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Graphene-supported hemin as a highly active biomimetic oxidation catalyst.

Together, our studies demonstrate that graphene-supported porphyrin derivatives show excellent catalytic characteristics that are more than two orders of magnitude better than free hemin, and more than one order of magnitude better than any other supported system, which opens up new perspectives for... Full description

Journal Title: Angewandte Chemie (International ed. in English) April 16, 2012, Vol.51(16), pp.3822-3825
Main Author: Xue, Teng
Other Authors: Jiang, Shan , Qu, Yongquan , Su, Qiao , Cheng, Rui , Dubin, Sergey , Chiu, Chin-Yi , Kaner, Richard , Huang, Yu , Duan, Xiangfeng
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1521-3773 ; DOI: 1521-3773 ; DOI: 10.1002/anie.201108400
Link: http://search.proquest.com/docview/993911310/?pq-origsite=primo
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title: Graphene-supported hemin as a highly active biomimetic oxidation catalyst.
format: Article
creator:
  • Xue, Teng
  • Jiang, Shan
  • Qu, Yongquan
  • Su, Qiao
  • Cheng, Rui
  • Dubin, Sergey
  • Chiu, Chin-Yi
  • Kaner, Richard
  • Huang, Yu
  • Duan, Xiangfeng
subjects:
  • Biomimetic Materials–Chemistry
  • Catalysis–Chemistry
  • Graphite–Chemistry
  • Hemin–Chemistry
  • Hydrogel, Polyethylene Glycol Dimethacrylate–Chemistry
  • Kinetics–Chemistry
  • Oxidation-Reduction–Chemistry
  • Oxides–Chemistry
  • Oxides
  • Hydrogel, Polyethylene Glycol Dimethacrylate
  • Hemin
  • Graphite
ispartof: Angewandte Chemie (International ed. in English), April 16, 2012, Vol.51(16), pp.3822-3825
description: Together, our studies demonstrate that graphene-supported porphyrin derivatives show excellent catalytic characteristics that are more than two orders of magnitude better than free hemin, and more than one order of magnitude better than any other supported system, which opens up new perspectives for other important oxidation reactions such as epoxidation and sulfoxidation. Our related studies have also shown that the hemin-graphene conjugate functions as an effective catalyst to facilitate the oxidation reaction of larginine (for nitric oxide generation) and the oxidation reaction of toluene. The fundamental reason for such a substantial enhancement of catalytic activity is a particularly interesting topic to be investigated in the future both experimentally and theoretically. In general, several combined features of the graphene support may contribute to the performance enhancement. First, graphene-supported hemin or FeTMPyP could prevent molecules from self-dimerization to form catalytically inactive species. Second, graphene as a support can block one side of the porphyrin molecule which could prevent hydrogen peroxide attack from both sides, and thus lowering the possibility of oxidative destruction of the catalyst molecules themselves. Third, compared to a hydrogel support and other three-dimensional (3D) porous supports, graphene provides a two-dimensional (2D) support with a large open and accessible surface area; therefore, the diffusion of the substrate and product away from the catalytic centers is much easier, which could be beneficial to the reaction turnover rate and the binding interactions. Previous studies also demonstrated that a metalloporphyrin immobilized on a silica surface showed a higher catalytic activity than those trapped in a 3D silica matrix. Fourth, graphene can function as a π donor to the iron centers of hemin through cation-π interactions. The cation-π interaction between the iron centers and graphene mimics the role of cysteine or histidine in enzymes, which have been proven as axial ligands to the hemin center from a Glu mutation study. Enzymatic studies also showed that axial ligands can serve multiple functions to enhance the catalytic characteristics, such as enhancement of the rate of O-O cleavage, promotion of heterolytic splitting rather than homolytic O-O splitting, and stabilization of the ferryl (FeO4+) moiety because of resonance and enhanced electrophilicity, which is crucial for the catalytic activity.
language: eng
source:
identifier: E-ISSN: 1521-3773 ; DOI: 1521-3773 ; DOI: 10.1002/anie.201108400
fulltext: fulltext
issn:
  • 15213773
  • 1521-3773
url: Link


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titleGraphene-supported hemin as a highly active biomimetic oxidation catalyst.
creatorXue, Teng ; Jiang, Shan ; Qu, Yongquan ; Su, Qiao ; Cheng, Rui ; Dubin, Sergey ; Chiu, Chin-Yi ; Kaner, Richard ; Huang, Yu ; Duan, Xiangfeng
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subjectBiomimetic Materials–Chemistry ; Catalysis–Chemistry ; Graphite–Chemistry ; Hemin–Chemistry ; Hydrogel, Polyethylene Glycol Dimethacrylate–Chemistry ; Kinetics–Chemistry ; Oxidation-Reduction–Chemistry ; Oxides–Chemistry ; Oxides ; Hydrogel, Polyethylene Glycol Dimethacrylate ; Hemin ; Graphite
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descriptionTogether, our studies demonstrate that graphene-supported porphyrin derivatives show excellent catalytic characteristics that are more than two orders of magnitude better than free hemin, and more than one order of magnitude better than any other supported system, which opens up new perspectives for other important oxidation reactions such as epoxidation and sulfoxidation. Our related studies have also shown that the hemin-graphene conjugate functions as an effective catalyst to facilitate the oxidation reaction of larginine (for nitric oxide generation) and the oxidation reaction of toluene. The fundamental reason for such a substantial enhancement of catalytic activity is a particularly interesting topic to be investigated in the future both experimentally and theoretically. In general, several combined features of the graphene support may contribute to the performance enhancement. First, graphene-supported hemin or FeTMPyP could prevent molecules from self-dimerization to form catalytically inactive species. Second, graphene as a support can block one side of the porphyrin molecule which could prevent hydrogen peroxide attack from both sides, and thus lowering the possibility of oxidative destruction of the catalyst molecules themselves. Third, compared to a hydrogel support and other three-dimensional (3D) porous supports, graphene provides a two-dimensional (2D) support with a large open and accessible surface area; therefore, the diffusion of the substrate and product away from the catalytic centers is much easier, which could be beneficial to the reaction turnover rate and the binding interactions. Previous studies also demonstrated that a metalloporphyrin immobilized on a silica surface showed a higher catalytic activity than those trapped in a 3D silica matrix. Fourth, graphene can function as a π donor to the iron centers of hemin through cation-π interactions. The cation-π interaction between the iron centers and graphene mimics the role of cysteine or histidine in enzymes, which have been proven as axial ligands to the hemin center from a Glu mutation study. Enzymatic studies also showed that axial ligands can serve multiple functions to enhance the catalytic characteristics, such as enhancement of the rate of O-O cleavage, promotion of heterolytic splitting rather than homolytic O-O splitting, and stabilization of the ferryl (FeO4+) moiety because of resonance and enhanced electrophilicity, which is crucial for the catalytic activity.
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