Sulfur Poisoning and Self-Recovery of Single-Site Rh1 /Porous Organic Polymer Catalysts for Olefin Hydroformylation.
Angew Chem Int Ed Engl
; 62(30): e202304282, 2023 Jul 24.
Article
in En
| MEDLINE
| ID: mdl-37159106
ABSTRACT
Sulfur poisoning and regeneration are global challenges for metal catalysts even at the ppm level. The sulfur poisoning of single-metal-site catalysts and their regeneration is worthy of further study. Herein, sulfur poisoning and self-recovery are first presented on an industrialized single-Rh-site catalyst (Rh1 /POPs). A decreased turnover frequency of Rh1 /POPs from 4317â
h-1 to 318â
h-1 was observed in a 1000â
ppm H2 S co-feed for ethylene hydroformylation, but it self-recovered to 4527â
h-1 after withdrawal of H2 S, whereas the rhodium nanoparticles demonstrated poor activity and self-recovery ability. H2 S reduced the charge density of the single Rh atom and lowered its Gibbs free energy with the formation of inactive (SH)Rh(CO)(PPh3 -frame)2 , which could be regenerated to active HRh(CO)(PPh3 -frame)2 after withdrawing H2 S. The mechanism and the sulfur-related structure-activity relationship were highlighted. This work provides an understanding of heterogeneous ethylene hydroformylation and sulfur-poisoned regeneration in the science of single-atom catalysts.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2023
Document type:
Article
Affiliation country:
China