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Calcium Bismuthate Nanoparticulates with Orthorhombic and Rhombohedral Crystalline Lattices: Effects of Composition and Structure on Photoactivity
Author(s) -
Shtarev Dmitry S.,
Ryabchuk Vladimir K.,
Makarevich Konstantin S.,
Shtareva Anna V.,
Blokh Artem I.,
Astapov Ivan A.,
Serpone Nick
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201702204
Subject(s) - orthorhombic crystal system , materials science , annealing (glass) , absorption edge , band gap , crystal structure , calcium titanate , photocatalysis , oxygen , analytical chemistry (journal) , crystallography , ceramic , chemistry , metallurgy , biochemistry , optoelectronics , organic chemistry , chromatography , catalysis
Calcium bismuthate nanoparticles with orthorhombic and rhombohedral crystal lattices were synthesized and characterized by various techniques. The syntheses caused the formation of oxygen and cationic vacancies in bismuth‐deficient samples. Heat treatment of samples with anionic vacancies led to thermal annealing of oxygen vacancies in ambient air; the annealing process was reversible. Oxygen vacancies in Bi‐deficient CaBi 6 O 10 governed the optical absorption beyond the fundamental absorption edge at E (hν) < E bg ≈ 2.5 eV. Bandgap energies of the bismuthates with orthorhombic and rhombohedral lattices were 2.51 eV prior to annealing and 2.47 eV after annealing at 350 °C. The trend in photoactivity toward the degradation of methylene blue dye under visible light showed that the photoactivity of the orthorhombic samples ( 1‐3 ) increased with a decrease in the [Ca]:[Bi] ratio (1.0:6.3 to 1.0:4.3); the sample with lowest ratio (1.0:4.3) displayed highest photoactivity. By contrast, the rhombohedral samples ( 4‐6 ) showed increased photoactivity with increase in the number of Bi atoms; sample with highest ratio (1.0:6.3) displayed highest photoactivity.