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<p>The local reaction microenvironment within the electrochemical double layer plays a decisive role in governing electrocatalytic activity and selectivity, particularly in nanoparticle-based catalytic systems. Beyond their intrinsic electronic structures, nanoparticles (NPs) can induce distinct local microenvironments by virtue of their morphology, size, spatial distribution, and surface characteristics. In this review, we summarize recent advances in understanding how these NPs structural parameters modulate local microenvironments as well as their roles in regulating reaction kinetics, selectivity, and efficiency in energy-related electrocatalytic reactions. We also systematically analyze critical microenvironment factors such as local electric field strength, ion distribution, interfacial pH, mass transport, and intermediate coverage. Simultaneously, <i>in situ</i> and <i>operando</i> characterization techniques, together with theoretical simulations, are highlighted to elucidate the formation and dynamic evolution of nanoparticle-induced microenvironments during electrocatalysis. Finally, current challenges and future perspectives are discussed, including the precise characterization of local microenvironments, the identification of key microenvironment descriptors, and machine learning-assisted prediction of interfacial catalytic activity for advanced electrocatalyst design.</p>

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Nanoparticle-induced local microenvironments and their roles in electrocatalysis

  • 期刊论文

  • 发表日期：

    2026年4月13日

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  • Yanwei Zhu,
  • Li Tao,
  • Xian-Zhu Fu,
  • Shuangyin Wang

摘要

The local reaction microenvironment within the electrochemical double layer plays a decisive role in governing electrocatalytic activity and selectivity, particularly in nanoparticle-based catalytic systems. Beyond their intrinsic electronic structures, nanoparticles (NPs) can induce distinct local microenvironments by virtue of their morphology, size, spatial distribution, and surface characteristics. In this review, we summarize recent advances in understanding how these NPs structural parameters modulate local microenvironments as well as their roles in regulating reaction kinetics, selectivity, and efficiency in energy-related electrocatalytic reactions. We also systematically analyze critical microenvironment factors such as local electric field strength, ion distribution, interfacial pH, mass transport, and intermediate coverage. Simultaneously, in situ and operando characterization techniques, together with theoretical simulations, are highlighted to elucidate the formation and dynamic evolution of nanoparticle-induced microenvironments during electrocatalysis. Finally, current challenges and future perspectives are discussed, including the precise characterization of local microenvironments, the identification of key microenvironment descriptors, and machine learning-assisted prediction of interfacial catalytic activity for advanced electrocatalyst design.