硫化物在铂电极上电氧化时空动力学的模型模拟和分析

doi:10.3866/PKU.WHXB201402142

物理化学学报 >> 2014, Vol. 30 >> Issue (4): 686-692.doi: 10.3866/PKU.WHXB201402142

硫化物在铂电极上电氧化时空动力学的模型模拟和分析

杨加平, 于辉耀, 何瑜庥, 解京选, 毕文彦, 高庆宇

中国矿业大学化工学院, 江苏徐州221116

收稿日期:2013-12-06 修回日期:2014-02-09 发布日期:2014-03-31
通讯作者: 高庆宇 E-mail:gaoqy@cumt.edu.cn
基金资助:
国家自然科学基金（21073232，51221462），中央高校基础研究基金（2013XK05）及江苏省高校优势学科平台项目和江苏省普通高校研究生科研创新计划项目（CXLX13-947）资助

Model Simulation and Analysis of Spatiotemporal Dynamics for the Electro-Oxidation of Sulfide on Platinum

YANG Jia-Ping, YU Hui-Yao, HE Yu-Xiu, XIE Jing-Xuan, BI Wen-Yan, GAO Qing-Yu

College of Chemical Engineering, China University of Mining and Technology, Xuzhou 221116, Jiangsu Province, P. R. China

Received:2013-12-06 Revised:2014-02-09 Published:2014-03-31
Contact: GAO Qing-Yu E-mail:gaoqy@cumt.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (21073232, 51221462), Fundamental Research Funds for the Central Universities, China (2013XK05), Priority Academic Program Development of Jiangsu Higher Education Institutions and the Program for Graduate Research and Innovation in Universities of Jiangsu Province, China (CXLX13-947).

摘要/Abstract

摘要：

根据铂电极上硫化物电催化氧化的反应机理，本文提取动力学模型并利用数值模拟研究了N型负微分阻抗（N-NDR）振荡区域的电极表面时空反应动力学. 在均相体系模拟中观察到电流简单振荡和复杂振荡，其来源于双电层电势自催化与传质限制和毒化物种吸附负反馈的相互耦合. 为了更接近于真实体系，在模型中考虑了平行和垂直于电极表面两个方向的传质过程. 模拟结果发现了与实验现象具有相同演化行为的复杂斑图，如行波和闪烁波；同时在传质耦合体系模拟中观察到双电层电势双臂螺旋波. 本研究工作促进对电化学体系时空斑图的理解和预测.

关键词: N型负微分阻抗, 振荡与复杂振荡, 斑图形成, 硫化物电化学氧化, 模型模拟

Abstract:

Based on the reaction mechanism of the electro-oxidation of sulfide on platinum, we propose a simplified model for studying the spatiotemporal dynamics on the electrode surface in the oscillatory region of the N-shaped negative differential resistance (N-NDR) through numerical simulation. Simple and complex current oscillations were observed during the homogeneous simulation, and these were caused by coupling between one positive feedback, i.e., double-layer potential autocatalysis, and two negative feedbacks consisting of a mass-transport limited step and a poison-adsorption process. To obtain a better simulation of the experimental situation, the transport of electroactive species in both the parallel and vertical directions of the electrode was taken into account to simulate pattern formation on the electrode. The model simulations gave complicated patterns including twinkling-eye patterns and traveling waves, which agree qualitatively with the experimental results and possess the same evolution principles. Meanwhile, for certain parameters more complex patterns were obtained, e.g., two-arm spiral waves of the double-layer potential. This opens an interesting perspective in the explanation and prediction of pattern formation in electrochemical systems.

Key words: N-shaped negative differential resistance, Oscillation and complex oscillation, Pattern formation, Electrochemical oxidation of sulfide, Model simulation

MSC2000:

O646

点击下载补充材料ZIP格式文件

杨加平, 于辉耀, 何瑜庥, 解京选, 毕文彦, 高庆宇. 硫化物在铂电极上电氧化时空动力学的模型模拟和分析[J]. 物理化学学报, 2014, 30(4): 686-692.

YANG Jia-Ping, YU Hui-Yao, HE Yu-Xiu, XIE Jing-Xuan, BI Wen-Yan, GAO Qing-Yu. Model Simulation and Analysis of Spatiotemporal Dynamics for the Electro-Oxidation of Sulfide on Platinum[J]. Acta Phys. -Chim. Sin., 2014, 30(4): 686-692.

参考文献

(1) O′Brien, J. A.; Hinkley, J. T.; Donne, S.W. Electrochim. Acta 2011, 56, 4224. doi: 10.1016/j.electacta.2011.01.092
(2) Dutta, P. K.; Rabaey, K.; Yuan, Z.; Keller, J. Water Res. 2008, 42, 4965. doi: 10.1016/j.watres.2008.09.007
(3) Cai, J.; Zheng, P. Bioresource Technol. 2013, 128, 760. doi: 10.1016/j.biortech.2012.08.046
(4) Haner, J.; Bejan, D.; Bunce, N. J. J. Appl. Electrochem. 2009, 39, 1733. doi: 10.1007/s10800-009-9873-7
(5) Helms, H.; Schlömer, E.; Jansen,W. Monatsh. Chem. 1998, 129, 617.
(6) Miller, B.; Chen, A. J. Electroanal. Chem. 2006, 588, 314. doi: 10.1016/j.jelechem.2006.01.006
(7) Strasser, P.; Eiswirth, M.; Koper, M. T. M. J. Electroanal. Chem. 1999, 478, 50. doi: 10.1016/S0022-0728(99)00412-X
(8) Kiss, I. Z.; Sitta, E.; Varela, H. J. Phys. Chem. C 2012, 116, 9561.
(9) Feng, J.; Gao, Q.; Xu, L.;Wang, J. Electrochem. Commun. 2005, 7, 1471. doi: 10.1016/j.elecom.2005.10.004
(10) Zhao, Y.;Wang, S.; Varela, H.; Gao, Q.; Hu, X.; Yang, J.; Epstein, I. R. J. Phys. Chem. C 2011, 115, 12965. doi: 10.1021/jp202881h
(11) Yang, J.; Song, Y.; Varela, H.; Epstein, I. R.; Bi,W.; Yu, H.; Zhao, Y.; Gao, Q. Electrochim. Acta 2013, 98, 116. doi: 10.1016/j.electacta.2013.03.042
(12) Waterston, K.; Bejan, D.; Bunce, N. J. Appl. Electrochem. 2007, 37, 367. doi: 10.1007/s10800-006-9267-z
(13) Parker, G. K.;Watling, K. M.; Hope, G. A.;Woods, R. Colloid. Surf. A: Physicochem. Eng. Aspects 2008, 318, 151. doi: 10.1016/j.colsurfa.2007.12.029
(14) O′Brien, J. A.; Hinkley, J. T.; Donne, S.W.; Lindquist, S. E. Electrochim. Acta 2010, 55, 573. doi: 10.1016/j.electacta.2009.09.067
(15) Hamilton, I. C.;Woods, R. J. Appl. Electrochem. 1983, 13, 783. doi: 10.1007/BF00615828
(16) Krischer, K. In Advance in Electrochemical Science and Engineering;Wielry-VCH:Weinheim, 2003; Vol. 8, pp 90-203.
(17) Kapusta, S.; Viehbeck, A.;Wilhelm, S. M.; Hackerman, N. J. Electroanal. Chem. Interfacial Electrochem. 1983, 153, 157. doi: 10.1016/S0022-0728(83)80011-4
(18) Krischer, K.; Varela, H.; Bîrzu, A.; Plenge, F.; Bonnefont, A. Electrochim. Acta 2003, 49, 103. doi: 10.1016/j.electacta.2003.04.006
(19) Mazouz, N.; Krischer, K. J. Phys. Chem. B 2000, 104, 6081. doi: 10.1021/jp000203+
(20) Koper, M. T. M. Electrochim. Acta 1992, 37, 1771. doi: 10.1016/0013-4686(92)85080-5
(21) Flätgen, G.; Krischer, K. J. Chem. Phys. 1995, 103, 5428. doi: 10.1063/1.470578
(22) Galea, N. M.; Kadantsev, E. S.; Ziegler, T. J. Phys. Chem. C 2007, 111, 14457. doi: 10.1021/jp072450k
(23) Fu, Y.; Zu, C.; Manthiram, A. J. Am. Chem. Soc. 2013, 135 (48), 18044-7. doi: 10.1021/ja409705u
(24) Flätgen, G.; Krischer, K. Phys. Rev. E 1995, 51, 3397. doi: 10.1103/PhysRevB.51.3397
(25) Mazouz, N.; Flätgen, G.; Krischer, K. Phys. Rev. E 1997, 55, 2260. doi: 10.1103/PhysRevE.55.2260
(26) Plenge, F.; Li, Y. J.; Krischer, K. J. Phys. Chem. B 2004, 108, 14255. doi: 10.1021/jp037955z

[1]	王易, 霍旺晨, 袁小亚, 张育新. 二氧化锰与二维材料复合应用于超级电容器[J]. 物理化学学报, 0, (): 1904007 -0 .
[2]	刘文燚, 栗林坡, 桂秋月, 邓伯华, 李园园, 刘金平. 基于阵列电极的新型混合电容器[J]. 物理化学学报, 0, (): 1904049 -0 .
[3]	魏风, 毕宏晖, 焦帅, 何孝军. 超级电容器用相互连接的类石墨烯纳米片[J]. 物理化学学报, 0, (): 1903043 -0 .
[4]	赵攀, 杨兵军, 陈江涛, 郎俊伟, 张天芸, 阎兴斌. 基于三维多孔活性炭构筑安全、高性能以及长循环寿命的锌离子混合电容器[J]. 物理化学学报, 0, (): 1904050 -0 .
[5]	梁旭, 贾宇峰, 刘宗怀, 雷志斌. 碳海绵上电化学沉积Fe₂O₃纳米片及其增强电容性能[J]. 物理化学学报, 0, (): 1903034 -0 .
[6]	李海霞, 王纪伟, 焦丽芳, 陶占良, 梁静. 碳包覆纳米SnSb合金作为高性能钠离子电池负极材料[J]. 物理化学学报, 0, (): 1904017 -0 .
[7]	郭楠楠, 张苏, 王鲁香, 贾殿赠. 植物基多孔炭材料在超级电容器中的应用[J]. 物理化学学报, 0, (): 1903055 -0 .
[8]	葛杨, 牟许霖, 卢岳, 隋曼龄. 空气下光诱导有机金属卤化钙钛矿薄膜的降解机理[J]. 物理化学学报, 0, (): 1905039 -0 .
[9]	方波, 冯立纲. Pt纳米颗粒结合ZIF-67衍生的PtCo-NC催化剂用于醇类燃料电氧化[J]. 物理化学学报, 0, (): 1905023 -0 .
[10]	陈光海, 白莹, 高永晟, 吴锋, 吴川. 全固态钠离子电池硫系化合物电解质[J]. 物理化学学报, 0, (): 1905009 -0 .
[11]	潘雯丽, 关文浩, 姜银珠. 聚阴离子型钠离子电池正极材料的研究进展[J]. 物理化学学报, 0, (): 1905017 -0 .
[12]	费慧芳, 刘永鹏, 魏传亮, 张煜婵, 冯金奎, 陈传忠, 于慧君. 基于聚碳酸丙烯酯基聚合物电解质和有机正极的全固态钠电池[J]. 物理化学学报, 0, (): 1905015 -0 .
[13]	曾桂芳, 刘以宁, 顾春燕, 张凯, 安永灵, 魏传亮, 冯金奎, 倪江锋. 不可燃氟代碳酸酯基钠离子电池电解液[J]. 物理化学学报, 0, (): 1905006 -0 .
[14]	徐来强, 李佳阳, 刘城, 邹国强, 侯红帅, 纪效波. 无机钠离子电池固体电解质研究进展[J]. 物理化学学报, 0, (): 1905013 -0 .
[15]	史永超, 唐明学. 可充电池的磁共振研究[J]. 物理化学学报, 0, (): 1905004 -0 .

硫化物在铂电极上电氧化时空动力学的模型模拟和分析

Model Simulation and Analysis of Spatiotemporal Dynamics for the Electro-Oxidation of Sulfide on Platinum

PDF (PC)

赞

可视化

摘要/Abstract

支持信息

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 10