Plasmon-driven photocatalysis has emerged as a paradigm-shifting approach, based on which the energy of photons can be judiciously harnessed to trigger interfacial molecular transformations on metallic nanostructure surfaces in a regioselective manner with nanoscale precision. Over the past decade, the formation of aromatic azo compounds through plasmon-driven oxidative coupling of thiolated aniline-derivative adsorbates has become a testbed for developing detailed mechanistic understanding of plasmon-mediated photochemistry. Such photocatalytic bimolecular coupling reactions may occur not only between thiolated aniline-derivative adsorbates but also between their nonthiolated analogs. How the nonthiolated adsorbates behave differently from their thiolated counterparts during the plasmon-driven coupling reactions, however, remains largely unexplored. Here, we systematically compare an alkynylated aniline-derivative, para-ethynylaniline, to its thiolated counterpart, para-mercaptoaniline, in terms of their adsorption conformations, structural flexibility, photochemical reactivity, and transforming kinetics on Ag nanophotocatalyst surfaces. We employ surface-enhanced Raman scattering as an in situ spectroscopic tool to track the detailed structural evolution of the transforming molecular adsorbates in real time during the plasmon-driven coupling reactions. Rigorous analysis of the spectroscopic results, further aided by density functional theory calculations, lays an insightful knowledge foundation that enables us to elucidate how the alteration of the chemical nature of metal–adsorbate interactions profoundly influences the transforming behaviors of the molecular adsorbates during plasmon-driven photocatalytic reactions.
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Structural Features Promoting Photocatalytic Degradation of Contaminants of Emerging Concern: Insights into Degradation Mechanism Employing QSA/PR Modeling
Although heterogeneous photocatalysis has shown promising results in degradation of contaminants of emerging concern (CECs), the mechanistic implications related to structural diversity of chemicals, affecting oxidative (by HO•) or reductive (by O2•−) degradation pathways are still scarce. In this study, the degradation extents and rates of selected organics in the absence and presence of common scavengers for reactive oxygen species (ROS) generated during photocatalytic treatment were determined. The obtained values were then brought into correlation as K coefficients (MHO•/MO2•−), denoting the ratio of organics degraded by two occurring mechanisms: oxidation and reduction via HO• and O2•−. The compounds possessing K >> 1 favor oxidative degradation over HO•, and vice versa for reductive degradation (i.e., if K << 1 compounds undergo reductive reactions driven by O2•−). Such empirical values were brought into correlation with structural features of CECs, represented by molecular descriptors, employing a quantitative structure activity/property relationship (QSA/PR) modeling. The functional stability and predictive power of the resulting QSA/PR model was confirmed by internal and external cross-validation. The most influential descriptors were found to be the size of the molecule and presence/absence of particular molecular fragments such as C − O and C − Cl bonds; the latter favors HO•-driven reaction, while the former the reductive pathway. The developed QSA/PR models can be considered robust predictive tools for evaluating distribution between degradation mechanisms occurring in photocatalytic treatment.
more » « less- Award ID(s):
- 2019077
- NSF-PAR ID:
- 10488276
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 28
- Issue:
- 6
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 2443
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/molecules28062443
