Sulfur Poisoning and Self-Recovery of Single-Site Rh1/Porous Organic Polymer Catalysts for Olefin Hydroformylation

Feng，Siquan1; Jiang，Miao1; Song，Xiangen1; Qiao，Panzhe2; Yan，Li1; Cai，Yutong1,4; Li，Bin1,4; Li，Cunyao1; Ning，lili1; Liu，Siyue3; Zhang，Weiqing3; Wu，Guorong3; Yang，Jiayue3; Dong，Wenrui3; Yang，Xueming3,5; Jiang，Zheng2; Ding，Yunjie1,6

2023-07-24

10.1002/anie.202304282

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

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 (Rh/POPs). A decreased turnover frequency of Rh/POPs from 4317 h to 318 h was observed in a 1000 ppm HS co-feed for ethylene hydroformylation, but it self-recovered to 4527 h after withdrawal of HS, whereas the rhodium nanoparticles demonstrated poor activity and self-recovery ability. HS reduced the charge density of the single Rh atom and lowered its Gibbs free energy with the formation of inactive (SH)Rh(CO)(PPh-frame), which could be regenerated to active HRh(CO)(PPh-frame) after withdrawing HS. 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.

Olefin Hydroformylation Rhodium Single-Site Catalysts Structure-Activity Relationship Sulfur Poisoning

SCI ; EI

英语

NI论文

其他

Youth Innovation Promotion Association of the Chinese Academy of Sciences[2021181];Youth Innovation Promotion Association of the Chinese Academy of Sciences[2022179];National Natural Science Foundation of China[22002156];National Natural Science Foundation of China[22108275];National Natural Science Foundation of China[22288201];

Chemistry

Chemistry, Multidisciplinary

WOS:001001979800001

WILEY-V C H VERLAG GMBH

20232314192018

Catalyst activity ; Catalyst poisoning ; Ethylene ; Gibbs free energy ; Hydroformylation ; Recovery ; Rhodium compounds ; Sulfur

Thermodynamics:641.1 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1

CHEMISTRY

2-s2.0-85160945915

Scopus

1.Dalian National Laboratory for Clean Energy,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,116023,China
2.Shanghai Synchrotron Radiation Facility,Shanghai Institute of Applied Physics,and Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai,201204,China
3.State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,116023,China
4.University of Chinese Academy of Sciences,Beijing,100049,China
5.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
6.State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,116023,China

Feng，Siquan,Jiang，Miao,Song，Xiangen,et al. Sulfur Poisoning and Self-Recovery of Single-Site Rh1/Porous Organic Polymer Catalysts for Olefin Hydroformylation[J]. Angewandte Chemie - International Edition,2023,62(30).

Feng，Siquan.,Jiang，Miao.,Song，Xiangen.,Qiao，Panzhe.,Yan，Li.,...&Ding，Yunjie.(2023).Sulfur Poisoning and Self-Recovery of Single-Site Rh1/Porous Organic Polymer Catalysts for Olefin Hydroformylation.Angewandte Chemie - International Edition,62(30).

Feng，Siquan,et al."Sulfur Poisoning and Self-Recovery of Single-Site Rh1/Porous Organic Polymer Catalysts for Olefin Hydroformylation".Angewandte Chemie - International Edition 62.30(2023).