Department of Physics, The University of Texas at El Paso, El Paso, Texas 79968, United States.
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States.
Chem Rev. 2023 May 24;123(10):6413-6544. doi: 10.1021/acs.chemrev.2c00130. Epub 2023 May 15.
Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.
界面反应驱动着地球上所有元素的循环，并在农业、水净化、能源生产和储存、环境污染修复以及核废料储存管理等人类活动中发挥着关键作用。21 世纪的开始标志着人们对矿物水界面的理解有了更深入的认识，这得益于技术的进步，这些技术使用可调谐的高通量聚焦超快激光和 X 射线源提供近原子测量分辨率，以及纳米制造方法，使液体池中的透射电子显微镜成为可能。这种向原子和纳米尺度测量的飞跃揭示了依赖于尺度的现象，其反应热力学、动力学和途径与以前在较大系统中观察到的情况不同。第二个关键进展是为科学家们假设但以前无法验证的新实验证据提供了依据，即界面化学反应通常是由“异常”或“非理想性”驱动的，例如缺陷、纳米限制和其他非典型化学结构。第三，计算化学的进展提供了新的见解，使人们能够超越简单的示意图，从而建立这些复杂界面的分子模型。结合表面敏感测量，我们获得了界面结构和动力学的知识，包括基础固体表面以及紧邻的水和水合离子，从而更好地定义了氧化物和硅酸盐-水界面的构成。这篇评论文章讨论了科学如何从理解理想的固-水界面发展到更现实的系统，重点介绍了过去 20 年的成就，并确定了科学界面临的挑战和未来的机遇。我们预计，未来 20 年的重点将是在更大的空间和时间范围内以及具有更大结构和化学复杂性的系统中，理解和预测动态瞬态和反应性结构。理论和实验专家之间更密切的跨学科合作将继续是实现这一伟大目标的关键。
