| 1. |
- Abdellah, Mohamed, et al.
(författare)
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Competitive Hole Transfer from CdSe Quantum Dots to Thiol Ligands in CdSe-Cobaloxime Sensitized NiO Films Used as Photocathodes for H-2 Evolution
- 2017
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Ingår i: ACS Energy Letters. - : American Chemical Society (ACS). - 2380-8195. ; 2:11, s. 2576-2580
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Tidskriftsartikel (refereegranskat)abstract
- Quantum dot (QD) sensitized NiO photocathodes rely on efficient photoinduced hole injection into the NiO valence band. A system of a mesoporous NiO film co-sensitized with CdSe QDs and a molecular proton reduction catalyst was studied. While successful electron transfer from the excited QDs to the catalyst is observed, most of the photogenerated holes are instead quenched very rapidly (ps) by hole trapping at the surface thiols of the capping agent used as linker molecules. We confirmed our conclusion by first using a thiol free capping agent and second varying the thiol concentration on the QD's surface. The later resulted in faster hole trapping as the thiol concentration increased. We suggest that this hole trapping by the linker limits the H-2 yield for this photocathode in a device.
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| 2. |
- Abdellah, Mohamed, et al.
(författare)
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Time-Resolved IR Spectroscopy Reveals a. Mechanism with TiO2 as a Reversible Electron Acceptor in a TiO2-Re Catalyst System for CO2 Photoreduction
- 2017
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Ingår i: Journal of the American Chemical Society. - : AMER CHEMICAL SOC. - 0002-7863 .- 1520-5126. ; 139:3, s. 1226-1232
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Tidskriftsartikel (refereegranskat)abstract
- Attaching the phosphonated molecular catalyst [(ReBr)-Br-I(bpy)-(CO)(3)](0) to the wide-bandgap semiconductor TiO2 strongly enhances the rate of visible-light-driven reduction of CO2 to CO in dimethylformamide with triethanolamine (TEOA) as sacrificial electron donor. Herein, we show by transient mid-IR spectroscopy that the mechanism of catalyst photoreduction is initiated by ultrafast electron injection into TiO2, followed by rapid (ps-ns) and sequential two-electron oxidation of TEOA that is coordinated to the Re center. The injected electrons can be stored in the conduction band of TiO2 on an ms-s time scale, and we propose that they lead to further reduction of the Re catalyst and completion of the catalytic cycle. Thus, the excited Re catalyst gives away one electron and would eventually get three electrons back. The function of an electron reservoir would represent a role for TiO2 in photocatalytic CO2 reduction that has previously not been considered. We propose that the increase in photocatalytic activity upon heterogenization of the catalyst to TiO2 is due to the slow charge recombination and the high oxidative power of the Re-II species after electron injection as compared to the excited MLCT state of the unbound Re catalyst or when immobilized on ZrO2, which results in a more efficient reaction with TEOA.
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| 3. |
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| 4. |
- Abrahamsson, Maria, et al.
(författare)
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Microsecond (MLCT)-M-3 excited state lifetimes in bis-tridentate Ru(II)-complexes : significant reductions of non-radiative rate constants
- 2017
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Ingår i: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 46:39, s. 13314-13321
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Tidskriftsartikel (refereegranskat)abstract
- In this paper we report the photophysical properties of a series of bis-tridentate Ru-II-complexes, based on the dqp-ligand (dqp = 2,6-di(quinolin-8-yl) pyridine), which display several microsecond long excited state lifetimes for triplet metal-to-ligand charge transfer ((MLCT)-M-3) at room temperature. Temperature dependence of the excited state lifetimes for [Ru(dqp)(2)](2+) and [Ru(dqp)(ttpy)](2+) (ttpy = 4'-tolyl-2,2': 6', 2 ''-terpyridine) is reported and radiative and non-radiative rate constants for the whole series are reported and discussed. We can confirm previous assumptions that the near-octahedricity of the bis-dqp complexes dramatically slows down activated decay at room temperature, as compared to most other and less long-lived bis-tridentate RuII-complexes, such as [Ru(tpy)(2)](2+) with tau = 0.25 ns at room temperature (tpy = 2,2': 6', 2 ''-terpyridine). Moreover, the direct non-radiative decay to the ground state is comparatively slow for similar to 700 nm room-temperature emission when considering the energy-gap law. Analysis of the 77 K emission spectra suggests that this effect is not primarily due to smaller excited state distortion than that for comparable complexes. Instead, an analysis of the photophysical parameters suggests a weaker singlet-triplet mixing in the MLCT state, which slows down both radiative and non-radiative decay.
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| 5. |
- Ahlstedt, Jonatan, et al.
(författare)
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Evaluating vacquinol-1 in rats carrying glioblastoma models RG2 and NS1
- 2018
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Ingår i: Oncotarget. - : Impact Journals, LLC. - 1949-2553. ; 9:9, s. 8391-8399
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Tidskriftsartikel (refereegranskat)abstract
- Glioblastoma multiforme (GBM) is the most common malignant primary brain tumor, and available experimental and routine therapies result in limited survival benefits. A vulnerability of GBM cells to catastrophic vacuolization and cell death, a process termed methuosis, induced by Vacquinol-1 (VQ-1) has been described earlier. In the present study, we investigate the efficacy of VQ-1 treatment in two syngeneic rat GBM models, RG2 and NS1. VQ-1 treatment affected growth of both RG2 and NS1 cells in vitro. Intracranially, significant reduction in RG2 tumor size was observed, although no effect was seen on overall survival. No survival advantage or effect on tumor size was seen in animals carrying the NS1 models compared to untreated controls. Furthermore, immunological staining of FOXP3, CD4 and CD8 showed no marked difference in immune cell infiltrate in tumor environment following treatment. Taken together, a survival advantage of VQ-1 treatment alone could not be demonstrated here, even though some effect upon tumor size was seen. Staining for immune cell markers did not indicate that VQ-1 either reduced or increased host anti-tumor immune response.
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| 6. |
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| 7. |
- Antila, Liisa J., et al.
(författare)
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Dynamics and Photochemical H-2 Evolution of Dye-NiO Photocathodes with a Biomimetic FeFe-Catalyst
- 2016
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Ingår i: ACS Energy Letters. - : American Chemical Society (ACS). - 2380-8195. ; 1:6, s. 1106-1111
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Tidskriftsartikel (refereegranskat)abstract
- Mesoporous NiO films were cosensitized with a coumarin 343 dye and a proton reduction catalyst of the [Fe-2(CO)(6)(bdt)] (bdt = benzene-1,2-dithiolate) family. Femtosecond ultraviolet visible transient absorption experiments directly demonstrated subpicosecond hole injection into NiO from excited dyes followed by rapid (t(50%) similar to 6 ps) reduction of the catalyst on the surface with similar to 70% yield. The reduced catalyst was long-lived (2 mu s to 20 ms), which may allow protonation and a second reduction step of the catalyst to occur. A photo electrochemical device based on this photocathode produced H-2 with a Faradaic efficiency of similar to 50%. Fourier transform infrared spectroscopy and gas chromatography experiments demonstrated that the observed device deterioration with time was mainly due to catalyst degradation and desorption from the NiO surface. The insights gained from these mechanistic studies, regarding development of dye-catalyst cosensitized photocathodes, are discussed.
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| 8. |
- Antila, Liisa J., et al.
(författare)
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Hunting for the elusive shallow traps in TiO2 anatase
- 2015
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 51:54, s. 10914-10916
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Tidskriftsartikel (refereegranskat)abstract
- Understanding electron mobility on TiO2 is crucial because of its applications in photocatalysis and solar cells. This work shows that shallow traps believed to be involved in electron migration in TiO2 conduction band are formed upon band gap excitation, i.e., are not pre-existing states. The shallow traps in TiO2 results from large polarons and are not restricted to surface.
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| 9. |
- Aster, Alexander, et al.
(författare)
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Metal vs. ligand protonation and the alleged proton-shuttling role of the azadithiolate ligand in catalytic H-2 formation with FeFe hydrogenase model complexes
- 2019
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 10:21, s. 5582-5588
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Tidskriftsartikel (refereegranskat)abstract
- Electron and proton transfer reactions of diiron complexes [Fe(2)adt(CO)(6)] (1) and [Fe(2)adt(CO)(4)(PMe3)(2)] (4), with the biomimetic azadithiolate (adt) bridging ligand, have been investigated by real-time IR- and UV-vis-spectroscopic observation to elucidate the role of the adt-N as a potential proton shuttle in catalytic H-2 formation. Protonation of the one-electron reduced complex, 1(-), occurs on the adt-N yielding 1H and the same species is obtained by one-electron reduction of 1H(+). The preference for ligand vs. metal protonation in the Fe-2(i,0) state is presumably kinetic but no evidence for tautomerization of 1H to the hydride 1Hy was observed. This shows that the adt ligand does not work as a proton relay in the formation of hydride intermediates in the reduced catalyst. A hydride intermediate 1HHy(+) is formed only by protonation of 1H with stronger acid. Adt protonation results in reduction of the catalyst at much less negative potential, but subsequent protonation of the metal centers is not slowed down, as would be expected according to the decrease in basicity. Thus, the adtH(+) complex retains a high turnover frequency at the lowered overpotential. Instead of proton shuttling, we propose that this gain in catalytic performance compared to the propyldithiolate analogue might be rationalized in terms of lower reorganization energy for hydride formation with bulk acid upon adt protonation.
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| 10. |
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