SCIENCE CHINA Materials, Volume 62 , Issue 10 : 1445-1453(2019) https://doi.org/10.1007/s40843-019-9457-5

Metal-organic framework film for fluorescence turn-on H2S gas sensing and anti-counterfeiting patterns

More info
  • ReceivedApr 24, 2019
  • AcceptedJun 10, 2019
  • PublishedJun 27, 2019


Funded by

the National Natural Science Foundation of China(U1609219,51632008,61721005,51432001,51772268)

and Zhejiang Provincial Natural Science Foundation(LD18E020001)


This work was supported by the National Natural Science Foundation of China (U1609219, 51632008, 61721005, 51432001 and 51772268), and Zhejiang Provincial Natural Science Foundation (LD18E020001).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Zhang J designed and performed the experiments, analyzed the data and wrote the paper; Liu F designed partial experiments. Gan J, Yang Y and Li B analyzed the data; Cui Y and Qian G conceived the framework of this paper and revised the paper. All authors contributed to the general discussion.

Author information

Jun Zhang was born in Auhui, China. He received his bachelor’s degree in materials science and engineering from Zhejiang University (2015). He is now a PhD student at the School of Materials Science and Engineering at Zhejiang University under the supervision of Prof. Guodong Qian. His current research interest focuses on photonic application of MOF films.

Yuanjing Cui was born in Jiangsu, China. He received his BSc and PhD in materials science and engineering from Zhejiang University in 1998 and 2006, respectively. Currently he is a full professor at the School of Materials Science and Engineering at Zhejiang University. His research interest focuses on organic-inorganic hybrid photonic materials.

Guodong Qian was born in Zhejiang, China. He received his bachelor’s (1988) and master’s (1992) degrees in materials science from Zhejiang University in China. He joined the Materials Department of Zhejiang University after obtaining his PhD degree from Zhejiang University in 1997. He was promoted to associate professor, full professor and Cheung Kong professor in 1999, 2002 and 2011, respectively. His current research interests include hybrid organic-inorganic photonic functional materials and multifunctional porous materials.


Supplementary information

Supplementary details are available in the online version of the paper.


[1] Kaushik A, Kumar R, Arya SK, et al. Organic–inorganic hybrid nanocomposite-based gas sensors for environmental monitoring. Chem Rev, 2015, 115: 4571-4606 CrossRef PubMed Google Scholar

[2] Vikrant K, Kumar V, Ok YS, et al. Metal-organic framework (MOF)-based advanced sensing platforms for the detection of hydrogen sulfide. TrAC Trends Anal Chem, 2018, 105: 263-281 CrossRef Google Scholar

[3] Sasakura K, Hanaoka K, Shibuya N, et al. Development of a highly selective fluorescence probe for hydrogen sulfide. J Am Chem Soc, 2011, 133: 18003-18005 CrossRef PubMed Google Scholar

[4] Meng C, Cui X, Qi S, et al. Lung inflation with hydrogen sulfide during the warm ischemia phase ameliorates injury in rat donor lungs via metabolic inhibition after cardiac death. Surgery, 2017, 161: 1287-1298 CrossRef PubMed Google Scholar

[5] Wan X, Wu L, Zhang L, et al. Novel metal-organic frameworks-based hydrogen sulfide cataluminescence sensors. Sensor Actuat B-Chem, 2015, 220: 614-621 CrossRef Google Scholar

[6] Liu B, Chen Y. Responsive lanthanide coordination polymer for hydrogen sulfide. Anal Chem, 2013, 85: 11020-11025 CrossRef PubMed Google Scholar

[7] Modaberi MR, Rooydell R, Brahma S, et al. Enhanced response and selectivity of H2S sensing through controlled Ni doping into ZnO nanorods by using single metal organic precursors. Sensor Actuat B-Chem, 2018, 273: 1278-1290 CrossRef Google Scholar

[8] Tian K, Wang XX, Yu ZY, et al. Hierarchical and hollow Fe2O3 nanoboxes derived from metal–organic frameworks with excellent sensitivity to H2S. ACS Appl Mater Interfaces, 2017, 9: 29669-29676 CrossRef Google Scholar

[9] Cui Y, Zhang J, He H, et al. Photonic functional metal–organic frameworks. Chem Soc Rev, 2018, 47: 5740-5785 CrossRef PubMed Google Scholar

[10] Kreno LE, Leong K, Farha OK, et al. Metal–organic framework materials as chemical sensors. Chem Rev, 2012, 112: 1105-1125 CrossRef PubMed Google Scholar

[11] Chen S, Chen Z, Ren W, et al. Reaction-based genetically encoded fluorescent hydrogen sulfide sensors. J Am Chem Soc, 2012, 134: 9589-9592 CrossRef PubMed Google Scholar

[12] Wu Z, Li Z, Yang L, et al. Fluorogenic detection of hydrogen sulfide via reductive unmasking of o-azidomethylbenzoyl-coumarin conjugate. Chem Commun, 2012, 48: 10120-10122 CrossRef PubMed Google Scholar

[13] Qian Y, Karpus J, Kabil O, et al. Selective fluorescent probes for live-cell monitoring of sulphide. Nat Commun, 2011, 2: 495 CrossRef PubMed ADS Google Scholar

[14] Liu C, Pan J, Li S, et al. Capture and visualization of hydrogen sulfide by a fluorescent probe. Angew Chem Int Ed, 2011, 50: 10327-10329 CrossRef PubMed Google Scholar

[15] Hai Z, Bao Y, Miao Q, et al. Pyridine–biquinoline–metal complexes for sensing pyrophosphate and hydrogen sulfide in aqueous buffer and in cells. Anal Chem, 2015, 87: 2678-2684 CrossRef PubMed Google Scholar

[16] Yang Q, Xu Q, Jiang HL. Metal–organic frameworks meet metal nanoparticles: synergistic effect for enhanced catalysis. Chem Soc Rev, 2017, 46: 4774-4808 CrossRef PubMed Google Scholar

[17] Hu Z, Mahdi EM, Peng Y, et al. Kinetically controlled synthesis of two-dimensional Zr/Hf metal–organic framework nanosheets via a modulated hydrothermal approach. J Mater Chem A, 2017, 5: 8954-8963 CrossRef Google Scholar

[18] Li B, Chrzanowski M, Zhang Y, et al. Applications of metal-organic frameworks featuring multi-functional sites. Coord Chem Rev, 2016, 307: 106-129 CrossRef Google Scholar

[19] Li B, Leng K, Zhang Y, et al. Metal–organic framework based upon the synergy of a brønsted acid framework and lewis acid centers as a highly efficient heterogeneous catalyst for fixed-bed reactions. J Am Chem Soc, 2015, 137: 4243-4248 CrossRef PubMed Google Scholar

[20] Zhang Y, Yuan S, Day G, et al. Luminescent sensors based on metal-organic frameworks. Coord Chem Rev, 2018, 354: 28-45 CrossRef Google Scholar

[21] Lustig WP, Mukherjee S, Rudd ND, et al. Metal–organic frameworks: functional luminescent and photonic materials for sensing applications. Chem Soc Rev, 2017, 46: 3242-3285 CrossRef PubMed Google Scholar

[22] Wang H, Lustig WP, Li J. Sensing and capture of toxic and hazardous gases and vapors by metal–organic frameworks. Chem Soc Rev, 2018, 47: 4729-4756 CrossRef PubMed Google Scholar

[23] Cui Y, Zhu F, Chen B, et al. Metal–organic frameworks for luminescence thermometry. Chem Commun, 2015, 51: 7420-7431 CrossRef PubMed Google Scholar

[24] Zhang M, Feng G, Song Z, et al. Two-dimensional metal–organic framework with wide channels and responsive turn-on fluorescence for the chemical sensing of volatile organic compounds. J Am Chem Soc, 2014, 136: 7241-7244 CrossRef PubMed Google Scholar

[25] Zhou X, Cheng J, Li L, et al. A europium(III) metal-organic framework as ratiometric turn-on luminescent sensor for Al3+ ions. Sci China Mater, 2018, 61: 752-757 CrossRef Google Scholar

[26] Yin W, Tao C, Wang F, et al. Tuning optical properties of MOF-based thin films by changing the ligands of MOFs. Sci China Mater, 2018, 61: 391-400 CrossRef Google Scholar

[27] Zhang D, Xu Y, Liu Q, et al. Encapsulation of CH3NH3PbBr3 perovskite quantum dots in MOF-5 microcrystals as a stable platform for temperature and aqueous heavy metal ion detection. Inorg Chem, 2018, 57: 4613-4619 CrossRef PubMed Google Scholar

[28] Zhang J, Xia T, Zhao D, et al. In situ secondary growth of Eu(III)-organic framework film for fluorescence sensing of sulfur dioxide. Senss Actuators B-Chem, 2018, 260: 63-69 CrossRef Google Scholar

[29] Zhang J, Yue D, Xia T, et al. A luminescent metal-organic framework film fabricated on porous Al2O3 substrate for sensitive detecting ammonia. Micropor Mesopor Mater, 2017, 253: 146-150 CrossRef Google Scholar

[30] Dou Z, Yu J, Cui Y, et al. Luminescent metal–organic framework films as highly sensitive and fast-response oxygen sensors. J Am Chem Soc, 2014, 136: 5527-5530 CrossRef PubMed Google Scholar

[31] Rocha J, Brites CDS, Carlos LD. Lanthanide organic framework luminescent thermometers. Chem Eur J, 2016, 22: 14782-14795 CrossRef PubMed Google Scholar

[32] Long GL, Voigtman EG, Kosinski MA, et al. Reduction of electronic noise in inductively coupled plasma atomic emission and fluorescence spectrometric measurements. Anal Chem, 1983, 55: 1432-1434 CrossRef Google Scholar

[33] Dalapati R, Balaji SN, Trivedi V, et al. A dinitro-functionalized Zr(IV)-based metal-organic framework as colorimetric and fluorogenic probe for highly selective detection of hydrogen sulphide. Sensor Actuat B-Chem, 2017, 245: 1039-1049 CrossRef Google Scholar

[34] Xin X, Wang J, Gong C, et al. Cyclodextrin-based metal-organic nanotube as fluorescent probe for selective turn-on detection of hydrogen sulfide in living cells based on H2S-involved coordination mechanism. Sci Rep, 2016, 6: 21951 CrossRef PubMed ADS Google Scholar

[35] Legrand A, Pastushenko A, Lysenko V, et al. Enhanced ligand-based luminescence in metal-organic framework sensor. ChemNanoMat, 2016, 2: 866-872 CrossRef Google Scholar

[36] Buragohain A, Biswas S. Cerium-based azide- and nitro-functionalized UiO-66 frameworks as turn-on fluorescent probes for the sensing of hydrogen sulphide. CrystEngComm, 2016, 18: 4374-4381 CrossRef Google Scholar

[37] Cao YY, Guo XF, Wang H. High sensitive luminescence metal-organic framework sensor for hydrogen sulfide in aqueous solution: A trial of novel turn-on mechanism. Sensor Actuat B-Chem, 2017, 243: 8-13 CrossRef Google Scholar

[38] Ma Y, Su H, Kuang X, et al. Heterogeneous nano metal–organic framework fluorescence probe for highly selective and sensitive detection of hydrogen sulfide in living cells. Anal Chem, 2014, 86: 11459-11463 CrossRef PubMed Google Scholar

[39] Nagarkar SS, Desai AV, Ghosh SK. A nitro-functionalized metal-organic framework as a reaction-based fluorescence turn-on probe for rapid and selective H2S detection. Chem Eur J, 2015, 21: 9994-9997 CrossRef PubMed Google Scholar

[40] Das A, Banesh S, Trivedi V, et al. Extraordinary sensitivity for H2S and Fe(III) sensing in aqueous medium by Al-MIL-53-N3 metal–organic framework: in vitro and in vivo applications of H2S sensing. Dalton Trans, 2018, 47: 2690-2700 CrossRef PubMed Google Scholar

[41] Zhang X, Zhang Q, Yue D, et al. Flexible metal-organic framework-based mixed-matrix membranes: a new platform for H2S sensors. Small, 2018, 14: 1801563 CrossRef PubMed Google Scholar

[42] Li H, Feng X, Guo Y, et al. A malonitrile-functionalized metal-organic framework for hydrogen sulfide detection and selective amino acid molecular recognition. Sci Rep, 2014, 4: 4366 CrossRef PubMed ADS Google Scholar

[43] Dong X, Su Y, Lu T, et al. MOFs-derived dodecahedra porous Co3O4: An efficient cataluminescence sensing material for H2S. Sensor Actuat B-Chem, 2018, 258: 349-357 CrossRef Google Scholar

[44] Balouria V, Ramgir NS, Singh A, et al. Enhanced H2S sensing characteristics of Au modified Fe2O3 thin films. Sensor Actuat, 2015, 219: 125-132 CrossRef Google Scholar

[45] White KA, Chengelis DA, Gogick KA, et al. Near-infrared luminescent lanthanide MOF barcodes. J Am Chem Soc, 2009, 131: 18069-18071 CrossRef PubMed Google Scholar

[46] Liu J, Zhuang Y, Wang L, et al. Achieving multicolor long-lived luminescence in dye-encapsulated metal–organic frameworks and its application to anticounterfeiting stamps. ACS Appl Mater Interfaces, 2018, 10: 1802-1809 CrossRef Google Scholar

[47] Kaczmarek AM, Liu YY, Wang C, et al. Lanthanide “Chameleon” multistage anti-counterfeit materials. Adv Funct Mater, 2017, 27: 1700258 CrossRef Google Scholar

[48] Du BB, Zhu YX, Pan M, et al. Direct white-light and a dual-channel barcode module from Pr(III)-MOF crystals. Chem Commun, 2015, 51: 12533-12536 CrossRef PubMed Google Scholar

[49] Cui Y, Chen B, Qian G. Lanthanide metal-organic frameworks for luminescent sensing and light-emitting applications. Coord Chem Rev, 2014, 273-274: 76-86 CrossRef Google Scholar

  • Scheme 1

    Schematic diagram of the fluorescence turn-on sensor for H2S gas of MIL-100(In)@Eu3+/Cu2+ film. (a) The supertetrahedra of MIL-100(In) film and the coordinated BTC ligands; fluorescence state of MIL-100(In)@Eu3+/Cu2+ film in (b) absence and (c) presence of H2S.

  • Figure 1

    XRD patterns of the films. (a) Simulated MIL-100(Al). (b) As-synthesized MIL-100(In) film. (c) MIL-100(In)@Eu3+/Cu2+ film. (d) MIL-100(In)@Eu3+/Cu2+ film after heating to 100°C. (e) MIL-100(In)@Eu3+/Cu2+ film after exposure to H2S gas at 100°C. (f) MIL-100(In)@Eu3+/Cu2+ film after putting into air for two months.

  • Figure 2

    SEM images of (a) top view and (b) cross section of MIL-100(In)@Eu3+/Cu2+ film. (c, d) Energy-dispersive X-ray spectroscopy of MIL-100(In)@Eu3+/Cu2+ film. SEM images of (e) top view and (f) cross section of MIL-100(In)@Eu3+/Cu2+ film after exposure to H2S at 40°C. (g, h) Energy-dispersive X-ray spectroscopy of MIL-100(In)@Eu3+/Cu2+ film after exposure to H2S at 40°C.

  • Figure 3

    The enhancement fold of the emission intensity of 5D07F2 transition of Eu3+ of MIL-100(In)@Eu3+/Cu2+ film towards various gases (1% v/v diluted with N2) at 40°C.

  • Figure 4

    Emission spectra (a) and KSV curve (b) of MIL-100(In)@Eu3+/Cu2+ film in the presence of different concentration of H2S at 40°C.

  • Figure 5

    Photographs of the patterns written by the lanthanide ions ink on MIL-100(In) film pad under nature light (a1) and UV excitation (a2–a5); Photographs of the patterns after immersed in hot water under nature light (b1) and UV excitation (b2–b5). a2: Eu3+ ink; a3: Tb3+ ink; a4: Dy3+ ink.

  • Table 1   Comparison of the sensing properties of various HS sensors



    Sensing medium

    Detection limit

    Temperature (°C)


    Test conc. (ppm)

    LOD (ppm)

    MIL-100(In)@Eu3+/Cu2+ film






    This work



    HEPES buffer









    0. 002












    HEPES buffer







    HEPES buffer














    BBS butter







    HEPES buffer







    HEPES buffer





    Al-MIL-53-NO2 MMM


































    Fe2O3 nanoboxes















Contact and support