Highly Efficient and Selective Nitrogen Reduction Reaction Catalysis of Cluster-Modified MXene Nanosheets

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F24%3A10486119" target="_blank" >RIV/00216208:11320/24:10486119 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989100:27740/24:10255625

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=voSpDVqcf0" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=voSpDVqcf0</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acscatal.4c01369" target="_blank" >10.1021/acscatal.4c01369</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Highly Efficient and Selective Nitrogen Reduction Reaction Catalysis of Cluster-Modified MXene Nanosheets

Popis výsledku v původním jazyce

The electrocatalytic synthesis of NH3 holds immense significance for energy conservation in industrial and agricultural production. Herein, an efficient solution is proposed for MXene-based high-activity nitrogen reduction reaction (NRR) catalysts that are modified using tetranuclear non-noble 3d transition metal clusters (M-4). The thorough exploration of M-4/Ti2CO2 candidates reveals that the thermodynamically and kinetically stable Cr-4/Ti2CO2 possesses the lowest overpotential (0.35 V) and high selectivity, comparable to those of well-known NRR catalysts such as Ru(0001) (0.43 V) and Au(310) (1.91 V). In addition, the doping of Fe into Cr-4 clusters can further reduce the overpotential and kinetic barriers by 31 and 46%, respectively. The analysis of the complicated bonding nature reveals the mechanism of the catalytic activity, which demonstrates the role of clusters pulling pi/sigma electrons from N-2 while simultaneously back-donating d orbital electrons to the pi* orbital. A descriptor (phi), related to intrinsic transferred charges (Delta e) of the cluster, is proposed to accurately determine the NRR catalytic activity using simple calculations, and the linear correlation between them can reach 0.98. This work provides guidance for designing promising cluster-modified MXene catalysts for NRR and an elucidation of the electronic factors governing catalytic activity.

Název v anglickém jazyce

Highly Efficient and Selective Nitrogen Reduction Reaction Catalysis of Cluster-Modified MXene Nanosheets

Popis výsledku anglicky

The electrocatalytic synthesis of NH3 holds immense significance for energy conservation in industrial and agricultural production. Herein, an efficient solution is proposed for MXene-based high-activity nitrogen reduction reaction (NRR) catalysts that are modified using tetranuclear non-noble 3d transition metal clusters (M-4). The thorough exploration of M-4/Ti2CO2 candidates reveals that the thermodynamically and kinetically stable Cr-4/Ti2CO2 possesses the lowest overpotential (0.35 V) and high selectivity, comparable to those of well-known NRR catalysts such as Ru(0001) (0.43 V) and Au(310) (1.91 V). In addition, the doping of Fe into Cr-4 clusters can further reduce the overpotential and kinetic barriers by 31 and 46%, respectively. The analysis of the complicated bonding nature reveals the mechanism of the catalytic activity, which demonstrates the role of clusters pulling pi/sigma electrons from N-2 while simultaneously back-donating d orbital electrons to the pi* orbital. A descriptor (phi), related to intrinsic transferred charges (Delta e) of the cluster, is proposed to accurately determine the NRR catalytic activity using simple calculations, and the linear correlation between them can reach 0.98. This work provides guidance for designing promising cluster-modified MXene catalysts for NRR and an elucidation of the electronic factors governing catalytic activity.

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

2024

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

—

Svazek periodika

14

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

10568-10582

Kód UT WoS článku

001259872100001

EID výsledku v databázi Scopus

2-s2.0-85197646875