Covalent Organic Framework Nanosheets for Fluorescence Sensing

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Covalent Organic Framework Nanosheets for Fluorescence Sensing via Metal Coordination Wei-Rong Cui, Cheng-Rong Zhang, Wei Jiang, Ru-Ping Liang, and Jian-Ding Qiu ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.9b01366 • Publication Date (Web): 30 Jul 2019 Downloaded from pubs.acs.org on July 30, 2019

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ACS Applied Nano Materials

Covalent Organic Framework Nanosheets for Fluorescence Sensing via Metal Coordination

Wei-Rong Cui,† Cheng-Rong Zhang,† Wei Jiang,† Ru-Ping Liang,† Jian-Ding Qiu†,‡* †College

of Chemistry, Nanchang University, Nanchang 330031, China

‡Engineering

Technology Research Center for Environmental Protection Materials

and Equipment of Jiangxi Province, Pingxiang University, Pingxiang 337055, China *Corresponding authors. Tel/Fax: +86-791-83969518. E-mail: [email protected].

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ABSTRACT: Covalent organic framework nanosheets (COF NSs) provide well-ordered π-π structures that can be used to develop luminescent materials. However, most COF NSs have problems of weak in luminescence and low fluorescence quantum yield. In this work, we prepared covalent organic framework nanosheets (Bpy-NSs) with good water dispersibility, nitrogen-rich functional groups and regular pore structure. We explored the coordination of Bpy-NSs with Al3+ to eliminate the fluorescence quenching process caused by photoinduced electron transfer (PET). Thus, the fluorescence “turn-on” signal linearly increases with Al3+ concentration and achieving a 15.7-fold improved in fluorescence, and the absolute fluorescence quantum yield increased from 0.15 to 1.74%. Furthermore, this is the first COF fluorescence sensor that can be used for high sensitivity and selectivity detection of Al3+ in the aqueous phase. We anticipate that the expansion of metal ions coordination strategy in the aqueous phase will not only significantly enhances the fluorescence of COF NSs, but will also extends the functional range of COF NSs. KEYWORDS: Covalent organic framework, nanosheets, Fluorescence improving, aqueous phase, detection, Al3+

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INTRODUCTION Covalent organic framework (COF) is a kind of crystalline, porous polymers that has shown widely used

in energy storage,1-4 metal ions detection and remediation,5-9

catalysis,10-13 and gas separation and adsorption.14-15 In particular, two-dimensional (2D) COF is unique owing to the excellent adjustable functionality, regular pore structure, and flexible topological connectivity.16-18 At present, various linking monomers, condensation reactions, and geometry have been explored, which greatly expand the utility and diversity of the framework.19-20 These advances in the synthesis have also driven a developing trend in exploring the properties and function of the extended 2D COF structure.20-21 However, the development of luminescence function COF is yet in its infancy compared to the wide range of π building blocks for the structural design and skeleton synthesis.22-23 Building blocks and linking monomers are critical for the luminescent activity of 2D COF.24-25 Because these layers are formed through π-π stacking, the luminescence properties of the 2D COF will be affected by the aggregation-quenched characteristics of the chromophores, which can be adjusted by exfoliation.26-27 Therefore, the potential applications of COF nanosheets (COF NSs) in chemical sensing are receiving increasing attention.28-29 In most cases, the luminescent properties of COF NSs are primarily dependent on the linkages.28,30-31 Especially, the linkages may cause excitation energy dissipation by photoinduced electron transfer (PET) process, thereby quenching the photoluminescence of the COF NSs.24,32-33 For instance, due to the presence of PET process in the COF NSs, even with highly luminescent linkers, 3



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the luminescence properties of the bipyridine-containing COF NSs are poor. In this case, preventing the fluorescent quenching process by coordinating COF NSs with metal ions to relieve the limitations inherent in the framework would provide a promising approach to enhancing the luminescence of COF NSs.

Scheme 1. Schematic diagram for preparation of Bpy-NSs and detection of Al3+. Among the various linkers, we chose bipyridine because it has a strong coordination ability with metal ions.34-35 Here, bipyridine-containing COF (Bpy-COF) was synthesized by the Schiff base reaction of 5, 5'-diamino-2, 2'-bipyridine (Bpy) and 2, 4, 6-triformylphloroglucinol (Tp). Subsequently, Bpy-NSs were prepared by grinding and ultrasonic assisted stripping of the bulk Bpy-COF. The coordination of Bpy-NSs with Al3+ eliminates the PET process from the linkage to Bpy-NSs skeleton, thereby

improving

the

luminescence

activity

of

Bpy-NSs

(Scheme

1).

Simultaneously, we designed a control experiment to verify the decisive role of 4


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bipyridine in this mechanism. Under the same preparation conditions, we prepared benzidine-containing NSs (BD-NSs). By comparing BD-NSs with Bpy-NSs under the same measurement conditions, it has been confirmed that the coordination of Bpy-NSs with Al3+ significantly improves the fluorescence of Bpy-NSs.

EXPERIMENTAL SECTION Synthesis of Bpy-NSs. Bpy-NSs was prepared by a new method of grinding and pulverization. A 50 mg of Bpy-COF was weighed into an agate mortar and ground at room temperature for 15 min. The obtained solid was dispersed in 100 mL of ultrapure water and then stripping in the ultrasonic bath (Scientz, JY92-IIN, 650 W, 25 KHz, 25 °C) for 8 h. The aqueous dispersion was then centrifuged at 3000 rpm for 30 min and undisturbed overnight to separate the bulk materials. The supernatant after standing was collected and dried at 80 °C under vacuum. Then, 5 mg of Bpy-NSs was weighed and dispersed in 25 mL of water for further characterization and application. BD-NSs were prepared by exfoliating bulk BD-COF, and the preparation method was completely consistent with BPy-NSs. Preparation of metal ions stock solutions. The metal ions stock solutions (1 mM) required for the experiments were prepared by dissolving the nitrate salts of Al3+, Zn2+, Cd2+, Mn2+, Cr3+, Pb2+, Mg2+, Ag+, Ba2+, Ca2+, Na+, K+, Co2+, Fe3+, Li+, Hg2+, Ni2+, and Cu2+in ultrapure water. Metal ions sensing (sensitivity and selectivity) testing. The fluorescence spectra were measured immediately after an appropriate aliquot of the metal ions stock solution. All measurements were excited at λex = 275 nm and the corresponding 5



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emission wavelengths were tested from λem = 300 to 700 nm unless otherwise stated. After adding different metal ions stock solutions, the shape of the emission spectra did not change. Repeat each test at least three times to get accurate data.

RESULTS AND DISCUSSION Characterization of Bpy-COF and Bpy-NSs. Under the same preparation conditions,

we

prepared

bipyridine-containing

COF

(Bpy-COF)

and

benzidine-containing COF (BD-COF). As shown in Figure 1, the powder X-ray diffraction (PXRD) patterns at 3.6° (2θ) is ascribed to the reflection from the (100) plane, and the other peaks at 7.2° and 26.9° (2θ) are ascribed to the (200) and (002) planes reflections, respectively.10,36-37 The appearance of a strong diffraction peak for (100) plane indicates the high crystallinity of Bpy-COF. The PXRD pattern of Bpy-COF matches well with the simulated eclipsed model structure (Table S1 in Supporting Information).10,36-37 As shown by the FT-IR spectra in Figure S1 (See the Supporting Information), the characteristic absorption bands of Bpy (-NH2 at ~3282 cm-1) and Tp (-CHO at ~2896 cm-1) disappear, and a new stretching vibration band at 1288 cm-1 (C-N) in Bpy-COF is observed, indicating the successful preparation of Bpy-COF.27,34 The structure of Bpy-COF was further confirmed by the 13C solid-state NMR spectroscopy (Figure S2). The signal located at ~135 ppm is attributed to the C-N, which is consistent with the keto-enol tautomerized structure of Bpy-COF.10,34 The above results fully confirm that Bpy-COF with high crystallinity has been successfully prepared

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Figure 1. (A) Comparison of the PXRD patterns of the Bpy-COF sample with simulated Bpy-COF. (B) Comparison of the PXRD patterns of the BD-COF sample with simulated BD-COF. Bpy-NSs were prepared by grinding and ultrasonic assisted methods. By comparing the PXRD patterns of Bpy-NSs and Bpy-COF (Figure S3), it is clear that exfoliation process does not affect the structure and crystalline phase of Bpy-COF.21,38-39 As shown in Figures 2A and 2B, the TEM images of Bpy-NSs and BD-NSs appear as flat sheet topography. Simultaneously, the AFM images demonstrate that the thicknesses of the prepared Bpy-NSs are about 1 nm and 1.5 nm, respectively (Figure 2C, Figure S4 and Figure 2D), indicating about few layers of Bpy-NSs. The TEM and AFM images of Bpy-NSs further confirmed the successful exfoliation

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Figure 2. TEM images of Bpy-NSs (A) and BD-NSs (B), AFM images of Bpy-NSs (C) and BD-NSs (D). of Bpy-COF. The exfoliated Bpy-NSs exhibit a uniform sheet shape, so that the hydrophilic group can be quickly and sufficiently exposed to the aqueous solution. Thus, Bpy-NSs can be stably dispersed in water for a long time (Figure S5), and Bpy-NSs can be further applied to detect metal ions in the aqueous phase. We measured the thermal stability of Bpy-NSs by thermogravimetric analysis. The experimental results indicate that Bpy-NSs still have good thermal stability up to 300 °C (Figure S6). The N2 adsorption-desorption experiment of Bpy-NSs was carried out at 77 K (Figure S7), and the results showed that it was a type-I N2 adsorption curve, indicating the existence of a large number of

microporous 8


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structure. The specific surface area of Bpy-NSs was calculated to be 755 m2 g-1. As shown in Figure S8, the pore size distribution of Bpy-NSs was calculated by non-local density functional theory (NLDFT) and shows a narrow pore size distribution (1.69 nm).40-41 These experimental results demonstrate that Bpy-NSs have well-ordered porous structure, excellent water dispersibility and thermal stability, showing great potential as a fluorescent sensor for metal ions in aqueous solutions. Fluorescence Determination of Al3+. The fluorescence excitation and emission spectra of Bpy-NSs dispersed in aqueous phase are shown in Figure S9. The emission band of Bpy-COF is significantly blue-shifted compared with Tp and Bpy dispersed in aqueous phase, which can be attributed to the π-conjugation extending over the framework layer (Figure S10).42-43 After excitation at 275 nm, Bpy-NSs dispersed in aqueous phase emit weak blue fluorescence at 370 nm (Figure 3A, black curve), showing a lower absolute fluorescence quantum yield of 0.15%. Then, the prepared Bpy-NSs are directly added to the aqueous solutions containing different metal ions, including (Al3+, Zn2+, Cd2+, Mn2+, Cr3+, Pb2+, Mg2+, Ag+, Ba2+, Ca2+, Na+, K+, Co2+, Fe3+, Li+, Hg2+, Ni2+, and Cu2+), and the metal ion-introduced Bpy-NSs dispersions (Bpy-NSs-M) was formed for fluorescence investigation. Results show that the fluorescence emission intensity is dependent on the nature of metal ions. For example, the addition of alkaline and alkaline earth metal ions has little effect on the fluorescence of Bpy-NSs, probably because of the weak coordination of these ions with bipyridine.48 Bipyridine has been reported to have a strong coordination with some transition metal ions (such as Cu2+, Fe3+, and Co2+).12,34,48 Interestingly, the 9



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addition of transition metal ions with different electronic configurations also has little effect on the fluorescence of Bpy-NSs, whereas the Al3+-introduced (with 3s and 3p empty orbits) fluorescence emission is significantly enhanced (Figure 3B). This is because the electronic arrangement follows the minimum energy principle and the electrons occupy the lowest energy orbit as much as possible. Simultaneously, the Bpy-NSs were exploited for the binding and specific response of Al3+ through Lewis acid-base coordinate interactions.12 It is worth noting that Bpy-NSs responds very quickly to Al3+ and reaches equilibrium within 2 seconds (Figure S11). By contrast, the other metal ion-introduced BD-NSs dispersions (BD-NSs-M) including (Al3+, Zn2+, Cd2+, Mn2+, Cr3+, Pb2+, Mg2+, Ag+, Ba2+, Ca2+, Na+, K+, Co2+, Fe3+, Li+, Hg2+, Ni2+, and Cu2+) do not show distinguished change in luminescence (Figures 3C and 3D).

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Figure 3. (A) Fluorescence spectra of Bpy-NSs before and after addition of various metal ions. (B) Fluorescence intensity of Bpy-NSs at 370 nm in the presence of various metal ions. (C) Fluorescence spectra of BD-NSs before and after addition of various metal ions. (D) Fluorescence intensity of BD-NSs at 562 nm in the presence of various metal ions. The concentrations of all the metal ions were 350 μM. In order to explore the fluorescence enhancement process of Al3+, we measured the fluorescence emission spectra of Bpy-NSs in aqueous solutions containing different concentrations of Al3+. Figure 4A shows that the fluorescence intensity of Bpy-NSs linearly increases with Al3+ concentration and reaches equilibrium at 350 μM. After the formation of Bpy-NSs-Al, the fluorescence intensity increases by 15.7 times, and the fluorescence quantum yield increases to 1.74%. In addition, we measured the Al3+ content in Bpy-NSs-Al by ICP analysis and found that Bpy-NSs-Al 11



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contained 5.5% Al3+ content (corresponding to 0.69 Al atoms per unit of bipyridine ligand). The cation interference experiments were conducted to investigate the effects of other metal ions such as Zn2+, Cd2+, Mn2+, Cr3+, Pb2+, Mg2+, Ag+, Ba2+, Ca2+, Na+, K+, Co2+, Fe3+, Li+, Hg2+, Ni2+, and Cu2+ binding with Bpy-NSs on Al3+ detection. Results show that the fluorescence enhancement caused by mixing Al3+ with various other metal ions is similar to the fluorescence enhancement caused by Al3+ alone (Figure 4B). Simultaneously, the anion interference experiments were conducted to investigate the effects of other counter anion. The experimental results show that the addition of different counter anions hardly affects the fluorescence intensity. Therefore, Bpy-NSs can be used for the selectivity and sensitivity detection of Al3+.

Figure 4. (A) Fluorescence spectra changes of Bpy-NSs after addition of different concentrations of Al3+. Inset shows the linear calibration plot for Al3+ detection. (B) Fluorescence intensity changes of Bpy-NSs at 370 nm in the presence of Al3+ and other metal ions. The concentrations of all the metal ions were 350 μM. Fluorescence

Enhancement

Mechanism.

The

fluorescence

enhancement

mechanism of Bpy-NSs by introduction of Al3+ was explored and is illustrated in Figure 5. It is suggested that the linkages may cause excitation energy dissipation by 12


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PET process, thereby quenching the photoluminescence of the Bpy-NSs. However, the coordination of Bpy-NSs with Al3+ to form Bpy-NSs-Al eliminates the

Figure 5. Fluorescence enhancement mechanism. fluorescence quenching process caused by PET. As shown in Figure 6, the proposed fluorescence enhancement mechanism is supported by the X-ray photoelectron spectroscopy (XPS) data. After treatment of the Bpy-NSs with Al3+, the binding energy peak at 74.5 eV (Al 2p) is observed (Figure 6B), indicating the successful formation of Bpy-NSs-Al.44-45 In the high-resolution XPS spectrum of N 1s of the Bpy-NSs (Figure 6C), the two peaks at 399.70 and 398.45 eV are attributed to C-N and C=N, which correspond to the nitrogen atoms in the Bpy-NSs structure, respectively.34, 46-47 Under the same conditions, the high resolution XPS spectrum of N 1s of Bpy-NSs-Al was observed (Figure 6D). Comparing the two N 1s peaks of the Bpy-NSs and Bpy-NSs-Al, it is clearly observed that the peak located at 398.45 eV of the Bpy-NSs (Figure 6C) moved 0.17 eV to higher binding energy after the formation of Bpy-NSs-Al (Figure 6D). However, the N 1s peak at 399.70 eV in Figures 6C and 6D show no movement before and after detecting Al3+, indicating that the nitrogen atoms of the C-N do not participate in the coordination with Al3+. Based on these 13



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results, it is inferred that the Bpy-NSs fluorescence improving is a chemical process and only the nitrogen atoms in the bipyridine have coordination interaction with Al3+ in the detection process.34, 44-45

Figure 6. XPS survey spectra of Bpy-NSs (A), Al 2p spectra of Bpy-NSs-Al (B), N 1s spectra of Bpy-NSs (C), and N 1s spectra of Bpy-NSs-Al (D). By measuring the PXRD patterns of Bpy-NSs before and after treatment with Al3+ (Figure S11), it is apparent that the crystallinity and structure of Bpy-NS are not affected after treatment with Al3+. However, the resulting peaks are broad, and the relative intensity of the first peak corresponding to the (100) plane decreases after the formation of Bpy-NSs-Al.35, 48-49 This may be owing to the presence of a large number of flexible chains in the pores of the Bpy-NSs-Al, which reduces the diffractions.12, 34 13C

CP/MAS NMR spectroscopy further provides sufficient evidence for the intense 14


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and selective coordination between Al3+ and the bipyridine. As shown in Figure 7A, after the Bpy-NSs coordinate with Al3+, the chemical shift of the 13C NMR signal at 119 ppm, which is attributed to the carbons adjacent to the N atoms in the bipyridine, is upfield shifted to 122 ppm, while the other signals do not change.34, 50-51 The above results confirm the strong coordination ability of Bpy-NSs to Al3+ in the Bpy-NSs-Al.

Figure 7. (A)

13C

CP/MAS NMR spectra of Bpy-NSs before and after addition of

Al3+. (B) Fluorescence decay curves of Bpy-NSs before and after addition of Al3+.

As shown in Figure 7B, the fluorescence lifetime of Bpy-NSs is determined by time-resolved fluorescence spectroscopy to be 2.29 ns. After the formation of Bpy-NSs-Al, the fluorescence lifetime increases to 3.35 ns. A significant increase in fluorescence lifetime indicates that the coordination of Al3+ with Bpy-NSs inhibits the electron transfer process from the linkage to the Bpy-NSs skeleton, thereby greatly enhancing the fluorescence emission intensity. These results fully confirm the fluorescence enhancement mechanism proposed above.

CONCLUSIONS 15



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In conclusion, we have demonstrated the first example of enhanced fluorescence of COF NSs by coordination with cations. The formation of Bpy-NSs-Al eliminates the PET process from the linkage to Bpy-NSs skeleton, thus effectively suppressing fluorescence quenching, thereby improving the luminescence activity in a proportional manner. In addition, we have verified by various characterization methods that Bpy-NSs is the first COF NSs fluorescence “turn-on” sensor that can be used for highly selective and sensitive detection of Al3+ in the aqueous phase, which greatly improves its practical application value. We expect that this new strategy for significantly enhancing COF or COF NSs fluorescence through metal ions coordination will open a new frontier for the design and development of novel materials for various potential luminescent applications.

ASSOCIATED CONTENT Supporting Information Additional experimental details and figures including FT-IR spectra; solid-state 13C

CP-MAS NMR spectra; PXRD patterns; AFM images; Optical photos; TGA

results; N2-adsorption and desorption isotherms; Pore size distributions; Fluorescence excitation and emission spectra; Time-dependent fluorescence spectra; Counter anions research results; and TEM images. AUTHOR INFORMATION Corresponding Author Tel/Fax: +86-791-83969518. E-mail: [email protected]. Notes 16


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The authors declare no competing financial interest. Acknowledgements We gratefully acknowledge the supports from the National Natural Science Foundation of China (21675078), and the Natural Science Foundation of Jiangxi Province (20165BCB18022). REFERENCES

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