| 1. |
- Basagni, Andrea, et al.
(författare)
-
On-surface photo-dissociation of C-Br bonds: towards room temperature Ullmann coupling
- 2015
-
Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1364-548X .- 1359-7345. ; 51:63, s. 12593-12596
-
Tidskriftsartikel (refereegranskat)abstract
- The surface-assisted synthesis of gold-organometallic hybrids on the Au(111) surface both by thermo-and light-initiated dehalogenation of bromo-substituted tetracene is reported. Combined X-ray photoemission (XPS) and scanning tunneling microscopy (STM) data reveal a significant increase of the surface order when mild reaction conditions are combined with 405 nm light irradiation.
|
|
| 2. |
- Carrasco-Jaim, Omar A., et al.
(författare)
-
Photocatalytic hydrogen production by biomimetic indium sulfide using Mimosa pudica leaves as template
- 2019
-
Ingår i: International Journal of Hydrogen Energy. - : Elsevier BV. - 0360-3199. ; 44:5, s. 2770-2783
-
Tidskriftsartikel (refereegranskat)abstract
- Biomimetic sulfur-deficient indium sulfide (In2.77S4) was synthesized by a template-assisted hydrothermal method using leaves of Mimosa pudica as a template for the first time. The effect of this template in modifying the morphology of the semiconductor particles was determined by physicochemical characterization, revealing an increase in surface area, decrease in microsphere size and pore size and an increase in pore volume density in samples synthesized with the template. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of organic sulfur (S–O/S–C/S–H) and sulfur oxide species (–SO2, SO3 2−, SO4 2−) at the surface of the indium sulfide in samples synthesized with the template. Biomimetic indium sulfide also showed significant amounts of Fe introduced as a contaminant present on the Mimosa pudica leaves. The presence of these sulfur and iron species favors the photocatalytic activity for hydrogen production by their acting as a sacrificial reagent and promoting water oxidation on the surface of the templated particles, respectively. The photocatalytic hydrogen production rates over optimally-prepared biomimetic indium sulfide and indium sulfide synthesized without the organic template were 73 and 22 μmol g−1, respectively, indicating an improvement by a factor of three in the templated sample.
|
|
| 3. |
- Chábera, Pavel, et al.
(författare)
-
A low-spin Fe(iii) complex with 100-ps ligand-to-metal charge transfer photoluminescence
- 2017
-
Ingår i: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 543:7647, s. 695-699
-
Tidskriftsartikel (refereegranskat)abstract
- Transition-metal complexes are used as photosensitizers1, in light-emitting diodes, for biosensing and in photocatalysis2. A key feature in these applications is excitation from the ground state to a charge-transfer state3,4; the long charge-transfer-state lifetimes typical for complexes of ruthenium5 and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron6 and copper7 being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs6,8,9,10, it remains a formidable scientific challenge11 to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered12 photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers13,14,15. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes4,16,17. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.
|
|
| 4. |
- Clark, Pip C.J., et al.
(författare)
-
The passivating effect of cadmium in PbS/CdS colloidal quantum dots probed by nm-scale depth profiling
- 2017
-
Ingår i: Nanoscale. - : Royal Society of Chemistry (RSC). - 2040-3364 .- 2040-3372. ; 9:18, s. 6056-6067
-
Tidskriftsartikel (refereegranskat)abstract
- Achieving control of the surface chemistry of colloidal quantum dots (CQDs) is essential to fully exploit their properties in solar cells, but direct measurement of the chemistry and electronic structure in the outermost atomic layers is challenging. Here we probe the surface oxidation and passivation of cation-exchanged PbS/CdS core/shell CQDs with sub nm-scale precision using synchrotron-radiation-excited depth-profiling photoemission. We investigate the surface composition of the topmost 1-2.5 nm of the CQDs as a function of depth, for CQDs of varying CdS shell thickness, and examine how the surface changes after prolonged air exposure. We demonstrate that the Cd is localized at the surface of the CQDs. The surface-localized products of oxidation are identified, and the extent of oxidation quantified. We show that oxidised sulfur species are progressively eliminated as Cd replaces Pb at the surface. A sub-monolayer surface 'decoration' of Cd is found to be effective in passivating the CQDs. We show that the measured energy-level alignments at PbS/CdS colloidal quantum dot surfaces differ from those expected on the basis of bulk band offsets, and are strongly affected by the oxidation products. We develop a model for the passivating action of Cd. The optimum shell thickness (of around 0.1 nm, previously found to give maximised power conversion efficiency in PbS/CdS solar cells) is found to correspond to a trade-off between the rate of oxidation and the introduction of a surface barrier to charge transport.
|
|
| 5. |
- Ericson, Fredric, et al.
(författare)
-
Electronic structure and excited state properties of iron carbene photosensitizers - A combined X-ray absorption and quantum chemical investigation
- 2017
-
Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614. ; 683, s. 559-566
-
Tidskriftsartikel (refereegranskat)abstract
- The electronic structure and excited state properties of a series of iron carbene photosensitizers are elucidated through a combination of X-ray absorption measurements and density functional theory calculations. The X-ray absorption spectra are discussed with regard to the unusual bonding environment in these carbene complexes, highlighting the difference between ferrous and ferric carbene complexes. The valence electronic structure of the core excited FeIII-3d5 complex is predicted by calculating the properties of a CoIII-3d6 carbene complex using the Z+1 approximation. Insight is gained into the potential of sigma-donating ligands as strategy to tune properties for light harvesting applications.
|
|
| 6. |
- Fogarty, Richard M., et al.
(författare)
-
Electron spectroscopy of ionic liquids : Experimental identification of atomic orbital contributions to valence electronic structure
- 2019
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 21:35, s. 18893-18910
-
Tidskriftsartikel (refereegranskat)abstract
- The atomic contributions to valence electronic structure for 37 ionic liquids (ILs) are identified using a combination of variable photon energy XPS, resonant Auger electron spectroscopy (RAES) and a subtraction method. The ILs studied include a diverse range of cationic and anionic structural moieties. We introduce a new parameter for ILs, the energy difference between the energies of the cationic and anionic highest occupied fragment orbitals (HOFOs), which we use to identify the highest occupied molecular orbital (HOMO). The anion gave rise to the HOMO for 25 of the 37 ILs studied here. For 10 of the ILs, the energies of the cationic and anionic HOFOs were the same (within experimental error); therefore, it could not be determined whether the HOMO was from the cation or the anion. For two of the ILs, the HOMO was from the cation and not from the anion; consequently it is energetically more favourable to remove an electron from the cation than the anion for these two ILs. In addition, we used a combination of area normalisation and subtraction of XP spectra to produce what are effectively XP spectra for individual ions; this was achieved for 10 cations and 14 anions.
|
|
| 7. |
- Gibson, Andrew J., et al.
(författare)
-
Resonant core spectroscopies of the charge transfer interactions between C60 and the surfaces of Au(111), Ag(111), Cu(111) and Pt(111)
- 2017
-
Ingår i: Surface Science. - : Elsevier BV. - 0039-6028. ; 657, s. 69-78
-
Tidskriftsartikel (refereegranskat)abstract
- Charge transfer interactions between C60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C60/Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 ± 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface.
|
|
| 8. |
- Kokkonen, Esko, et al.
(författare)
-
Upgrade of the SPECIES beamline at the MAX IV Laboratory
- 2021
-
Ingår i: Journal of Synchrotron Radiation. - 1600-5775. ; 28, s. 588-601
-
Tidskriftsartikel (refereegranskat)abstract
- The SPECIES beamline has been transferred to the new 1.5 GeV storage ring at the MAX IV Laboratory. Several improvements have been made to the beamline and its endstations during the transfer. Together the Ambient Pressure X-ray Photoelectron Spectroscopy and Resonant Inelastic X-ray Scattering endstations are capable of conducting photoelectron spectroscopy in elevated pressure regimes with enhanced time-resolution and flux and X-ray scattering experiments with improved resolution and flux. Both endstations offer a unique capability for experiments at low photon energies in the vacuum ultraviolet and soft X-ray range. In this paper, the upgrades on the endstations and current performance of the beamline are reported.
|
|
| 9. |
- Koust, Stig, et al.
(författare)
-
Coverage-dependent oxidation and reduction of vanadium supported on anatase TiO2(1 0 1)
- 2018
-
Ingår i: Journal of Catalysis. - : Elsevier BV. - 0021-9517. ; 360, s. 118-126
-
Tidskriftsartikel (refereegranskat)abstract
- © 2018 Elsevier Inc. Using a multi-technical approach, we studied the oxidation of anatase TiO 2 (1 0 1)-supported vanadium (V) clusters at room temperature. We found by ex situ XPS that the highest oxidation state is +4 at sub-monolayer coverage regardless of the O 2 pressure, and STM studies revealed that the initial oxidation proceeds through oxygen-induced disintegration of V clusters into monomeric VO 2 species. By contrast, for ∼2 monolayer V coverage, a partial oxidation to V 5+ is achieved. By in situ APXPS measurements, we found that V can be maintained in the V 5+ oxidation state irrespective of the coverage; however, in the sub-monolayer range, an O 2 pressure of at least ∼1 × 10 −5 mbar is needed. Our results suggest an enhanced reducibility of V in direct contact with the TiO 2 support compared to V in the 2nd layer, which is in line with the observed optimum V 2 O 5 loading in catalytic applications just slightly below a full monolayer.
|
|
| 10. |
- O'Shea, James N., et al.
(författare)
-
Exploring ultra-fast charge transfer and vibronic coupling with N 1s RIXS maps of an aromatic molecule coupled to a semiconductor
- 2017
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 147:13
-
Tidskriftsartikel (refereegranskat)abstract
- We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for the depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the time scale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond time scale in this system.
|
|
