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Ultra-small amorphous carbon dots: preparation, photoluminescence properties, and their application as TiO2 photosensitizers

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Abstract

Ultra-small carbon quantum dots (s-CQDs) with excitation wavelength-independent fluorescence had been obtained by hydrothermal-followed acid precipitation method and were characterized by FT-IR, TEM, XPS, UV–Vis and XRD. It was found that as-prepared s-CQDs were amorphous spherical particles with an average diameter of 1.51 nm, and there were abundant hydroxyl and carbonyl groups on their surfaces. Moreover, fluorescence emission study found that the luminescence of s-CQDs was aroused by oxygen group decorated on its surface, and the fluorescence properties of s-CQDs were much different from those of large CQDs (l-CQDs), which showed higher quantum yield and better photoluminescence (PL) property than that of l-CQDs. The PL of s-CQDs possessed two emission centers and was exhibited to be excitation independent. When s-CQDs was used as photosensitizer for TiO2 to photocatalytic degradation of methylene blue under visible light irradiation, it showed significantly improved photocatalytic activities compared with 1-CQDs, and the degradation efficiency of methylene blue reached up to 96.6%. The high degradation efficiency was attributed to the ultra-small particle size, abundant acidic groups, and excellent optical properties of s-CQDs.

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References

  1. Pan J, Zheng Z, Yang J, Wu Y, Lu F, Chen Y, Gao W (2017) A novel and sensitive fluorescence sensor for glutathione detection by controlling the surface passivation degree of carbon quantum dots. Talanta 166:1–7

    Article  Google Scholar 

  2. Tao S, Song Y, Zhu S, Shao J, Yang B (2017) A new type of polymer carbon dots with high quantum yield: from synthesis to investigation on fluorescence mechanism. Polymer 116:472–478

    Article  Google Scholar 

  3. Zheng XT, Ananthanarayanan A, Luo KQ, Chen P (2015) Glowing graphene quantum dots and carbon dots: properties, syntheses, and biological applications. Small 11:1620–1636

    Article  Google Scholar 

  4. Li CX, Yu C, Wang CF, Chen S (2013) Facile plasma-induced fabrication of fluorescent carbon dots toward high-performance white LEDs. J Mater Sci 48:6307–6311. https://doi.org/10.1007/s10853-013-7430-6

    Article  Google Scholar 

  5. Chang Q, Li KK, Hu SL, Dong YG, Yang JL (2016) Hydroxyapatite supported n-doped carbon quantum dots for visible-light photocatalysis. Mater Lett 175:44–47

    Article  Google Scholar 

  6. Majumder T, Mondal SP (2016) Advantages of nitrogen-doped graphene quantum dots as a green sensitizer with ZnO nanorod based photoanodes for solar energy conversion. J Electroanal Chem 769:48–52

    Article  Google Scholar 

  7. Feng Z, Li Z, Zhang X, Xu G, Zhou N (2018) Fluorescent carbon dots with two absorption bands: luminescence mechanism and ion detection. J Mater Sci 53:6459–6470. https://doi.org/10.1007/s10853-018-2017-x

    Article  Google Scholar 

  8. Tu Z, Zhang Q, Liu M, Qian Y, Wang L, Huang W (2016) One-pot synthesis of a photostable green fluorescent probe for biological imaging. J Mater Sci 51:2972–2979. https://doi.org/10.1007/s10853-015-9606-8

    Article  Google Scholar 

  9. Weng CI, Chang HT, Lin CH, Shen YW, Unnikrishnan B, Li YJ, Huang C (2015) One-step synthesis of biofunctional carbon quantum dots for bacterial labeling. Biosens Bioelectron 68:1–6

    Article  Google Scholar 

  10. Mehta VN, Jha S, Basu H, Singhal RK, Kailasa SK (2015) One-step hydrothermal approach to fabricate carbon dots from apple juice for imaging of mycobacterium and fungal cells. Sens Actuators B Chem 213:434–443

    Article  Google Scholar 

  11. Yu H, Zhao Y, Zhou C, Shang L, Peng Y, Cao Y, Wu LZ, Tung CH, Zhang T (2014) Carbon quantum dots/TiO2 composites for efficient photocatalytic hydrogen evolution. J Mater Chem A 2:3344–3351

    Article  Google Scholar 

  12. Tian J, Leng Y, Zhao Z, Xia Y, Sang Y, Hao P, Zhan J, Li M, Liu H (2015) Carbon quantum dots/hydrogenated TiO2 nanobelt heterostructures and their broad spectrum photocatalytic properties under UV, visible, and near-infrared irradiation. Nano Energy 11:419–427

    Article  Google Scholar 

  13. Liu J, Zhu W, Yu S, Yan X (2014) Three dimensional carbogenic dots/TiO2 nanoheterojunctions with enhanced visible light-driven photocatalytic activity. Carbon 79:369–379

    Article  Google Scholar 

  14. Nguyen V, Si J, Yan L, Hou X (2016) Direct demonstration of photoluminescence originated from surface functional groups in carbon nanodots. Carbon 108:268–273

    Article  Google Scholar 

  15. Loukanov A, Sekiya R, Yoshikawa M, Kobayashi N, Moriyasu Y, Nakabayashi S (2016) Photosensitizer-conjugated ultrasmall carbon nanodots as multifunctional fluorescent probes for bioimaging. J Phys Chem C 120:15867–15874

    Article  Google Scholar 

  16. Wang Y, Hu A (2014) Carbon quantum dots: synthesis, properties and applications. J Mater Chem C 2:6921–6939

    Article  Google Scholar 

  17. Sharma S, Umar A, Sood S, Mehta SK, Kansal SK (2018) Photoluminescent C-dots: an overview on the recent development in the synthesis, physiochemical properties and potential applications. J Alloys Compd 748:818–853

    Article  Google Scholar 

  18. Rahy A, Zhou C, Zheng J, Park SY, Kim MJ, Jang I, Cho SJ, Yang DJ (2012) Photoluminescent carbon nanoparticles produced by confined combustion of aromatic compounds. Carbon 50:1298–1302

    Article  Google Scholar 

  19. Wang J, Sahu S, Sonkar S, Tackettii K, Sun K, Liu Y, Maimaiti H, Anilkumar P, Sun YP (2013) Versatility with carbon dots—from overcooked bbq to brightly fluorescent agents and photocatalysts. RSC Adv 3:15604–15607

    Article  Google Scholar 

  20. Hou J, Li H, Wang L, Zhang P, Zhou T, Ding H, Ding L (2015) Rapid microwave-assisted synthesis of molecularly imprinted polymers on carbon quantum dots for fluorescent sensing of tetracycline in milk. Talanta 146:34–40

    Article  Google Scholar 

  21. Li H, He X, Liu Y, Huang H, Lian S, Lee ST, Kang Z (2011) One-step ultrasonic synthesis of water-soluble carbon nanoparticles with excellent photoluminescent properties. Carbon 49:605–609

    Article  Google Scholar 

  22. Cai A, Wang Q, Chang Y, Wang X (2017) Graphitic carbon nitride decorated with S, N co-doped graphene quantum dots for enhanced visible-light-driven photocatalysis. J Alloys Compd 692:183–189

    Article  Google Scholar 

  23. Yao S, Hu Y, Li G (2014) A one-step sonoelectrochemical preparation method of pure blue fluorescent carbon nanoparticles under a high intensity electric field. Carbon 66:77–83

    Article  Google Scholar 

  24. Lu S, Liao F, Wang T, Zhu L, Shao M (2016) Tuning surface properties of graphene oxide quantum dots by gamma-ray irradiation. J Lumin 175:88–93

    Article  Google Scholar 

  25. Li H, He X, Liu Y, Yu H, Kang Z, Lee ST (2011) Synthesis of fluorescent carbon nanoparticles directly from active carbon via a one-step ultrasonic treatment. Mater Res Bull 46:147–151

    Article  Google Scholar 

  26. Peng J, Gao W, Gupta BK, Liu Z, Romero-Aburto R, Ge L, Song LB (2012) Graphene quantum dots derived from carbon fibers. Nano Lett 12:844–849

    Article  Google Scholar 

  27. Umrao S, Jang MH, Oh JH, Kim G, Sahoo S, Cho YH, Srivastva A, Oh IK (2015) Microwave bottom-up route for size-tunable and switchable photoluminescent graphene quantum dots using acetylacetone: new platform for enzyme-free detection of hydrogen peroxide. Carbon 81:514–524

    Article  Google Scholar 

  28. Wu P, Li W, Wu Q, Liu Y, Liu S (2017) Hydrothermal synthesis of nitrogen-doped carbon quantum dots from microcrystalline cellulose for the detection of Fe3+ ions in an acidic environment. RSC Adv 7:44144–44153

    Article  Google Scholar 

  29. Wu Q, Li W, Wu P, Li J, Liu S, Jin C, Zhan X (2015) Effect of reaction temperature on properties of carbon nanodots and their visible-light photocatalytic degradation of tetracyline. RSC Adv 5:75711–75721

    Article  Google Scholar 

  30. Cao X, Xi Peng, Sun S, Zhong L, Chen W, Wang S, Sun R (2015) Hydrothermal conversion of xylose, glucose, and cellulose under the catalysis of transition metal sulfates. Carbohydr Polym 118:44–51

    Article  Google Scholar 

  31. Sevilla M, Fuertes AB (2009) Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides. Chem Eur J 15:4195–4203

    Article  Google Scholar 

  32. Zhou C, He X, Ya D, Zhong J, Deng B (2017) One step hydrothermal synthesis of nitrogen-doped graphitic quantum dots as a fluorescent sensing strategy for highly sensitive detection of metacycline in mice plasma. Sens Actuators B Chem 249:256–264

    Article  Google Scholar 

  33. He G, Shu M, Yang Z, Ma Y, Huang D, Xu S, Wang Y, Hu N, Zhang Y, Xu L (2017) Microwave formation and photoluminescence mechanisms of multi-states nitrogen doped carbon dots. Appl Surf Sci 422:257–265

    Article  Google Scholar 

  34. Lu W, Gong X, Ming N, Yang L, Shuang S, Dong C (2015) Comparative study for N and S doped carbon dots: synthesis, characterization and applications for Fe3+, probe and cellular imaging. Anal Chim Acta 898:116–127

    Article  Google Scholar 

  35. Gong X, Lu W, Paau MC, Hu Q, Wu X, Shuang S, Dong C, Choi MMF (2015) Facile synthesis of nitrogen-doped carbon dots for Fe (3+) sensing and cellular imaging. Anal Chim Acta 861:74–84

    Article  Google Scholar 

  36. Chen X, Zhang W, Wang Q, Fan J (2014) C8-structured carbon quantum dots: synthesis, blue and green double luminescence, and origins of surface defects. Carbon 79:165–173

    Article  Google Scholar 

  37. Miao X, Qu D, Yang D, Nie B, Zhao Y, Fan H, Sun Z (2017) Synthesis of carbon dots with multiple color emission by controlled graphitization and surface functionalization. Adv Mater 30:1704740. https://doi.org/10.1002/adma.201704740

    Article  Google Scholar 

  38. Zhang Y, Cui P, Zhang F, Fen X, Wang Y, Yang Y, Liu X (2016) Fluorescent probes for “off-on” highly sensitive detection of Hg2+ and l-cysteine based on nitrogen-doped carbon dots. Talanta 152:288–300

    Article  Google Scholar 

  39. Yu X, Liu J, Yu Y, Zuo S, Li B (2014) Preparation and visible light photocatalytic activity of carbon quantum dots/TiO2, nanosheet composites. Carbon 68:718–724

    Article  Google Scholar 

  40. Li M, Hu C, Yu C, Wang S, Zhang P, Qiu J (2015) Organic amine-grafted carbon quantum dots with tailored surface and enhanced photoluminescence properties. Carbon 91:291–297

    Article  Google Scholar 

  41. Tan D, Zhou S, Xu B, Chen P, Shimotsuma Y, Miura K, Qiu J (2013) Simple synthesis of ultra-small nanodiamonds with tunable size and photoluminescence. Carbon 62:374–381

    Article  Google Scholar 

  42. Majumder T, Debnath K, Dhar S, Hmar JJL, Mondal SP (2016) Nitrogen-doped graphene quantum dot-decorated ZnO nanorods for improved electrochemical solar energy conversion. Energy Technol 4:1–10

    Article  Google Scholar 

  43. Wang C, Xu Z, Cheng H, Lin H, Humphrey MG, Zhang C (2015) A hydrothermal route to water-stable luminescent carbon dots as nanosensors for pH and temperature. Carbon 82:87–95

    Article  Google Scholar 

  44. Ha HD, Jang MH, Liu F, Cho YH, Seo TS (2015) Upconversion photoluminescent metal ion sensors via two photon absorption in graphene oxide quantum dots. Carbon 81:367–375

    Article  Google Scholar 

  45. Gan Z, Wu X, Zhou G, Shen J, Chu PK (2013) Is there real upconversion photoluminescence from graphene quantum dots? Adv Opt Mater 1:554–558

    Article  Google Scholar 

  46. Wen X, Yu P, Toh YR, Ma X, Tang J (2014) On the upconversion fluorescence in carbon nanodots and graphene quantum dots. Chem Commun 50:4703–4706

    Article  Google Scholar 

  47. Han L, Liu SG, Dong JX, Liang JY, Li LJ, Li NB, Luo HQ (2017) Facile synthesis of multicolor photoluminescent polymer carbon dots with surface-state energy gap-controlled emission. J Mater Chem C 5:10785–10793

    Article  Google Scholar 

  48. Zhu S, Song Y, Wang J, Wan H, Zhang Y, Ning Y, Yang B (2017) Photoluminescence mechanism in graphene quantum dots: quantum confinement effect and surface/edge state. Nano Today 13:10–14

    Article  Google Scholar 

  49. Ming H, Ma Z, Liu Y, Pan K, Yu H, Wang F, Kang Z (2012) Large scale electrochemical synthesis of high quality carbon nanodots and their photocatalytic property. Dalton Trans 41:9526–9531

    Article  Google Scholar 

  50. Qu A, Xie H, Xu X, Zhang Y, Wen S, Cui Y (2016) High quantum yield graphene quantum dots decorated TiO2, nanotubes for enhancing photocatalytic activity. Appl Surf Sci 375:230–241

    Article  Google Scholar 

  51. Hou Y, Lu Q, Wang H, Li H, Zhang Y, Zhang S (2016) One-pot electrochemical synthesis of carbon dots/TiO2 nanocomposites with excellent visible light photocatalytic activity. Mater Lett 173:13–17

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 31570567, 31500467, and 61705063) and the Fundamental Research Funds for the Central Universities (2572017ET02). We thank Andrew Jackson, PhD, from Liwen Bianji, Edanz Group China (www.liwenbianji.cn/ac), for editing the English text of a draft of this manuscript.

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  1. College of Materials Science and Engineering, Northeast Forestry University, Harbin, 150040, People’s Republic of China

    Peng Wu, Xueyun Wu, Wei Li, Yushan Liu, Zhijun Chen & Shouxin Liu

  2. College of Environmental and Chemical Engineering, Heilongjiang University of Science and Technology, Harbin, 150022, People’s Republic of China

    Peng Wu

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  1. Peng Wu
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Correspondence to Shouxin Liu.

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Wu, P., Wu, X., Li, W. et al. Ultra-small amorphous carbon dots: preparation, photoluminescence properties, and their application as TiO2 photosensitizers. J Mater Sci 54, 5280–5293 (2019). https://doi.org/10.1007/s10853-018-3135-1

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