CAREER: Directed Self-Assembly of 2D Plasmonic Nanoparticles in Block Copolymer Nanofibers to Form Hierarchical Nanostructures

职业：嵌段共聚物纳米纤维中二维等离子体纳米颗粒的定向自组装形成分层纳米结构

• 批准号: 1752611
• 负责人: Guoliang Greg Liu
• 金额: $ 58.5万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-03-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1752611&HistoricalAwards=false
• 关键词: CAREER; Directed; Self; Assembly; 2D

PART 1: NON-TECHNICAL SUMMARYPolymers containing two-dimensional (2D) plasmonic nanoparticles could contribute to transformative technologies such as waveguides, photovoltaics, sensors, actuators, and photo-responsive adhesives. This CAREER project addresses the fundamental issue of designing the interface between polymers and 2D plasmonic nanoparticles. The solutions to this issue will lay the foundation for integrating 2D plasmonic nanoparticles into polymeric materials and creating hybrid functional composites with advanced optical, photo-thermal, and plasmonic properties. In particular, fibers and filaments of polymers with hierarchically stacked 2D plasmonic nanoparticles can be used as inks for additive manufacturing of plasmonic functional constructs. The hybrid material can help design photovoltaics with superior power conversion efficiencies, as well as other functional devices in energy and environmental sciences that are of industrial and societal importance.The educational impacts involve the training of underrepresented and first-generation college students in Appalachia. In particular, a mini summer research camp for underrepresented students from neighboring Historically Black Colleges and Universities (HBCUs)will be developed, and the PI will serve as a senior fellow in the university's Residential College to promote STEM and improve the success rate of underrepresented and first-generation college students. In this way, the effort presented here will train underrepresented local youth, especially first-generation college students in isolated Appalachia, to become future polymer scientists and engineers who will build and reshape the regional polymer industries.PART 2: TECHNICAL SUMMARYFibers possess attractive properties that thin films and bulk samples lack, for instance, large surface area, low density, high strength, and peripherally confined self-assembly. The goal of the proposed project is to exploit electrospinning and block copolymer directed self-assembly to create hierarchical structures of block copolymers and 2D plasmonic nanoparticles in fibers, which have fascinating structural and photo-thermal properties. The main scopes are to understand the mechanism of polymer brush formation on 2D plasmonic nanoparticles and design tailored polymer/nanoparticle interfaces for creating hierarchical nanostructures in fibers. The central hypothesis states that, by exploiting the unique plasmonic properties of 2D plasmonic nanoparticles, the polymer brush formation mechanism will be discovered, block copolymer/2D plasmonic nanoparticle interface for hierarchical directed self-assembly in fibers will be prepared, and structural and photothermal properties that are distinctive features of plasmonic polymers will be understood. The proposed goal will be realized via three main tasks: 1) employ 2D plasmonic nanoparticles to unveil the mechanism of polymer brush formation, 2) utilize block copolymers to direct the self-assembly of 2D plasmonic nanoparticles and form hierarchical structures in fibers, 3) understand the domain spacing and photothermal properties of block copolymers upon mixing with 2D plasmonic nanoparticles. The block copolymers are expected to exhibit preferred domain orientation in the fibers, and the 2D nanoparticles to form stacked layers with monolayers of 2D nanoparticles in each block copolymer domain. The hierarchical nanostructures will bestow on polymers novel plasmonic properties and be active candidates for applications in waveguides, photovoltaics, adhesives, and 3D printing inks.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

第 1 部分：非技术摘要含有二维 (2D) 等离子体纳米颗粒的聚合物可能有助于波导、光伏、传感器、执行器和光响应粘合剂等变革性技术。该职业项目解决了设计聚合物和二维等离子体纳米颗粒之间界面的基本问题。该问题的解决方案将为将二维等离子体纳米粒子集成到聚合物材料中以及创建具有先进光学、光热和等离子体特性的混合功能复合材料奠定基础。特别是，具有分层堆叠的二维等离子体纳米粒子的聚合物纤维和长丝可以用作用于等离子体功能结构的增材制造的墨水。这种混合材料可以帮助设计具有卓越功率转换效率的光伏器件，以及具有工业和社会重要性的能源和环境科学中的其他功能器件。教育影响包括对阿巴拉契亚地区代表性不足的第一代大学生的培训。特别是，将为邻近历史上黑人学院和大学（HBCU）的代表性不足的学生开发一个小型夏季研究营，PI将担任大学住宿学院的高级研究员，以推广STEM并提高代表性不足的第一代大学生的成功率。通过这种方式，这里介绍的努力将培训代表性不足的当地年轻人，特别是偏僻的阿巴拉契亚地区的第一代大学生，成为未来的聚合物科学家和工程师，他们将建立和重塑该地区的聚合物产业。 第 2 部分：技术摘要纤维具有薄膜和块状样品所缺乏的有吸引力的特性，例如大表面积、低密度、高强度和外围限制自组装。该项目的目标是利用静电纺丝和嵌段共聚物定向自组装来创建纤维中嵌段共聚物和二维等离子体纳米颗粒的分层结构，这些结构具有令人着迷的结构和光热性能。主要范围是了解二维等离子体纳米颗粒上聚合物刷形成的机制，并设计定制的聚合物/纳米颗粒界面以在纤维中创建分层纳米结构。中心假设指出，通过利用二维等离子体纳米颗粒独特的等离子体特性，将发现聚合物刷形成机制，制备用于纤维中分级定向自组装的嵌段共聚物/二维等离子体纳米颗粒界面，并了解等离子体聚合物的独特特征的结构和光热特性。所提出的目标将通过三个主要任务来实现：1）利用2D等离激元纳米颗粒揭示聚合物刷形成的机制，2）利用嵌段共聚物引导2D等离激元纳米颗粒的自组装并在纤维中形成分层结构，3）了解嵌段共聚物与2D等离激元混合后的域间距和光热性能 纳米颗粒。预计嵌段共聚物在纤维中表现出优选的域取向，并且2D纳米颗粒在每个嵌段共聚物域中形成具有单层2D纳米颗粒的堆叠层。分层纳米结构将赋予聚合物新颖的等离子体特性，并成为波导、光伏、粘合剂和 3D 打印油墨应用的积极候选者。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力优点和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

A Generic Platform for Upcycling Polystyrene to Aryl Ketones and Organosulfur Compounds

• DOI: 10.1002/anie.202307042
• 发表时间: 2023-07-24
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Munyaneza，Nuwayo Eric;Posada，Carlos;Liu，Guoliang
• 通讯作者: Liu，Guoliang

Critical Role of Polystyrene Layer on Plasmonic Silver Nanoplates in Organic Photovoltaics

• DOI: 10.1021/acsaem.8b01860
• 发表时间: 2019-03
• 期刊: ACS Applied Energy Materials
• 影响因子: 6.4
• 作者: Jonathan Metzman;Assad U. Khan;B. Magill;G. Khodaparast;J. Heflin;Guoliang Liu

Chemical upcycling of polyethylene, polypropylene, and mixtures to high-value surfactants

• DOI: 10.1126/science.adh0993
• 发表时间: 2023-08
• 期刊: Science
• 影响因子: 56.9
• 作者: Zhen Xu;N. E. Munyaneza;Qikun Zhang;Mengqi Sun;C. Posada;P. Venturo;Nicholas A. Rorrer;Joel Miscall;B. Sumpter;Guoliang Liu

Janus Plasmonic Silver Nanoplatelets for Interface Stabilization

• DOI: 10.1021/acsanm.8b01141
• 发表时间: 2018-10-01
• 期刊: ACS APPLIED NANO MATERIALS
• 影响因子: 5.9
• 作者: Guo, Yichen;Khan, Assad U.;Liu, Guoliang
• 通讯作者: Liu, Guoliang

Porous carbon fibers from gel-spun polyacrylonitrile and poly(methyl methacrylate)-block-poly(acrylonitrile)

• DOI: 10.1016/j.carbon.2022.02.044
• 发表时间: 2022-02
• 期刊: Carbon
• 影响因子: 10.9
• 作者: Jyotsna Ramachandran;Joel M. Serrano;Tianyu Liu;Jinwon Cho;Pedro J. Arias‐Monje;Mingxuan Lu;Mohammad H