Spectroelectrochemistry of Redox-Active Colloidal Nanocrystals

氧化还原活性胶体纳米晶体的光谱电化学

• 批准号: 1904436
• 负责人: Daniel Gamelin
• 金额: $ 58.98万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-06-15 至 2023-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1904436&HistoricalAwards=false
• 关键词: Spectroelectrochemistry; Redox; Active; Colloidal; Nanocrystals

It is now possible to grow crystals from many different semiconductors that are just a few nanometers in size, or about 100,000 times smaller than a strand of hair. At these very small sizes, semiconductor nanocrystals take on novel physical and chemical properties that can be adjusted by changing their size, shape, and chemical composition, making them attractive for use in many next-generation photonic and energy technologies. Although they hold great promise, these nanocrystals also present unique challenges. For example, as one charges a nanocrystal up by adding electrons, it can change color and new chemical reactions can take place at its surface. With support from the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Daniel Gamelin of the University of Washington is studying how electrons that are transferred into (and out of) semiconductor nanocrystals alter their physical properties and chemical reactivity. Working with his students, Professor Gamelin is developing new experimental methods that enable them to precisely alter the nanocrystal charge while monitoring changes in their physico-chemical properties. Their discoveries could have important implications for new technologies in energy conversion, energy storage, and efficient energy usage. The project is also providing advanced interdisciplinary education and training for students, preparing them to be future leaders in science, engineering, technology innovation, and education. Integration of research and education is emphasized through involvement of undergraduates in the project, incorporation of project concepts into the UW undergraduate laboratory curriculum, and outreach activities at Seattle K-12 schools and community STEM events.Despite extensive studies and progress in controlling the formation of high-quality colloidal reduced or oxidized semiconductor nanocrystals over recent years, the redox properties of colloidal nanocrystals remain poorly understood, particularly in the multiple-carrier regime relevant to charge-tunable plasmonics, high-density charge storage, or multi-electron catalysis. This project targets the development and application of new methods for measuring, controlling, and understanding the properties of redox-active colloidal semiconductor nanocrystals emphasizing spectroelectrochemical probes of nanoscale chemical transformations. The goal is to elucidate the redox reactivities and associated physico-chemical properties of such nanocrystals that possess excess delocalized electrons or holes. Specific nanocrystal research foci include: metal-coupled electron-transfer reactions relevant to charge-tunable plasmonics, soluble supercapacitors relevant to energy storage, and band-edge potentials of nanostructures relevant to photochemistry and electron transfer. All of these are anticipated to play central roles in future nanocrystal technologies. Spectroelectrochemical potentiometry has been identified as a particularly powerful and quantitative probe of the redox properties of free-standing colloidal semiconductor NCs, and it is enabling unique in situ monitoring of nanocrystal redox manipulations and composition transformations.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.

现在，可以从许多不同的半导体中种植晶体，这些半导体的大小仅几纳米，大约比头发小的100,000倍。 在这些很小的尺寸下，半导体纳米晶体采用新颖的物理和化学特性，可以通过改变其大小，形状和化学成分来调整它们，从而使它们在许多下一代光子和能量技术中都有吸引力。 尽管它们具有巨大的希望，但这些纳米晶体也带来了独特的挑战。 例如，由于人们通过添加电子会为纳米晶体充电，因此它可以改变颜色，并且可以在其表面发生新的化学反应。 在化学系的大分子，超分子和纳米化学计划的支持下，华盛顿大学的丹尼尔·加米林教授正在研究如何转移到半导体纳米晶体中的电子改变其物理性质和化学反应。 Gamelin教授与他的学生合作，正在开发新的实验方法，使他们能够精确改变纳米晶体费用，同时监视其物理化学特性的变化。他们的发现可能对新技术在能源转化，能源存储和有效的能源使用方面具有重要意义。 该项目还为学生提供高级跨学科教育和培训，使他们成为科学，工程，技术创新和教育的未来领导者。通过将大学概念纳入项目，将项目概念纳入大学本科实验室课程以及西雅图K-12学校和社区STEM事件的宣传活动来强调研究和教育的整合。尽管如此，促进了高质量胶体胶体胶合物构成的胶合物，在西雅图K-12学校和社区STEM事件中进行宣传活动。纳米晶体仍然了解不足，特别是在与可触发的血浆，高密度电荷储存或多电子催化有关的多载波方案中。该项目针对的是开发和应用新方法，用于测量，控制和理解氧化还原活性胶体半导体纳米晶体的特性，强调纳米级化学转化的光谱电性化学探针。 目的是阐明具有多余的分离电子或孔的氧化还原活性和相关的物理化学特性。特定的纳米晶体研究焦点包括：金属偶联的电子转移反应与可荷型等离子间有关，与储能相关的可溶性超级电容器以及与光化学和电子传递相关的纳米结构的带边势。 预计所有这些都将在未来的纳米晶体技术中扮演核心角色。 Spectroelectrochemical potentiometry has been identified as a particularly powerful and quantitative probe of the redox properties of free-standing colloidal semiconductor NCs, and it is enabling unique in situ monitoring of nanocrystal redox manipulations and composition transformations.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审查标准。

项目成果

Using Redox Titrations to Probe the Role of Trivalent Impurity Ions in the Ferromagnetism of Colloidal EuS Nanocrystals

使用氧化还原滴定法探讨三价杂质离子在胶体 EuS 纳米晶体铁磁性中的作用

• DOI: 10.1021/acs.chemmater.0c03020
• 发表时间: 2020
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: De Siena, Michael C.;Rachkov, Alexander G.;Fainblat, Rachel;James, Derak;Creutz, Sidney E.;Stoll, Sarah L.;Gamelin, Daniel R.
• 通讯作者: Gamelin, Daniel R.

Multivariate Analysis on the Structure–Activity Parameters for Nano-CuOx-Catalyzed Reduction Reactions

• DOI: 10.1021/acsanm.3c04897
• 发表时间: 2024-01
• 期刊: ACS Applied Nano Materials
• 影响因子: 5.9
• 作者: Lorianne R. Shultz-Johnson;Matthew Chang;Neil N. Bisram;J. T. Bryant;Christopher P. Martin;Azina Rahmani-Azina

Tunable Band-Edge Potentials and Charge Storage in Colloidal Tin-Doped Indium Oxide (ITO) Nanocrystals

• DOI: 10.1021/acsnano.1c04660
• 发表时间: 2021-08-13
• 期刊: ACS NANO
• 影响因子: 17.1
• 作者: Araujo, Jose J.;Brozek, Carl K.;Gamelin, Daniel R.
• 通讯作者: Gamelin, Daniel R.

Electron Beam Infrared Nano-Ellipsometry of Individual Indium Tin Oxide Nanocrystals

• DOI: 10.1021/acs.nanolett.0c02772
• 发表时间: 2020-11-11
• 期刊: NANO LETTERS
• 影响因子: 10.8
• 作者: Olafsson, Agust;Busche, Jacob A.;Camden, Jon P.
• 通讯作者: Camden, Jon P.

Imaging Infrared Plasmon Hybridization in Doped Semiconductor Nanocrystal Dimers

掺杂半导体纳米晶体二聚体中的红外等离激元杂交成像

• DOI: 10.1021/acs.jpclett.1c02741
• 发表时间: 2021
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Olafsson, Agust;Khorasani, Siamak;Busche, Jacob A.;Araujo, Jose J.;Idrobo, Juan Carlos;Gamelin, Daniel R.;Masiello, David J.;Camden, Jon P.
• 通讯作者: Camden, Jon P.