Karla S. Feu Topics included in this group meeting: Graphene background, synthesis, application as catalysts, characterization and perspectives. Family of Graphene: Not covered in this group meeting: Applications in photocatalysis, sensors, supercapacitors, drug delivery and Full cells/. UPAC definition: Graphene is a single carbon layer of the graphite structure, describing its nature by analogy to a polycyclic aromatic hydrocarbon of quasi infinite size. Why study graphene and its derivatives? Graphene is an exciting and unique material which shows peculiar electronic, optical, mechanical and chemical properties, among others, which have found application in numerous scientific and technological areas. Synthetic rganic Chemistry? Graphene? Can we make organic synthesis on two-dimensional planes? rganic chemistry can be defined as the the study of the structure, properties, reactions, and preparation of carbon-containing compounds Graphene, as others hydrocarbons, can undergo many reactions in order to afford necessary flexibility to adapt it into specific performances. Timeline of selected events in the history of the preparation, isolation and characterization of graphene. 1840-1958 Blakely and co-workes prepare monolayer graphite by segregation carbon on the surface of Ni(100); several subsequent reports follow Morgan and Somorjai obtain LEED patterns produced by smallmolecule adsorption onto Pt(100) Graphite oxide prepared by Schafhaeutl, Brodie, Staudenmaier, ummers and others 1968 1962 Boehm and co-workers prepare reduced graphene oxide (rg) by the chemical and thermal reduction of graphite oxide 1970 1969 May interprets the data collect by Morgan and Somorjai as the presence of monolayer of graphite on the Pt surface Boehm and co-workers recommend that the term graphene be used to describe single layers of graphite-like carbon 1986 1975 van Bommel and co-workers prepare monolayer graphite by subliming silicon from silicon cabide uoff and co-workers micromechanically exfoliate graphite into thin lamellae comprised of multiple layers of graphene 1997 1999 UPAC formalizes the definition of graphene: The term graphene should be used only when the reactions, structural relations or other properties of individual layers are discussed Dreyer et al. ACE. 2010, 49, 9336. Geim and co-workers prepare graphene via micromechanical exfoliation; numerous reports follow 2004 2010
Synthesis of Graphene and its derivatives Graphene layers without functionalization are insoluble and infusible, which limits their application capabilities. The essential purpose of graphene derivatisation is to tailor its physical and chemical properties.the synthesis of graphene derivatives can be divided in two major process: a) bottom-up and b) top-down. verview of Principals Methods of Synthesis for Graphene-based Materials: Chemical xidation ummers method (1958) ther methods: Brodie, Staudenmaier, ofman and Tour. Advantages: Most Used method, Large scale production, Medium quality GM. Disadvantages: mpurities and defects, GM of low electrical conductivity, Large production of liquid wastes. Mechanical exfoliation Advantages: igh quality graphene Disadvantages: Time consuming, Low production. Chemical vapor deposition (CVD) Advantages: igh quality graphene, absence of impurities. Disadvantages: Low production. Pyrolysis of precursors Advantages: Low cost, Large scale production, Green synthesis method, easy doping. Disadvantages: Medium quality graphene. ummers method and subsequent sonication Wang et al. Nat. ev. Chem. 2017, 2, 00100. Navalon et al. Chem. ev. 2014, 114, 6179. Graphene oxide (G) Proposed structure of G based on the Lerf Klinowski model G is currently the principal precursor used for the synthesis of graphene materials. Morover, G itself has attracted considerable attention due the oxygen functional groups on its surfaces. G has attracted considerable attention as potential material for use in photovotaic cells, capacitors, sensor and catalysis.
Synthesis of Graphene-based Materials: G - simplified structure G as starting material: Graphene (G) as starting material: G a) b) + e- -N 2 N 2 N 2 Fluorographene (FG) as starting material: F F F BrMg F F F F FG -N 2 N 2 X N N N 2 NC X X 1. NaB 4 or 2. K/ 2 or 3. N 2 4 G SCl 2 or DCC, DMAP 1. (CF 3 C) 2,acidic alumina 2. Fe NaN 3 N N N N 3 Fe mchair edge Diagram of Active Sites of Graphene - Based Nanomaterials Solid acids C N N N N S 3 Zigzag edge π-system Amine N 2 Pyridine N Active defects sites Solid bases Ma et. al. ACS Catal. 2016, 6, 6948. Quinone-diol redox site X=, N Navalon et al. Chem. ev. 2014, 114, 6179.
Application as catalysts: G 34-80% yield 21 examples 1 2 Fan et al. Asian JC 2018, 7, 355. C-C coupling NC CN N 2 ne-pot enry-michael 87% yield 6 x recycled Zhang et al. ACS Appl. Mat. nterfaces 2015, 7, 1662. C- coupling 0-92% yield 15 examples 5 x recycled Gao et al. ACE 2016, 55, 3124. = Graphene oxide (G) 68-82% yield 20 examples 5 x recycled C 3 S N Synthesis of thioethers Alkylation of enes odination Basu et al. SC Adv. 2013, 3, 22130. Zhang et al. ChemCatChem 2018, 10, 376. G as catalyst C-N coupling Sulfoxidation S S 35-92% yield 29 examples a-ketoamides Majumdar et al. ACS Sustain. Chem. Eng. 2017, 5, 9286. Me or 81% yield Goncalves et al. Chem. Commun 2014, 50, 7673. 62-99% yield (mono) 20, 6 examples 40% yield 4 x recycled 1 2 1 2 Alkylation of enes 57-99% yield 15 examples 82-95% yield 2 examples u et al. JACS 2015, 137, 14473. 1 Me 1 2 Proposed mechanism G 1 1 = = Me Me Me G, air CCl 3, 100 C Me Me =, 82% = Me, 95% 1 G 1 Me 2 1 1 G Me 1 1 G (200 wt%), air CCl 3, 100 C u et al. JACS 2015, 137, 14473. 1 1 Me 2 1 G 1 Me 2 2 - via 1 2
C-C coupling odination G (40mg) C 3 CN, 100 C, argon, 12h or G(20mg), 2 (1.1 equiv) C 3 N 2 (0.7 ml) 120 C, 1h, air or G shell G shell G shell Proposed mechanism Proposed mechanism G shell adical coupling nitiation Fan et al. Asian JC 2018, 7, 355. SET e Application as catalysts: rg omatization adical addition 2 2 Zhang et al. ChemCatChem 2018, 10, 376. k 2 2 + 2 rg Proposed mechanism rg 333K rg k 3 By-products rg, MeCN 2 2 18% yield 5 x recycled Yang et al. Energy Environ. Sci. 2013, 6, 793.
Characterization Techniques: Analytical Techniques: *Atomic emission (AES), *absorption spectroscopy (AAS) or *inductively coupled plasma mass spectrometry (CP -MS): Presence of metal impurities. *Combustion elemental analysis: composition *TPD: thermal stability Spectroscopy: functional groups and metal oxidation date *aman *FT- *XPS *UV-Vis *Solid-state NM Textural characterization BET: surface area of powders XD: crystallinity and stacking Microscopy (M): morphology and single layer confirmation *Transmission electron M (TEM) *Scanning electron M (SEM) *Atomic force M (AFM) *Elemental mapping (Energy dispersive X-ray) Thermal Analysis: interaction with oxidizing reducing agents *Thermogravimetry *Thermodesorption aman XPS UV-vis SS-NM Adsorption isotherm: BET PXD Thermal analysis: ATG
TEM SEM AFM Energy dispersive X-ray: EDX thers Appllications and Perspectives: # Lithium ion battery # Solar cells # Supercapacitores #Bio applications # Sensors # Water desalination
Applications : Biosensors Schematic of the Desorption Mechanism of the Probe DNA adsorved on G, driven by the addition of (A) cdna and (B) Non-cDNA Park et al. Langmuir 2014, 30, 12587. Perspectives # More complex derivatives of graphene; # The research should also focus on well defined graphene; # A more intensive collaboration between synthetic chemists, polymer chemists and biologists; # n the field of catalysis, the exploration in the unchartered territory of enantioselective transformations; # The potencial of the graphene-based materials are huge and still in the begin.