Abstract
A highly porous graphitic carbon material, dually-doped with P and S, was studied as a metal free catalyst for aerobic oxidation reactions. Catalytic mechanism studies suggest that the active centers, originated from P-and S-doping, additively/synergistically catalyze the aerobic oxidation of benzylic alcohols but with different pathways. For the first time, catalytic centers stemming from S-doping were experimentally identified to be exocyclic S species (C-S-C, sulfur out of the carbon ring), which are different from those proposed for electrochemical oxygen reduction reactions (ORR) with a 4e− pathway and oxygen evaluation reactions (OER). Notably, all the catalytic sites from both P and S doping share a similar “protruding out” pyramid structure, which is in contrast to the planar structure of the catalytic sites in N- or B-doped graphitic materials. The unique geometric structure of the catalytic sites can minimize substrate steric hindrance effects, endowing the P, S co-doped catalysts with a wide substrate scope and functional group tolerance. Furthermore, the unambiguous distinguishment of the catalytic sites from those in OER and ORR provides valuable guidance for designing and developing carbon materials with controlled active sites to satisfy different catalytic applications.
| Original language | English |
|---|---|
| Pages (from-to) | 383-392 |
| Number of pages | 10 |
| Journal | Carbon |
| Volume | 114 |
| DOIs | |
| Publication status | Published - Apr 1 2017 |
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ASJC Scopus subject areas
- Chemistry(all)
Cite this
P and S dual-doped graphitic porous carbon for aerobic oxidation reactions : Enhanced catalytic activity and catalytic sites. / Patel, Mehulkumar A.; Luo, Feixiang; Savaram, Keerthi; Kucheryavy, Pavel; Xie, Qiaoqiao; Flach, Carol; Mendelsohn, Richard; Garfunkel, Eric; Lockard, Jenny V.; He, Huixin.
In: Carbon, Vol. 114, 01.04.2017, p. 383-392.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - P and S dual-doped graphitic porous carbon for aerobic oxidation reactions
T2 - Enhanced catalytic activity and catalytic sites
AU - Patel, Mehulkumar A.
AU - Luo, Feixiang
AU - Savaram, Keerthi
AU - Kucheryavy, Pavel
AU - Xie, Qiaoqiao
AU - Flach, Carol
AU - Mendelsohn, Richard
AU - Garfunkel, Eric
AU - Lockard, Jenny V.
AU - He, Huixin
PY - 2017/4/1
Y1 - 2017/4/1
N2 - A highly porous graphitic carbon material, dually-doped with P and S, was studied as a metal free catalyst for aerobic oxidation reactions. Catalytic mechanism studies suggest that the active centers, originated from P-and S-doping, additively/synergistically catalyze the aerobic oxidation of benzylic alcohols but with different pathways. For the first time, catalytic centers stemming from S-doping were experimentally identified to be exocyclic S species (C-S-C, sulfur out of the carbon ring), which are different from those proposed for electrochemical oxygen reduction reactions (ORR) with a 4e− pathway and oxygen evaluation reactions (OER). Notably, all the catalytic sites from both P and S doping share a similar “protruding out” pyramid structure, which is in contrast to the planar structure of the catalytic sites in N- or B-doped graphitic materials. The unique geometric structure of the catalytic sites can minimize substrate steric hindrance effects, endowing the P, S co-doped catalysts with a wide substrate scope and functional group tolerance. Furthermore, the unambiguous distinguishment of the catalytic sites from those in OER and ORR provides valuable guidance for designing and developing carbon materials with controlled active sites to satisfy different catalytic applications.
AB - A highly porous graphitic carbon material, dually-doped with P and S, was studied as a metal free catalyst for aerobic oxidation reactions. Catalytic mechanism studies suggest that the active centers, originated from P-and S-doping, additively/synergistically catalyze the aerobic oxidation of benzylic alcohols but with different pathways. For the first time, catalytic centers stemming from S-doping were experimentally identified to be exocyclic S species (C-S-C, sulfur out of the carbon ring), which are different from those proposed for electrochemical oxygen reduction reactions (ORR) with a 4e− pathway and oxygen evaluation reactions (OER). Notably, all the catalytic sites from both P and S doping share a similar “protruding out” pyramid structure, which is in contrast to the planar structure of the catalytic sites in N- or B-doped graphitic materials. The unique geometric structure of the catalytic sites can minimize substrate steric hindrance effects, endowing the P, S co-doped catalysts with a wide substrate scope and functional group tolerance. Furthermore, the unambiguous distinguishment of the catalytic sites from those in OER and ORR provides valuable guidance for designing and developing carbon materials with controlled active sites to satisfy different catalytic applications.
UR - http://www.scopus.com/inward/record.url?scp=85007158392&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85007158392&partnerID=8YFLogxK
U2 - 10.1016/j.carbon.2016.11.064
DO - 10.1016/j.carbon.2016.11.064
M3 - Article
AN - SCOPUS:85007158392
VL - 114
SP - 383
EP - 392
JO - Carbon
JF - Carbon
SN - 0008-6223
ER -