Spatial positioning of single-atom Zr dictating the electronic structure of metal nanoparticles for efficient dehydrogenation

Electronic control of nanoparticle active sites via a single-atom promoter remains challenging in heterogeneous catalysis. Here we show that spatial positioning of single-atom Zr promoters on hydroxyapatite, either surface-decorated or near-surface lattice-incorporated, possesses different electronic modulation mechanisms. Characterizations and DFT indicate that surface-decorated Zr exhibits limited electron donation to the metal while minimally perturbing the support electronic structure. Lattice-incorporated Zr induces directional charge reconstruction accompanied by support-promoter-metal electronic coupling, thereby enabling significant tuning of the electronic structure of the metal nanoparticles. In 1,2-propanediol dehydrogenation to hydroxyacetone, the lattice-incorporated architecture delivers 83% yield, and 100 h stability under optimized conditions. The same spatial-positioning principle extends beyond Cu and is reproduced in Ni/Zr-HAP and Pt/Zr-HAP. Lattice-incorporated Pt also steers cyclohexanol conversion toward deep ring dehydrogenation, enhancing phenol formation while suppressing dehydration by-products. Overall, axial promoter placement is a transferable lever to engineer interfacial charge distribution for efficient dehydrogenation.