Unifying Design for Homogeneous and Heterogeneous Catalysis via d-Band Center Alignment

A longstanding challenge in catalysis is the absence of unifying principles that couple the molecular-level reactivity of homogeneous catalysts with the durability and separability inherent to heterogeneous catalysts. Here, we present a computation-guided framework for the rational design of heterogeneous Rh-P nanoparticles that emulate the catalytic properties of homogeneous catalysts. By employing the d-band center as a transferable electronic descriptor, we align the electronic structure of Rh–P nanoparticles with that of benchmark Rh–phosphine complexes, enabling predictive control over hydroformylation activity. The workflow integrates machine learning-accelerated molecular dynamics, density functional theory, and experimental validation to screen a compositional library of Rh–P phases. A strong quantitative correlation is established between the deviation in d-band center and catalytic activity (R² = 0.994). Experimental evaluation reveals that Rh₃P, identified as the optimal composition through electronic structure matching, exhibits superior catalytic activity than the previously reported most active phase. In particular, Rh₃P achieved a reaction rate of 13,357 h⁻¹, representing a 25% increase over the state-of-the-art RhP nanoparticle system. This work establishes a generalizable framework for electronically guided catalyst design at the molecular level.