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Ratiometric Luminescent Thermometer Based on the Lanthanide Metal–Organic Frameworks by Thermal Curing
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-03-30 , DOI: 10.1021/acsami.3c01897 Huiru Guan 1 , Mixiang Qi 1, 2, 3 , Lifeng Shi 1 , Weisheng Liu 1 , Lizi Yang 1 , Wei Dou 1
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2023-03-30 , DOI: 10.1021/acsami.3c01897 Huiru Guan 1 , Mixiang Qi 1, 2, 3 , Lifeng Shi 1 , Weisheng Liu 1 , Lizi Yang 1 , Wei Dou 1
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The high-performance optical thermometer probes are of great significance in diverse areas; lanthanide metal–organic frameworks (Ln-MOFs) are a promising candidate for luminescence temperature sensing owing to their unique luminescence properties. However, Ln-MOFs have poor maneuverability and stability in complex environments due to the crystallization properties, which then hinder their application scope. In this work, the Tb-MOFs@TGIC composite was successfully prepared using simple covalent crosslinking through uncoordinated −NH2 or COOH on Tb-MOFs reacting with the epoxy groups on TGIC {Tb-MOFs = [Tb2(atpt)3(phen)2(H2O)]n; H2atpt = 2-aminoterephthalic acid; phen = 1,10-phenanthroline monohydrate}. After curing, the fluorescence properties, quantum yield, lifetime, and thermal stability of Tb-MOFs@TGIC were remarkably enhanced. Meanwhile, the obtained Tb-MOFs@TGIC composites exhibit excellent temperature sensing properties in the low-temperature (Sr = 6.17% K–1 at 237 K), physiological temperature (Sr = 4.86% K–1 at 323 K), or high-temperature range (Sr = 3.88% K–1 at 393 K) with high sensitivity. In the temperature sensing process, the sensing mode of single emission changed into double emission for ratiometric thermometry owing to the back energy transfer (BenT) from Tb-MOFs to TGIC linkers, and the BenT process enhanced with the increase of temperature, which further improved the accuracy and sensitivity of temperature sensing. Most notably, the temperature-sensing Tb-MOFs@TGIC can be easily coated on the surface of polyimide (PI), glass plate, silicon pellet (SI), and poly(tetrafluoroethylene) plate (PTFE) substrates by a simple spraying method, which also exhibited an excellent sensing property, making it applicable for a wider T range measurement. This is the first example of a postsynthetic Ln-MOF hybrid thermometer operative over a wide temperature range including the physiological and high temperature based on back energy transfer.
中文翻译：
基于热固化镧系金属有机骨架的比例发光温度计
高性能光学测温探头在不同领域具有重要意义；镧系金属有机框架（Ln-MOFs）由于其独特的发光特性而成为发光温度传感的有前途的候选者。然而，由于Ln-MOFs的结晶特性，其在复杂环境中的机动性和稳定性较差，从而阻碍了其应用范围。在这项工作中，Tb-MOFs@TGIC 复合材料是通过 Tb-MOFs 上未配位的 -NH 2或 COOH 与 TGIC 上的环氧基反应的简单共价交联成功制备的{Tb-MOFs = [Tb 2 (atpt) 3 (phen ) 2 (H 2 O)] n ; 氢2atpt = 2-氨基对苯二甲酸；phen = 1,10-菲咯啉一水合物}。固化后，Tb-MOFs@TGIC 的荧光性能、量子产率、寿命和热稳定性显着增强。同时，获得的Tb-MOFs@TGIC复合材料在低温（S r = 6.17% K –1 at 237 K）、生理温度（S r = 4.86% K –1 at 323 K）、或高温范围 ( S r = 3.88% K –1在 393 K) 具有高灵敏度。在温度传感过程中，由于Tb-MOFs向TGIC连接体的反向能量转移（BenT），比例测温的单发射传感模式转变为双发射，并且BenT过程随着温度的升高而增强，进一步提高了温度传感的准确性和灵敏度。最值得注意的是，温度敏感的 Tb-MOFs@TGIC 可以很容易地通过简单的喷涂方法涂覆在聚酰亚胺（PI）、玻璃板、硅颗粒（SI）和聚（四氟乙烯）板（PTFE）基板的表面上，这也表现出优异的传感性能，使其适用于更广泛的T范围测量。这是后合成 Ln-MOF 混合温度计的第一个例子，可在很宽的温度范围内运行，包括基于反向能量转移的生理和高温。
更新日期：2023-03-30
中文翻译：
基于热固化镧系金属有机骨架的比例发光温度计
高性能光学测温探头在不同领域具有重要意义；镧系金属有机框架（Ln-MOFs）由于其独特的发光特性而成为发光温度传感的有前途的候选者。然而，由于Ln-MOFs的结晶特性，其在复杂环境中的机动性和稳定性较差，从而阻碍了其应用范围。在这项工作中，Tb-MOFs@TGIC 复合材料是通过 Tb-MOFs 上未配位的 -NH 2或 COOH 与 TGIC 上的环氧基反应的简单共价交联成功制备的{Tb-MOFs = [Tb 2 (atpt) 3 (phen ) 2 (H 2 O)] n ; 氢2atpt = 2-氨基对苯二甲酸；phen = 1,10-菲咯啉一水合物}。固化后，Tb-MOFs@TGIC 的荧光性能、量子产率、寿命和热稳定性显着增强。同时，获得的Tb-MOFs@TGIC复合材料在低温（S r = 6.17% K –1 at 237 K）、生理温度（S r = 4.86% K –1 at 323 K）、或高温范围 ( S r = 3.88% K –1在 393 K) 具有高灵敏度。在温度传感过程中，由于Tb-MOFs向TGIC连接体的反向能量转移（BenT），比例测温的单发射传感模式转变为双发射，并且BenT过程随着温度的升高而增强，进一步提高了温度传感的准确性和灵敏度。最值得注意的是，温度敏感的 Tb-MOFs@TGIC 可以很容易地通过简单的喷涂方法涂覆在聚酰亚胺（PI）、玻璃板、硅颗粒（SI）和聚（四氟乙烯）板（PTFE）基板的表面上，这也表现出优异的传感性能，使其适用于更广泛的T范围测量。这是后合成 Ln-MOF 混合温度计的第一个例子，可在很宽的温度范围内运行，包括基于反向能量转移的生理和高温。
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