Dual-Mode Operando Raman Spectroscopy and Upconversion Thermometry for Probing Thermal Contributions to Plasmonic Photocatalysis,Advanced Optical Materials

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Dual-Mode Operando Raman Spectroscopy and Upconversion Thermometry for Probing Thermal Contributions to Plasmonic Photocatalysis
Advanced Optical Materials ( IF 8.0 ) Pub Date : 2023-06-15 , DOI: 10.1002/adom.202300824
Ziyang Ye ₁ , Dinesh Kumar Bommidi ₂ , Andrea Danielle Pickel _{1,

2}

Affiliation

Operando thermometry can help resolve open questions about the importance of thermal contributions to plasmonic photocatalysis, but identifying high-fidelity thermometers with the requisite chemical inertness, thermal stability, and spatial resolution remains challenging. Here, it is demonstrated that a single near-infrared laser can simultaneously excite upconverting nanoparticles (UCNPs) that serve as luminescent thermometers and photocatalyze the dimerization of 4-nitrothiophenol (4-NTP), which is employed as a model reaction. Due to its large anti-Stokes shift, the UCNP thermometry signal naturally separates from the 4-NTP Raman signal, which is used to monitor the chemical reaction, in the spectral domain. The surface temperature rise of plasmonic substrates under varying illumination intensity is systematically correlated with the reaction progress. Temperature rises exceeding 40 K are recorded at the maximum intensity used, yet lower intensities combined with external heating to achieve the same temperature rise are shown to catalyze the reaction less effectively. Furthermore, measurements performed using equivalent external heating and an intensity too low to photocatalyze the reaction display no evidence of the reaction occurring. By providing high-fidelity operando surface temperature measurements, this method offers a valuable tool for elucidating thermal contributions to plasmonic photocatalysis.

中文翻译：

双模式操作拉曼光谱和上转换测温法探测等离激元光催化的热贡献

操作测温可以帮助解决有关热对等离子体光催化的重要性的悬而未决的问题，但识别具有必要的化学惰性、热稳定性和空间分辨率的高保真温度计仍然具有挑战性。在这里，证明单个近红外激光可以同时激发用作发光温度计的上转换纳米颗粒（UCNP）并光催化 4-硝基苯硫酚（4-NTP）的二聚，该二聚被用作模型反应。由于其较大的反斯托克斯位移，UCNP 测温信号自然与用于监测化学反应的 4-NTP 拉曼信号在光谱域中分离。不同光照强度下等离激元基板的表面温度升高与反应进程系统相关。在使用的最大强度下记录了超过 40 K 的温升，但较低的强度与外部加热相结合以实现相同的温升则表明催化反应的效率较低。此外，使用等效的外部加热和太低的强度进行的测量显示没有发生反应的证据。通过提供高保真操作表面温度测量，该方法为阐明等离激元光催化的热贡献提供了有价值的工具。

更新日期：2023-06-15

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