SCIENCE CHINA Materials, Volume 61 , Issue 7 : 1001-1006(2018) https://doi.org/10.1007/s40843-017-9209-8

Fluorescein supramolecular nanosheets: A novel organic photocatalyst for visible-light-driven H2 evolution from water

More info
  • ReceivedDec 10, 2017
  • AcceptedJan 4, 2018
  • PublishedFeb 10, 2018


氢能源是未来最理想的清洁能源, 可以利用太阳能和光催化材料分解水获得. 开发廉价、资源丰富、环境友好的光催化材料, 成为近年来能源和环境领域的研究热点. 基于此, 我们报道了一种新型有机光催化材料-不含金属的荧光素超分子纳米片, 其在可见光下显示出高效的光催化分解水产氢活性, 产氢速率接近341 μmol g−1 h−1,420±10 nm的波段下表观量子效率达到1.2%. 这是荧光素超分子晶体首次被报道并应用于可见光下分解水产氢, 这一发现丰富了有机和超分子光催化剂的种类.

Funded by

the National Natural Science Foundation of China(51502174,21401190)

Science and Technology Project of the Research Foundation of China Postdoctoral Science(2017M612710,2016M592519)

Shenzhen Peacock Plan(827-000059,827-000113,KQTD2016053112042971)

Science and Technology Planning Project of Guangdong Province(2016B050501005)


This work was jointly supported by the National Natural Science Foundation of China (51502174 and 21401190), Science and Technology Project of the Research Foundation of China Postdoctoral Science (2017M612710 and 2016M592519), Shenzhen Peacock Plan (827-000059, 827-000113 and KQTD2016053112042971), Science and Technology Planning Project of Guangdong Province (2016B050501005).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Zhang GQ performed the experiments, and wrote the manuscript under the guidance of Xu YS. All authors contributed to the general discussion and article revision.

Author information

Guo-Qiang Zhang received his BSc degree majored in material chemistry from Lanzhou University in 2012. Then he obtained his PhD degree at the University of Chinese Academy of Sciences under the supervision of Prof. Da-Bing Li. His research interest is the semiconductor photocatalytic water spliting.

Yang-Sen Xu received his BSc degree at Yangtze University in 2006 and MSc degree at Shenzhen University in 2009 both majored in applied chemistry. He obtained his PhD in applied chemistry from the South China University of Technology in 2013 under the supervision of Prof. Wei-De Zhang. He joined Fujian Institute of Research on the Structure of Mater, Chinese Academy of Sciences in 2013 as an assistant professor and then an associate professor. He moved to SZU-NUS Collaborative Center and International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology in Shenzhen University in 2017. His research interest focuses on the synthesis and application of novel 2D carbon nitride based materials for energy storage and environmental protection.


Supplementary information

Supporting information is available in the online version of the paper.


[1] Chen X, Shen S, Guo L, et al. Semiconductor-based photocatalytic hydrogen generation. Chem Rev, 2010, 110: 6503-6570 CrossRef PubMed Google Scholar

[2] Han T, Chen Y, Tian G, et al. Hydrogenated TiO2/SrTiO3 porous microspheres with tunable band structure for solar-light photocatalytic H2 and O2 evolution. Sci China Mater, 2016, 59: 1003-1016 CrossRef Google Scholar

[3] Hao R, Jiang B, Li M, et al. Fabrication of mixed-crystalline-phase spindle-like TiO2 for enhanced photocatalytic hydrogen production. Sci China Mater, 2015, 58: 363-369 CrossRef Google Scholar

[4] Meng R, Jiang J, Liang Q, et al. Design of graphene-like gallium nitride and WS2/WSe2 nanocomposites for photocatalyst applications. Sci China Mater, 2016, 59: 1027-1036 CrossRef Google Scholar

[5] Yanagida S, Kabumoto A, Mizumoto K, et al. Poly(p-phenylene)-catalysed photoreduction of water to hydrogen. Chem Commun, 1985, 8: 474-475 CrossRef Google Scholar

[6] Shibata T, Kabumoto A, Shiragami T, et al. Novel visible-light-driven photocatalyst. Poly(p-phenylene)-catalyzed photoreductions of water, carbonyl compounds, and olefins. J Phys Chem, 1990, 94: 2068-2076 CrossRef Google Scholar

[7] Wang X, Maeda K, Thomas A, et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater, 2009, 8: 76-80 CrossRef PubMed ADS Google Scholar

[8] Luo J, Zhang X, Zhang J. Carbazolic porous organic framework as an efficient, metal-free visible-light photocatalyst for organic synthesis. ACS Catal, 2015, 5: 2250-2254 CrossRef Google Scholar

[9] Ghosh S, Kouamé NA, Ramos L, et al. Conducting polymer nanostructures for photocatalysis under visible light. Nat Mater, 2015, 14: 505-511 CrossRef PubMed ADS Google Scholar

[10] Ge J, Lan M, Liu W, et al. Graphene quantum dots as efficient, metal-free, visible-light-active photocatalysts. Sci China Mater, 2016, 59: 12-19 CrossRef Google Scholar

[11] Liang Q, Li Z, Bai Y, et al. Reduced-sized monolayer carbon nitride nanosheets for highly improved photoresponse for cell imaging and photocatalysis. Sci China Mater, 2017, 60: 109-118 CrossRef Google Scholar

[12] Xu YS, Zhang WD. Ag/AgBr-grafted graphite-like carbon nitride with enhanced plasmonic photocatalytic activity under visible light. ChemCatChem, 2013, 5: 2343-2351 CrossRef Google Scholar

[13] Pu C, Wan J, Liu E, et al. Two-dimensional porous architecture of protonated GCN and reduced graphene oxide via electrostatic self-assembly strategy for high photocatalytic hydrogen evolution under visible light. Appl Surf Sci, 2017, 399: 139-150 CrossRef ADS Google Scholar

[14] Wang B, Zhang J, Huang F. Enhanced visible light photocatalytic H2 evolution of metal-free g-C3N4/SiC heterostructured photocatalysts. Appl Surf Sci, 2016, 391: 449-456 CrossRef ADS Google Scholar

[15] Chen F, Yang H, Wang X, et al. Facile synthesis and enhanced photocatalytic H2-evolution performance of NiS2-modified g-C3N4 photocatalysts. Chin J Catal, 2017, 38: 296-304 CrossRef Google Scholar

[16] Xia P, Zhu B, Yu J, et al. Ultra-thin nanosheet assemblies of graphitic carbon nitride for enhanced photocatalytic CO2 reduction. J Mater Chem A, 2016, 5: 3230-3238 CrossRef Google Scholar

[17] Yu W, Chen J, Shang T, et al. Direct Z-scheme g-C3N4/WO3 photocatalyst with atomically defined junction for H2 production. Appl Catal B-Environ, 2017, 219: 693-704 CrossRef Google Scholar

[18] Moulton B, Zaworotko MJ. From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids. Chem Rev, 2001, 101: 1629-1658 CrossRef Google Scholar

[19] Wasielewski MR. Photoinduced electron transfer in supramolecular systems for artificial photosynthesis. Chem Rev, 1992, 92: 435-461 CrossRef Google Scholar

[20] Astruc D, Boisselier E, Ornelas Ć. Dendrimers designed for functions: from physical, photophysical, and supramolecular properties to applications in sensing, catalysis, molecular electronics, photonics, and nanomedicine. Chem Rev, 2010, 110: 1857-1959 CrossRef PubMed Google Scholar

[21] Cook TR, Zheng YR, Stang PJ. Metal–organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal–organic materials. Chem Rev, 2013, 113: 734-777 CrossRef PubMed Google Scholar

[22] Stupp SI. Supramolecular materials: self-organized nanostructures. Science, 1997, 276: 384-389 CrossRef Google Scholar

[23] Zhu M, Li Z, Xiao B, et al. Surfactant assistance in improvement of photocatalytic hydrogen production with the porphyrin noncovalently functionalized graphene nanocomposite. ACS Appl Mater Interfaces, 2013, 5: 1732-1740 CrossRef PubMed Google Scholar

[24] Wang J, Zhong Y, Wang L, et al. Morphology-controlled synthesis and metalation of porphyrin nanoparticles with enhanced photocatalytic performance. Nano Lett, 2016, 16: 6523-6528 CrossRef PubMed ADS Google Scholar

[25] Liu D, Wang J, Bai X, et al. Self-assembled PDINH supramolecular system for photocatalysis under visible light. Adv Mater, 2016, 28: 7284-7290 CrossRef PubMed Google Scholar

[26] Walkup GK, Burdette SC, Lippard SJ, et al. A new cell-permeable fluorescent probe for Zn2+. J Am Chem Soc, 2000, 122: 5644-5645 CrossRef Google Scholar

[27] Kobayashi H, Ogawa M, Alford R, et al. New strategies for fluorescent probe design in medical diagnostic imaging. Chem Rev, 2009, 110: 2620-2640 CrossRef PubMed Google Scholar

[28] Munkholm C, Parkinson DR, Walt DR. Intramolecular fluorescence self-quenching of fluoresceinamine. J Am Chem Soc, 1990, 112: 2608-2612 CrossRef Google Scholar

[29] Kojima H, Nakatsubo N, Kikuchi K, et al. Detection and imaging of nitric oxide with novel fluorescent indicators: diaminofluoresceins. Anal Chem, 1998, 70: 2446-2453 CrossRef Google Scholar

[30] Batistela VR, da Costa Cedran J, Moisés de Oliveira HP, et al. Protolytic fluorescein species evaluated using chemometry and DFT studies. Dyes Pigments, 2010, 86: 15-24 CrossRef Google Scholar

[31] Mu Y, Wang N, Sun Z, et al. Carbogenic nanodots derived from organo-templated zeolites with modulated full-color luminescence. Chem Sci, 2016, 7: 3564-3568 CrossRef Google Scholar

[32] Dong Y, Pang H, Yang HB, et al. Carbon-based dots co-doped with nitrogen and sulfur for high quantum yield and excitation-independent emission. Angew Chem Int Ed, 2013, 52: 7800-7804 CrossRef PubMed Google Scholar

[33] Yang C, Ma BC, Zhang L, et al. Molecular engineering of conjugated polybenzothiadiazoles for enhanced hydrogen production by photosynthesis. Angew Chem Int Ed, 2016, 55: 9202-9206 CrossRef PubMed Google Scholar

[34] Kronik L, Shapira Y. Surface photovoltage phenomena: theory, experiment, and applications. Surf Sci Rep, 1999, 37: 1-206 CrossRef ADS Google Scholar

[35] Zhang G, Jiang W, Hua S, et al. Constructing bulk defective perovskite SrTiO3 nanocubes for high performance photocatalysts. Nanoscale, 2016, 8: 16963-16968 CrossRef PubMed Google Scholar

[36] Schroder DK. Surface voltage and surface photovoltage: history, theory and applications. Meas Sci Technol, 2001, 12: R16-R31 CrossRef ADS Google Scholar

[37] Khalfaoui M, Knani S, Hachicha MA, et al. New theoretical expressions for the five adsorption type isotherms classified by BET based on statistical physics treatment. J Colloid Interface Sci, 2003, 263: 350-356 CrossRef ADS Google Scholar

[38] Wang J, Yang X, Wu D, et al. The porous structures of activated carbon aerogels and their effects on electrochemical performance. J Power Sources, 2008, 185: 589-594 CrossRef ADS Google Scholar

[39] Zhang Y, Liu J, Wu G, et al. Porous graphitic carbon nitride synthesized via direct polymerization of urea for efficient sunlight-driven photocatalytic hydrogen production. Nanoscale, 2012, 4: 5300-5303 CrossRef PubMed ADS Google Scholar

[40] Lau VW, Yu VW, Ehrat F, et al. Urea-modified carbon nitrides: enhancing photocatalytic hydrogen evolution by rational defect engineering. Adv Energy Mater, 2017, 7: 1602251 CrossRef Google Scholar

[41] Han Q, Wang B, Gao J, et al. Graphitic carbon nitride/nitrogen-rich carbon nanofibers: highly efficient photocatalytic hydrogen evolution without cocatalysts. Angew Chem Int Ed, 2016, 55: 10849-10853 CrossRef PubMed Google Scholar

[42] Zhang G, Lan ZA, Wang X. Conjugated polymers: catalysts for photocatalytic hydrogen evolution. Angew Chem Int Ed, 2016, 55: 15712-15727 CrossRef PubMed Google Scholar

[43] Zhang H, Zong R, Zhu Y. Photocorrosion inhibition and photoactivity enhancement for zinc oxide via hybridization with monolayer polyaniline. J Phys Chem C, 2009, 113: 4605-4611 CrossRef Google Scholar

[44] Fu H, Xu T, Zhu S, et al. Photocorrosion inhibition and enhancement of photocatalytic activity for ZnO via hybridization with C60. Environ Sci Technol, 2008, 42: 8064-8069 CrossRef ADS Google Scholar

[45] Hu Y, Gao X, Yu L, et al. Carbon-coated CdS petalous nanostructures with enhanced photostability and photocatalytic activity. Angew Chem, 2013, 125: 5746-5749 CrossRef Google Scholar

[46] Jing D, Guo L. A novel method for the preparation of a highly stable and active CdS photocatalyst with a special surface nanostructure. J Phys Chem B, 2006, 110: 11139-11145 CrossRef PubMed Google Scholar

[47] Ran J, Zhang J, Yu J, et al. Enhanced visible-light photocatalytic H2 production by ZnxCd1−xS modified with earth-abundant nickel-based cocatalysts. ChemSusChem, 2014, 7: 3426-3434 CrossRef PubMed Google Scholar

[48] Higashi M, Domen K, Abe R. Highly stable water splitting on oxynitride TaON photoanode system under visible light irradiation. J Am Chem Soc, 2012, 134: 6968-6971 CrossRef PubMed Google Scholar

  • Figure 1

    The structure formula (a), optimized structure with Gaussian09 package (C, gray; H, white; and O, red) (b) of fluorescein single molecule. The electronic density distribution of HOMO (c) and LUMO (d).

  • Figure 2

    Experimental schematic diagram (a). FE-SEM images of fluorescein-P (b, c) and supramolecular NS (d, e). XRD pattern (f) and UV-vis DRS spectra (g) of fluorescein-P and supramolecular NSs. Inset of g is the optical image.

  • Figure 3

    TEM images of supramolecular NSs before (a, b) and after (c, d) loading 1 wt% Pt nanoparticles as cocatalyst. Inset of d is the HR-TEM image of Pt nanoparticles.

  • Figure 4

    The comparison of H2 production (λ>420 nm) between fluorescein supramolecular NSs and PCN prepared from urea (a), and the recycling measurements of H2 production (b). TEM image of supramolecular NSs after photocatalysis for 15 h (c). The XRD pattern of supramolecular NSs before and after photocatalysis for 15 h (d).

  • Figure 5

    The UPS spectrum and possible photocatalytic H2 production mechanism of fluorescein supramolecular NSs.

Copyright 2020 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有

京ICP备17057255号       京公网安备11010102003388号