The nitrogen–boron paramagnetic center in visible light sensitized N–B co-doped TiO2. Experimental and theoretical characterization

Literature Information

Publication Date 2010-11-01
DOI 10.1039/C0CP00143K
Impact Factor 3.676
Authors

A. M. Czoska, S. Livraghi, M. C. Paganini, E. Giamello, C. Di Valentin, G. Pacchioni


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Abstract

Nitrogen boron co-doped TiO2 prepared via sol–gel synthesis and active under visible light, contains two types of paramagnetic extrinsic defects, both exhibiting a well resolved EPR spectrum. The first center is the well characterized [NiO]˙ species (i = interstitial) also present in N-doped TiO2, while the second one involves both N and B. This latter center (labeled [NOB]˙) exhibits well resolved EPR spectra obtained using either 14N or 15N which show a high spin density in a N 2p orbital. The structure of the [NOB]˙ species is different from that previously proposed in the literature and is actually based on the presence of interstitial N and B atoms both bound to the same lattice oxygen ion. The interstitial B is also linked to two other lattice oxygen ions reproducing the trigonal planar structure typical of boron compounds. The energy level of the [NOB]˙ center lies near the edge of the valence band of TiO2 and, as such, does not contribute to the visible light absorption. However, [NOB]˙ can easily trap one electron generating the [NOB]− diamagnetic center which introduces a gap state at about 0.4 eV above the top of the valence band. This latter species can contribute to the visible light activity.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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