Abstract

We report a 3.6 nm Ti52-oxo cluster with precise atomic structure, which presents a largest size record in the family of titanium-oxo clusters (TOCs). The crystal growth of such large Ti52 is based on a stepwise interlayer assembly approach from Ti6 substructures. The possible growth mechanism of Ti52 could be deduced from crystal structures of two substructures, Ti6 and Ti17, which were also synthesized under similar conditions as Ti52. Moreover, these TOCs show cluster-size-dependent photocatalytic hydrogen evolution activities with Ti52 giving a H2 production rate up to 398 μmol/h/g, which is also the highest record in the family of TOCs. This work not only represents a milestone in constructing large TOCs with comparable sizes as TiO2 nanoparticles but also brings significant advances in improving photocatalytic behaviors of TOCs.

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