Host-guest tuning of the CO2 reduction activity of an iron porphyrin cage

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00563303" target="_blank" >RIV/61388955:_____/23:00563303 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0335302" target="_blank" >https://hdl.handle.net/11104/0335302</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ntls.20220019" target="_blank" >10.1002/ntls.20220019</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Host-guest tuning of the CO2 reduction activity of an iron porphyrin cage

Popis výsledku v původním jazyce

Efficient electrocatalytic CO2 reduction requires developing catalysts with high selectivities and high activities, which is simultaneously difficult to achieve. Here, we present a new approach to tune the CO2 reduction activity based on host-guest chemistry enabled by an iron porphyrin cage catalyst. The cage design allows the hosting of alkali metals in the side walls causing a change in the electrostatic potential inside the cage cavity. Density functional theory calculations show that the guest potassium ions assist the reduction of CO2 by inverting the two-electron transfer from iron(0) to CO2 from endothermic to exothermic. Accordingly, electrochemical experiments with the cage catalyst show that in the presence of the potassium ions, the overpotential for the CO2 reduction decreases, and the catalytic activity increases while the high selectivity of the cage is retained. A novel coupling between the electrochemical cell and a mass spectrometer allowed the trapping of the key intermediates. Cryogenic ion spectroscopy characterization of the intermediates showed the details of the potassium ions hosting in the reduced cage and of the stabilization of the Fe-COOH intermediates by the interaction with the potassium ions at the single-molecule level.n

Název v anglickém jazyce

Host-guest tuning of the CO2 reduction activity of an iron porphyrin cage

Popis výsledku anglicky

Efficient electrocatalytic CO2 reduction requires developing catalysts with high selectivities and high activities, which is simultaneously difficult to achieve. Here, we present a new approach to tune the CO2 reduction activity based on host-guest chemistry enabled by an iron porphyrin cage catalyst. The cage design allows the hosting of alkali metals in the side walls causing a change in the electrostatic potential inside the cage cavity. Density functional theory calculations show that the guest potassium ions assist the reduction of CO2 by inverting the two-electron transfer from iron(0) to CO2 from endothermic to exothermic. Accordingly, electrochemical experiments with the cage catalyst show that in the presence of the potassium ions, the overpotential for the CO2 reduction decreases, and the catalytic activity increases while the high selectivity of the cage is retained. A novel coupling between the electrochemical cell and a mass spectrometer allowed the trapping of the key intermediates. Cryogenic ion spectroscopy characterization of the intermediates showed the details of the potassium ions hosting in the reduced cage and of the stabilization of the Fe-COOH intermediates by the interaction with the potassium ions at the single-molecule level.n

Druh

J_ost - Ostatní články v recenzovaných periodicích

CEP obor

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OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Natural Science

ISSN

2150-4091

e-ISSN

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Svazek periodika

3

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

e20220019

Kód UT WoS článku

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EID výsledku v databázi Scopus

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