| 000 | 04676nlm1a2200637 4500 | ||
|---|---|---|---|
| 001 | 669229 | ||
| 005 | 20231030042215.0 | ||
| 035 | _a(RuTPU)RU\TPU\network\40469 | ||
| 035 | _aRU\TPU\network\37505 | ||
| 090 | _a669229 | ||
| 100 | _a20230302a2023 k y0engy50 ba | ||
| 101 | 0 | _aeng | |
| 135 | _adrcn ---uucaa | ||
| 181 | 0 | _ai | |
| 182 | 0 | _ab | |
| 200 | 1 |
_aUncovering the Role of Chemical and Electronic Structures in Plasmonic Catalysis: The Case of Homolysis of Alkoxyamines _fD. Votkina, P. Petunin, E. Miliutina [et al.] |
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| 203 |
_aText _celectronic |
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| 300 | _aTitle screen | ||
| 320 | _a[References: 45 tit.] | ||
| 330 | _aThe local surface plasmon resonances of gold nanoparticles have the potential to create alternative pathways for organic chemical reactions. These transformations depend on various physical factors, such as the temperature, illumination regime, and nanoparticle type. However, the role of chemical factors associated with organic reactants, including the molecular structure, electronic effects, and bonding with the metal surface, is often underestimated. To explore the role of these chemical factors, we synthesized five alkoxyamines (AAs) with different chemical and electronic structures and used electron paramagnetic resonance spectroscopy to study the kinetics of plasmon-induced homolysis. The kinetic data revealed that the rate constant (kd) for plasmon-assisted homolysis is dependent on the highest occupied molecular orbital (HOMO) energy of the AAs, which cannot be described by the kinetic parameters or activation energies observed in thermal homolysis experiments. The proximity of the HOMO to the Fermi energy (Ef) of Au led to a more active decrease in the energy required to excite the adsorbate. The observed trend in kd indicates that the intramolecular excitation mechanism plays a key role instead of other commonly accepted mechanisms, which is supported by DFT calculations, spectroscopic characterization, and numerous control experiments. The intramolecular excitation mechanism is the most relevant explanation for the plasmon-induced homolysis of AAs. This observation suggests that the electronic structures of the organic molecules may play a key role in other related reactions used to study the mechanisms of plasmon catalysis. | ||
| 333 | _aРежим доступа: по договору с организацией-держателем ресурса | ||
| 461 | _tACS Catalysis | ||
| 463 |
_tVol. 13, iss. 5 _v[P. 2822–2833] _d2023 |
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| 610 | 1 | _aэлектронный ресурс | |
| 610 | 1 | _aтруды учёных ТПУ | |
| 610 | 1 | _aplasmon | |
| 610 | 1 | _ahomolysis | |
| 610 | 1 | _aalkoxyamines | |
| 610 | 1 | _aplasmon-induced reaction | |
| 610 | 1 | _aphotocatalysis | |
| 610 | 1 | _aплазмоны | |
| 610 | 1 | _aгомолиз | |
| 610 | 1 | _aалкоксиамины | |
| 610 | 1 | _aиндуцированные реакции | |
| 610 | 1 | _aфотокатализ | |
| 701 | 1 |
_aVotkina _bD. E. _cchemical engineer _cAssociate Scientist of the Tomsk Polytechnic University _f1995- _gDarjya Evgenjevna _2stltpush _3(RuTPU)RU\TPU\pers\45598 |
|
| 701 | 1 |
_aPetunin _bP. V. _cchemist _cEngineer of Tomsk Polytechnic University _f1982- _gPavel Vasilievich _2stltpush _3(RuTPU)RU\TPU\pers\36904 |
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| 701 | 1 |
_aMiliutina _bE. _gElena |
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| 701 | 1 |
_aTrelin _bA. _gAndrii |
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| 701 | 1 |
_aLyutakov _bO. _gOleksiy |
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| 701 | 1 |
_aSvorcik _bV. _gVaclav |
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| 701 | 1 |
_aAudran _bG. _gGerard |
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| 701 | 1 |
_aHavot _bJ. _gJeffrey |
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| 701 | 1 |
_aValiev _bR. R. _cchemist _cAssistant of Tomsk Polytechnic University _f1983- _gRashid Rinatovich _2stltpush _3(RuTPU)RU\TPU\pers\34114 |
|
| 701 | 1 |
_aValiulina _bL. I. _gLenara |
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| 701 | 1 |
_aJoly _bJ. P. _gJean-Patrick |
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| 701 | 1 |
_aYamauchi _bYu. _gYusuke |
|
| 701 | 1 |
_aMokkath _bJ. H. _gJunais Habeeb |
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| 701 | 1 |
_aHenzie _bJ. _gJoel |
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| 701 | 1 |
_aGuselnikova _bO. A. _cchemist _cResearcher at Tomsk Polytechnic University, Candidate of Chemical Sciences _f1992- _gOlga Andreevna _2stltpush _3(RuTPU)RU\TPU\pers\34478 |
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| 701 | 1 |
_aMarque _bS. R. A. _gSylvain |
|
| 701 | 1 |
_aPostnikov _bP. S. _corganic chemist _cAssociate Professor of Tomsk Polytechnic University, Candidate of chemical sciences _f1984- _gPavel Sergeevich _2stltpush _3(RuTPU)RU\TPU\pers\31287 |
|
| 712 | 0 | 2 |
_aНациональный исследовательский Томский политехнический университет _bИсследовательская школа химических и биомедицинских технологий _c(2017- ) _h8120 _2stltpush _3(RuTPU)RU\TPU\col\23537 |
| 801 | 2 |
_aRU _b63413507 _c20230712 _gRCR |
|
| 856 | 4 | _uhttps://doi.org/10.1021/acscatal.2c04685 | |
| 942 | _cCF | ||