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Metal-Free Heteroatom Doped-Carbon Nanomaterials for Energy Conversion and Storage

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Metal-Free Heteroatom Doped-Carbon Nanomaterials for Energy Conversion and Storage METAL-FREE HETEROATOM DOPED-CARBON NANOMATERIALS FOR ENERGY CONVERSION AND STORAGE by MIN WANG Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Dissertation Adviser: Professor Liming Dai Department of Macromolecular Science and Engineering CASE WESTERN RESERVE UNIVERSITY May, 2017 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of Min Wang Candidate for the degree of Doctor of Philosophy* (Signed) Professor Liming Dai__________________________________________________ (Chair of the committee) Professor David Schiraldi_______________________________________________ (Committee member) Professor Rigoberto Advincula___________________________________________ (Committee member) Professor Clemens Burda________________________________________________ (Committee member) Date of Defense Dec, 19th, 2016 *We also certify that written approval has been obtained for any proprietary material contained therein. TABLE OF CONTENTS LIST OF TABELS……………………………………………………………………...………. .I LIST OF FIGURES…………………………………………………………………………….. II ACKNOWLEDGMENTS…………………………………………………………..……...XXIII ABSTRACTS………………………………………….…………………………………… XXIV CHAPTER I. Introduction…………………………………………………………………….1 1.1 Introduction of Carbon Nanomaterials 1.1.1 Carbon Nanotubes 1.1.2 Graphenes 1.1.3 Porous Carbon Nanomaterials 1.2 Oxygen Reduction and PEMFC for Energy Conversion 1.2.1 Electrochemical Oxygen Reduction Reaction (ORR) 1.2.2 Current State of ORR Electrocatalysts 1.3 Metal-free Carbon Based Electrocatalysts for ORR 1.3.1 Heteroatom-doped Carbon Nanomaterials for ORR 1.3.2 Role of Heteroatom Doping 1.3.3 Other Strategies for ORR Electrocatalysis 1.4 Research Objectives CHAPTER II………………………………………………………………………………….34 Heteroatoms-codoped Carbon Nanotubes as High-Performance Metal-free Electrocatalysts for Energy Conversion CHAPTER III…………………………………………………………………………………72 Graphitic Carbon Nitrides Supported by Nitrogen-doped Graphene as Efficient Metal-free Electrocatalysts for Oxygen Reduction CHAPTER IV…………………………………………………………………………………95 Rational Design of 3 Dimensional Metal-free Nitrogen-doped Graphene / Carbon Nanotube Composites for Energy Conversion and Storage CHAPTER V……………………………………………………………………………...…...132 Metal-free Nitrogen-doped Hierarchical Porous Carbons derived from Biomass for Energy Conversion and Storage REFERENCES………………………………………………………………………………...163 LIST OF TABLES CHAPTER I. Introduction Table 1.1 Electrocatalytic performance and preparation methods of metal-free carbon nanomaterials. Reprinted with permission from Ref. 222. Copyright 2015 American Chemical Society. ………………………..……...………………………..……...………………………..32 CHAPTER II. Heteroatoms-codoped Carbon Nanotubes for Electrocatalysis Table 2.1 XPS analysis of heteroatoms doped carbon nanotubes. ………………………..……...55 CHAPTER III Graphitic Carbon Nitrides Supported by Nitrogen-doped Graphene as Efficient Metal-free Electrocatalysts for Oxygen Reduction Table 3.1 Preparation methods and electrocatalytic performance of C3N4 based electrocatalysts for ORR in 0.1M O2-saturated KOH. ………………………..……...………………………..…94 CHAPTER IV Rational Design of 3D Metal-free Nitrogen-doped Graphene / Carbon Nanotubes Composites for Energy Conversion and Storage Table 4.1 XPS results of N-CNT, N-G, G-CNT and N-G-CNT. ………………………..……...104 Table 4.2 BET results of N-CNT, N-G, G-CNT and N-G-CNT. ………………………..…....107 I LIST OF FIGURES CHAPTER I. Introduction Figure 1.1 Structures of fullerene (0D), CNT (1D), graphene (2D), and 3D carbon nanomaterials, indicating that the 2D graphene is a building block for other graphitic carbon materials. Reprinted with permission from Chem. Rev., 2015, 115 (11), 4823-4892. Copyright 2015 American Chemical Society. ………………………..……...…………………………..……………………2 Figure 1.2 Important synthesis methods of graphene. (a). Chemical vapor deposition (CVD) (b). Mechanical exfoliation (c). Liquid phase exfoliation. Reprinted from Ref 143 “Nature 490, 192-200 (2012)” with permission from the Nature Publishing Group. (d). Reduction of graphite oxide (GO). Graphite is oxidized to GO and thermal reduction of GO yields reduced graphene oxide (R-GO). Reproduced from Ref. 144 with permission from the PCCP Owner Societies. (e). Schematic representation of the mechanochemical reaction between in situ generated active carbon species and reactant gases in a sealed ball-mill crusher. The cracking of graphite by ball milling in the presence of corresponding gases and subsequent exposure to air moisture resulted in the formation of EFGnPs. Reprinted with permission from Ref 145. Copyright 2013 American Chemical Society. ………………………..……...…………………………..……………………6 Figure 1.3 Advanced carbon nanomaterials from different synthesis routes. (a). Template- free fabrication of hierarchical porous carbon by constructing carbonyl crosslinking bridges between polystyrene chains. Adapted from Ref. 162 with permission from Copyright 2010 Royal Society of Chemistry. (b). Chemically bonded graphene/carbon nanotube composites as flexible II supercapacitor electrode materials are synthesized by amide bonding. Reprinted with permission from Ref 163. Copyright 2013 Wiley-VCH. (c). Hierarchical porous carbons from carbonized metal-organic frameworks for lithium sulphur batteries. Adapted from Ref. 164 with permission from Copyright 2013 Royal Society of Chemistry. (d). N and P co-doped porous carbons (NPMC): schematic illustration of the preparation process for the NPMC foams. An aniline-phytic acid complex is formed, followed by oxidative polymerization into a 3D PANi hydrogel crosslinked with phytic acids. The PANi hydrogel is freeze-dried into an aerogel and pyrolysed in Ar to produce the NPMC. Reprinted from Ref. 165 with permission from the Nature Publishing Group. (e). Schematic diagrams showing the synthesis and microstructures of a 3D graphene- radially aligned CNT fiber. Reproduced with permission from Ref.166 Copyright 2015 AAAS. ………9 Figure 1.4 (a) Schematics of a fuel cell. Reprinted with permission from Ref. 15 Chem. Rev., 2015, 115 (11), 4823-4892. Copyright 2015 American Chemical Society. (b). Typical polarization curve of PEMFCs. The typical polarization curve describes the relationship between cell voltage and current density used to evaluate cell performance. Reprinted with permission from Ref. 174 Copyright 2015 AAAS. ………………………..……...…………………………..……………12 Figure 1.5 (a). The process and thermodynamic electrode potentials of electrochemical oxygen reduction reaction in acid and alkaline media, respectively. Adapted from Ref.177 with permission of Springer. (b). LSV curves of electrocatalysts in oxygen-saturated electrolyte with different rotating rates. (c) Oxygen reduction curves on the disc and ring electrodes of RRDE at 5 mV s−1 scan rate at 1600 rpm, respectively. Reprinted with permission from Ref. 174 Copyright 2015 AAAS. ………………………..……...……………………………………………..……………14 III Figure 1.6 Metal-free carbon nanomaterials for oxygen reduction. (a). Vertically aligned nitrogen-doped carbon nanotubes (VA-NCNT): (1). Scanning electron microscopy (SEM) image of the as-synthesized VA-NCNTs on a quartz substrate. (2). TEM image of the electrochemically purified VANCNTs. (3). CVs for oxygen reduction at the unpurified (upper) and electrochemically purified (bottom) VA-NCNT/GC electrodes in the argon-protected (dotted curves) or air-saturated 0.1 M KOH (solid red curves) at the scan rate of 100 mVs−1. Reproduced with permission from Ref.91 Copyright 2009 AAAS. (b). Nitrogen-doped graphene: (1). Digital photo image of a transparent N-doped graphene film floating on water after removal of the nickel layer by dissolving in an aqueous acid solution. (2) AFM images of the N-doped graphene film. (3). RRDE voltammograms for the ORR in air-saturated 0.1 M KOH at the C-graphene electrode (red line), Pt/C electrode (green line), and N-doped graphene electrode (blue line). Reprinted with permission from Ref. 37 Copyright 2010 American Chemical Society. (c). BCN graphene: (1). BCN graphene model, C gray, H white, B pink, N blue. (2). SEM image of BCN graphene, scale bar: 500nm. (3). LSV curves of ORR on BCN graphene with different compositions in O2-saturated 0.1 M KOH solution at 10 mV s-1 and compared with the commercial Pt/C electrocatalyst. Reprinted with permission from Ref 191. Copyright 2012 Wiley-VCH. (d). Vertically aligned BCN: SEM (1) and TEM (2) images of VA-BCN nanotubes. (3). LSV curves of various electrodes in O2-saturated 0.1 M KOH electrolyte at a scan rate of 10 mVs-1 at a rotation rate of 1000 rpm. Reprinted with permission from Ref 182. Copyright 2011 Wiley-VCH. (e). Nitrogen-doped holey graphitic carbon: (1). Schematic representation of the synthesis of COP-4 through monomers tris(4- bromophenyl)amine (TBA), 2,4,6-tris(4-bromo-phenyl)-[1,3,5] triazine (TBT), (4’-bromo- biphenyl-4-yl)-porphyrine (TBBPP), and 2,4,6-tris(5-bromothiophen-2-yl)-1,3,5-triazine (TBYT), IV respectively, using nickel-catalyzed Yamamoto-type Ullmann cross-coupling reaction. (2). LSV −1 curves of COP graphene in O2-saturated 0.1 M KOH at 1600 rpm at a sweep rate of 5 mV s . Reprinted with permission from Ref.195 Copyright 2014 Wiley-VCH. (f). Nitrogen-doped graphene quantum dots: (1). Synthesis of Quantum Dots 1-3. (2). CV curves (50 mV s−1) of N- −1 GQD-1 on a RDE in a N2- and an O2-saturated 0.1 M KOH solution. (3). LSV curves (10 mV s ) for N-GQD-1, N-GQD-2, GQD-3 and Pt/C on a RDE (1600 rpm) in an O2-saturated 0.1 M KOH solution. Also shown is the LSV curve for 11, a much smaller N-substituted
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