Subnanoscale Platinum by Repeated UV Irradiation: From One and Few Atoms to Clusters for the Automotive PEMFC.

The unaffordable costs of the automotive proton exchange membrane fuel cell (PEMFC), remaining a roadblock for commercial applications as an alternative to combustion engine vehicles, can be overcome partially by remarkably increasing the utilization of irreplaceable platinum (Pt). Herein, atomically precise Pt with scalable atoms ranging from 1 to 43 atoms, stabilized by a homemade carbon from white radish without any ligands, is prepared by a repeated UV irradiation method that is industrially scalable. Compared with the isolated Pt in the form of Pt-N, octahedral Pt, and icosahedron Pt, the ordered Pt cluster (∼0.75 nm) with higher metal coordination number displays much higher oxygen reduction reaction performance with a mass activity, which is about 1036% higher than that obtained by state-of-the-art Pt/C, an increase by a factor of ∼3.3 as compared with the DOE 2020 target (0.44 A mg). The utilization rate of Pt atoms reaches up to 94.7%, much higher than that of Pt (2 nm, 56%), capable of further reducing the amount of platinum that is required for PEMFCs. Moreover, the cluster exhibits an outstanding stability due to the improved Pt vacancy formation energy raised by stronger atom interaction in the close-packed cluster. The cluster exhibits a unique finite size effect from self-tuned energy band and strain levels. A clear strain effect on the d-band center is first presented for pure Pt without distortion from ligands like a second metal. Therefore, the assembly of subnanometer Pt with atom alteration opens up new horizons in designing efficient platinum group metal (PGM) catalysts by reducing the size to subnanometer scale.