Defect-Enhanced CO(2)Reduction Catalytic Performance in O-Terminated MXenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989100%3A27740%2F20%3A10245534" target="_blank" >RIV/61989100:27740/20:10245534 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cssc.202001624" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cssc.202001624</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cssc.202001624" target="_blank" >10.1002/cssc.202001624</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Defect-Enhanced CO(2)Reduction Catalytic Performance in O-Terminated MXenes

Popis výsledku v původním jazyce

Electrochemical carbon dioxide reduction reaction (CO2RR) represents a promising way to generate fuels and chemical feedstock sustainably. Recently, studies have shown that two-dimensional metal carbides and nitrides (MXenes) can be promising CO2RR electrocatalysts due to the alternating -C and -H coordination with intermediates that decouples scaling relations seen on transition metal catalysts. However, further by tuning the electronic and surface structure of MXenes it should still be possible to reach higher turnover number and selectivities. To this end, defect engineering of MXenes for electrochemical CO2RR has not been investigated to date. In this work, first-principles modelling simulations are employed to systematically investigate CO2RR on M2XO2-type MXenes with transition metal and carbon/nitrogen vacancies. We found that the -C-coordinated intermediates take the form of fragments (e. g., *COOH, *CHO) whereas the -H-coordinated intermediates form a complete molecule (e. g., *HCOOH, *H2CO). Interestingly, the fragment-type intermediates become more strongly bound when transition-metal vacancies are present on most MXenes, while the molecule-type intermediates are largely unaffected, allowing the CO2RR overpotential to be tuned. The most promising defective MXene is Hf(2)NO(2)containing Hf vacancies, with a low overpotential of 0.45 V. More importantly, through electronic structure analysis it could be observed that the Fermi level of the MXene changes significantly in the presence of vacancies, indicating that the Fermi level shift can be used as an ideal descriptor to rapidly predict the catalytic performance of defective MXenes. Such an evaluation strategy is applicable to other catalysts beyond MXenes, which could enhance high throughput screening efforts for accelerated catalyst discovery.

Název v anglickém jazyce

Defect-Enhanced CO(2)Reduction Catalytic Performance in O-Terminated MXenes

Popis výsledku anglicky

Electrochemical carbon dioxide reduction reaction (CO2RR) represents a promising way to generate fuels and chemical feedstock sustainably. Recently, studies have shown that two-dimensional metal carbides and nitrides (MXenes) can be promising CO2RR electrocatalysts due to the alternating -C and -H coordination with intermediates that decouples scaling relations seen on transition metal catalysts. However, further by tuning the electronic and surface structure of MXenes it should still be possible to reach higher turnover number and selectivities. To this end, defect engineering of MXenes for electrochemical CO2RR has not been investigated to date. In this work, first-principles modelling simulations are employed to systematically investigate CO2RR on M2XO2-type MXenes with transition metal and carbon/nitrogen vacancies. We found that the -C-coordinated intermediates take the form of fragments (e. g., *COOH, *CHO) whereas the -H-coordinated intermediates form a complete molecule (e. g., *HCOOH, *H2CO). Interestingly, the fragment-type intermediates become more strongly bound when transition-metal vacancies are present on most MXenes, while the molecule-type intermediates are largely unaffected, allowing the CO2RR overpotential to be tuned. The most promising defective MXene is Hf(2)NO(2)containing Hf vacancies, with a low overpotential of 0.45 V. More importantly, through electronic structure analysis it could be observed that the Fermi level of the MXene changes significantly in the presence of vacancies, indicating that the Fermi level shift can be used as an ideal descriptor to rapidly predict the catalytic performance of defective MXenes. Such an evaluation strategy is applicable to other catalysts beyond MXenes, which could enhance high throughput screening efforts for accelerated catalyst discovery.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

ChemSusChem

ISSN

1864-5631

e-ISSN

—

Svazek periodika

13

Číslo periodika v rámci svazku

21

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

"5690–5698"

Kód UT WoS článku

000567456100001

EID výsledku v databázi Scopus

2-s2.0-85090434186