Sandia National Laboratories, Geochemistry Department, Albuquerque, New Mexico, USA; email:
Sandia National Laboratories, Nuclear Waste Disposal Research and Analysis, Albuquerque, New Mexico, USA; email:
Annu Rev Phys Chem. 2023 Apr 24;74:169-191. doi: 10.1146/annurev-physchem-083022-030802. Epub 2023 Feb 3.
Reactions at solid-water interfaces play a foundational role in water treatment systems, catalysis, and chemical separations, and in predicting chemical fate and transport in the environment. Over the last century, experimental measurements and computational models have made tremendous progress in capturing reactions at solid surfaces. The interfacial reactivity of a solid surface, however, can change dramatically and unexpectedly when it is confined to the nanoscale. Nanoconfinement can arise in different geometries such as pores/cages (3D confinement), channels (2D confinement), and slits (1D confinement). Therefore, measurements on unconfined surfaces, and molecular models parameterized based on these measurements, fail to capture chemical behaviors under nanoconfinement. This review evaluates recent experimental and theoretical advances, with a focus on adsorption at solid-water interfaces. We review how nanoconfinement alters the physico-chemical properties of water, and how the structure and dynamics of nanoconfined water dictate energetics, pathways, and products of adsorption in nanopores. Finally, the implications of these findings and future research directions are discussed.
固-液界面反应在水处理系统、催化和化学分离中起着基础性作用,并在预测环境中化学物质的归宿和迁移中具有重要意义。在过去的一个世纪中,实验测量和计算模型在捕捉固体表面反应方面取得了巨大的进展。然而,当固体表面被限制在纳米尺度时,其界面反应性会发生显著且出人意料的变化。纳米限域可以在不同的几何形状中出现,如孔/笼(三维限域)、通道(二维限域)和狭缝(一维限域)。因此,在无约束表面上的测量以及基于这些测量参数化的分子模型无法捕捉纳米限域下的化学行为。本综述评估了最近的实验和理论进展,重点关注固-液界面的吸附。我们综述了纳米限域如何改变水的物理化学性质,以及纳米限域水的结构和动力学如何决定纳米孔中吸附的能量学、途径和产物。最后,讨论了这些发现的意义和未来的研究方向。