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Semiconductor photocatalysis with commercial TiO2 (Degussa P25) has shown significant potential in water treatment of organic pollutants. However, the photoinduced reactions of adsorbed catechol, a phenolic air pollutant from biomass burning and combustion emissions, at the air–solid interface of TiO2 remain unexplored. Herein we examine the photocatalytic decay of catechol in the presence of water vapor, which acts as an electron acceptor. Experiments under variable cut-off wavelengths of irradiation (λcut-off ≥ 320, 400, and 515 nm) distinguish the mechanistic contribution of a ligand-to-metal charge-transfer (LMCT) complex of surface chemisorbed catechol on TiO2. The LMCT complex injects electrons into the conduction band of TiO2 from the highest occupied molecular orbital of catechol by visible light (≥2.11 eV) excitation. The deconvolution of diffuse reflectance UV–visible spectral bands from LMCT complexes of TiO2 with catechol, o-semiquinone radical, and quinone and the quantification of the evolving gaseous products follow a consecutive kinetic model. CO2(g) and CO(g) final oxidation products are monitored by gas chromatography and Fourier-transform infrared spectroscopy. The apparent quantum efficiency at variable λcut-off are determined for reactant loss (Φ−TiO2/catechol = 0.79 ± 0.19) and product growth ΦCO2 = 0.76 ± 0.08). Spectroscopic and electrochemical measurements reveal the energy band diagram for the LMCT of TiO2/catechol. Two photocatalytic mechanisms are analyzed based on chemical transformations and environmental relevance.
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Photophysical Characterization and Excited State Dynamics of Decamethylruthenocenium
Understanding the landscape of molecular photocatalysis is vital to enable efficient conversion of feedstock molecules to targeted products and inhibit off-cycle reactivity. In this study, the light-promoted reactivity of [RuCp*2]+ was explored via electronic structure, photophysical, and photostability studies and the reactivity of [RuCp*2]+ within a photocatalytic hydrogen evolution cycle was assessed. TD-DFT calculations support the assignment of a low-energy ligand-to-metal charge transfer transition (LMCT) centered at 500 nm, where an electron from a ligand-based orbital delocalized across both Cp* ligands is promoted to a dx2–y2-based β-LUMO orbital. Upon irradiating the LMCT absorption feature, ultrafast transient absorption spectroscopy measurements show that an initial excited state (τ1 = 1.3 ± 0.1 ps) is populated, which undergoes fast relaxation to a longer-lived state (τ2 = 12.0 ± 0.9 ps), either via internal conversion or vibrational relaxation. Despite the short-lived nature of these excited states, bulk photolysis of [RuCp*2]+ demonstrates that photochemical conversion to decomposition products is possible upon prolonged illumination. Collectively, these studies reveal that [RuCp*2]+ undergoes light-driven decomposition, highlighting the necessity to construct molecular photocatalytic systems resistant to off-cycle reactivity in both the ground and excited states.
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- PAR ID:
- 10621099
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 129
- Issue:
- 6
- ISSN:
- 1089-5639
- Page Range / eLocation ID:
- 1558 to 1565
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/acs.jpca.4c06564
