Enzymes often show catalytic allostery in which reactions occurring at different sites communicate cooperatively over distances of up to a few nanometres. Whether such effects can occur with non-biological nanocatalysts remains unclear, even though these nanocatalysts can undergo restructuring and molecules can diffuse over catalyst surfaces. Here we report that phenomenologically similar, but mechanistically distinct, cooperative effects indeed exist for nanocatalysts. Using spatiotemporally resolved single-molecule catalysis imaging, we find that catalytic reactions on a single Pd or Au nanocatalyst can communicate with each other, probably via hopping of positively charged holes on the catalyst surface, over ~10² nanometres and with a temporal memory of ~10¹ to 10² seconds, giving rise to positive cooperativity among its surface active sites. Similar communication is also observed between individual nanocatalysts, however it operates via a molecular diffusion mechanism involving negatively charged product molecules, and its communication distance is many micrometres. Generalization of these long-range intra- and interparticle catalytic communication mechanisms may introduce a novel conceptual framework for understanding nanoscale catalysis.

酶通常表现出催化变构，其中在不同位点发生的反应在长达几纳米的距离内协同通信。尽管这些纳米催化剂可能会发生结构重组并且分子可以扩散到整个催化剂表面，但对于非生物纳米催化剂是否会发生这种影响仍不清楚。在这里，我们报告的现象学上相似，但在机理上截然不同的协同作用确实存在于纳米催化剂上。使用时空分辨的单分子催化成像，我们发现单个Pd或Au纳米催化剂上的催化反应可以相互通信，可能是通过跃迁在催化剂表面上带正电的空穴超过约10 ²纳米，并且具有时间记忆的。 〜10 ¹至10 ²秒，在其表面活性位之间产生正合作性。在各个纳米催化剂之间也观察到类似的连通，但是它通过涉及带负电荷的产物分子的分子扩散机制起作用，并且其连通距离为许多微米。这些远程的内部和粒子间催化通讯机制的一般化可能会引入一个新颖的概念框架，以了解纳米级催化。