Mordenite (MOR) zeolite is efficient catalyst for dimethyl ether (DME) carbonylation and syngas to ethylene due to the unique confinement effect and catalytic activity in 8-membered ring (8-MR) side pockets....
Sulfur
poisoning is a severe problem in industrial applications,
attracting broad interest in fundamental research studies. Although
a number of studies about sulfur resistance have been implemented
in many reactions on nanoparticle catalysts, few investigations focus
on carbonylation reactions using heterogeneous single-metal-site catalysts
(HSMSCs). Herein, we present an unanticipated sulfur-promoted performance
in olefin hydrocarboxylation reactions on a single-Rh-site catalyst
supported on porous ionic polymers (Rh1/PIPs) with 1000
ppm H2S in CO feed. Ex situ EXAFS and in situ DRIFTS revealed a ternary cycle mechanism of olefin
hydrocarboxylation reactions with Rh–H complexes as predominant
active species in both pure and H2S-containing feedstock.
Moreover, the transformation of the Rh mononuclear complex with the
addition of H2S was also demonstrated. Density functional
theory studies were performed to verify the feasibility of the proposed
pathway and confirm that the energy barriers of transition states
with the sulfur ligand were much lower than those in normal feed,
for example, a decline of 3.4 kcal/mol for the rate-determining step
of migration and insertion of CO. This work provides a distinctive
example for the insight of sulfur effect on carbonylation, which could
be potentially beneficial for further applications of HSMSCs.
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