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固液界面的力−电−化学耦合及在电催化体系中的应用

邓齐波 贾涵杏 杨波 齐正磐 张哲绎 阿拉木斯 胡宁

邓齐波, 贾涵杏, 杨波, 齐正磐, 张哲绎, 阿拉木斯, 胡宁. 固液界面的力−电−化学耦合及在电催化体系中的应用. 力学进展, 2022, 52(2): 221-252 doi: 10.6052/1000-0992-21-042
引用本文: 邓齐波, 贾涵杏, 杨波, 齐正磐, 张哲绎, 阿拉木斯, 胡宁. 固液界面的力−电−化学耦合及在电催化体系中的应用. 力学进展, 2022, 52(2): 221-252 doi: 10.6052/1000-0992-21-042
Deng Q B, Jia H X, Yang B, Qi Z P, Zhang Z Y, Lee A, Hu N. The electro-chemo-mechanical coupling at the solid-liquid interfaces and its applications to electrocatalysis . Advances in Mechanics, 2022, 52(2): 221-252 doi: 10.6052/1000-0992-21-042
Citation: Deng Q B, Jia H X, Yang B, Qi Z P, Zhang Z Y, Lee A, Hu N. The electro-chemo-mechanical coupling at the solid-liquid interfaces and its applications to electrocatalysis . Advances in Mechanics, 2022, 52(2): 221-252 doi: 10.6052/1000-0992-21-042

固液界面的力−电−化学耦合及在电催化体系中的应用

doi: 10.6052/1000-0992-21-042
基金项目: 国家科技重大专项(2017-Ⅶ-0011-0106)、国家自然科学基金项目(12172118, 11602171, U1864208)、河北省自然科学基金创新群体研究项目(A2020202002)、河北省研究发展重点计划(202030507040009)、中央引导地方科技发展资金项目(216Z4402G) 、天津市自然科学基金重点项目 (S20ZDF077) 、天津市科技计划项目(20ZYJDJC00030)和河北工业大学“元光学者”人才项目资助.
详细信息
    作者简介:

    邓齐波, 男, 1985年生, 教授, 博士生导师, 天津市“海外高层次人才引进计划”获得者, 国际先进材料协会会士(IAAM Fellow). 目前兼任北京能源与环境学会京津冀专家委员会委员, 全国材料与器件科学家智库专家委员会常务委员. 主要从事电化学能源材料力化学耦合、新型电催化/储能体系构筑与性能优化技术等相关领域科学研究工作. 获2019年度国际先进材料协会科学家奖章, 国际Vebleo Fellow Award, 中国产学研合作促进奖, 中国发明协会发明创业创新奖二等奖等多项学术科技奖励

    胡宁, 男, 1965年生, 教授, 博士生导师, 现任河北工业大学副校长兼机械工程学院院长. 国家杰出青年基金(海外杰青)获得者、国家“海外高层次人才引进计划”(A类)、国务院政府特殊津贴专家、中国力学学会理事、中国复合材料常务理事. 长期致力于固体力学、计算材料科学、结构与材料的力·热·电·化学等各类性能评价及相互耦合关系、结构型与功能型等各类复合材料研发、结构与材料的在线监测及线下无损检测技术等方面的研究工作. 出版英文书籍3部、教材1部; 发表SCI期刊论文380余篇, 论文被引用12000余次, H-index = 54; 连续7年入选爱思唯尔高被引学者榜单, 近2年连续入选全球前2%顶尖科学家榜单(“终身科学影响力排行耪”和“年度科学影响力排行耪”). 先后承担了包括国家自然科学重点基金、国家重点研发计划、国家科技重大专项等科研项目50余项

    通讯作者:

    qibodeng@hebut.edu.cn

  • 中图分类号: O646, TM911.4

The electro-chemo-mechanical coupling at the solid-liquid interfaces and its applications to electrocatalysis

More Information
  • 摘要: 目前许多新型高效金属催化剂在设计制备中都考虑到表面力学因素, 例如层状结构、核壳结构等, 其表面高活性原子受到不同程度的应变作用. 应变可直接改变金属的能带带隙, 对催化剂表面的电化学反应产生显著影响, 是一种有效提升材料催化活性的新思路和制备高性能催化剂的新途径, 因此受到了科研工作者的广泛关注. 传统的材料应变工程手段存在着活性物质层的应变值难以精确定量, 并缺少实时调控以及制备工艺繁琐等难题, 导致应变与电催化活性相关性规律识别方面的理论和实验研究进展缓慢. 相比于传统的材料手段, 交变载荷产生的应变具有幅值和频率的可变性以及连续的调控性, 在实验中可以完全排除噪声、缺陷、空位、基底效应等其他外部或材料本征的影响因素. 该综述从经典固液界面热力学表述出发, 简要介绍了电催化体系中的力−电−化学耦合效应, 归纳总结目前电催化体系中应变施加的实验手段和分析方法, 并基于目前相关研究着重讨论在交变载荷作用下应变对金属表面电催化反应的作用机理, 最后从力学角度展望了表面力学在电催化体系中的研究重点及发展趋势.

     

  • 图  1  在电极电势保持恒定时, 对电极施加弹性应变(ε)作用(图1右侧), 金属材料面内原子间距从${r}_{0}^{{N}{N}}$增大到$ {r}_{0}^{{N}{N}}\left(1+\dfrac{1}{2} \varepsilon \right) $, 进而增大电极物理表面积($ \overline{A} $). 另外,拉格朗日面积A和表面原子数目N保持不变. 系统吉布斯自由能的变化量与表面应力 (f sl) 成比例, 即${\text{δ }}{G^{{\rm{sl}}}} = {A_0}{f^{{\text{sl}}}}\varepsilon$ (Weissmüller 2013)

    图  2  d带模型理论: 对于前过渡金属(a)和后过渡金属(b)拉伸应变对其d带位置的影响. 拉伸应变都会使前过渡和后过渡金属的d带宽度变窄, 为了保持d带填充程度(即电荷守恒), 前过渡金属d带中心将下移, 而后过渡金属d带中心上移 (Luo & Guo 2017)

    图  3  应变效应和配位效应对氢在Pd表面吸附自由能的影响 (Maark & Peterson 2014)

    图  4  以不同铜钯组分(a)和厚度(b)为壳层, 银(或金)为核体的核壳结构材料, 氧相对结合能(ΔEO)随应变的变化关系(c). 黑色、红色和绿色的曲线分别代表壳层组分Cu∶Pd的原子比值为2∶7、1∶2和2∶1. 相同颜色的不同曲线对应于氧在不同的面中心立方空心吸附. Pt(111)表面上的ΔEO用水平虚线表示 (Guo et al. 2014)

    图  5  (a)金属钯Pd(111)以及外延生长在不同基底上的钯单原子层(PdML)晶格关系图, (b)不同双相层状结构表层Pd原子间隔(1 Å = 0.1 nm), (c) Pd(111)以及PdML的析氢反应性能 (Kibler et al. 2005, Kibler 2008)

    图  6  (a)以Pt50Fe50合金为核Pt为壳的结构模型, 压应变梯度从−4% ~ −2% (相对Pt体相材料); (b)晶格收缩应变图 (Seh et al. 2017)

    图  7  基于锂离子电池电极材料LiCoO2(LCO)的充放电来改变催化活性物质Pt纳米颗粒的晶格应变 (Wang et al. 2016)

    图  8  (a)析氢反应交换电流密度(j0)与晶格应变的关联性, (b)氢吸附电势(EH upd)与晶格应变的关联性 (图中数据来自于图5)

    图  9  (a)预变形的NiTi衬底的相变行为, (b)表面不同应变状态下Pt薄膜的电化学性能 (Du et al. 2015)

    图  10  (a) NiTi合金丝不同应变状态, (b)表面不同应变状态下镍基氧化物薄膜的电化学性能 (Muralidharan et al. 2016)

    图  11  (a)电化学过程静载荷加载装置示意图, (b)电化学循环伏安过程的加载与卸载, (c)不同拉伸和压缩应变对电化学性能的影响 (Yan et al. 2016)

    图  12  (a)通过弯曲Ag/PET基底将应变引入到二维材料, 其中R为弯曲半径, T为PET衬底厚度, ε = T/2R为估算的应变大小; (b)与应变相关的析氢反应极化曲线 (Lee et al. 2014)

    图  13  (a)动态应变以及电极在电解液中的开路电势随时间的变化关系, (b)开路电势与应变呈现出极好的线性负相关性 (Smetanin et al. 2008)

    图  14  交变载荷作用下应变效应研究平台电路示意图. (a)电极电流−应变响应; (c) 电极电势−应变响应. WE为工作电极, 即金属薄膜; RE、CE分别为电化学实验中的参比电极和对电极; Lock-In为锁相放大器. (b)和(d)分别为动态机械应变诱导的电流、电势响应信号, 其中横坐标为测量时间, 各个纵坐标分别为应变ε、 电流I、电势E (Smetanin et al. 2011, Deng 2014)

    图  15  (a)交变应变作用下循环伏安测试的电流响应信号(I)在时间域(t)的变化, 电极电势扫速为10 mV/s, 施加应变频率υ = 20 Hz, 其中蓝色实线为没有应变作用的常规电流变化情况; (b)恒电势下示波器同步记录的电流变化和频率为2 Hz的应变信号; (c)基于锁定测量技术得到的电流−应变响应系数的幅值和相位结果 (Deng & Yuan 2019)

    图  16  (a)在电势为0.6 V时, 电流−应变响应系数(Λ)实部、虚部与应变频率υ的函数关系, 插图中金属−电解液界面等效电路模型; (b)电流−应变响应系数(Λ)的幅值和相位移分别与应变频率υ的函数关系. 图中散点为实验数据, 实线为等效电路模拟结果 (Deng & Yuan 2019)

    图  17  电势−应变响应系数(ς)的两种测量方法比较: DECMA锁相技术直接测量(红色曲线)以及通过电流−应变响应系数与固液界面阻抗信息(蓝色曲线). 电化学体系: Au薄膜在10 mmol/L的 HClO4溶液中. (Smetanin et al. 2011)

    图  18  (a)电化学吸附过程的示意图; 氢离子(H+)和氢氧根(OH)在金属Au电极表面(b)、Pt电极表面(c)吸附过程的响应系数ς(E). 图中Had/de表示氢吸脱附, OHad/de表示氢氧根吸脱附, Cap.表示电容过程. (Deng & Weissmüller 2014)

    图  19  (a)铜在金电极表面电化学沉积过程响应系数ς与电化学信号、铜原子覆盖度之间的关系; 不同电化学过程响应系数ς的幅值(b)、相位差(c)与应变频率的关系 (Yang et al. 2017)

    图  20  区分应变对反应电流和双电层电容电流作用的实验结果. (a)反应电流−应变参数 ι 在电化学析氢反应的变化规律, (b)析氢反应占主导时实部和虚部与应变频率的关系, (c)电容过程占主导时实部和虚部与应变频率的关系, 电化学体系为Au在0.5 M H2SO4中 (Deng et al. 2014)

    图  21  (a)应变在电化学析氢反应中的作用主要影响吸附焓以及活化焓, (b)数学模型预测的反应电流−应变参数随着电极电势变化规律, (c)表面应变对氢析出电化学反应影响的实验和模型结果对比图 (Deng et al. 2014)

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  • 收稿日期:  2021-09-06
  • 录用日期:  2021-12-21
  • 网络出版日期:  2021-12-22
  • 刊出日期:  2022-06-25

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