TY - JOUR
T1 - Pentadecanuclear Fe-Containing Polyoxometalate Catalyst for Visible-Light-Driven Generation of Hydrogen
AU - Cui, Tingting
AU - Qin, Lin
AU - Fu, Fangyu
AU - Xin, Xing
AU - Li, Huijie
AU - Fang, Xikui
AU - Lv, Hongjin
N1 - Publisher Copyright:
©
PY - 2021/3/15
Y1 - 2021/3/15
N2 - The structurally new, carbon-free pentadecanuclear Fe-containing polyoxometalate, Na21[NaFe15(OH)12(PO4)4(A-α-SiW9O34)4]·85H2O (Na21-Fe15P4(SiW9)4), was synthesized using a facile one-pot, solution-based synthetic approach and systematically characterized by various spectroscopic techniques. Single-crystal X-ray diffraction reveals that the title complex is composed of two [Fe4(A-α-SiW9O34)] fragments and two [Fe3.5(A-α-SiW9O34)] fragments stabilized by four PO4 linkers in a tetrameric style with idealized Td point group symmetry. When coupling with (4,4′-ditert-butyl-2,2′-dipyridyl)-bis(coumarin)-iridium(III) hexafluorophosphate ([Ir(coumarin)2(dtbbpy)][PF6]) photosensitizer and triethanolamine (TEOA) sacrificial electron donor, polyoxoanion Fe15P4(SiW9)4 effectively catalyzed hydrogen production with a minimally optimized TON of 986, which represents, to our knowledge, one of the highest values among known Fe-substituted POM-catalyzed hydrogen production systems. Both a mercury-poisoning test and FT-IR characterizations proved the structural stability of Fe15P4(SiW9)4 catalyst under photocatalytic conditions. The photocatalytic mechanism of the present hydrogen-evolving system was investigated by time-solved luminescence and static emission quenching measurements.
AB - The structurally new, carbon-free pentadecanuclear Fe-containing polyoxometalate, Na21[NaFe15(OH)12(PO4)4(A-α-SiW9O34)4]·85H2O (Na21-Fe15P4(SiW9)4), was synthesized using a facile one-pot, solution-based synthetic approach and systematically characterized by various spectroscopic techniques. Single-crystal X-ray diffraction reveals that the title complex is composed of two [Fe4(A-α-SiW9O34)] fragments and two [Fe3.5(A-α-SiW9O34)] fragments stabilized by four PO4 linkers in a tetrameric style with idealized Td point group symmetry. When coupling with (4,4′-ditert-butyl-2,2′-dipyridyl)-bis(coumarin)-iridium(III) hexafluorophosphate ([Ir(coumarin)2(dtbbpy)][PF6]) photosensitizer and triethanolamine (TEOA) sacrificial electron donor, polyoxoanion Fe15P4(SiW9)4 effectively catalyzed hydrogen production with a minimally optimized TON of 986, which represents, to our knowledge, one of the highest values among known Fe-substituted POM-catalyzed hydrogen production systems. Both a mercury-poisoning test and FT-IR characterizations proved the structural stability of Fe15P4(SiW9)4 catalyst under photocatalytic conditions. The photocatalytic mechanism of the present hydrogen-evolving system was investigated by time-solved luminescence and static emission quenching measurements.
UR - http://www.scopus.com/inward/record.url?scp=85102013422&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.1c00267
DO - 10.1021/acs.inorgchem.1c00267
M3 - Article
C2 - 33621075
AN - SCOPUS:85102013422
SN - 0020-1669
VL - 60
SP - 4124
EP - 4132
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 6
ER -
