26
网络出版日期: 2018-01-08
基金资助
国家自然科学基金项目（21376070）
Lead Modified Nanoporous Platinum Electro-Catalysts for Formic Acid Oxidation
Received date: 2017-07-07
Revised date: 2017-12-26
Online published: 2018-01-08
Supported by
National Natural Science Foundation of China(21376070)
用合适金属修饰的铂催化剂能够显著增强其对甲酸氧化的电活性. 本文以水热法制备了钛负载的纳米多孔铂电极（nanoPt/Ti），然后采用循环伏安法，通过扫描不同的周数（n），用适量的铅对nanoPt/Ti电极进行修饰，得到一种新型的铅修饰的纳米多孔铂电极（nanoPb(n)-Pt/Ti）. 采用循环伏安（CV）、计时电流和计时电位法研究其对对甲酸氧化的电活性. CV结果显示nanoPt/Ti和nanoPb(n)-Pt/Ti电极对甲酸氧化表现出较高的催化活性，并且nanoPb(20)-Pt/Ti电极对甲酸氧化的起始电位为-0.06 V，相比nanoPt/Ti电极的起始电位（0.06 V），明显有所负移. 此外，nanoPb(20)-Pt/Ti电极的第一个氧化峰电流密度为12.7 mA·cm-2，远远大于nanoPt电极（4.4 mA·cm-2）；计时电流显示在电位为0.1 V时，在0.5 mol·L-1 H2SO4 + 1 mol·L-1 HCOOH溶液中，nanoPb(20)-Pt/Ti电极达到稳定时的电流为8.09 mA·cm-2，是nanoPt电极的60倍，表明铅修饰的nanoPt/Ti对甲酸氧化的电活性急剧增加；在1.5 mA、2 mA、2.2 mA和2.5 mA下的计时电位结果表明，nanoPb(20)-Pt/Ti电极上甲酸氧化过程表现出显著的电化学振荡，且和nanoPt/Ti电极相比，振荡现象能持续更长的时间，说明nanoPb(20)-Pt/Ti电极具有更强的表面抗毒化能力.
关键词： 甲酸氧化；纳米多孔Pt; 纳米多孔Pb-Pt；电化学震荡
张媛媛 , 易清风 , 左葛琨琨 , 邹涛 , 刘小平 , 周秀林 . 铅修饰的纳米多孔铂催化剂对甲酸氧化的电活性[J]. 电化学, 2018 , 24(3) : 270 -278 . DOI: 10.13208/j.electrochem.170707
Platinum (Pt) catalysts modified by other suitable metals significantly enhance their electrochemical activities for formic acid oxidation. In this work, a titanium-supported nanoporous network platinum (nanoPt/Ti) electrode was prepared using a hydrothermal method. The as-prepared nanoPt/Ti electrode was modified with a certain amount of lead by using cyclic voltammetry for different scan cycle numbers (n), namely, n = 10, 15, 20 and 30, to synthesize the novel lead-modified nanoporous Pt (nanoPb(n)-Pt/Ti) electrodes. Electro-oxidation of formic acid on these electrodes was studied with cyclic voltammetry (CV), chronoamperometry and chronopotentiometry in sulfuric acid solution. CV curves showed that both nanoPt/Ti and nanoPb(n)-Pt/Ti electrodes displayed high electrocatalytic activities for formic acid oxidation, and the onset potential of formic acid oxidation on the nanoPb(20)-Pt/Ti electrode was -0.06 V, which was more negative than that on the nanoPt/Ti electrode (0.06 V). In addition, the first oxidation peak current density on the nanoPb(20)-Pt/Ti electrode was 12.7 mA·cm-2, which was far larger than that on the nanoPt electrode (4.4 mA·cm-2). Chronoamperommetric data at 0.1 V in 0.5 mol·L-1 H2SO4 + 1 mol·L-1 HCOOH suggested that the nanoPb(20)-Pt/Ti electrode exhibited the stable current density of 8.09 mA·cm-2 which was 60 times higher than the nanoPt electrode, indicating the dramatic enhancement of electroactivity on the lead-modified nanoPt/Ti electrode for formic acid oxidation with comparison to the nanoPt/Ti electrode. Chronopotentiometric responses on the electrode at 1.5 mA, 2 mA, 2.2 mA and 2.5 mA in 0.5 mol·L-1 H2SO4 + 1 mol·L-1 HCOOH revealed notable electrochemical oscillations which lasted longer time than those on the nanoPt/Ti electrode. It was demonstrated that the lead-modified nanoPb(20)-Pt/Ti electrode presented the most significant enhancement on surface anti-poisoning ability.
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