Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F20%3A00523057" target="_blank" >RIV/61388955:_____/20:00523057 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0307465" target="_blank" >http://hdl.handle.net/11104/0307465</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cctc.201901795" target="_blank" >10.1002/cctc.201901795</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics

Popis výsledku v původním jazyce

Supported subnanometer clusters can exhibit catalytic properties not observed in their bulk analogues. Partially-oxidized Pd and Cu clusters are reported to catalyze the oxidative dehydrogenation of cyclohexane with high activity, and with distinctly different selectivity, producing primarily benzene or cyclohexene, respectively. Under the appliedreaction conditions, the structure and oxidation state of the two catalysts evolve differently, which leads to either the desorption of the cyclohexene intermediate or to its deeper dehydrogenation. Under the applied reaction conditions, the initially oxidized Pd and Cu clusters undergo partial reduction, which we show to be required for the selectivity to emerge. Both systems also have thermal access to multiple distinct structural forms yielding statistical ensembles. The structures within these ensembles evolve with the changing nature of the bound reaction intermediates differently for the two metals. The evolution is found pronounced in the Cu clusters, but only modest in Pd. Ultimately, the different selectivity observed experimentally for the Cu versus Pd clusters is controlled by differences in the collective structural and redox dynamics of their ensembles.

Název v anglickém jazyce

Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics

Popis výsledku anglicky

Supported subnanometer clusters can exhibit catalytic properties not observed in their bulk analogues. Partially-oxidized Pd and Cu clusters are reported to catalyze the oxidative dehydrogenation of cyclohexane with high activity, and with distinctly different selectivity, producing primarily benzene or cyclohexene, respectively. Under the appliedreaction conditions, the structure and oxidation state of the two catalysts evolve differently, which leads to either the desorption of the cyclohexene intermediate or to its deeper dehydrogenation. Under the applied reaction conditions, the initially oxidized Pd and Cu clusters undergo partial reduction, which we show to be required for the selectivity to emerge. Both systems also have thermal access to multiple distinct structural forms yielding statistical ensembles. The structures within these ensembles evolve with the changing nature of the bound reaction intermediates differently for the two metals. The evolution is found pronounced in the Cu clusters, but only modest in Pd. Ultimately, the different selectivity observed experimentally for the Cu versus Pd clusters is controlled by differences in the collective structural and redox dynamics of their ensembles.

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

2020

Kód důvěrnosti údajů

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

Název periodika

ChemCatChem

ISSN

1867-3880

e-ISSN

—

Svazek periodika

12

Číslo periodika v rámci svazku

JAN 2020

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

1307-1315

Kód UT WoS článku

000505076200001

EID výsledku v databázi Scopus

2-s2.0-85078066446