Periodic DFT calculations for the heterogeneous formation of 2-chlorothiophenoxy radical from 2-chlorothiophenol on Cu(111) surface in fly ash.
Ecotoxicol Environ Saf
; 274: 116186, 2024 Apr 01.
Article
em En
| MEDLINE
| ID: mdl-38471341
ABSTRACT
Copper plays a crucial role in the heterogenous dissociation of chlorothiophenols (CTPs) to form chlorothiophenoxy radicals (CTPRs), which is the initial and critical step in the formation of polychlorinated thianthrenes/dibenzothiophenes (PCTA/DTs). Here, first-principles calculations were performed to investigate the activity of Cu(111) surface towards the formation of adsorbed 2-CTPR from 2-CTP. The interaction between 2-CTP and Cu(111) surface was explored to find stable adsorption configurations. Besides, the decomposition routes of 2-CTP on the Cu(111) surface were further explored. Moreover, the effects of water on the formation of absorbed 2-CTPR on the Cu(111) surface were examined. Our results demonstrate that the flat adsorption of 2-CTP on the surface with adsorption energy in the range of -33.21â¯kcal/mol to -28.37â¯kcal/mol is more stable than the vertical adsorption with adsorption energy ranging from -23.53â¯kcal/mol to -13.38â¯kcal/mol. The Cu(111) surface catalyzes the conversion of 2-CTP into the adsorbed 2-CTPR with a modest energy barrier of 9.46â¯kcal/mol. Furthermore, water molecules exhibit stronger catalytic activity in this process with a decreased energy barrier of 5.87â¯kcal/mol through "water bridge" and hydrogen bonding. Specifically, the water accepts the hydrogen atom from 2-CTP and donates another hydrogen to the surface via "water bridge". This research provides a molecular-level understanding of the heterogeneous formation of PCTA/DTs by fly ash, suggesting novel approaches for control strategy and legislation of dioxin analogues.
Palavras-chave
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Tiofenos
/
Cobre
/
Cinza de Carvão
Idioma:
En
Revista:
Ecotoxicol Environ Saf
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
China
País de publicação:
HOLANDA
/
HOLLAND
/
NETHERLANDS
/
NL
/
PAISES BAJOS
/
THE NETHERLANDS