Atomically precise heterometallic clusters constitute a new family of model catalysts for understanding the fundamental catalysis process widely occurred in supported nanocatalysts, however, their syntheses and structure/composition modulations are nonetheless daunting challenges. Herein, three novel heterometallic Ag/Ti clusters with different Ag-doping ratios, Ag₄Ti₁₄, Ag₄Ti₆ and Ag₄Ti₂, have been readily synthesized in decagram-scale quantities through ligand engineering strategy. Thereinto, Ag₄Ti₂ can be efficiently prepared within 3 h in a quite high yield > 95 %. More remarkably, Ag₄Ti₂ shows unprecedented catalytic activity (>90 % conversion within 1 min) and selectivity (nearly 100 %) towards oxidation of thioethers with a wide substrate scope even including notorious 2-chloroethyl ethyl sulfide (CEES) at room temperature (turnover frequency = 11,880 h⁻¹), which is mainly attributed to its full-surface-exposure-doping Ag atoms (affinity for binding of substrate) on TiO support and their cooperativity, whereas the other two are not the same case. Moreover, the Ag₄Ti₂ is highly robust in catalysis process and can be readily recovered and reused at least six cycles without observable loss of activity and selectivity, enabling this cluster hold great promise in industrial applications. This work not only establishes a general method to scale-up synthesis of Ag/Ti clusters but also provides an atom-precise model catalyst to understand the structure–property correlations of real-world conventional nanocatalysts such as silver doped-TiO₂ nanoparticles.

原子精确的异金属簇构成了一个新的模型催化剂家族，用于理解负载型纳米催化剂中广泛发生的基本催化过程，然而，它们的合成和结构/组成调制仍然是艰巨的挑战。在此，三种具有不同 Ag 掺杂比的新型异金属 Ag/Ti 簇Ag ₄ Ti ₁₄、Ag ₄ Ti ₆和Ag ₄ Ti ₂已通过配体工程策略以十克规模的量很容易地合成。其中，Ag ₄ Ti ₂可在 3 小时内高效制备，产率 > 95%。更值得注意的是，Ag ₄ Ti ₂在室温下对具有广泛底物范围甚至包括臭名昭著的 2-氯乙基乙基硫醚 (CEES) 的硫醚的氧化显示出前所未有的催化活性（1 分钟内 >90% 的转化率）和选择性（接近 100%） （转换频率= 11,880 h ^-1），这主要归因于其在Ti O 载体上的全表面暴露掺杂Ag原子（与基板结合的亲和力）及其协同性，而其他两者则不同。此外，Ag ₄ Ti ₂在催化过程中非常稳健，可以很容易地回收和重复使用至少六个循环，而不会观察到活性和选择性的损失，使该簇在工业应用中具有广阔的前景。这项工作不仅建立了一种放大合成 Ag/Ti 团簇的通用方法，而且还提供了一种原子精确的模型催化剂，以了解现实世界中传统纳米催化剂（例如掺银 TiO ₂纳米颗粒）的结构-性质相关性。