CAS: Dual-Mode Operando Nanothermometry and Reaction Monitoring for Probing Photochemical and Photothermal Transformations

CAS：用于探测光化学和光热转化的双模式操作纳米测温和反应监测

• 批准号: 2304570
• 负责人: Andrea Pickel
• 金额: $ 36万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-09-01 至 2026-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2304570&HistoricalAwards=false
• 关键词: CAS; Dual; Mode; Operando; Nanothermometry

With support from the Chemical Measurement and Imaging (CMI) Program in the Division of Chemistry, Andrea Pickel of the University of Rochester is developing a combined nanoscale thermometry and chemical reaction monitoring technique to study thermal contributions to plasmon-enhanced photocatalysis. In plasmon-driven photocatalysis, the collective oscillation of free electrons drives chemical reactions on the surfaces of metal nanostructures, but the relative contributions of non-thermal plasmonic effects versus surface heating to the observed enhancement are debated. The Pickel group will develop a spectroscopic technique that employs the temperature-dependent luminescence of individual upconverting nanoparticles for thermometry while simultaneously monitoring the chemical reaction via enhanced Raman scattering from the reacting molecules. Their discoveries could lead to a better understanding of whether heating plays an important role in catalyzing plasmon-enhanced reactions. Dr. Pickel will also develop an undergraduate lab course based on luminescence thermometry and an educational activity focused on plasmonic sensing for local elementary school students. Current approaches for isolating thermal contributions to plasmonic photocatalysis measure temperature via the same surface-enhanced Raman scattering spectra used to monitor the chemical reactions. These spectra, however, depend on local chemical and electromagnetic effects that can vary through a measurement, which makes elucidation of plasmonic heating difficult to separate. To provide high-fidelity operando thermometry during plasmonic photocatalysis, a single laser will be used to both excite upconverting nanoparticle (UCNP) thermometers and photocatalyze a chemical reaction. The thermometry and reaction monitoring signals naturally separate in the spectral domain due to the large anti-Stokes shift of the UCNP luminescence. Several objectives will be investigated including understanding how different the plasmonic environment affects the temperature-dependent UCNP luminescence, fabricating substrates with different thermal properties yet near-identical plasmonic properties, and using nanomanipulation to place UCNP thermometers with spectrally distinct emission at strategic locations on plasmonic nanostructures. These studies have the potential to elucidate the importance of thermal contributions to plasmonic photocatalysis as well as have broad applications in chemistry for systems in which the intrinsic spectral separation of the UCNP emission and Raman spectra originating from analytes or biomolecules is likewise advantageous.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.

在化学划分中的化学测量和成像（CMI）计划的支持下，罗切斯特大学的安德里亚·皮克尔（Andrea Pickel）正在开发一种纳米级的热度法和化学反应监测技术，以研究对普拉斯蒙增强光催化的热贡献。在等离子驱动的光催化中，游离电子的集体振荡使金属纳米结构表面上的化学反应驱动化学反应，但是在观察到的增强方面，非热等离子体效应与表面加热与表面加热的相对贡献是辩论的。 Pickel组将开发一种光谱技术，该技术采用单个上向转换纳米颗粒的温度依赖性发光进行温度计，同时通过从反应分子中增强的拉曼散射来同时监测化学反应。他们的发现可能会更好地理解加热是否在催化等离子体增强反应中起重要作用。 Pickel博士还将根据发光温度计开发一门本科实验室课程，以及针对当地小学生等离子体感测的教育活动。电流通过用于监测化学反应的相同表面增强的拉曼散射光谱来分离血浆光催化的热贡献的方法。然而，这些光谱取决于局部化学和电磁效应，这些效应可能会因测量而变化，这使得难以分离的等离子加热。为了在等离子光催化期间提供高保真的操作热度法，将使用单个激光激发向上转化的纳米颗粒（UCNP）温度计和光启动化学反应。由于UCNP发光的较大反stokes偏移，温度和反应监测信号自然在光谱域中分离。将研究几个目标，包括了解不同的等离子环境如何影响依赖温度的UCNP发光，制造具有不同的热性能但几乎相同的等离子性能的底物，并使用纳米掌管将UCNP温度计放置在等离子纳米结构的策略性位置的频谱发射的UCNP温度计。这些研究有可能阐明热贡献对等离子光催化的重要性，并在化学中广泛应用化学对UCNP发射的固有光谱分离和源自分析或生物分类的拉曼光谱的固有光谱分离的重要性。影响审查标准。