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Modification of MOF catalysts by manipulation of counter-ions: experimental and theoretical studies of photochemical hydrogen production from water over microporous diruthenium (II, III) coordination polymers.
- Source :
-
Supramolecular Chemistry . Mar/Apr2011, Vol. 23 Issue 3/4, p287-296. 10p. 3 Diagrams, 3 Charts, 6 Graphs. - Publication Year :
- 2011
-
Abstract
- In this study we investigated the photochemical production of hydrogen from water using three heterogeneous microporous ruthenium coordination polymers [Ru2(p-BDC)2X]n (p-BDC = 1,4-benzenedicarboxylate, X = Cl, Br and BF4) in the presence of multi-component systems. The order of catalytic performances is [Ru2(p-BDC)2Br]n>[Ru2(p-BDC)2BF4]n>[Ru2(p-BDC)2Cl]n. The most active catalyst, [Ru2(p-BDC)2Br]n, caused the evolution of 46.7 μmol hydrogen molecules with a turn-over number of 18.7 based on [Ru2(p-BDC)2Br]n under visible light irradiation for 4 h. We ascertained that the differences in catalytic activities originated from (1) the efficiency of the quenching of methyl-viologen radicals by [Ru2(p-BDC)2X]n and (2) the durability of the structure in the reaction. In order to examine the catalytic reaction mechanism, we performed theoretical calculations for neutral model structures [Ru2(HCOO)4X(H2O)] (X = Cl, Br), one-electron reduction model complexes [Ru2(HCOO)4X(H2O)]- and deduced intermediate model structures [H-Ru2(HCOO)4X] using broken-symmetry hybrid density functional theory methods. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 10610278
- Volume :
- 23
- Issue :
- 3/4
- Database :
- Academic Search Index
- Journal :
- Supramolecular Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 60040376
- Full Text :
- https://doi.org/10.1080/10610278.2010.527976