Subnanometric palladium zeolite catalysts improve selectivity in alkyne semihydrogenation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10500527" target="_blank" >RIV/00216208:11310/25:10500527 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=F9TU5F44q3" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=F9TU5F44q3</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.cattod.2025.115479" target="_blank" >10.1016/j.cattod.2025.115479</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Subnanometric palladium zeolite catalysts improve selectivity in alkyne semihydrogenation

Popis výsledku v původním jazyce

Alkyne semihydrogenation to alkenes yields polymer-grade olefins and fine chemicals. However, over state-ofthe-art palladium catalysts, such as Lindlar catalysts, this reaction entails complex steps, low atom efficiency and high toxicity due to Pb used for partial poisoning. Because these factors hamper further applications of alkyne semihydrogenation, developing single-metal catalysts with low Pd content without compromising their selectivity may bring both economic and environmental benefits. In this study, we report on the development of such catalysts by downsizing Pd species to nanoclusters (NCs) and, ultimately, to single atoms (SAs) while stabilizing them on layered zeolite carriers. On layered aluminosilicate zeolites MCM-56 and ZSM-5, Pd-SAs, NCs and nanoparticles (NPs, for comparison) were formed by ion-exchange with [PdCl2(CH3CN)2] to prepare both Pd-NCs and Pd-SA and by impregnation with [Pd(NH3)4](NO3)2 to prepare Pd-NPs. Over these catalysts, 1-octyne and 2-methyl-3-butyn-2-ol semihydrogenation showed increased alkene selectivity when downsizing Pd particles from 2 to 10 nm NPs (e.g., 76 % 1-octene selectivity at 98 % conversion) to NCs smaller than 1 nm (e.g., 1-octene selectivity 92 % at 96-98 % conversion). In addition, Pd-SAs and Pd-NCs on a layered ZSM-5 support (TOF=3574h(-1) and TOF=4757h(-1), respectively) outperformed the commercial Lindlar catalyst (TOF=335 h(-1)). These findings demonstrate that supporting Pd-NCs and SAs on 2D zeolites paves the way for greener and more cost-effective alkyne-selective hydrogenation catalysts.

Název v anglickém jazyce

Subnanometric palladium zeolite catalysts improve selectivity in alkyne semihydrogenation

Popis výsledku anglicky

Alkyne semihydrogenation to alkenes yields polymer-grade olefins and fine chemicals. However, over state-ofthe-art palladium catalysts, such as Lindlar catalysts, this reaction entails complex steps, low atom efficiency and high toxicity due to Pb used for partial poisoning. Because these factors hamper further applications of alkyne semihydrogenation, developing single-metal catalysts with low Pd content without compromising their selectivity may bring both economic and environmental benefits. In this study, we report on the development of such catalysts by downsizing Pd species to nanoclusters (NCs) and, ultimately, to single atoms (SAs) while stabilizing them on layered zeolite carriers. On layered aluminosilicate zeolites MCM-56 and ZSM-5, Pd-SAs, NCs and nanoparticles (NPs, for comparison) were formed by ion-exchange with [PdCl2(CH3CN)2] to prepare both Pd-NCs and Pd-SA and by impregnation with [Pd(NH3)4](NO3)2 to prepare Pd-NPs. Over these catalysts, 1-octyne and 2-methyl-3-butyn-2-ol semihydrogenation showed increased alkene selectivity when downsizing Pd particles from 2 to 10 nm NPs (e.g., 76 % 1-octene selectivity at 98 % conversion) to NCs smaller than 1 nm (e.g., 1-octene selectivity 92 % at 96-98 % conversion). In addition, Pd-SAs and Pd-NCs on a layered ZSM-5 support (TOF=3574h(-1) and TOF=4757h(-1), respectively) outperformed the commercial Lindlar catalyst (TOF=335 h(-1)). These findings demonstrate that supporting Pd-NCs and SAs on 2D zeolites paves the way for greener and more cost-effective alkyne-selective hydrogenation catalysts.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

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

2025

Kód důvěrnosti údajů

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

Název periodika

Catalysis Today

ISSN

0920-5861

e-ISSN

1873-4308

Svazek periodika

460

Číslo periodika v rámci svazku

December

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

9

Strana od-do

115479

Kód UT WoS článku

001544927600001

EID výsledku v databázi Scopus

2-s2.0-105012188642