Brønsted acidity in zeolites measured by deprotonation energy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00557524" target="_blank" >RIV/61388963:_____/22:00557524 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/22:39919518

Výsledek na webu

<a href="https://doi.org/10.1038/s41598-022-11354-x" target="_blank" >https://doi.org/10.1038/s41598-022-11354-x</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41598-022-11354-x" target="_blank" >10.1038/s41598-022-11354-x</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Brønsted acidity in zeolites measured by deprotonation energy

Popis výsledku v původním jazyce

Acid forms of zeolites have been used in industry for several decades but scaling the strength of their acid centers is still an unresolved and intensely debated issue. In this paper, the Bronsted acidity strength in aluminosilicates measured by their deprotonation energy (DPE) was investigated for FAU, CHA, IFR, MOR, FER, MFI, and TON zeolites by means of periodic and cluster calculations at the density functional theory (DFT) level. The main drawback of the periodic DFT is that it does not provide reliable absolute values due to spurious errors associated with the background charge introduced in anion energy calculations. To alleviate this problem, we employed a novel approach to cluster generation to obtain accurate values of DPE. The cluster models up to 150 T atoms for the most stable Bronsted acid sites were constructed on spheres of increasing diameter as an extension of Harrison's approach to calculating Madelung constants. The averaging of DPE for clusters generated this way provides a robust estimate of DPE for investigated zeolites despite slow convergence with the cluster size. The accuracy of the cluster approach was further improved by a scaled electrostatic embedding scheme proposed in this work. The electrostatic embedding model yields the most reliable values with the average deprotonation energy of about 1245 +/- 9 kJ center dot mol(-1) for investigated acidic zeolites. The cluster calculations strongly indicate a correlation between the deprotonation energy and the zeolite framework density. The DPE results obtained with our electrostatic embedding model are highly consistent with the previously reported QM/MM and periodic calculations.

Název v anglickém jazyce

Brønsted acidity in zeolites measured by deprotonation energy

Popis výsledku anglicky

Acid forms of zeolites have been used in industry for several decades but scaling the strength of their acid centers is still an unresolved and intensely debated issue. In this paper, the Bronsted acidity strength in aluminosilicates measured by their deprotonation energy (DPE) was investigated for FAU, CHA, IFR, MOR, FER, MFI, and TON zeolites by means of periodic and cluster calculations at the density functional theory (DFT) level. The main drawback of the periodic DFT is that it does not provide reliable absolute values due to spurious errors associated with the background charge introduced in anion energy calculations. To alleviate this problem, we employed a novel approach to cluster generation to obtain accurate values of DPE. The cluster models up to 150 T atoms for the most stable Bronsted acid sites were constructed on spheres of increasing diameter as an extension of Harrison's approach to calculating Madelung constants. The averaging of DPE for clusters generated this way provides a robust estimate of DPE for investigated zeolites despite slow convergence with the cluster size. The accuracy of the cluster approach was further improved by a scaled electrostatic embedding scheme proposed in this work. The electrostatic embedding model yields the most reliable values with the average deprotonation energy of about 1245 +/- 9 kJ center dot mol(-1) for investigated acidic zeolites. The cluster calculations strongly indicate a correlation between the deprotonation energy and the zeolite framework density. The DPE results obtained with our electrostatic embedding model are highly consistent with the previously reported QM/MM and periodic calculations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA19-19542S" target="_blank" >GA19-19542S: Prediktivní model založený na struktuře katalyzátoru pro reakce katalyzované Bronstedovskými kyselými centry</a><br>

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

Scientific Reports

ISSN

2045-2322

e-ISSN

2045-2322

Svazek periodika

12

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

7301

Kód UT WoS článku

000790941900036

EID výsledku v databázi Scopus

2-s2.0-85129429595