Nanoporous solids, including microporous, mesoporous and hierarchically structured porous materials, are of scientific and technological interest because of their high surface-to-volume ratio and ability to impose shape- and size-selectivity on molecules diffusing through them. Enormous efforts have been put in the mechanistic understanding of diffusion–reaction relationships of nanoporous solids, with the ultimate goal of developing materials with improved catalytic performance. Single-molecule localization microscopy can be used to explore the pore space via the trajectories of individual molecules. This ensemble-free perspective directly reveals heterogeneities in diffusion and diffusion-related reactivity of individual molecules, which would have been obscured in bulk measurements. In this article, we review developments in the spatial and temporal characterization of nanoporous solids using single-molecule localization microscopy. We illustrate various aspects of this approach, and showcase how it can be used to follow molecular diffusion and reaction behaviors in nanoporous solids.

纳米多孔固体，包括微孔，中孔和分层结构的多孔材料，由于其高的体积比和对通过其扩散的分子施加形状和尺寸选择性的能力，因此具有科学和技术意义。对纳米多孔固体的扩散-反应关系的机械理解已做出了巨大的努力，其最终目标是开发具有改进催化性能的材料。单分子定位显微镜可用于通过单个分子的轨迹探索孔空间。这种无合奏的视角直接揭示了单个分子的扩散和与扩散相关的反应性中的异质性，这在批量测量中会被掩盖。在本文中，我们使用单分子定位显微镜回顾了纳米多孔固体的时空表征发展。我们说明了这种方法的各个方面，并展示了如何将其用于跟踪纳米多孔固体中的分子扩散和反应行为。