Fluorescence detection of phosphate in an aqueous environment by an aluminum-based metal-organic framework with amido functionalized ligands

doi:10.1007/s11783-022-1594-8

Front. Environ. Sci. Eng.

2022, Vol. 16

Issue (12) : 159 https://doi.org/10.1007/s11783-022-1594-8

RESEARCH ARTICLE

Fluorescence detection of phosphate in an aqueous environment by an aluminum-based metal-organic framework with amido functionalized ligands

Peng Li^1,²(

), Lingqian Dong^1,², Han Jin³, Jingren Yang¹, Yonghui Tu¹, Chao Wang^1,², Yiliang He^1,²

¹. School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
². China-UK Low Carbon College, Shanghai Jiao Tong University, Shanghai 200240, China
³. Department of Instrument Science and Engineering, School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Download: PDF(13324 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

● A novel Al-MOF was successfully synthesized by a facile solvothermal method.

● Al-MOF showed superior performance for phosphate detection.

● High selectivity and anti-interference for detection were demonstrated.

● The high coordination between Al-O and PO₄³⁻ was the key in fluorescence sensing.

The on-site monitoring of phosphate is important for environmental management. Conventional phosphate detection methods are not appropriate to on-site monitoring owing to the use of complicated detection procedures, and the consequent high cost and maintenance requirements of the detection apparatus. Here, a highly sensitive fluorescence-based method for phosphate detection with a wide detection range was developed based on a luminescent aluminum-based metal-organic framework (Al-MOF). The Al-MOF was prepared by introducing amine functional groups to conventional MIL to enhance phosphate binding, and exhibited excellent fluorescence properties that originated from the ligand-to-metal charge transfer (LMCT). The detection limit was as low as 3.25 μmol/L (0.10 mg/L) and the detection range was as wide as 3–350 μmol/L (0.10–10.85 mg/L). Moreover, Al-MOF displayed specific recognition toward phosphate over most anions and metal cations, even for a high concentration of the co-existent ions. The mechanism of phosphate detection was analyzed through the characterization of the combination of Al-MOF and phosphate, and the results indicated the high affinity between Al-O and phosphate inhibited that the LMCT process and recovered the intrinsic fluorescence of NH₂-H₂BDC. The recovery of the developed detection method reached a satisfactory range of 85.1%–111.0%, and the feasibility of on-site phosphate detection was verified using a prototype sensor for tap water and lake water samples. It was demonstrated that the prepared Al-MOF is highly promising for on-site detection of phosphate in an aqueous environment.

Keywords Fluorescence Metal-organic framework Phosphate Detection Al-MOF

Corresponding Author(s): Peng Li

Issue Date: 11 July 2022

Cite this article:

Peng Li,Lingqian Dong,Han Jin, et al. Fluorescence detection of phosphate in an aqueous environment by an aluminum-based metal-organic framework with amido functionalized ligands[J]. Front. Environ. Sci. Eng., 2022, 16(12): 159.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-022-1594-8
https://academic.hep.com.cn/fese/EN/Y2022/V16/I12/159

Fig.1 (a) XRD patterns of Al-MOF and Al-MOF after PO₄^3– detection; (b) comparison of the FT-IR spectra of NH₂-H₂BDC, Al-MOF, and Al-MOF after PO₄^3– detection.

Fig.2 (a) and (b) SEM image of Al-MOF; (c)–(e) TEM images of Al-MOF; (f)–(i) element mapping of Al, C, N, and O, respectively.

Fig.3 (a) Full range XPS spectra of Al-MOF and Al-MOF after PO₄^3– detection; (b) XPS spectra of P 2p; (c) XPS spectra of Al 2p; (d) XPS spectra of Q1s; (e) the magnified O 1s XPS spectra of Al-MOF; (f) the magnified O 1s XPS spectra of Al-MOF after PO₄^3– detection.

Tab.1 Comparison of the phosphate detection capabilities of Al-MOF and other fluorescent materials

Fig.4 (a), (c) and (e) Fluorescence emission spectra of Al-MOF with the concentrations of 20, 100, and 200 mg/L in the presence of different concentrations of PO₄^3– under λ_ex=330 nm at room temperature. (b), (d) and (f) Linear plots of the fluorescence enhancement efficiency of Al-MOF with the concentrations of 20, 100, and 200 mg/L as a function of PO₄^3– concentration.

Fig.5 (a) Comparison of the fluorescence of the Al-MOF (20 mg/L) in the presence of different anions (20 μmol/L); (b) effects of different coexistent anions (1 mmol/L; for SO₄^2– and HCO₃^–, the concentration is 10 mmol/L) on the fluorescence response of Al-MOF (20 mg/L) upon the addition of 20 μmol/L PO₄^3–. F₀ and F₁ indicate the fluorescence intensity of Al-MOF without and with anions, respectively (λ_ex=330 nm, λ_em=402 nm).

Fig.6 (a) Comparison of the fluorescence response of the Al-MOF (20 mg/L) towards different metal ions (20 μmol/L); (b) effects of different coexistent metal ions (1 mmol/L) on the fluorescence response of Al-MOF (20 mg/L) upon the addition of 20 μmol/L PO₄^3–. F₀ and F₁ indicate the fluorescence intensity of Al-MOF without and with anions, respectively (λ_ex=330 nm, λ_em=402 nm).

Tab.2 Results for on-site detection of phosphate in water samples

1	P Chandra Rao , S Mandal . (2018). Europium-based metal-organic framework as a dual luminescence sensor for the selective detection of the phosphate anion and Fe3+ ion in aqueous media. Inorganic Chemistry, 57( 19): 11855– 11858 https://doi.org/10.1021/acs.inorgchem.8b02017
2	B Chen , N W Ockwig , A R Millward , D S Contreras , O M Yaghi . (2005). High H2 adsorption in a microporous metal-organic framework with open metal sites. Angewandte Chemie (International ed. in English), 44( 30): 4745– 4749 https://doi.org/10.1002/anie.200462787
3	B B Chen , R Sheng Li , M Li Liu , H Yan Zou , H Liu , C Z Huang . (2018). Highly selective detection of phosphate ion based on a single-layered graphene quantum dots-Al3+ strategy. Talanta, 178 : 172– 177 https://doi.org/10.1016/j.talanta.2017.09.007
4	W Chen , P Westerhoff , J A Leenheer , K Booksh . (2003). Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter. Environmental Science & Technology, 37( 24): 5701– 5710 https://doi.org/10.1021/es034354c
5	Y Cheng , H Zhang , B Yang , J Wu , Y Wang , B Ding , J Huo , Y Li . (2018). Highly efficient fluorescence sensing of phosphate by dual-emissive lanthanide MOFs. Dalton Trans, 47( 35): 12273– 12283 https://doi.org/10.1039/C8DT01515E
6	M Colina , P H E Gardiner . (1999). Simultaneous determination of total nitrogen, phosphorus and sulphur by means of microwave digestion and ion chromatography. Journal of Chromatography. A, 847( 1−2): 285– 290 https://doi.org/10.1016/S0021-9673(99)00024-2
7	C Dai , C X Yang , X P Yan . (2015). Ratiometric fluorescent detection of phosphate in aqueous solution based on near infrared fluorescent silver nanoclusters/metal-organic shell composite. Analytical Chemistry, 87( 22): 11455– 11459 https://doi.org/10.1021/acs.analchem.5b03086
8	Das A, Biswas S (2017). A multi-responsive carbazole-functionalized Zr(IV)-based metal-organic framework for selective sensing of Fe(III), cyanide and p-nitrophenol. Sensors and Actuators. B, Chemical, 250: 121−131
9	A Das , S Das , V Trivedi , S Biswas . (2019). A dual functional MOF-based fluorescent sensor for intracellular phosphate and extracellular 4-nitrobenzaldehyde. Dalton Trans, 48( 4): 1332– 1343 https://doi.org/10.1039/C8DT03964J
10	C Fan , X Lv , M Tian , Q Yu , Y Mao , W Qiu , H Wang , G Liu . (2020). A terbium(III)-functionalized zinc(II)-organic framework for fluorometric determination of phosphate. Mikrochimica Acta, 187( 1): 84 https://doi.org/10.1007/s00604-019-4066-5
11	G Férey . (2008). Hybrid porous solids: Past, present, future. Chemical Society Reviews, 37( 1): 191– 214 https://doi.org/10.1039/B618320B
12	N Gao , J Huang , L Y Wang , J Y Feng , P C Huang , F Y Wu . (2018). Ratiometric fluorescence detection of phosphate in human serum with a metal-organic frameworks-based nanocomposite and its immobilized agarose hydrogels. Applied Surface Science, 459 : 686– 692 https://doi.org/10.1016/j.apsusc.2018.08.092
13	He J, Wang J, Chen Y, Zhang J, Duan D, Wang Y, Yan Z (2014). A dye-sensitized Pt@UiO-66(Zr) metal-organic framework for visible-light photocatalytic hydrogen production. Chemical Communications (Cambridge, England), 50(53): 7063–706624848342
14	P Horcajada , R Gref , T Baati , P K Allan , G Maurin , P Couvreur , G Férey , R E Morris , C Serre . (2012). Metal-organic frameworks in biomedicine. Chemical Reviews, 112( 2): 1232– 1268 https://doi.org/10.1021/cr200256v
15	L Kröckel , H Lehmann , T Wieduwilt , M A Schmidt . (2014). Fluorescence detection for phosphate monitoring using reverse injection analysis. Talanta, 125 : 107– 113 https://doi.org/10.1016/j.talanta.2014.02.072
16	C M Li , Y F Li , J Wang , C Z Huang . (2010). Optical investigations on ATP-induced aggregation of positive-charged gold nanoparticles. Talanta, 81( 4−5): 1339– 1345 https://doi.org/10.1016/j.talanta.2010.02.032
17	Z P Li , Z W Huang , N Xie , X N Gao , Y T Fang , Z G Zhang . (2018). Preparation of Al2O3-coated expanded graphite with enhanced hydrophilicity and oxidation resistance. Ceramics International, 44( 14): 16256– 16264 https://doi.org/10.1016/j.ceramint.2018.06.017
18	R T Liu , L N Chi , X Z Wang , Y Wang , Y M Sui , T T Xie , H Arandiyan . (2019). Effective and selective adsorption of phosphate from aqueous solution via trivalent-metals-based amino-MIL-101 MOFs. Chemical Engineering Journal, 357 : 159– 168 https://doi.org/10.1016/j.cej.2018.09.122
19	Z Z Lu , R Zhang , Y Z Li , Z J Guo , H G Zheng . (2011). Solvatochromic behavior of a nanotubular metal-organic framework for sensing small molecules. Journal of the American Chemical Society, 133( 12): 4172– 4174 https://doi.org/10.1021/ja109437d
20	L Ma , C Abney , W Lin . (2009). Enantioselective catalysis with homochiral metal-organic frameworks. Chemical Society Reviews, 38( 5): 1248– 1256 https://doi.org/10.1039/b807083k
21	C Orellana-Tavra , R J Marshall , E F Baxter , I A Lázaro , A Tao , A K Cheetham , R S Forgan , D Fairen-Jimenez . (2016). Drug delivery and controlled release from biocompatible metal-organic frameworks using mechanical amorphization. Journal of Materials Chemistry. B, 4( 47): 7697– 7707 https://doi.org/10.1039/C6TB02025A
22	A K Saini , M Srivastava , V Sharma , V Mishra , S M Mobin . (2016). A highly selective, sensitive and reversible fluorescence chemosensor for Zn2+ and its cell viability. Dalton Trans, 45( 9): 3927– 3935 https://doi.org/10.1039/C5DT04945H
23	P Serra-Crespo , E V Ramos-Fernandez , J Gascon , F Kapteijn . (2011). Synthesis and Characterization of an amino functionalized MIL-101(Al): Separation and catalytic properties. Chemistry of Materials, 23( 10): 2565– 2572 https://doi.org/10.1021/cm103644b
24	B B Shi Y M Zhang T B Wei Q Lin H Yao P Zhang X M You ( 2014). A fluorescent and colorimetric chemosensor for dihydrogen phosphate ions based on 2-pyridine-1H-imidazo[4,5-b]phenazine-zinc ensemble. Sensors and Actuators. B, Chemical, 190: 555− 561
25	Y Song , Y Li , Y Liu , X Su , Q Ma . (2015). Highly sensitive and selective detection of phosphate using novel highly photoluminescent water-soluble Mn-doped ZnTe/ZnSe quantum dots. Talanta, 144 : 680– 685 https://doi.org/10.1016/j.talanta.2015.07.025
26	Z J Sun , J Z Jiang , Y F Li . (2015). A sensitive and selective sensor for biothiols based on the turn-on fluorescence of the Fe-MIL-88 metal-organic frameworks-hydrogen peroxide system. The Analyst, 140( 24): 8201– 8208 https://doi.org/10.1039/C5AN01673H
27	B Wang , Q Yang , C Guo , Y Sun , L H Xie , J R Li . (2017). Stable Zr(IV)-based metal-organic frameworks with predesigned functionalized ligands for highly selective detection of Fe(III) ions in water. ACS Applied Materials & Interfaces, 9( 11): 10286– 10295 https://doi.org/10.1021/acsami.7b00918
28	R Wang , Q Zhang , Y Zhang , H Shi , K T Nguyen , X Zhou . (2019). Unconventional split aptamers cleaved at functionally essential sites preserve biorecognition capability. Analytical Chemistry, 91( 24): 15811– 15817 https://doi.org/10.1021/acs.analchem.9b04115
29	L H Xie , X M Liu , T He , J R Li . (2018). Metal-organic frameworks for the capture of trace aromatic volatile organic compounds. Chem, 4( 8): 1911– 1927 https://doi.org/10.1016/j.chempr.2018.05.017
30	Xu H, Cao C S, Zhao B (2015). A water-stable lanthanide-organic framework as a recyclable luminescent probe for detecting pollutant phosphorus anions. Chemical Communications (Cambridge, England), 51(51): 10280–1028325940110
31	M M Xu , X J Kong , T He , X Q Wu , L H Xie , J R Li . (2018). A stable Zr(IV)-based metal-organic framework constructed from C=C bridged Di-isophthalate ligand for sensitive detection of Cr2O72– in water. Inorganic Chemistry, 57( 22): 14260– 14268 https://doi.org/10.1021/acs.inorgchem.8b02282
32	C X Yang , H B Ren , X P Yan . (2013). Fluorescent metal-organic framework MIL-53(Al) for highly selective and sensitive detection of Fe3+ in aqueous solution. Analytical Chemistry, 85( 15): 7441– 7446 https://doi.org/10.1021/ac401387z
33	J Yang Y Dai X Y Zhu Z Wang Y S Li Q X Zhuang J L Shi J L Gu ( 2015). Metal-organic frameworks with inherent recognition sites for selective phosphate sensing through their coordination-induced fluorescence enhancement effect. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 3( 14): 7445− 7452
34	Y Zhang , S Sheng , S Mao , X Wu , Z Li , W Tao , I R Jenkinson . (2019). Highly sensitive and selective fluorescent detection of phosphate in water environment by a functionalized coordination polymer. Water Research, 163 : 114883 https://doi.org/10.1016/j.watres.2019.114883
35	Zhang Z, Zhao Y, Gong Q, Li Z, Li J (2013). MOFs for CO2 capture and separation from flue gas mixtures: The effect of multifunctional sites on their adsorption capacity and selectivity. Chemical communications (Cambridge, England), 49(7): 653–66123150882
36	D Zhao X Y Wan H J Song L Y Hao Y Y Su Y (2014) Lv. Metal-organic frameworks (MOFs) combined with ZnO quantum dots as a fluorescent sensing platform for phosphate. Sensors and Actuators. B, Chemical, 197: 50− 57
37	L Zhu , X H Zhou , H C Shi . (2014a). A potentiometric cobalt-based phosphate sensor based on screen-printing technology. Frontiers of Environmental Science & Engineering, 8( 6): 945– 951 https://doi.org/10.1007/s11783-013-0615-z
38	Zhu X, Gu J, Wang Y, Li B, Li Y, Zhao W, Shi J (2014b). Inherent anchorages in UiO-66 nanoparticles for efficient capture of alendronate and its mediated release. Chemical Communications (Cambridge, England), 50(63): 8779–878224967656

[1]

FSE-22042-OF-LP_suppl_1

Download

[1]	Huan Xi, Fanlu Min, Zhanhu Yao, Jianfeng Zhang. Facile fabrication of dolomite-doped biochar/bentonite for effective removal of phosphate from complex wastewaters[J]. Front. Environ. Sci. Eng., 2023, 17(6): 71-.
[2]	Jiachuang Shao, Penghui Shao, Mingming Peng, Min Li, Ziwei Yao, Xiuqin Xiong, Caiting Qiu, Yufan Zheng, Liming Yang, Xubiao Luo. A pyrazine based metal-organic framework for selective removal of copper from strongly acidic solutions[J]. Front. Environ. Sci. Eng., 2023, 17(3): 33-.
[3]	Wenping Zhang, Changsheng Guo, Jiapei Lv, Xu Li, Jian Xu. Organophosphate esters in sediment from Taihu Lake, China: Bridging the gap between riverine sources and lake sinks[J]. Front. Environ. Sci. Eng., 2022, 16(3): 30-.
[4]	Athiyanam Venkatesan Ramya, Manoj Balachandran. Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor: Ultrasensitive detection of potentially hazardous tropane alkaloid[J]. Front. Environ. Sci. Eng., 2022, 16(3): 27-.
[5]	Yicai Huang, Jiayuan Chen, Qiannan Duan, Yunjin Feng, Run Luo, Wenjing Wang, Fenli Liu, Sifan Bi, Jianchao Lee. A fast antibiotic detection method for simplified pretreatment through spectra-based machine learning[J]. Front. Environ. Sci. Eng., 2022, 16(3): 38-.
[6]	Shengdong Liu, Enxiang Shang, Jingnan Liu, Yining Wang, Nanthi Bolan, M.B. Kirkham, Yang Li. What have we known so far for fluorescence staining and quantification of microplastics: A tutorial review[J]. Front. Environ. Sci. Eng., 2022, 16(1): 8-.
[7]	Zuyin Chen, Lihua Li, Lichong Hao, Yu Hong, Wencai Wang. *Hormesis-like growth and photosynthetic physiology of marine diatom Phaeodactylum tricornutum* Bohlin exposed to polystyrene microplastics**[J]. Front. Environ. Sci. Eng., 2022, 16(1): 2-.
[8]	Xiao Deng, Yixuan Chen, Yang Yang, Liang Peng, Luo Si, Qingru Zeng. The implications of planting mode on cadmium uptake and remobilization in rice: Field experiments across growth stages[J]. Front. Environ. Sci. Eng., 2021, 15(6): 137-.
[9]	Sanjena Narayanasamydamodaran, Jian’e Zuo, Haiteng Ren, Nawnit Kumar. Scrap Iron Filings assisted nitrate and phosphate removal in low C/N waters using mixed microbial culture[J]. Front. Environ. Sci. Eng., 2021, 15(4): 66-.
[10]	Jinbiao Ma, Manman Du, Can Wang, Xinwu Xie, Hao Wang, Qian Zhang. Advances in airborne microorganisms detection using biosensors: A critical review[J]. Front. Environ. Sci. Eng., 2021, 15(3): 47-.
[11]	Sana Ullah, Xuejun Guo, Xiaoyan Luo, Xiangyuan Zhang, Siwen Leng, Na Ma, Palwasha Faiz. Rapid and long-effective removal of broad-spectrum pollutants from aqueous system by ZVI/oxidants[J]. Front. Environ. Sci. Eng., 2020, 14(5): 89-.
[12]	Nima Kamali, Abdollah Rashidi Mehrabadi, Maryam Mirabi, Mohammad Ali Zahed. Synthesis of vinasse-dolomite nanocomposite biochar via a novel developed functionalization method to recover phosphate as a potential fertilizer substitute[J]. Front. Environ. Sci. Eng., 2020, 14(4): 70-.
[13]	Muhammad Farooq Saleem Khan, Jing Wu, Cheng Cheng, Mona Akbar, Chuanyang Liu, Bo Liu, Jian Shen, Yu Xin. Insight into fluorescence properties of 14 selected toxic single-ring aromatic compounds in water: Experimental and DFT study[J]. Front. Environ. Sci. Eng., 2020, 14(3): 42-.
[14]	Ziwen Du, Chuyi Huang, Jiaqi Meng, Yaru Yuan, Ze Yin, Li Feng, Yongze Liu, Liqiu Zhang. Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars[J]. Front. Environ. Sci. Eng., 2020, 14(3): 43-.
[15]	Jinlan Yu, Kang Xiao, Wenchao Xue, Yue-xiao Shen, Jihua Tan, Shuai Liang, Yanfen Wang, Xia Huang. Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles, methods and applications[J]. Front. Environ. Sci. Eng., 2020, 14(2): 31-.

Viewed

Full text

Abstract

Cited

Shared

Discussed