Synergize Strong and Reactive Metal‐Support Interactions to Construct Sub‐2 nm Metal Phosphide Cluster for Enhanced Selective Hydrogenation Activities

Strong metal‐support interactions (SMSI) are crucial for stabilizing sub‐2 nm metal sites, e.g. single atom (M 1 ) or cluster (M n ). However, further optimizing sub‐2 nm sites to break the activity–stability trade‐off due to excessive interactions remains significant challenges. Accordingly, for the first time, we propose synergizing SMSI with reactive metal‐support interactions (RMSI). Comprehensive characterization confirms that the SMSI stabilizes the metal and regulates the aggregation of Ni 1 into Ni n site within sub‐2 nm. Meanwhile, RMSI modulates Ni n through sufficiently activating P in the support and eventually generates sub‐2 nm metal phosphide Ni 2 P cluster (Ni 2 P n ). The synergetic metal‐support interactions triggered the adaptive coordination and electronic structure optimization of Ni 2 P n , leading to the desired substrate adsorption‐desorption kinetics. Consequently, the activity of Ni 2 P n site greatly enhanced towards the selective hydrogenations of p ‐chloronitrobenzene and alkynyl alcohol. The formation rates of target products are up to 20.2 and 3.0 times greater than that of Ni 1 and Ni n site, respectively. This work may open a new direction for metal‐support interactions and promote innovation and application of active sites below 2 nm.