Anchoring ultrafine metallic and oxidized Pt nanoclusters on yolk-shell TiO2 for unprecedentedly high photocatalytic hydrogen production
We demonstrate an alkali modification process to produce highly dispersed ultrafine Pt nanoclusters with metallic Pt$^0$ and oxidized Pt$^{2+}$ species as co-catalyst anchored on nanosheet-constructed yolk-shell TiO$_2$ (NYTiO$_2$-Pt) acting as light harvesting reactor for highly efficient photocatalytic H$_2$ production. Benefiting from the high surface area, highly dispersed ultrafine Pt nanoclusters (~0.6 nm) with Pt$^0$ and Pt$^{2+}$ species and special nanosheet-constructed yolk-shell structure, this novel light harvesting reactor exhibits excellent performance for photocatalytic H$_2$ production. The NYTiO$_2$-Pt-0.5 (0.188 wt% Pt) demonstrates an unprecedentedly high H$_2$ evolution rate of 20.88 mmol h$^{−1}$ g$^{−1}$ with excellent photocatalytic stability, which is 87 times than that of NYTiO$_2$-Pt-3.0 (0.24 mmol h$^{−1}$ g$^{−1}$, 1.88 wt% Pt), and also much higher than those of other TiO$_2$ nanostructures with the same Pt content. Such H$_2$ evolution rate is the highest reported for photocatalytic H$_2$ production with such a low Pt content under simulated solar light. Our strategy here suggests that via alkali modifying the photocatalysts, we can not only enhance the H$_2$ production for solar energy conversion but also significantly decrease the noble metal content for cost saving. ; B. L. Su acknowledges the Chinese Central Government for an "Expert of the State" position in the Program of the "Thousand Talents" and a Life Membership at the Clare Hall, Cambridge and the financial support of the Department of Chemistry, University of Cambridge. Y. Li acknowledges Hubei Provincial Department of Education for the "Chutian Scholar" program. T. H. acknowledges support from the Royal Academy of Engineering through a Research Fellowship and an EPSRC Impact acceleration grant. This work is supported by the National Key Research and Development Program of China (2016YFA0202602), Program for Changjiang Scholars and Innovative Research Team in University (IRT_15R52), International Science & Technology Cooperation Program of China (2015DFE52870), National Natural Science Foundation of China (51302204 and 51502225) and the Fundamental Research Funds for the Central Universities (WUT: 2016 029).