Yang WU

Department of Chemistry, Nagoya University, Science &

Agricultural Building 431, Furo-cho, Chikusa-ku, Nagoya, 464-

8602 Japan

Tel & Fax : +81-52-789-5106

E-mail: wu.yang@f.mbox.nagoya-u.ac.jp

Education

2012.10- 2015.09 Ph.D. in Structural Molecular Science

Adviser: Prof. Donglin JIANG

School of Physical Sciences, SOKENDAI (The Graduate University for Advanced

Studies), Japan

2009.9- 2012.4 M.S. in Orgainc Chemistry

Adviser: Prof. Wusong JIN

College of Chemistry, Chemical Engineering and Biotechnology, Donghua University,

Shanghai, P. R. China

2005.9- 2009.6 B.S. in Applied Chemistry

Adviser: Prof. Yingzhong SHEN

College of Materials Science and Engineering, Nanjing University of Aeronautics and

Astronautics, Nanjing, P. R. China

Employment

Oct. 2015 – present Postdoctoral Fellow

Adviser: Prof. Kunio AWAGA

Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya,

Japan

Oct. 2012 – Sept. 2015 Research Assistant

Adviser: Prof. Donglin JIANG

Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki, Japan

Research Experience

Nagoya University

Covalent organic frameworks (COFs)/ Conjugated microporous polymers (CMPs)/

Porous organic polymers(POPs) / Lithium-sulfur batteries

Institute for Molecular Science

Porous organic polymers/ Covalent organic frameworks (COFs)/ Conjugated

microporous polymers (CMPs)/ 2D layered COF films/ Heterogeneous catalyst/ Gas

storage/ Gas separation/ Light harvesting/ Energy transfer.

Donghua University

Supramolecular/ Self-assembly/ Soft materials/ Metal complex/ HBC.

Nanjing University of Aeronautics and Astronautics

Atomic layer deposition (ALD)/ Metal complex.

Professional Skills

- Multi-step organic synthesis and polymerization.

- Handling, synthesis and characterization of self-organized porous materials,

especially Covalent Organic Frameworks (COFs).

- Handling, synthesis and characterization of self-assembled materials.

- Handling, synthesis, purification and characterization of various kinds of complex

organic compounds, including air- and moisture-sensitive metal complexes.

- Handling, preparation and characterization of single crystals (small organic

compounds or metal complexes).

- Handling and maintenance of glove box.

- Analysis of materials by following methods:

Nuclear Magnetic Resonance (NMR)/ Elemental Analysis (EA)/ Fourier-Transfer

Infrared (FT-IR)/ UV and PL spectrometers/ Mass Spectrometry: EI, FAB, MALDI-

TOF-MS, LC/GC-MS and ESI-MS/ Thermogravimetric Analysis (TGA)/ Differential

Scanning Calorimetry (DSC)/ Powder X-ray Diffractmeter (PXRD)/ Single Crystal X-

ray Diffractmeter (SXRD)/ Atomic Force Microscopy (AFM)/ Transmission Electron

Microscope (TEM)/ Scanning Electron Microscope (SEM)/ Electrochemical

measurements/ Gas sorption measurements

Honors and Awards

2012 Scholarship of Donghua University

2011 Scholarship of Donghua University

2009 Scholarship of Nanjing University of Aeronautics and Astronautics

2008 Excellent Student Leader of Nanjing University of Aeronautics and Astronautics

2007 Excellent Student Leader of Nanjing University of Aeronautics and Astronautics

Past Research Covalent organic frameworks (COFs) are a new class of porous architectures that allow the integration of organic units with atomic precision into long-range-ordered two- and three-dimensional structures. In 2D COFs, the building blocks for the vertices and edges are covalently linked to form extended 2D polygon sheets that stack to constitute layered frameworks. This covalently linked and topologically crystallized 2D architecture merges two structural characters, i.e., periodic π arrays and ordered one-dimensional channels. Characteristics of tunable functionality, regular pore structure, and high surface area, many COFs have recently been constructed with different building blocks and covalent linkages. However, potential applications (such as for gas storage, energy storage, optoelectricity, catalysis, and sensing) are still at the very early stages of fundamental research.

My research was focused on the design, synthesis and functional exploration of novel π-electronic two-dimensional covalent organic frameworks, with an emphasis on the development of new functional π-electronic molecular frameworks. I have developed same new strategies for exploring COFs structures especially their unique π-Columns and 1D Channels. On the basis of the characterization of their properties, π-electronic 2D COF can be developed to be heterogeneous catalysts with high catalytic activity and reusability or outstanding light-harvesting antenna by encapsulation of guest molecules into 1D channels. 1. A π-Electronic Covalent Organic Framework Catalyst: π-Walls as Catalytic Beds for Diels-Alder Reactions under Ambient Conditions A novel π-electronic mesoporous imine-based covalent organic framework (COF) was designed and synthesized by using 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPPy) and 2,6-diaminoanthracene (DAAn) as building blocks. This pyrene-anthracence COF (Py-An COF) with pyrene at the vertices and anthracene on the edges has high crystallinity, high porosity and high stability. These properties make Py-An COF a good material for potential applications in gas storage, gas separation, and heterogeneous catalysis. The Py-An COF was utilized as a heterogeneous catalyst for Diels-Alder reactions of 9-hydroxymethylanthracene and N-substituted maleimide derivatives. The Py-An COF exhibited the highest catalytic activities among the heterogeneous catalysts reported to date that work at elevated temperatures. And the COF catalyst remains its crystallinity, porosity, stability, catalytic activity and morphology after four consecutive cycles. The results suggest a tremendous potential of COFs for achieving novel catalytic systems via π-array structural design (Chem. Commun. 2015, 51,10096–10098.). 2. Light Harvesting with π-Electronic Covalent Organic Frameworks

The 2D COFs merge two structural characteristics, i.e., periodic π-columns and precise nano-channels, which allow chromophores to be located in two spatially separated domains, i.e. in the framework and nano-channels. This spatial configuration could potentially be exploited to promote the excitation energy transfer from the framework to nano-channels and enhancethe luminescence of dyes

Figure 1. A π-electronic covalent organic framework catalyst: π-walls as catalytic beds for Diels-Alder reactions under ambient conditions

in the nano-channels. In this research, a 2D π-electronic COF was functionalized by introduce chromophore, [4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran] (DCM, a laser dye), into the nano-channels. The framework and nano-channel was paired with an energy-donating and -accepting system, which lead to a light-harvesting and energy-transferring configuration. The highly ordered and densely packed-π-skeletons of COF serve as an outstanding light-harvesting antenna to harvest photons and trigger an ultrafast and quantitative energy transfer to the acceptor molecules that are spatially confined in the nano-channel domains of the antenna COFs. The emission gradually changes from deep blue to light green and finally to brilliant yellow when the DCM content was increased. By integrating energy acceptors into the pores, I demonstrated the first example of light harvesting with π-electronic covalent organic frameworks. The π columnar arrays serve as a light-harvesting antenna to channel the excitation energy to the acceptors in the pores. This system enables the construction of light-harvesting materials in both solid state and solutions.

In summary, my research was focused on developing new strategies for exploring COFs structures especially their unique π-Columns and 1D Channels. On the basis of the characterization of their properties, π-electronic 2D COF can be developed to be heterogeneous catalysts with high catalytic activity and reusability or outstanding light-harvesting antenna by encapsulation of guest molecules into 1D channels. It is believed that these strategies and research results may not only inspire the synthesis of new π-electronic 2D COFs with ideal building units, but also greatly facilitate the development of COFs as heterogeneous catalysts or light-harvesting antenna by their rational design with π-electronic molecular frameworks and pores. The results suggest great potential of 2D COFs as host material by utilizing their unique π-columns and 1D channels.

Figure 2. Light harvesting with π-electronic covalent organic frameworks.

List of Publications

1. Yang Wu, Hong Xu, Xiong Chen, Jia Gao and Donglin Jiang*,

A π-electronic covalent organic framework catalyst: π- walls as catalytic beds for Diels-

Alder reactions under ambient conditions,

Chem. Comm., Vol. 51, No 50, pp. 10096-10098, June, 2015. (Selected as Cover

Page.)

2. Cheng Gu, Ning Huang, Yang Wu, Hong Xu and Donglin Jiang*,

Design of highly photofunctional porous polymer films with controlled thickness and

prominent microporosity,

Angew. Chem. Int. Ed. Vol. 54, No 39, pp. 11540-11544, September, 2015.

3. Fei Xu, Hong Xu, Xiong Chen, Dingcai Wu, Yang Wu, Hao Liu, Cheng Gu, Ruowen

Fu and Donglin Jiang*,

Radical covalent organic frameworks: a general strategy to immobilize open-accessible

polyradicals for high-performance capacitive energy storage,

Angew. Chem. Int. Ed. Vol. 54, No 23, pp. 6814-6818, June, 2015.

4. Yang Wu, Dahai Xie, Dengqing Zhang, Xianying Li and Wusong Jin*,

Trichlorido [4-methoxy-2,6-bis(2-pyrimidin-2-yl-κN) phenyl-κC1] platinum(IV)

acetonitrile monosolvate,

Acta Crystallographica, Vol. E68, No 9, pp. m1210–m1211, September, 2012.

5. Yang Wu, Dengqing Zhang, Dahai Xie, Xianying Li and Wusong Jin*.

Synthesis of Novel N^C^N Tridentate Ligand 1.3-Bis(2’-pyrimidyl)-5-

methoxybenzene,

Chinese J. Synth. Chem., Vol. 20, No 5, pp. 596-598, October, 2012.

6. Jiena Hu, Yang Wu, Dengqing Zhang*, Xianying Li and Wusong Jin*,

2-[3-Methoxy-5-(pyrimidin-2-yl)phenyl]pyrimidine,

Acta Crystallographica, Vol. E69, No 3, pp. o333–o333, March, 2013.

7. Yang Zhang, Yang Wu, Dengqing Zhang and Wusong Jin*,

Selective Synthesis of Novel 5-Bromopyrimidine Derivatives,

Chinese J. Synth. Chem., Vol. 19, No 5, pp. 662-664, October, 2011.

Conference Papers

1. Yang Wu and Donglin Jiang, Design of covalent organic frameworks for light

harvesting and energy transfer. 64th SPSJ Annual Meeting (Sapporo, Japan) 2015.05.

(Oral)

2. Yang Wu and Donglin Jiang, Light harvesting with π-electronic covalent organic

frameworks. The 95th CSJ Annual Meeting (Tokyo, Japan) 2015.03. (Oral)

3. Yang Wu and Donglin Jiang, A 2D covalent organic framework as a heterogeneous

catalyst for Diels-Alder reactions at ambient temperature. Asian Winter School 2015

(Okazaki, Japan) 2015.02. (Poster)

4. Yang Wu and Donglin Jiang, A 2D covalent organic framework as a heterogeneous

catalyst for Diels-Alder reactions at ambient temperature. 63rd Symposium on

Macromolecules, SPSJ (Nagasaki, Japan) 2014.09. (Poster)

5. Yang Wu, Long Chen, Atsushi Nagai and Donglin Jiang, Oriented 2D covalent

organic framework thin films. Asian Winter School 2013 (Pusan, Republic of Korea)

2013.02. (Poster)

Research Plan

High surface area porous organic polymers: Potential host materials for lithium-sulfur batteries

Electrical energy storage is one of the most critical needs of 21st century society. Applications that depend on electrical energy storage include portable electronics, electric vehicles, and devices for renewable energy storage from solar and wind. Lithium-sulfur batteries have attracted considerable attention from both the academic and industrial communities for their potential capability of meeting practical applications in new electrical energy storage. Lithium-sulfur batteries have many conspicuous advantages, such as a high theoretical capacity of 1675 mA h/g, low cost, natural abundance and environmental friendliness, which making lithium-sulfur batteries become one of the most promising next-generation batteries. Unlike conventional insertion cathode materials, sulfur undergoes a series of compositional and structural changes during cycling, which involve soluble polysulfides and insoluble sulfides. As a result, researchers have struggled with the maintenance of a stable electrode structure, full utilization of the active material, and sufficient cycle life with good system efficiency.

In order to address the problems, various materials have been studied as matrix, such as porous carbons, graphene, carbon nanofiber, hollow carbon spheres, conducting polymers, metal oxides and metal-organic frameworks (MOF), which have been developed as sulfur container. These works inspired us to explore the optimal host material for sulfur impregnation which should be lightweight, vast permanent nanopores and with high surface area. Porous organic polymers (POPs) with intrinsic properties including large specific surface area, high chemical stability, and low skeleton density have exhibited potential applications in heterogeneous catalysis and gas storage and separation. Versatile porous organic polymers were obtained smoothly through a template-free chemical process by selection of proper building blocks and polymerization reactions, which show efficient preparation and high flexibility in the molecular design. Moreover, as for porous organic polymers, improvement of property and function can be accessible by functionalization approaches. Based on these advantages, porous organic polymers can act as great host materials for sulfur impregnation.

One of the most widely adopted approaches for sulfur impregnation is the physical encapsulation of elemental sulfur within host materials. Although these approaches have improved the cycling performance to large extents, these architectures and polymer coatings still suffer from a certain possibility of polysulfide dissolution, because complete encapsulation during repeated charge–discharge cycles is technically infeasible. In a similar sense, the negligible binding of sulfur within the matrices also prevents the complete elimination of polysulfide dissolution. To overcome this limitation, the impregnation of sulfur through the formation of strong covalent bonds between host and sulfur has been explored. Therefore, it is desirable to develop a framework structure that features 1) robust sulfur binding, 2) an ordered pore structure for regular sulfur distribution, 3) large void spaces for high sulfur loadings, and 4) good electronic/ionic conductivity.

As for the development of porous organic polymers that can form strong covalent bonds between the host framework and sulfur, I will focus on design and synthesize a series of novel porous organic polymers functionalized with alkenyl groups, alkinyl groups or thiol groups. It has long been known that under ambient conditions elemental sulfur exists primarily in the form of an eight-membered ring (S8 ) that melts into a clear yellow liquid phase at 120–124 ˚C. Rings with 8–35 sulfur atoms are formed and further heating of the liquid sulfur phase above 159 ̊ C results in equilibrium ring-opening polymerization (ROP) of the S8 monomer into a linear polysulfane with diradical chain ends, which subsequently polymerizes into polymeric sulfur of high molecular weight. Alkenyl groups, alkinyl groups and thiol

groups can copolymerize with the elemental sulfur monomer to form stable polymers by quenching of the radical chain ends. Thus, by copolymerization of sulfur and functional groups on the surface of the POP pores, the sulfur can be robustly impregnated into the pores through the strong covalent bonds between host and sulfur. In the collaboration with Professor Awaga during these months, I have already established a alkinyl group functionalized covalent organic framework (COF) as sulfur host for lithium–sulfur battery. After be copolymerize with sulfur, the electrochemical properties were tested. The highest capacity of bonded S@COF can reach 458 mAh/g at 0.1 C. After 50 cycles, 61% capacity and 98.9% Coulombic efficiency were recorded. While in the controlled experiment, the non-bonded S@COF showed only 30% capacity retention after 50 cycles. This stable cycling performance is due to the robust sulfur cathode structure in which sulfur is homogeneously distributed throughout the regular pores within the framework together with the C-S covalent links.

To get a series of novel porous organic polymers with large specific surface area and good electronic/ionic conductivity, I will focus on design and synthesize a series of POPs with polythiophene linkage. By introduce polythiophene linkage in the POPs, they can become conducting when electrons are added or removed from the conjugated π-orbitals via doping. A series of monomers was designed with functional cores (with alkenyl groups, alkinyl groups or thiol groups) and thiophene linkage. After polymerization, a series of POPs will be synthesized. They will great candidates for the host materials for lithium-sulfur batteries. These electrochemical properties of these S@POPs will be benefited from the formation of wellconfined sulfur species within the micropores, sulfur bonding with the framework, and the good electron and ion conductivity of the framework. In summary, the proposed research project will not only contribute to the basic sciences in the porous organic polymers, but also trigger the new development of the lithium-sulfur batteries.

Figure 1. Design of bonded S@COF.

Figure 2. Molecular design stategy of polythiophene linked POPs.