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
N1 - Funding Information:
Financial support was provided the National Science Foundation (CBET 1438493 and DMR 1507812). The Bruker 500?MHz spectrometer used in this study was supported by a NSF-MRI Grant (CHE-1229030). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We would like to thank Dr. Tianpin Wu at 9BM at APS for help with the S K-edge XAS measurements. The authors are grateful to Dr. Qihong Zhang from Department of Chemistry, Rutgers University-Newark, for her help with the Raman measurements of the PS-Gc catalyst. The authors are grateful to Mr. Gordon Osterman and Dr. Kristina Keating from Department of Earth and Environmental Sciences, Rutgers University- Newark, for help in BET and BJH measurement of PS-Gc catalyst.
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.
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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 -