Heterogeneous catalysts are vital to unlock superior efficiency, atom economy, and environmental friendliness in chemical conversions, with the size and speciation of the contained metals often playing a decisive role in the activity, selectivity and stability. This tutorial review analyses the impact of these catalyst parameters on the valorisation of biomass through hydrogenation and hydrodeoxygenation, oxidation, reforming and acid-catalysed reactions, spanning a broad spectrum of substrates including sugars and platform compounds obtained from (hemi)cellulose and lignin derivatives. It outlines multiple examples of classical structure sensitivity on nanoparticle-based materials with significant implications for the product distribution. It also shows how the recently emphasised application of metals in the form of ultrasmall nanoparticles (<2 nm), clusters and single atoms, while fulfilling superior metal utilisation and robustness, opens the door to unprecedented electronic and geometric properties. The latter can lead to facilitated activation of reactants as well as boosted selectivity control and synergy between distinct active sites in multifunctional catalysts. Based on the analysis conducted, guidelines for the selection of metals for diverse applications are put forward in terms of chemical identity and structure, and aspects that should be explored in greater depth for further improving the exploitation of metals in this research field and beyond are highlighted.

中文翻译：

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在金属基固体催化剂上从纳米粒子到单个原子的生物质平衡。

非均相催化剂对于在化学转化中释放出更高的效率，原子经济性和环境友好性至关重要，所含金属的尺寸和形态通常在活性，选择性和稳定性中起决定性作用。本教程概述通过氢化和加氢脱氧，氧化，重整和酸催化反应分析了这些催化剂参数对生物质增值的影响，涵盖了包括糖以及从（半）纤维素和木质素衍生物获得的平台化合物在内的各种底物。它概述了对基于纳米粒子的材料的经典结构敏感度的多个示例，这些示例对产品分布具有重要意义。它还显示了最近强调的如何以超小纳米颗粒（< 2 nm），团簇和单个原子，同时满足优异的金属利用率和坚固性，为前所未有的电子和几何特性打开了大门。后者可以促进反应物的活化以及增强的选择性控制和多功能催化剂中不同活性位之间的协同作用。根据进行的分析，就化学特性和结构提出了用于多种用途的金属选择指南，并着重指出了应进一步探索的方面，以进一步改善该研究领域及其他领域的金属开发。 。后者可以促进反应物的活化以及增强的选择性控制和多功能催化剂中不同活性位之间的协同作用。根据进行的分析，就化学特性和结构提出了用于各种用途的金属选择指南，并着重指出了应在更深层次上探索的方面，以进一步改善该研究领域及其他领域的金属开发。 。后者可以促进反应物的活化以及增强的选择性控制和多功能催化剂中不同活性位之间的协同作用。根据进行的分析，就化学特性和结构提出了用于多种用途的金属选择指南，并着重指出了应进一步探索的方面，以进一步改善该研究领域及其他领域的金属开发。 。