School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.
Molecules. 2023 Jan 16;28(2):897. doi: 10.3390/molecules28020897.
We provide a systematic overview of the mechanochemical reactions of inorganic solids, notably simple binary compounds, such as oxides, nitrides, carbides, sulphides, phosphides, hydrides, borides, borane derivatives, and related systems. Whereas the solid state has been traditionally considered to be of little synthetic value by the broader community of synthetic chemists, the solid-state community, and in particular researchers focusing on the reactions of inorganic materials, have thrived in building a rich and dynamic research field based on mechanically-driven transformations of inorganic substances typically seen as inert and high-melting. This review provides an insight into the chemical richness of such mechanochemical reactions and, at the same time, offers their tentative categorisation based on transformation type, resulting in seven distinct groupings: () the formation of adducts, () the reactions of dehydration; () oxidation-reduction (redox) reactions; () metathesis (or exchange) reactions; () doping and structural rearrangements, including reactions involving the reaction vessel (the milling jar); () acid-base reactions, and () other, mixed type reactions. At the same time, we offer a parallel description of inorganic mechanochemical reactions depending on the reaction conditions, as those that: () take place under mild conditions (e.g., manual grinding using a mortar and a pestle); () proceed gradually under mechanical milling; () are self-sustained and initiated by mechanical milling, i.e., mechanically induced self-propagating reactions (MSRs); and () proceed only via harsh grinding and are a result of chemical reactivity under strongly non-equilibrium conditions. By elaborating on typical examples and general principles in the mechanochemistry of hard and high-melting substances, this review provides a suitable complement to the existing literature, focusing on the properties and mechanochemical reactions of inorganic solids, such as nanomaterials and catalysts.
我们提供了一个关于无机固体的机械化学反应的系统概述，特别是简单的二元化合物，如氧化物、氮化物、碳化物、硫化物、磷化物、氢化物、硼化物、硼烷衍生物和相关体系。虽然传统上合成化学家更关注传统的固态合成，但固态化学领域，特别是专注于无机材料反应的研究人员，已经在基于机械驱动的无机物质转化的丰富而充满活力的研究领域中蓬勃发展，这些无机物质通常被认为是惰性的和高熔点的。本综述深入探讨了这些机械化学反应的化学丰富性，同时根据转化类型对其进行了试探性分类，形成了七个不同的分类：（1）加合物的形成，（2）脱水反应，（3）氧化还原（氧化还原）反应，（4）复分解（或交换）反应，（5）掺杂和结构重排，包括涉及反应容器（球磨罐）的反应，（6）酸碱反应，以及（7）其他混合类型的反应。同时，我们根据反应条件提供了无机机械化学反应的平行描述，这些条件包括：（1）在温和条件下进行（例如，使用研钵和研杵手动研磨），（2）在机械研磨下逐渐进行，（3）由机械研磨引发并自我维持，即机械诱导自蔓延反应（MSRs），以及（4）仅通过苛刻的研磨进行，是在强烈非平衡条件下化学反应的结果。通过详细阐述硬而高熔点物质机械化学中的典型实例和一般原理，本综述为现有文献提供了一个合适的补充，重点介绍了无机固体的性质和机械化学反应，如纳米材料和催化剂。
