Songbo Wang

Titanium-Defected Undoped Anatase TiO2 with p-Type Conductivity, Room-Temperature Ferromagnetism, and Remarkable Photocatalytic Performance

Defects are critically important for metal oxides in chemical and physical applications. Compared with the often studied oxygen vacancies, engineering metal vacancies in n-type undoped metal oxides is still a great challenge, and the effect of metal vacancies on the physiochemical properties is seldom reported. Here, using anatase TiO2, the most important and widely studied semiconductor, we demonstrate that metal vacancies (VTi) can be introduced in undoped oxides easily, and the presence of VTi results in many novel physiochemical properties. Anatase Ti0.905O2 was synthesized using solvothermal treatment of tetrabutyl titanate in an ethanol-glycerol mixture and then thermal calcination. Experimental measurements and DFT calculations on cell lattice parameters show the unstoichiometry is caused by the presence of VTi rather than oxygen interstitials. The presence of VTi changes the charge density and valence band edge of TiO2, and an unreported strong EPR signal at g = 1.998 presents under room temperature. Contrary to normal n-type and nonferromagnetic TiO2, Ti-defected TiO2 shows inherent p-type conductivity with high charge mobility, and room-temperature ferromagnetism stronger than Co-doped TiO2 nanocrystalline. Moreover, Ti-defected TiO2 shows much better photocatalytic performance than normal TiO2 in H2 generation (4.4-fold) and organics degradation (7.0-fold for phenol), owing to the more efficient charge separation and transfer in bulk and at semiconductor/electrolyte interface. Metal-defected undoped oxides represent a unique material; this work demonstrates the possibility to fabricate such material in easy and reliable way and thus provides new opportunities for multifunctional materials in chemical and physical devices.

C-doped ZnO ball-in-ball hollow microspheres for efficient photocatalytic and photoelectrochemical applications

ZnO is an important semiconductor and has been widely used in the field of photocatalysis, solar cell and environmental remediation. Herein, we fabricated C-doped ZnO ball-in-ball hollow microspheres (BHMs) by a facile solvothermal treatment of zinc acetate in ethylene glycol-ethanol mixture. The presence of ethylene glycol (EG) leads to the formation of initial single-layered hollow spheres and then a time-dependent evolution transforms them into uniform BHMs with tunable shell thickness and void space. XPS characterizations reveal that C-dopants are introduced into the lattice of ZnO BHMs, with its concentration increasing with solvothermal time and then becoming saturated in 12h. ZEG-12 (ZnO BHMs with 12-h solvothermal treatment), with an optimal hollow structure and C-doping concentration, performs the best optical absorption capability, efficiency of charge separation and transfer, and mass transfer in reaction media, as proved by SEM, TEM, PL, BET and EIS characterizations. When applied as photocatalyst for organic-pollutant degradation and as photoanode material for PEC water splitting, ZEG-12 exhibits respectively ca. 8.9-fold and 10.5-fold higher activity than pristine ZnO nanoparticles.