基于铂基电催化剂/电解液模型的燃料电池电催化反应动力学研究

燃料电池在改变能源结构方面具有巨大应用前景，但其性能受到电催化反应缓慢动力学的限制，而目前应用中普遍采用的是贵金属铂基催化剂，从而阻碍了燃料电池的商业化。目前大量的研究工作聚焦于寻找替代贵金属的非贵金属电催化剂，但收效甚微，这源自于实验研究中的盲目试错和理论研究中的简化反应热力学模拟。原位表征技术发展的滞后性导致电催化反应动力学信息匮乏，从而延缓了电催化剂的发展进程。有鉴于此，本文基于铂基电催化剂/电解液模型，通过对碱性氢氧化反应（Hydrogen oxidation reaction, HOR）、酸性氧还原反应（Oxygen reduction reaction, ORR）和酸性甲醇氧化反应（Methanol oxidation reaction, MOR）进行系统地反应动力学研究和实验测试验证，旨在阐明中间体吸附、速率控制步骤（Rate-determining step, RDS）、电化学双电层和电位对电催化反应动力学的影响机制。
进行碱性HOR动力学研究可以解决关于亲氧性还是电子性质对活性影响的争议，并实现从反应动力学模拟到电化学实验测试的有效统一。研究表明，基于铂基电催化剂/碱性电解液模型，Pt3M（M = Cr、Co、Pd和Ir）电催化剂碱性HOR动力学过程为Tafel-(Volmer-OH-)反应机理，并且RDS为（Volmer-OH-）反应，这表明亲氧性对碱性HOR活性影响甚微。为了进一步验证其影响，通过微动力学模拟发现，电催化剂表面很少有吸附的氢氧根离子，并且电催化剂表面被吸附氢中间体占据。从模拟碱性HOR极化曲线中获得的交换电流密度与电化学实验测试结果一致，这不仅证明了反应动力学模拟研究的可靠性，还揭示了电子性质通过调节氢中间体的吸附强度来调控碱性HOR动力学活性。
具有更多反应中间种类的酸性ORR动力学过程更加复杂，其中包括二电子机理、四电子机理和过氧化氢降解机理，确定RDS在酸性ORR动力学中的作用机制对酸性ORR动力学活性调控尤为重要。为此，通过以铂的三个低指数晶面和三种比例的铂镍合金为研究体系，并基于铂基电催化剂/酸性电解液模型进行酸性ORR动力学研究发现，酸性ORR动力学过程以四电子机理为主，并且RDS为R8（O* + H+ + e- → OH*）反应，以及氢通过Eley-Rideal机理参与反应动力学过程。再结合微动力学模拟、基于R8反应的电化学动力学方程以及电化学测试验证发现，R8反应是影响酸性ORR动力学活性的主要因素，并且从基于R8反应模拟的酸性ORR极化曲线中获得的半波电位与实验测试结果具有良好的一致性，从而证明了R8反应可以作为酸性ORR动力学模拟和实验活性测试结果直接匹配的桥梁。
为了进一步探究酸性ORR动力学活性的调控机制，通过合金工程调控策略选取六种铂基合金（Pt3M，M = Cr、Co、Cu、Pd、Sn和Ir）电催化剂作为研究体系，并且经过结构表征、反应动力学模拟和实验测试验证发现，铂基合金与铂的晶格常数差异在3.5%以内，并且它们的酸性ORR活性得到了有效调控。合金工程对酸性ORR动力学具有双重调控机制，电子效应通过调节价电子能级结构来调控中间体的吸附强度，而电化学双电层通过调节静电场强度来调控水合质子的溶剂化传输效率。与电子效应相比，电化学双电层与酸性ORR动力学活性具有更高的相关度，表明通过调节电化学双电层可以更有效地调控酸性ORR动力学活性。
鉴于更加复杂的酸性MOR实验测试电位区间（0.05 ~ 1.25 V vs. RHE）远离平衡电位（0.046 V vs. RHE），电位变化可以显著影响酸性MOR动力学。为此，基于铂基电催化剂/酸性电解液模型，通过利用电位相关酸性MOR动力学研究发现，Pt(111)和PtRu(101)电催化剂酸性MOR动力学中的RDS随着电位的升高而改变。进一步通过电位相关微动力学模拟和速率控制度研究发现，不同电位区间内的RDS是影响酸性MOR动力学活性的主要因素。通过将电位相关反应动力学模拟和电化学动力学原理相结合，获得的模拟酸性MOR极化曲线得到了实验测试极化曲线的验证，并且Pt(111)和PtRu(101)电催化剂酸性MOR极化曲线中最大电流密度误差分别为0.020和0.023 mA cm-2，以及在酸性MOR中主要存在从CHO*中间体脱氢到CO*中间体与OH*中间体结合脱氢的RDS转换机制。

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