Phosphine-borane catalysts for CO2 activation and reduction: a computational study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00558547" target="_blank" >RIV/61388963:_____/22:00558547 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1080/00268976.2022.2087566" target="_blank" >https://doi.org/10.1080/00268976.2022.2087566</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1080/00268976.2022.2087566" target="_blank" >10.1080/00268976.2022.2087566</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Phosphine-borane catalysts for CO2 activation and reduction: a computational study

Popis výsledku v původním jazyce

CO2 conversion to value-added chemicals requires efficient catalytic CO2 reduction. Activation of CO2 using 14 phosphine-borane frustrated Lewis pair catalysts was done computationally using B3LYP-D3/6-31++G(d,p)/PCM/THF and M06-2X/6-311++G(d,p)/PCM/THF methods. We designed 14 catalysts, 12 of which exhibit better catalytic activity towards CO2 activation. Moreover, the catalytic mechanisms of compounds 12 and 4 were predicted, and they showed an efficient catalytic system for CO2 reduction to CO, HCHO and HCOOH. Catalysts 2, 3 and 4, with the same methylene linker, have activation energies of 20.5, 18.3 and 10.4 kcal/mol, respectively. This indicates that the catalytic activity of the compound is highly influenced by the ligand bound to borane and phosphine. Compound 4 with the CO2 activation energy of 10.4 kcal/mol is the most efficient catalyst for CO2 activation ever reported among phosphine-borane catalysts. The energy barriers for H-2 activation with catalyst 12 (ΔG(double dagger) = 26.6 kcal/mol) and 4 (ΔG(double dagger) = 34.0 kcal/mol) are higher than the HCOOH releasing activation energy. The designed compounds will help to synthesise efficient metal-free phosphine-borane catalysts. Our results also indicate that phosphine-borane catalysts are promising candidates for CO2 reduction and direct hydrogenation.

Název v anglickém jazyce

Phosphine-borane catalysts for CO2 activation and reduction: a computational study

Popis výsledku anglicky

CO2 conversion to value-added chemicals requires efficient catalytic CO2 reduction. Activation of CO2 using 14 phosphine-borane frustrated Lewis pair catalysts was done computationally using B3LYP-D3/6-31++G(d,p)/PCM/THF and M06-2X/6-311++G(d,p)/PCM/THF methods. We designed 14 catalysts, 12 of which exhibit better catalytic activity towards CO2 activation. Moreover, the catalytic mechanisms of compounds 12 and 4 were predicted, and they showed an efficient catalytic system for CO2 reduction to CO, HCHO and HCOOH. Catalysts 2, 3 and 4, with the same methylene linker, have activation energies of 20.5, 18.3 and 10.4 kcal/mol, respectively. This indicates that the catalytic activity of the compound is highly influenced by the ligand bound to borane and phosphine. Compound 4 with the CO2 activation energy of 10.4 kcal/mol is the most efficient catalyst for CO2 activation ever reported among phosphine-borane catalysts. The energy barriers for H-2 activation with catalyst 12 (ΔG(double dagger) = 26.6 kcal/mol) and 4 (ΔG(double dagger) = 34.0 kcal/mol) are higher than the HCOOH releasing activation energy. The designed compounds will help to synthesise efficient metal-free phosphine-borane catalysts. Our results also indicate that phosphine-borane catalysts are promising candidates for CO2 reduction and direct hydrogenation.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Molecular Physics

ISSN

0026-8976

e-ISSN

1362-3028

Svazek periodika

120

Číslo periodika v rámci svazku

12

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

e2087566

Kód UT WoS článku

000812105300001

EID výsledku v databázi Scopus

2-s2.0-85131957503