Metal-organic frameworks (MOFs) have flourished as a library of promising precursors for synthesizing carbon-supported metal catalysts by pyrolysis, but it is extremely difficult to simultaneously achieve a high metal loading and an ultrasmall size, particularly for non-noble metal (Fe, Co, Ni, etc.) that are highly active and have a strong tendency to coarsen. Here, we report a general strategy for controllable synthesize thermodynamically metastable sub-3 nm non-noble metal nanoparticles (NPs) with ultrahigh metal loading up to 41.0 wt% (12.8 at%) by rapid pyrolysis of MOF (e.g., ~ 1000 °C in 0.3 s), at least four-fold higher than the reported strategy where ultrasmall NPs were obtained but with a significant sacrifice of metal loading (usually less than 10 wt%). Furthermore, we found that the formation of metal NPs during high-temperature pulse agrees with the LaMer model (sigmoidal coarsening kinetics), in which rapid pyrolysis triggers only the initial nucleation and avoids Ostwald ripening or further coalescence. We also demonstrate the generality of our strategy in synthesizing other MOF-derived ultrasmall NPs, including non-noble metal NPs (Ni), metallic compound (CoS₂), and alloy (CoPd). As a demonstration, the obtained CoPd-based catalyst showed high activity and robust stability during prolonged catalytic reactions. Therefore, our strategy and mechanistic insights enable the rational design and controlled synthesis of advanced catalysts with a good balance between ultrasmall size and a high metal loading, from more than 100,000 types of MOFs.

金属有机框架 (MOF) 作为一个有前途的前驱体库已经蓬勃发展，用于通过热解合成碳负载金属催化剂，但同时实现高金属负载和超小尺寸是极其困难的，特别是对于非贵金属 (Fe 、Co、Ni 等）具有高活性并具有很强的粗化倾向。在这里，我们报告了一种通过 MOF 快速热解（例如，~1000 °C在 0.3 秒内），至少比报道的策略高出四倍，其中获得了超小 NP，但金属负载显着牺牲（通常小于 10 wt%）。此外，我们发现在高温脉冲期间金属纳米颗粒的形成与 LaMer 模型（S 形粗化动力学）一致，其中快速热解仅触发初始成核并避免 Ostwald 熟化或进一步聚结。我们还展示了我们的策略在合成其他 MOF 衍生的超小 NPs 方面的普遍性，包括非贵金属 NPs (Ni)、金属化合物 (CoS₂ ) 和合金 (CoPd)。作为证明，所获得的 CoPd 基催化剂在长时间的催化反应中表现出高活性和稳健的稳定性。因此，我们的策略和机理见解能够从超过 100,000 种 MOF 中合理设计和控制合成在超小尺寸和高金属负载之间取得良好平衡的先进催化剂。