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Does the Zn2+ Species Introduced into H-ZSM-5 Zeolite Affect the Strength of Brønsted Acid Sites? / Gabrienko, Anton A.; Danilova, Irina G.; Arzumanov, Sergei S. et al.

In: ChemCatChem, Vol. 12, No. 2, 18.01.2020, p. 478-487.

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Gabrienko AA, Danilova IG, Arzumanov SS, Freude D, Stepanov AG. Does the Zn2+ Species Introduced into H-ZSM-5 Zeolite Affect the Strength of Brønsted Acid Sites? ChemCatChem. 2020 Jan 18;12(2):478-487. doi: 10.1002/cctc.201901637

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@article{0d74dc0763d942de876d38396768e9c7,
title = "Does the Zn2+ Species Introduced into H-ZSM-5 Zeolite Affect the Strength of Br{\o}nsted Acid Sites?",
abstract = "To clarify the issue on Br{\o}nsted acidity enhancement by the presence of zinc species in H-ZSM-5 zeolite (G.D. Qi, et al., Angew. Chem.-Int. Edit. 2016, 55, 15826), the influence of Zn2+ cationic species, introduced into the zeolite, on the strength of Br{\o}nsted acid sites (BAS) has been analyzed by solid-state NMR and FTIR techniques using trimethylphosphine (TMP) and CO as probe molecules. Comparative analysis of the acidity for H-ZSM-5 and Zn2+/H-ZSM-5 zeolites has been performed. TMP adsorbed on both zeolite samples exhibits same signals at 6.3 and −4.5 ppm in 1H and 31P MAS NMR spectra, respectively, assigned to protonated TMP. FTIR spectroscopy has shown that both zeolite samples, H-ZSM-5 and Zn2+/H-ZSM-5, display the same red frequency shift (ΔνOH⋅⋅⋅CO=−318 cm−1) of the O−H stretching band and the same blue frequency shift (ΔνCO=+32 cm−1) of the CO stretching band for CO adsorption complex with BAS. The results obtained do not provide any evidence for the existence of some specific BAS with enhanced acid strength for Zn2+-exchanged zeolite compared to the strength inherent to pure acid-form zeolite. It is thus inferred the strength of BAS in H-ZSM-5 zeolite is not affected by the modification of the zeolite with Zn2+ cationic species.",
keywords = "Br{\o}nsted acid sites, FTIR spectroscopy, solid-state NMR, zeolite, zinc, HYDROXYL-GROUPS, surface, heterogeneous catalysis, nanoreactor, Superaerophilic, DISSOCIATIVE ADSORPTION, METHANE ACTIVATION, PROTON AFFINITY, CARBON-MONOXIDE, LIGHT PARAFFINS, BRONSTED ACID SITES, TRIMETHYLPHOSPHINE OXIDE, STRETCHING BANDS, bursting, STATE NMR",
author = "Gabrienko, {Anton A.} and Danilova, {Irina G.} and Arzumanov, {Sergei S.} and Dieter Freude and Stepanov, {Alexander G.}",
year = "2020",
month = jan,
day = "18",
doi = "10.1002/cctc.201901637",
language = "English",
volume = "12",
pages = "478--487",
journal = "ChemCatChem",
issn = "1867-3880",
publisher = "Wiley - VCH Verlag GmbH & CO. KGaA",
number = "2",

}

RIS

TY - JOUR

T1 - Does the Zn2+ Species Introduced into H-ZSM-5 Zeolite Affect the Strength of Brønsted Acid Sites?

AU - Gabrienko, Anton A.

AU - Danilova, Irina G.

AU - Arzumanov, Sergei S.

AU - Freude, Dieter

AU - Stepanov, Alexander G.

PY - 2020/1/18

Y1 - 2020/1/18

N2 - To clarify the issue on Brønsted acidity enhancement by the presence of zinc species in H-ZSM-5 zeolite (G.D. Qi, et al., Angew. Chem.-Int. Edit. 2016, 55, 15826), the influence of Zn2+ cationic species, introduced into the zeolite, on the strength of Brønsted acid sites (BAS) has been analyzed by solid-state NMR and FTIR techniques using trimethylphosphine (TMP) and CO as probe molecules. Comparative analysis of the acidity for H-ZSM-5 and Zn2+/H-ZSM-5 zeolites has been performed. TMP adsorbed on both zeolite samples exhibits same signals at 6.3 and −4.5 ppm in 1H and 31P MAS NMR spectra, respectively, assigned to protonated TMP. FTIR spectroscopy has shown that both zeolite samples, H-ZSM-5 and Zn2+/H-ZSM-5, display the same red frequency shift (ΔνOH⋅⋅⋅CO=−318 cm−1) of the O−H stretching band and the same blue frequency shift (ΔνCO=+32 cm−1) of the CO stretching band for CO adsorption complex with BAS. The results obtained do not provide any evidence for the existence of some specific BAS with enhanced acid strength for Zn2+-exchanged zeolite compared to the strength inherent to pure acid-form zeolite. It is thus inferred the strength of BAS in H-ZSM-5 zeolite is not affected by the modification of the zeolite with Zn2+ cationic species.

AB - To clarify the issue on Brønsted acidity enhancement by the presence of zinc species in H-ZSM-5 zeolite (G.D. Qi, et al., Angew. Chem.-Int. Edit. 2016, 55, 15826), the influence of Zn2+ cationic species, introduced into the zeolite, on the strength of Brønsted acid sites (BAS) has been analyzed by solid-state NMR and FTIR techniques using trimethylphosphine (TMP) and CO as probe molecules. Comparative analysis of the acidity for H-ZSM-5 and Zn2+/H-ZSM-5 zeolites has been performed. TMP adsorbed on both zeolite samples exhibits same signals at 6.3 and −4.5 ppm in 1H and 31P MAS NMR spectra, respectively, assigned to protonated TMP. FTIR spectroscopy has shown that both zeolite samples, H-ZSM-5 and Zn2+/H-ZSM-5, display the same red frequency shift (ΔνOH⋅⋅⋅CO=−318 cm−1) of the O−H stretching band and the same blue frequency shift (ΔνCO=+32 cm−1) of the CO stretching band for CO adsorption complex with BAS. The results obtained do not provide any evidence for the existence of some specific BAS with enhanced acid strength for Zn2+-exchanged zeolite compared to the strength inherent to pure acid-form zeolite. It is thus inferred the strength of BAS in H-ZSM-5 zeolite is not affected by the modification of the zeolite with Zn2+ cationic species.

KW - Brønsted acid sites

KW - FTIR spectroscopy

KW - solid-state NMR

KW - zeolite

KW - zinc

KW - HYDROXYL-GROUPS

KW - surface

KW - heterogeneous catalysis

KW - nanoreactor

KW - Superaerophilic

KW - DISSOCIATIVE ADSORPTION

KW - METHANE ACTIVATION

KW - PROTON AFFINITY

KW - CARBON-MONOXIDE

KW - LIGHT PARAFFINS

KW - BRONSTED ACID SITES

KW - TRIMETHYLPHOSPHINE OXIDE

KW - STRETCHING BANDS

KW - bursting

KW - STATE NMR

UR - http://www.scopus.com/inward/record.url?scp=85074781925&partnerID=8YFLogxK

U2 - 10.1002/cctc.201901637

DO - 10.1002/cctc.201901637

M3 - Article

AN - SCOPUS:85074781925

VL - 12

SP - 478

EP - 487

JO - ChemCatChem

JF - ChemCatChem

SN - 1867-3880

IS - 2

ER -

ID: 22319652