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Dual-Emitting UiO-66(Zr&Eu) Metal-Organic Framework Films for Ratiometric Temperature Sensing Ji-fei Feng, Tian-Fu Liu, Jianlin Shi, Shui-Ying Gao, and Rong Cao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04889 • Publication Date (Web): 30 May 2018 Downloaded from http://pubs.acs.org on May 30, 2018

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ACS Applied Materials & Interfaces

Dual-Emitting

UiO-66(Zr&Eu)

Metal-Organic

Framework Films for Ratiometric Temperature Sensing Ji-fei Feng†,‡,§,∥, Tian-fu Liu‡, Jianlin Shi†,§,∥, Shui-ying Gao‡ and Rong Cao†,‡,∥*

†. School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China. ‡. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Mater, Chinese Academy of Sciences, Fuzhou 350002, China. §. State Key Laboratory of high Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China. ‖. University of Chinese Academy of Sciences, Beijing 100049, China.

KEYWORDS Metal-Organic Frameworks, Polymer Film, Mixed-Matrix, Dual-emitting, Ratiometric Temperature Sensing

ACS Paragon Plus Environment

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ABSTRACT

A novel dual-emitting Metal-Organic Framework (MOF) based on Zr and Eu, named as UiO66(Zr&Eu), was built using a clever secondary building units (SBU) based strategy. With the assistance of polymers, the obtained UiO-66(Zr&Eu) was subsequently deposited as thin films that can be utilized as smart thermometer. The UiO-66(Zr&Eu) polymer films can be used for the detection of the temperature change in the temperature range of 237-337 K due to the energy transfer both lanthanide ions (Eu in clusters) and luminescent ligands, and the supreme relative sensitivity reaches to 4.26% K-1 at 337 K. Moreover, the sensitivity can be improved to 19.67% K-1 by turning the film thickness. In addition, the temperature sensing performance of the films is superior to that of the powders and the sensor can be reused for 3 times without the loss of the performance.

INTRODUCTION Metal-Organic Frameworks (MOFs) are an exciting class of porous materials which constructs of an infinite network of metal ions or clusters bridged by organic ligands.1-9 Based on their excellent stability, adjustable metrics, organic functionality, and porosity, MOFs exhibit promising potential in a variety of applications such as gas separation, sensing and catalysis.10-20 Luminescent MOFs are a typical type of MOFs and have broad application prospects in biomedical imaging, small molecule detection, chemical sensing and temperature sensing.21-25 Temperature plays an important role in both science and industry.26-29 Since 2012, a series of mixed lanthanide MOF (Ln-MOF) materials as the solid temperature thermometers have been


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reported.30-40 Compared with intensity-based thermometers, lanthanide-based MOFs composed of multi-lanthanide ions exhibit unique advantage of self-calibration based on their dual-emitting mechanism and such ratiometric thermometers are more accurate without the interference from the excitation power or intensity. However, the previous reports of the dual-emitting centers in Ln-MOFs mainly focus on Terbium (λem=544 nm) and Europium (λem=616 nm) ions. In addition, the fixed level gap (approximately 3300 cm-1) between Tb and Eu or narrow emission range limit the performance of the thermometers, further affecting the practical applications of these materials. To overcome these limitations, Qian and co-workers reported the use of luminescent perylene molecule in ZJU-88 MOF materials to extend the emission range.33 We reported the use of luminescent ligand 1,4-Naphthalenedicarboxylic acid (H2NDC) and lanthanide ions in UiO-66-(COOH)2 MOFs by post-synthetic exchange and post-synthetic modification.38 However, three steps were required for the preparation of the material. Hence, it is challenging to synthesize dual-emitting MOF materials with the wide emission range in situ. Herein, a novel strategy is reported for one-step synthesis of a MOF material containing two luminescent centers, lanthanide ions and a luminescent ligand. Generally, the strong emission from lanthanide ions in this class of MOFs may shield the emission of the ligand. To address the problem, a transition metal Zr-based MOF with a luminescent ligand, UiO-66, is employed. In addition, Europium ions luminescent centers are introduced by replacing Zr ions in the secondary building units (SBU) in situ. Because of their nature crystalline property, MOFs are not malleable such as soft materials, limiting their further processing and applications.41 MOF films or membranes are promising alternative to circumvent the shortcoming. In recent years, a series of interesting approaches have been reported for fabricating MOF films on the substrates, such as seeding growth, layer-


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by-layer, electrochemical deposition.42-50 Unfortunately, these methods have some limitations: the substrates must be stable during the fabrication process, the MOFs must be prepared under mild condition, and the as-prepared films are robust and brittle. MOF-based mixed-matrix membranes (MMMs) may overcome these limitations.50-72 In addition, most researches on MMMs are focused on their applications such as gas and liquid separation, but MMMs is also valuable as a material for detecting temperature change. Scheme 1. Preparation of UiO-66(Zr&Eu) films.

Therefore, dual-emitting UiO-66(Zr&Eu) MOFs were synthesized through the in situ replacement of Zr ions in clusters by lanthanide ions (Eu). Subsequently, UiO-66(Zr&Eu) MOF films were further prepared using PVDF (polyvinylidene fluoride) as a binder (Scheme 1). The prepared films were successfully used for the detection of the temperature change in the range of 237-337 K. The resulting as-prepared UiO-66(Zr&Eu) films had an excellent temperature sensing characteristic. Among the films, the UiO-66(Zr&Eu)-1 film exhibits the best sensing performance with a highest sensitivity of 4.26% K-1 at 337 K, much better than that of the powders. EXPERIMENTAL SECTION CHEMICALS


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All chemicals, Zirconium (IV) chloride (ZrCl4, 99.95%) (Strem Chemical Industry), 2Fluorobenzoic acid (2-FBA, 98%) and 1,4-Naphthalenedicarboxylic acid (H2NDC, 98%) (Tansoole Industry (China)), Poly(vinylidene fluoride) (PVDF, Mw=534000) (Aldrich Chemistry), Europium nitrate hexahydrate (Eu(NO3)3·6H2O, 99.95%) (Energy Chemistry Industry), acetone, Ethanol and N,N-dimethylformamide (DMF) (Sinopharm Chemical Reagent Co. Ltd. (China)), are commercially purchased and used directly without further treatment. CHARACTERIZATION Powder X-ray diffraction (PXRD) was measured by a Miniflex 600 from 5º to 50º diffraction degree range with a scan speed of 1º/min. The Photolumines-cence (PL) spectra were recorded using an FLS 980. Scanning electron microscopy (SEM) images were recorded on the Phenom G2. Transmission electron microscopy (TEM) images were recorded using a Field Emission Transmission Electron Microscope, Tecnai G20 (JEOL, Tokyo, Japan) with an acceleration voltage of 200 kV. The N2 adsorption tests were conducted on the Micromeritics ASAP 2020 instrument at 77 K. Thermogravimetric analysis (TGA) was conducted with an SDT 600 instrument.

PREPARATION OF SAMPLES Preparation of UiO-66(Zr): Under ultrasonic condition, ZrCl4 (180 mg), H2NDC (94 mg) and 2-FBA (487 mg) was dissolved in a solution of H2O (5 mL), DMF (22 mL) and HNO3 (0.6 mL). The solution was then added to a 50 mL glass bottle and heated at 115 ℃ for 3000 minutes. Then, the solution was cooled to the room temperature and the resulted white powders were collected


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via centrifugation, cleaned 3 times using acetone and DMF and dried in vacuum at 70 oC overnight. Preparation of UiO-66(Eu): The UiO-66(Eu) material was prepared by the reported literature.54 In a typical process, a mixture of Eu(NO3)3·6H2O (180 mg), H2NDC (94 mg) and 2-FBA (487 mg) was dissolved in a solution of H2O (5 mL), DMF (22 mL) and HNO3 (0.6 mL) under ultrasonic condition. The solution was added to a 50 mL glass bottle and heated at 115 ℃ for 3600 minutes. Then, the solution was cooled to the room temperature and the resulted white powders were collected via centrifugation, cleaned 3 times using DMF and acetone and dried in vacuum at 70 oC overnight. Preparation of UiO-66(Zr&Eu)-Physical: UiO-66(Zr) (100 mg) and Eu(NO3)3·6H2O (100 mg) was dispersed in DMF (22 mL) under ultrasonic condition. The mixed solution was stirred at 2000 r/min for 3000 minutes at the room temperature. Then, the mixture was cooled to the room temperature and the resulted white powders were collected via centrifugation, cleaned 3 times using DMF and acetone and dried in vacuum at 70 oC overnight. Preparation of UiO-66(Zr&Eu)-1: ZrCl4 (140 mg), Eu(NO3)3·6H2O (50 mg), H2NDC (94 mg) and 2-FBA (487 mg) were dissolved in a solution of H2O (5 mL), DMF (22 mL) and HNO3 (0.6 mL) under ultrasonic condition. The solution was then added to a 50 mL glass bottle and heated at 115 ℃ for 3000 minutes. Then, the solution was cooled to room temperature, the resulted white powders were collected via centrifugation, cleaned 3 times using acetone and DMF and dried in vacuum at 70 oC overnight. Preparation of UiO-66(Zr&Eu)-2: ZrCl4 (90 mg), Eu(NO3)3·6H2O (90 mg), H2NDC (94 mg) and 2-FBA (487 mg) were dissolved in a solution of H2O (5 mL), DMF (22 mL) and HNO3 (0.6


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mL) under ultrasonic condition. The solution were transferred to a 50 mL glass vial and heated at 115 ℃ for 3000 minutes. Then, the solution was cooled to room temperature, the resulted white powders were collected via centrifugation, cleaned 3 times using acetone and DMF and dried in vacuum at 70 oC overnight. Preparation of UiO-66(Zr&Eu)-3: ZrCl4 (30 mg), Eu(NO3)3·6H2O (180 mg), H2NDC (94 mg) and 2-FBA (487 mg) were dissolved in a solution of H2O (5 mL), DMF (22 mL) and HNO3 (0.6 mL) under ultrasonic condition. The solution was then added to a 50 mL glass bottle and heated at 115 ℃ for 3000 minutes. Then, the solution was cooled to room temperature, the yielded white powders were collected via centrifugation, cleaned 3 times using acetone and DMF and dried in vacuum at 70 oC overnight. Preparation of UiO-66(Zr&Eu)-1 Film: Firstly, the UiO-66(Zr&Eu)-1 powders (50 mg) were dispersed in 5 mL of acetone under ultrasonic condition (solution A). Subsequently, PVDF (120 mg) was dissolved in DMF (1 mL) under ultrasonic condition (solution B). Solution A was then transferred to solution B and stirred at 2000 r/min for 30 minutes. The mixture was evaporated at 40℃ for 5 minutes. The remaining solution was tiled onto a 20×30 mm2 glass substrate, and the substrate was put in an 80 ℃ oven for 50 minutes. Then, the resulted film was removed from the substrate. The UiO-66(Zr&Eu)-1-1, UiO-66(Zr&Eu)-1-2 and UiO-66(Zr&Eu)-1-3 films were prepared similarly except that the mixture solution was tiled on 20×60, 20×40 and 10×10 mm2 glass substrates. Preparation of UiO-66(Zr&Eu)-2 Film: Firstly, the UiO-66(Zr&Eu)-2 powders (50 mg) were dispersed in 5 mL of acetone under ultrasonic condition (solution A). Subsequently, PVDF (120 mg) was dissolved in DMF (1 mL) under ultrasonic condition (solution B). Solution A was then


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transferred to solution B and stirred at 2000 r/min for 30 minutes. The solution mixture was evaporated at 40 ℃ for 5 minutes. The remaining solution was tiled onto a 20×30 mm2 glass substrate, and the substrate was put in an 80 ℃ oven for 50 minutes. Then, the resulted film was removed from the substrate. Preparation of UiO-66(Zr&Eu)-3 Film: Firstly, the UiO-66(Zr&Eu)-3 powders (50 mg) were dispersed in 5 mL of acetone under ultrasonic condition (solution A). Subsequently, PVDF (120 mg) was dissolved in DMF solution (1 mL) under ultrasonic condition (solution B). Solution A was then transferred to solution B and stirred at 2000 r/min for 30 minutes. The solution mixture was evaporated at 40 ℃ for 5 minutes. The remaining solution was tiled onto the 20×30 mm2 glass substrate, and the substrate was put in an 80 ℃ oven for 50 minutes. Then, the resulted film was removed from the substrate. RESULTS AND DISCUSSION


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Figure 1. (A) TEM and element mapping images of UiO-66(Zr&Eu)-1 (scale bar: 100 nm) (B) Emission spectra of UiO-66(Zr), UiO-66(Zr&Eu)-1, UiO-66(Zr&Eu)-2, UiO-66(Zr&Eu)-3, and UiO-66(Eu) films upon excitation at 360 nm. The inset is the CIE image of the films. As shown in Scheme 1, the UiO-66(Zr or Eu) and UiO-66(Zr&Eu) MOFs were synthesized with a modulator, 2-Fluorobenzoic acid (2-FBA), by in situ solvothermal method. The prepared UiO66(Zr&Eu) materials have the same diffraction peaks with the Zr-based UiO-66 which suggests


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the UiO-66(Zr&Eu) MOF is isostructural with the UiO-66, and the addition of Europium does not affect the structure of the MOFs (Figure S1). In addition, UiO-66(Zr) MOFs are mesoporous materials which have a pore size distribution of 9-220 angstroms (Figure S2). Moreover, the mole ratio of Zirconium and Europium can be turned by changing the addition of the metal salts during the preparation process. Herein, three MOF materials with different ratios, named UiO66(Zr&Eu)-1 (8.25), UiO-66(Zr&Eu)-2 (4.3) and UiO-66(Zr&Eu)-3 (1.9) based on the inductively coupled plasma spectroscopy results were prepared. According to the TEM images, the particle size of the as-synthesized MOFs is uniform and ~20 nm (Figure 1a and Figures S3-4). From the element mapping images, the distributions of the Eu ions in the MOFs are consistent with the Zr ions in the clusters which indicate that the Eu ions are uniformly dispersed in the MOFs without aggregation. UiO-66(Zr) exhibits blue fluorescence when excited with UV light at 365 nm. However, UiO66(Eu) exhibits red fluorescence. From the naked-eye results, UiO-66(Zr) and UiO-66(Eu) have only one emitting center. However, the as-synthesized MOFs exhibit a blue to red fluorescence shift with the addition of Europium ions under the excitation of 365 nm UV light. These results exhibit that the optical natures of the as-synthesized MOFs agree well with other reported Lanthanide-based MOFs (inset, Figure 1B). Mixed-matrix UiO-66(Zr&Eu) films were fabricated using the PVDF polymer as a binder, as shown in Scheme 1. The as-prepared UiO-66(Zr&Eu)-1 film can be folded over 90 degree without breaking, indicating that the robustness of the films can be improved by the addition of the PVDF polymer (Figure S5). Figure 1B illustrates that the emission intensity of the films can be turned via turning Zr to Eu ratio. The UiO-66(Zr) film has a maximum typical peak at 420 nm upon excitation at 360 nm. The UiO-66(Eu) film has a maximum peak at 617 nm. As expected,


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UiO-66(Zr&Eu)-1 film exhibits two typical emission peaks from the ligand (420 nm) and the Europium (617 nm). In addition, the relative intensity of the Eu (617 nm) and the ligand (420 nm) is comparable at 298 K. Compared with that of the UiO-66(Zr&Eu)-1 film, the emission peaks of the UiO-66(Zr&Eu)-2 film based on Eu (617 nm) is more intense and sharper, however, the peak from ligand is weaker. In addition, the intensity ratio increases 2.79. By further increasing the amount of Eu ions, the intensity ratio of UiO-66(Zr&Eu)-3 film can reach 7.25 at 298 K. Moreover, from the emission spectrum, the UiO-66(Zr&Eu)-Physical MOFs has only one emission peaks at 420 nm, without the emission peaks at 617 nm, indicating that the Eu ion in the MOFs was not adsorbed by physical function (Figure S6).

Figure 2 SEM (Scale bar: 100 µm) and cross-sectional images (Scale bar: 300 µm) of UiO66(Zr&Eu)-1-1(A and E), UiO-66(Zr&Eu)-1-2 (B and F), UiO-66(Zr&Eu)-1(C and G) and UiO66(Zr&Eu)-1-3 (D and H) films. Figure 2 shows that the morphology and thickness of the films can be turned by changing the size of substrates. With decreasing the substrate sizes, the films become more dense and thick,


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and the thickness of UiO-66(Zr&Eu)-1-1, UiO-66(Zr&Eu)-1-2, UiO-66(Zr&Eu)-1 and UiO66(Zr&Eu)-3 films is 30, 60, 90 and 270 µm, respectively. To evaluate the potential of the films for temperature sensing, the emission spectra of the UiO66(Zr&Eu)-1 film at different temperature were obtained in the range from 237 K to 337 K, (Figure 3A). When the temperature increased from 237 K to 337 K, the emission of the UiO66(Zr&Eu)-1 film was shifted from pink emission to blue emission (inset, Figure 3A). In addition, to prove the thermo-stability of the MOF materials, TGA and temperature-dependent PXRD experiments were carried out. From the TGA spectrum, shown in Figure S7, the prepared MOF materials are not destroyed till 673 K which indicated that our materials were stable before 673 K. Figure S8 exhibits that the UiO-66(Zr&Eu)-1 MOFs have similar typical diffraction peaks in the temperature range from 30 oC to 150 oC which proved that the structure of the materials is robust within 150 oC. Figure 2B shows that the emission intensity of the ligand (420 nm) and the Eu (617 nm) of the UiO-66(Zr&Eu)-1 film decreased with increasing the temperature because of non-radiative decay pathways. With the temperature enhancing from 237 K to 337 K, the intensity based on ligand decreases to 40% of original intensity at 237 K, and the intensity based on Eu ions decreases to 6% of original intensity at 237 K.


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Figure 3. (A) Variable temperature photoluminescence spectra of UiO-66(Zr&Eu)-1 film conducted in the temperature range of 237-337 K upon excitation at 360 nm. The inset illustrates the corresponding CIE picture of the film at different temperature. (B) Changes in intensity at 420 nm and 617 nm with changes in temperature (C) The red fitting line (R2=0.99945) represents the function relationship between the intensity ratio and the temperature in 237-337 K and the blue line represents the relative sensitivity at different temperature.


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Figure 3C exhibits the intensity ratio of Europium (617 nm) to ligand (420 nm) versus temperature. A perfect linear relationship can be found between the intensity ratio (Y) of Eu ions (617 nm) to ligand (420 nm) and the temperature (T) in the range from 237 to 337 K, and it may be fitted by the equation of: Y=7.21-0.020T

(1)

with a correlation coefficient of 0.99945. Although the emission intensity of the UiO66(Zr&Eu)-1 powder at 617 nm and 420 nm decreased gradually when temperature increased from 237 K to 337 K, the change of the emission intensity ratio (Y) and the temperature (T) was smaller than that of the film. In addition, there is a poor linear relationship between the intensity ratio and temperature, and the correlation coefficient is only 0.934. The results suggested that the temperature sensing performance of the films was superior to that of the powders (Figure S9). The sensing performance of the thermometer is also evaluated via the relative sensitivity(S), and it can be defined as a function of：

(2)

=

Figure S10 shows the relative sensitivity of the MOF based materials reported this far. The relative sensitivity of 4.26% K-1 for UiO-66(Zr&Eu)-1 film is much higher than those of the two typical

ratiometric

thermometers,

0.31%

K-1

for

mixed-lanthanide

based

MOF,

Tb0.99Eu0.01(BDC)1.5(H2O)228 , and 1.28% K-1 for ZJU-88⊃perylene32 (Figure 3C and Figure S10). In addition, the optimal relative sensitivity of 2.86% K-1 for the UiO-66(Zr&Eu)-1 powder is smaller than that of the UiO-66(Zr&Eu)-1 film. The result also suggests that the temperature sensing performance of the films is superior to that of the powders (Figure S9).


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A possible explanation is that the energy gap between Eu ions (617 nm) and the H2NDC ligand in UiO-66(Zr&Eu) is 6609 cm-1 which is greater than that between Eu3+ and Tb3+ ions， (approximately 3300 cm-1) (Figure S11).

Figure 4. (A) Temperature-dependent photoluminescence spectra of the UiO-66(Zr&Eu)-2 film conducted in the temperature range of 237-337 K upon excitation at 360 nm. (B) The inset exhibits the corresponding CIE picture of the UiO-66(Zr&Eu)-2 film at different temperature. (C) The red fitting line (R2=0.985) represents the function relationship both the intensity ratio and the temperature in the range from 237 K to 337 K and the blue line represents the relative sensitivity vs temperature. (D) Photoluminescence spectra of the UiO-66(Zr&Eu)-3 film


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conducted in the temperature range from 237 K to 337 K upon excitation of 360 nm. (E) The inset shows the corresponding CIE picture of the UiO-66(Zr&Eu)-3 film at different temperature. (F) The red fitting line (R2=0.97) represents the function relationship both the intensity ratio and the temperature in the range from 237 K to 337 K and the blue line represents the relative sensitivity at different temperature. Similarly, the UiO-66(Zr&Eu)-2 and UiO-66(Zr&Eu)-3 films showed satisfied temperature sensing characteristic (Figures 4A and D). In addition, when changing temperature from 237 K to 337 K, the films exhibited a shift from pink emission to blue emission which suggested that the temperature variation could be distinguished via naked eye (Figures 4B and E). As shown in Figure 4C, a good linear relationship can be found between the ratio and the temperature for UiO-66(Zr&Eu)-2 film, and it can be described as a function: Y=11.79-0.0324T

(3)

with a correlation coefficient of 0.985. As shown in Figure 4F, for the UiO-66(Zr&Eu)-3 film, the linear relationship can be observed between the ratio and the temperature, and which can be also described by a function: Y=26.70-0.074T

(4)

with a correlation coefficient of 0.97. Comparing with the UiO-66(Zr&Eu)-1 film, the UiO-66(Zr&Eu)-2 film has a smaller sensitivity of 3.8% K-1. Although the sensitivity of the UiO-66(Zr&Eu)-3 film (approximately 4.67% K-1) was higher than that of the UiO-66(Zr&Eu)-1 film, the UiO-66(Zr&Eu)-1 film exhibited a higher


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correlation coefficient of 0.99945. Therefore, among the three films, the UiO-66(Zr&Eu)-1 film exhibits the optimal temperature sensing performance. To explore the effect of the thickness of film on the performance of the film temperature sensor, the emission spectra of UiO-66(Zr&Eu)-1-1, UiO-66(Zr&Eu)-1-2 and UiO-66(Zr&Eu)-1-3 films were obtained at different temperature in the range from 237 K to 337 K (Figures S11-13). As shown in Figures S12-14, the highest relative sensitivity of UiO-66(Zr&Eu)-1-1, UiO66(Zr&Eu)-1-2, UiO-66(Zr&Eu)-1-3 films are 19.67% K-1, 7.45% K-1 and 2.98% K-1, respectively. Moreover, the optimal sensitivity of UiO-66(Zr&Eu)-1 film is 4.26% K-1. Hence, the thickness of films can affect the performance of temperature sensing, the thinner the film, the higher the relative sensitivity. To demonstrate the energy transfer between the dual emitting centers in the composites, the delay spectra were studied. From the spectra (Figure S15), the lifetime of UiO-66(Zr&Eu) 1-3 of ligand (H2NDC) at 298 K is 2.75 ns, 1.94 ns, and 1.94 ns, respectively. However, the lifetime of Europium (617 nm) at 298 K is 111 µs, 184 µs, and 325 µs. With increasing the Europium content, the lifetime of Europium at 617 nm is enhanced, and the lifetime based on ligand is decreased which clearly confirms that there is energy transfer between the dual emitting centers in composites (Figures S15 and S16). In addition, to further demonstrate the result, the delay spectra of UiO-66(Zr&Eu)-1 film at different temperature were obtained in the temperature range from 237 K to 337 K. With changing the temperature, the lifetimes of UiO-66(Zr&Eu)-1 film at 617 nm can increase from 100 µs to 732 µs, improved 7.32 times which also indicates that the energy can transfer from the bridging ligand to the Eu3+ ions.


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To prove the recycle characteristic of the film thermometer, PXRD patterns and PL spectra were recorded after the temperature-dependent PL test (Figures 5A and S18). As shown in Figure 5B, the intensity ratio is not changed by putting the film to temperature cycles from 237 K to 337 K, indicating that the film has a stable optical characteristic. Similarly, the UiO-66(Zr&Eu)-2 and 3 films also had the stable optical property in the tested temperature range shown in Figures S19 and 20. In addition, the PXRD patterns of the film after the cycle test are consistent with that before test, indicating that the crystal structure of the film is stable during the test process (Figure S18).

Figure 5. (A) Photoluminescence spectra of the UiO-66(Zr&Eu)-1 film at 237 K and 337 K in different cycles upon excitation of 360 nm. (B) Corresponding Eu (617 nm) to ligand (420 nm) emission intensity ratio versus cycles. To test the stability of the MOF material under biological conditions, the UiO-66(Zr&Eu)-1 film was submerged in a PBS buffer solution for 24 h. The solution content of Eu ions was only 0.0038 ppm by inductively coupled plasma spectroscopy, suggesting that our film is robust in the buffer solution. Moreover, the theoretical temperature sensing resolution67-72 is less than 0.04 K,


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which indicates as-prepared dual-emitting MOF is a promising material for the applications in biology (Figure S21). CONCLUSIONS In summary, a novel dual-emitting solid film thermometer has been fabricated by mixing UiO66(Zr&Eu) and PVDF. Here, UiO-66(Zr&Eu) was synthesized by replacing Zr ions in clusters with Eu ions using 2-FBA as a template in situ in hydrothermal conditions. The relative sensitivity of the UiO-66(Zr&Eu)-1 film is 4.26% K-1 at 337 K which is the highest reported to date for MOF materials at this temperature because of the unique energy transfer between the Eu ions in the clusters and the ligand. Moreover, the temperature sensing performance can be further improved by turning the ratio of two luminescent centers and the thickness of the films. In addition, the film can be reused 3 times without lowering the sensing performance. Due to this strategy, more and more dual-emitting film materials can be developed for use in practical application for the detection of temperature variation, small-molecule and for the other fields. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Additional characterization data (XRD patterns, Life-time, TGA, PL spectra) (PDF) AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] Notes


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The authors declare no competing financial interest. ACKNOWLEDGMENT Dedicated to Professor Xin-Tao Wu on the occasion of his 80th birthday. The authors thank for the support from NSFC (21331006, 21520102001 and 51572260), the 973 Program (2014CB845605), Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (QYZD-J-SSW-SLH045) and Strategic Priority Research Program of the Chinese Academy of Sciences (XDA20000000).

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Dual-Emitting UiO-66(Zr&Eu) Metal-Organic ... - ACS Publications

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