title: Understanding the high photocatalytic activity of (B, Ag)-codoped TiO2 under solar-light irradiation with XPS, solid-state NMR, and DFT calculations.
abstract: The origin of the exceptionally high activity of (B, Ag)-codoped TiO(2) catalysts under solar-light irradiation has been investigated by XPS and (11)B solid-state NMR spectroscopy in conjunction with density functional theory (DFT) calculations. XPS experimental results demonstrated that a portion of the dopant Ag (Ag(3+)) ions were implanted into the crystalline lattice of (B, Ag)-codoped TiO(2) and were in close proximity to the interstitial B (B(int.)) sites, forming [B(int.)-O-Ag] structural units. In situ XPS experiments were employed to follow the evolution of the chemical states of the B and Ag dopants during UV-vis irradiation. It was found that the [B(int.)-O-Ag] units could trap the photoinduced electron to form a unique intermediate structure in the (B, Ag)-codoped TiO(2) during the irradiation, which is responsible for the photoinduced shifts of the B 1s and Ag 3d peaks observed in the in situ XPS spectra. Solid-state NMR experiments including (11)B triple-quantum and double-quantum magic angle spinning (MAS) NMR revealed that up to six different boron species were present in the catalysts and only the tricoordinated interstitial boron (T*) species was in close proximity to the substitutional Ag species, leading to formation of [T*-O-Ag] structural units. Furthermore, as demonstrated by DFT calculations, the [T*-O-Ag] structural units were responsible for trapping the photoinduced electrons, which prolongs the life of the photoinduced charge carriers and eventually leads to a remarkable enhancement in the photocatalytic activity. All these unprecedented findings are expected to be crucial for understanding the roles of B and Ag dopants and their synergistic effect in numerous titania-mediated photocatalytic reactions.
authors: State Key Laboratory of Magnetic Resonance and Atomic Molecular Physics, Wuhan Center for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China.
authors: Ningdong
authors: N
authors: Feng
authors: Qiang
authors: Q
authors: Wang
authors: Anmin
authors: A
authors: Zheng
authors: Zhengfeng
authors: Z
authors: Zhang
authors: Jie
authors: J
authors: Fan
authors: Shang-Bin
authors: SB
authors: Liu
authors: Jean-Paul
authors: JP
authors: Amoureux
authors: Feng
authors: F
authors: Deng
mesh_terms: D001895:Boron / Q000737:chemistry*; D002384:Catalysis; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D055668:Photochemical Processes; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D013053:Spectrophotometry; D014025:Titanium / Q000737:chemistry*; D014965:X-Rays
chemical_list: C009495:titanium dioxide; D012834:Silver; D014025:Titanium; D001895:Boron