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Nanoscaled Bismuth Oxido Clusters: Probing Factors of Structure Formation and Photocatalytic Activity
Author(s) -
Schlesinger Maik,
Weber Marcus,
Rüffer Tobias,
Lang Heinrich,
Mehring Michael
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300889
Subject(s) - chemistry , bismuth , photocatalysis , photodegradation , monoclinic crystal system , oxide , aqueous solution , dimethyl sulfoxide , cluster (spacecraft) , inorganic chemistry , rhodamine b , crystallography , nuclear chemistry , medicinal chemistry , crystal structure , organic chemistry , catalysis , computer science , programming language
Hydrolysis of bismuth(III) nitrate in the presence of sodium benzoate (NaOBz) in dimethyl sulfoxide (DMSO) gave the bismuth oxido cluster [{Bi 38 O 45 (NO 3 ) 20 (OBz) 4 (DMSO) 24 } · 4DMSO][{Bi 38 O 45 (NO 3 ) 24 (DMSO) 26 } · 4DMSO] ( 1 ), which crystallizes in the monoclinic space group P 2 1 / c with cell parameters of a = 35.8728(12) Å, b = 20.2750(5) Å, c = 34.8624(11) Å, and β = 111.797(4)°. The asymmetric unit contains two crystallographically independent bismuth oxido clusters of different composition. Because of the distinct structural relationship of this type of bismuth oxido clusters with the photocatalytically active polymorph β‐Bi 2 O 3 , colloidal suspensions of nanoscaled 1 as well as colloids composed of the recently reported clusters [Bi 6 O 4 (OH) 4 (NO 3 ) 6 ] · H 2 O ( 2 ), [{Bi 38 O 45 (NO 3 ) 24 (DMSO) 26 } · 2DMSO][{Bi 38 O 45 (NO 3 ) 24 (DMSO) 24 } · 0.5DMSO] ( 3 ), and [Bi 38 O 45 (OMc) 24 (DMSO) 9 ] · 2DMSO · 7H 2 O ( 4 ) were probed for their photocatalytic activity. The bismuth oxido cluster 3 decomposes more than 85 % of a 1 × 10 –5 M aqueous solution of rhodamine B (RhB) under visible‐light irradiation within 150 min. Colloids of such clusters might serve as model compounds for indirect photodegradation processes of organic contaminants at the metal oxide surface.