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Design and Synthesis of functional COF

Design and Synthesis of functional COF. Yi Zeng. Background. What is COF. How to design and modify. Background. 分子波罗米恩环. 穴状配体. 路易斯点结构. 冠醚. graphene supplements. novel physical property. designable and functional. 索烃. Covalent bond development history.

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Design and Synthesis of functional COF

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  1. Design and Synthesis of functional COF Yi Zeng

  2. Background • What is COF • How to design and modify

  3. Background 分子波罗米恩环 穴状配体 路易斯点结构 冠醚 graphene supplements novel physical property designable and functional 索烃 Covalent bond development history Science , 2017 , 355 (6328) :eaal1585

  4. COF：covalent organic frameworks strong covalent bonds 2D and 3D organic solids with extended structures porous and crystalline and are made from light elements (H, B, C, N, and O) eg: diamond, graphite, boron nitride… high thermal stability 500- 600℃ hydrogen bonding,p–p stacking, dipole, van der Waals Science , 2006 , 2006 (03) :0231-0231

  5. Processing Yaghi synthesized the frst two 2D COFs, each containing BDBA Jiang reported the frstphotoconductive COFs，TP-COF is electrically conductive and capable of repetitive on–off current switching at room temperature gas capture and storage (Mendoza-Corte´s et al., 2010), photovoltaics (Wan et al., 2009), organocatalysis (Xu et al., 2015) … Science , 2017 , 355 (6328) :eaal1585

  6. Names 2009 2D Polymers Two-Dimensional Polymers: Just a Dream of Synthetic Chemists? 2011 PCPs porous coordination polymers Development and Evaluation of Porous Materials for Carbon Dioxide Separation and Capture COP covalent organic polymers Synthesis of luminescent covalent–organic polymers for detecting nitroaromatic explosives and small organic molecules 2017 CAP conjugated aromatic polymer A two-dimensional conjugated aromatic polymer via C–C coupling reaction

  7. Acs Energy Letters , 2017 , 2 (6)

  8. Topology diagrams repeat unit + monomers ring structure Science , 2016 , 351 (6271) :365 Nature Materials Reviews 2016

  9. Monomer design linkers + functional groups Science , 2017 , 355 (6328) :eaal1585

  10. 硼酸酯 硼氧六环 硼硅酸盐 硼螺环 亚胺 腙 吖嗪 方酸 恶唑 三嗪 吩嗪 烯烃 酰亚胺 酮烯胺 酰胺 硼吖嗪 Chem. Commun., 2013, 49, 3925--3936 Science , 2017 , 355 (6328) :eaal1585

  11. Different monomer Chem. Soc. Rev., 2013, 42, 548--568

  12. Reaction conditions

  13. Two-dimensional light-emitting materials :preparation, properties and applications

  14. Design COF functions topology structure + monomers linkers + functional groups monomers reaction + strategies Purification + characterization

  15. A two-dimensional conjugated aromatic polymer via C–C coupling reaction 2-TBQP NBS,调节低能溴化反应 2D-CAP crystals Molecular framework approaches offer advantages over surface strategies because they allow bulk synthesis on a larger scale To reduce the rotational misorientation, anisotropic Au(110) was used as the growth substrate Nature Chemistry , 2017 , 9 (6) :563-570

  16. Nano-architectures by covalent assembly of molecular building blocks on Au(111) after deposition at low evaporator temperatures of 550 K Knudsen cell, 610 K, Nature Nanotechnology , 2007 , 2 (11) :687-691

  17. coupling reaction J. Phys. Chem. C 2012, 116, 5974

  18. Nitrogen-Doped Holey Graphitic Carbon from 2D Covalent Organic Polymers for Oxygen Reduction Yamamoto coupling reaction Angew. Chem. 2012, 124, 2672

  19. Synthesis of luminescent covalent–organicpolymers for detecting nitroaromatic explosives and Small organic molecules COPs also show good solvent-dependent luminescence properties Macromol. Rapid Commun. 2012, 33, 1184

  20. 1,3,5-Tribromobenzene 1,3,5-tris(4-bromophenyl)benzene Tris(4-bromophenyl)amine 2,4,6-tris-(4-bromophenyl)-[1,3,5]triazine Tetra(4-bromophenyl)porphyrin (Br4TPP) (4′-bromo-biphenyl-4-yl)- porphyrine

  21. On the reticular construction concept of covalent organic frameworks densities of states (DOS) Larger number of carbon atoms in the unit cells in COFs causes smaller band gaps and vice versa Beilstein J. Nanotechnol. 2010, 1, 60.

  22. Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene Improved crystallinity solvothermal condensation reaction These vertically aligned, porous phthalocyanineCOFs are intriguing precursors of ordered heterojunction films long thought to be ideal for organic photovoltaic performance Science 332, 228–231 (2011)

  23. Chemistry physical MBE+SEM Debrominationcoupling reaction monomers + substrates DFT Density functional tight-binding (DFTB) First-principles calculations

  24. Tuneable near white-emissive two-dimensional covalent organic frameworks

  25. An n-Channel Two-Dimensional Covalent Organic Framework JACS, 2011 , 133 (37) :14510

  26. Oriented Covalent Organic Framework Film on Graphene for Robust AmbipolarVertical Organic Field-Effect Transistor ambipolar charge carrier Electrical Transporting high current density on/off ratio (>105) and high on-current density (>4.1 A cm-2) Chemistry of Materials , 2017 , 29 (10)

  27. Synthesis of metallophthalocyanine covalent organic frameworks that exhibit high carrier mobility and photoconductivity : Covalent Organic Frameworks with High Charge Carrier Mobility

  28. modify COF-M M=C、S =Fe, Co, Mn , Ni… doping and heterostructure COF@MOF New complex structure COF/MOF

  29. Conjugated organic framework with three-dimensionally ordered stable structure and delocalized πclouds π conjugation-spans the two-dimensional sheets Carrier mobility and photoelectric properties high on-off ratio photoswitches and photovoltaic cells AA stacking (29.01 kcal mol–1) and the staggered AB modes (74.15 kcal mol–1).

  30. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water time dependence of the relative UV-Vis UV-vis electrochemical and spectroelectrochemical characterizations and carbon dioxide reduction performance of the COFs high activity and selectivity

  31. High‐Rate Charge‐Carrier Transport in Porphyrin Covalent Organic Frameworks: Switching from Hole to Electron to Ambipolar Conduction ZnP-COF Angew. Chem. Int. Ed. 51, 2618–2622 (2012)

  32. COF/MOF higher selectivity of the H2/CO2gas mixture than the individual COF and MOF counterparts J. Am. Chem. Soc. 2016, 138, 7673−7680

  33. Hybridization of MOFs and COFs: A New Strategy for Construction of MOF@COF Core–Shell Hybrid Materials NH2-MIL-68@TPA-COF Photocatalytic

  34. light response conductivity graded pore structure doping and heterostructure activity and selectivity crystallinity magnetic

  35. Summary design and synthesis of materials characterization optical / electrical / magnetic properties large conjugate structure covalent bond reversibility epitaxial growth+exfoliation How to improve its performance • organic compounds are easy to sublimate or decompose Stability appropriate building blocks Layered large single crystal ?

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