Pseudo Single-Atom SiO x -Co Interfaces for Selectivity Control in Fischer-Tropsch Catalysis

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F25%3A43933760" target="_blank" >RIV/60461373:22310/25:43933760 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acscatal.5c05048" target="_blank" >https://pubs.acs.org/doi/10.1021/acscatal.5c05048</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acscatal.5c05048" target="_blank" >10.1021/acscatal.5c05048</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Pseudo Single-Atom SiO x -Co Interfaces for Selectivity Control in Fischer-Tropsch Catalysis

Popis výsledku v původním jazyce

Fischer-Tropsch synthesis (FTS) is a cornerstone catalytic process for converting synthesis gas into liquid hydrocarbons, yet it suffers from limited selectivity and excessive methane formation. Here, we demonstrate that surface modification of cobalt oxide (Co3O4) nanoparticles with trimethylchlorosilane (TMCS), followed by calcination, yields pseudo single-atom SiO x species that form a distinct SiO x -Co interface. Unlike conventional silica coatings, these isolated SiO x moieties are ligand-like, electronically modifying surface cobalt atoms, without forming bulk SiO2 or siloxane domains. This interface enhances pi-back-donation to carbon monoxide (CO), increases the heat of adsorption, and promotes CO bond cleavage, as confirmed by CO chemisorption and CO-temperature-programmed desorption (TPD). Catalysts modified in this way show over an order of magnitude increase in turnover frequency (TOF), alongside a marked decrease in methane selectivity and a shift toward C2-C5 hydrocarbons and oxygenates. These findings establish pseudo single-atom SiO x -Co interfaces as a powerful route to engineer activity and selectivity in FTS. Importantly, the approach avoids chlorine residues and is consistent with Cl removal during calcination. Beyond suppressing methane, the SiO x interface selectively promotes aldehydes, aligning with recent reports on oxide-modified Co catalysts. Pseudo single-atom oxide-metal interfaces emerge as a tunable strategy for enhancing both activity and selectivity in cobalt-based FTS catalysts.

Název v anglickém jazyce

Pseudo Single-Atom SiO x -Co Interfaces for Selectivity Control in Fischer-Tropsch Catalysis

Popis výsledku anglicky

Fischer-Tropsch synthesis (FTS) is a cornerstone catalytic process for converting synthesis gas into liquid hydrocarbons, yet it suffers from limited selectivity and excessive methane formation. Here, we demonstrate that surface modification of cobalt oxide (Co3O4) nanoparticles with trimethylchlorosilane (TMCS), followed by calcination, yields pseudo single-atom SiO x species that form a distinct SiO x -Co interface. Unlike conventional silica coatings, these isolated SiO x moieties are ligand-like, electronically modifying surface cobalt atoms, without forming bulk SiO2 or siloxane domains. This interface enhances pi-back-donation to carbon monoxide (CO), increases the heat of adsorption, and promotes CO bond cleavage, as confirmed by CO chemisorption and CO-temperature-programmed desorption (TPD). Catalysts modified in this way show over an order of magnitude increase in turnover frequency (TOF), alongside a marked decrease in methane selectivity and a shift toward C2-C5 hydrocarbons and oxygenates. These findings establish pseudo single-atom SiO x -Co interfaces as a powerful route to engineer activity and selectivity in FTS. Importantly, the approach avoids chlorine residues and is consistent with Cl removal during calcination. Beyond suppressing methane, the SiO x interface selectively promotes aldehydes, aligning with recent reports on oxide-modified Co catalysts. Pseudo single-atom oxide-metal interfaces emerge as a tunable strategy for enhancing both activity and selectivity in cobalt-based FTS catalysts.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10400 - Chemical sciences

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

ACS Catalysis

ISSN

2155-5435

e-ISSN

2155-5435

Svazek periodika

15

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

20573-20583

Kód UT WoS článku

001628393300001

EID výsledku v databázi Scopus

2-s2.0-105023398259