The experimental procedure is shown in Fig. S1. Commercial P25 powders were used as source materials for liquid N2 quenching. Two pieces of samples were first annealed at different temperatures over 500 to 800 °C for 2 h. One piece was kept in furnace to undergo a normal cooling down to room temperature; another one was quickly taken out at the pre-annealed temperature and thrown into liquid N2 for a fast quenching. The normally-cooled and quenched samples were named asn-TiO2 and q-TiO2.