| 1. |
- Abrahamsson, M. L. A., et al.
(författare)
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Ruthenium-manganese complexes for artificial photosynthesis : Factors controlling intramolecular electron transfer and excited-state quenching reactions
- 2002
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 41:6, s. 1534-1544
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Tidskriftsartikel (refereegranskat)abstract
- Continuing our work toward a system mimicking the electron-transfer steps from manganese to P-680(+) in photosystem II (PS II), we report a series of ruthenium(II)-manganese(II) complexes that display intramolecular electron transfer from manganese(II) to photooxidized ruthenium(III). The electron-transfer rate constant (k(ET)) values span a large range, 1 X 10(5)-2 x 10(7) s(-1), and we have investigated different factors that are responsible for the variation. The reorganization energies determined experimentally (lambda = 1.5-2.0 eV) are larger than expected for solvent reorganization in complexes of similar size in polar solvents (typically lambda approximate to 1.0 eV). This result indicates that the inner reorganization energy is relatively large and, consequently, that at moderate driving force values manganese complexes are not fast donors. Both the type of manganese ligand and the link between the two metals are shown to be of great importance to the electron-transfer rate. In contrast, we show that the quenching of the excited state of the ruthenium(II) moiety by manganese(II) in this series of complexes mainly depends on the distance between the metals. However, by synthetically modifying the sensitizer so that the lowest metal-to-ligand charge transfer state was localized on the nonbridging ruthenium(II) ligands, we could reduce the quenching rate constant in one complex by a factor of 700 without changing the bridging ligand. Still, the manganese(II)-ruthenium (III) electrontransfer rate constant was not reduced. Consequently, the modification resulted in a complex with very favorable properties.
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| 2. |
- Berg, K. E., et al.
(författare)
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Covalently linked ruthenium(II)-manganese(II) complexes : Distance dependence of quenching and electron transfer
- 2001
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Ingår i: European Journal of Inorganic Chemistry. - 1434-1948 .- 1099-1948. ; 2001:4, s. 1019-1029
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Tidskriftsartikel (refereegranskat)abstract
- Continuing our development of artificial models for photosystem II in green plants, a series of compounds have been prepared in which a RU(bpy)(3)(2+) photosensitizer is covalently Linked to a manganese(II) electron donor. In addition to a trispicolylamine Ligand, two other manganese Ligands, dipicolylamine and aminodiacetic acid, have been introduced in order to study Ligands that are appropriate for the construction of manganese dimers with open coordination sites for the binding of water. Coordination equilibria of the manganese ions were monitored by EPR. The interactions between the ruthenium and manganese moieties were probed by flash photolysis, cyclic voltammetry and steady-state and time-resolved emission measurements. The quenching of the Ru-II excited state by Mn-II was found to be rapid in complexes with short Ru-Mn distances. Nevertheless, each Run species could be photo-oxidized by bimolecular quenching with methylviologen, and the subsequent electron transfer from Mn-II to Ru-III could be monitored.
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| 3. |
- Tran, K. Q., et al.
(författare)
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On the application of surface ionization detector for the study of alkali capture by kaolin in a fixed bed reactor
- 2004
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Ingår i: Fuel. ; 83:7-8, s. 807-812
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Tidskriftsartikel (refereegranskat)abstract
- Alkali metals, mainly potassium, together with other ash forming inorganic components in biomass are believed to be responsible for bed agglomeration in fluidized bed boilers burning biomass. A solution to the problem is to capture alkali vapor released from the fuel during combustion by inorganic solid additives such as kaolin. In this study, the capture of vaporous potassium chloride was investigated in a fixed bed reactor equipped with an on-line alkali detector. The detector, which is based on surface ionization, is capable of operating at alkali metal concentrations as low as those encountered after reaction with kaolin during biomass combustion (of the order of 1 ppb). Various experiments of KCl capture by kaolin powder were made at a reactor temperature of 850 degreesC. Kaolin removed up to 99% of alkali species in gas phase. The efficiency slightly decreased when KCl concentration decreased. The effect of kaolin addition on the release of alkali metals during wood combustion was studied at 650 degreesC in air. During pyrolysis, the alkali metal release increased slightly when kaolin was mixed with the wood due to the release of alkali metal impurities in the kaolin additive. The alkali metal release during char combustion was reduced to approximately 50% of the original value. The reduction increased as the amount of kaolin addition increased. Overall, the addition of kaolin suppressed the alkali metal release from the wood by approximately 20%. (C) 2004 Elsevier Ltd. All rights reserved.
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| 4. |
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| 5. |
- Tran, K. Q., et al.
(författare)
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A novel particle trap impactor for use with the gas-quenching probe sampling system
- 2004
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Ingår i: Aerosol Science and Technology. - : Informa UK Limited. - 0278-6826 .- 1521-7388. ; 38:10, s. 955-962
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Tidskriftsartikel (refereegranskat)abstract
- A novel particle trap impactor has been developed for use with the gas-quenching probe in order to exclude solid particles from entering into the probe during sampling of gaseous metallic species in fluidized bed combustion conditions. The impactor must be small in size (empty set(impactor)less than or equal toempty set(probe) = 45 mm) but capable of collecting a relatively large amount of particles at elevated temperatures. As the first step, the impactor was designed, constructed, and tested at room temperature for KCl aerosol particles. The impactor with a nozzle of 0.95 mm in diameter, in combination with the orifice-to-jet diameter ratio of 1.5 and the ratio of the jet-to-plate spacing to jet diameter at 1.4 yielded a sharp cutoff curve with a maximum collection efficiency of about 0.9 and a rootStk(50) value of about 0.22. In addition, the collection efficiency of the impactor was compared with the particle removal efficiency of a filter of the same type as the filter previously used with the gas-quenching probe. The difference from the comparison is very small, indicating that the impactor can be used to replace the filter to prevent fly ash particles from entering the gas-quenching probe in fluidized bed combustion conditions.
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