Further Understanding of the Electronic Interactions between N719 Sensitizer and Anatase TiO<sub>2</sub> Films: A Combined X-ray Absorption and X-ray Photoelectron Spectroscopic Study
Bibliographic record
Abstract
In this study, the electronic properties of N719 adsorbed onto anatase were comparably investigated by using X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) techniques. Sensitized TiO 2 films made from two different nanocrystalline anatase powders were investigated: a commercial one (Solaronix) and our synthetic variety produced through aqueous synthesis. This was done to investigate how our aqueous-produced nanocrystalline anatase substrates compared with commercial products and to observe whether both nanocrystalline anatase anodes behaved in a similar manner in terms of their bonding and electronic interactions. Surface coordination changes to Ti−O groups previously reported via Ti K-edge extended X-ray absorption fine structure (EXAFS) data [using transmission or fluorescence yield (FY)] between the pure TiO 2 and the adsorbed state were not observed in our measurements via the Ti L or K X-ray absorption near-edge structure (XANES) (nor EXAFS) data for both substrates via a surface-sensitive detection technique (total electron yield, TEY). This is likely due to the probing depth of TEY mode (5−10 nm), in which the coordination changes that occur to the surface groups, which should in turn affect the XANES spectrum, are not observed at Ti K- or L-edge XANES spectrum. The C and N K-edge XANES spectra of the N719 adsorbed onto two TiO 2 films were for the first time evaluated in this work. From the C K-edge XANES data, the spectral changes revealed that additional electronic states occur between dye molecules and TiO 2 surface. The C K-edge XANES spectra allowed us to propose that electronic interactions do not only occur through the covalent bonding of the anchoring groups but also through the aromatic electron density of the bipyridine groups and the d states found in TiO 2 . This was further confirmed via XPS analysis by monitoring the N bipyridine groups before and after sensitization. XPS used in combination with XAS (in TEY mode) provided complementary information owing to its higher surface sensitivity. The Ti 2p and O 1s XPS spectra showed that adsorption of the dye on TiO 2 leads to a change of the surface dipole and/or a change in the Fermi level position in the band gap, which shifts all the core levels of TiO 2 . These are not equal for both TiO 2 substrates in spite of them being nanocrystallnine anatase. This effect was found to be greater for the N719−aqueous TiO 2 system than the respective Solaronix one. For the N 1s and S 2p XPS, the shift toward higher energy indicated that there exists an additional H-bonding interaction of the NCS ligand of the dye molecule with the TiO 2 surface groups (OH/H 2 O).
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".