Ultrasmall nanoparticles with tunable photo-optical properties and colloidal nature are ideal for a wide range of photocatalytic reaction. Herein, we reported the facile synthesis of ultrasmall aluminum nanoparticles (AlNPs), which exhibited unique UV-B photoluminescence and excitation wavelength dependent fluorescence characteristic. Spherical aberration-corrected scanning transmission electron microscope (ACTEM) and X-ray photoelectron spectroscopy (XPS) were used to study the microstructure and verify the successful synthesis of AlNPs. Time-resolved photoluminescence spectroscopy was employed to gain insight into the unique photoluminescence behavior. The photocatalytic activity of ultrasmall AlNPs was evaluated by the photoreduction of resazurin (RZ) to resorufin (RF) under UV light irradiation. This photodegradation of RZ obeyed the pseudo-first-order reaction kinetics with reaction rate achieved 6.62 × 10-2 min-1. Our study suggested that the prepared ultrasmall AlNPs have a great potential application in photocatalytic field.
2. Duan, H. and S. Nie, "Etching colloidal gold nanocrystals with hyperbranched and multivalent polymers: A new route to fluorescent and water-soluble atomic clusters," Journal of the American Chemical Society, Vol. 129, No. 9, 2412-2413, Mar. 1, 2007.
doi:10.1021/ja067727t
3. Zhou, C., G. Hao, P. Thomas, J. Liu, M. Yu, S. Sun, O. K. Oz, X. Sun, and J. Zheng, "Near-infrared emitting radioactive gold nanoparticles with molecular pharmacokinetics," Angewandte Chemie International Edition, Vol. 51, No. 40, 10118-10122, Oct. 1, 2012.
doi:10.1002/anie.201203031
4. Zeng, C., T. Li, A. Das, N. L. Rosi, and R. Jin, "Chiral structure of thiolate-protected 28-gold-atom nanocluster determined by X-ray crystallography," Journal of the American Chemical Society, Vol. 135, No. 27, 10011-10013, Jul. 10, 2013.
doi:10.1021/ja404058q
5. Kim, B. H., N. Lee, H. Kim, K. An, Y. I. Park, Y. Choi, K. Shin, Y. Lee, S. G. Kwon, H. B. Na, J.-G. Park, T.-Y. Ahn, Y.-W. Kim, W. K. Moon, S. H. Choi, and T. Hyeon, "Large-scale synthesis of uniform and extremely small-sized iron oxide nanoparticles for high-resolution T1 magnetic resonance imaging contrast agents," Journal of the American Chemical Society, Vol. 133, No. 32, 12624-12631, Aug. 17, 2011.
doi:10.1021/ja203340u
6. Shellaiah, M., K. Awasthi, S. Chandran, B. Aazaad, K. W. Sun, N. Ohta, S.-P. Wu, and M.-C. Lin, "Methylammonium tin tribromide quantum dots for heavy metal ion detection and cellular imaging," ACS Applied Nano Materials, Vol. 5, No. 2, 2859-2874, Feb. 25, 2022.
doi:10.1021/acsanm.2c00028
7. Wang, N., Q. Sun, and J. Yu, "Ultrasmall metal nanoparticles confined within crystalline nanoporous materials: A fascinating class of nanocatalysts," Advanced Materials, Vol. 31, No. 1, 1803966, Jan. 1, 2019.
doi:10.1002/adma.201803966
8. Liu, Z., Z. Wu, Q. Yao, Y. Cao, O. J. H. Chai, and J. Xie, "Correlations between the fundamentals and applications of ultrasmall metal nanoclusters: Recent advances in catalysis and biomedical applications," Nano Today, Vol. 36, 101053, Feb. 1, 2021.
9. Ma, Z., Y. Zhang, J. Zhang, W. Zhang, M. F. Foda, X. Dai, and H. Han, "Ultrasmall peptide-coated platinum nanoparticles for precise NIR-II photothermal therapy by mitochondrial targeting," ACS Applied Materials & Interfaces, Vol. 12, No. 35, 39434-39443, Sep. 2, 2020.
doi:10.1021/acsami.0c11469
10. Jin, R., C. Zeng, M. Zhou, and Y. Chen, "Atomically precise colloidal metal nanoclusters and nanoparticles: Fundamentals and opportunities," Chemical Reviews, Vol. 116, No. 18, 10346-10413, Sep. 28, 2016.
doi:10.1021/acs.chemrev.5b00703
11. Liang, H., B.-J. Liu, B. Tang, S.-C. Zhu, S. Li, X.-Z. Ge, J.-L. Li, J.-R. Zhu, and F.-X. Xiao, "Atomically precise metal nanocluster-mediated photocatalysis," ACS Catalysis, Vol. 12, No. 7, 4216-4226, Apr. 1, 2022.
doi:10.1021/acscatal.2c00841
12. Kawawaki, T., Y. Kataoka, M. Hirata, Y. Akinaga, R. Takahata, K. Wakamatsu, Y. Fujiki, M. Kataoka, S. Kikkawa, A. S. Alotabi, S. Hossain, D. J. Osborn, T. Teranishi, G. G. Andersson, G. F. Metha, S. Yamazoe, and Y. Negishi, "Creation of high-performance heterogeneous photocatalysts by controlling ligand desorption and particle size of gold nanocluster," Angewandte Chemie International Edition, Vol. 60, No. 39, 21340-21350, Sep. 20, 2021.
doi:10.1002/anie.202104911
13. Christopher, P., H. Xin, A. Marimuthu, and S. Linic, "Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures," Nature Materials, Vol. 11, No. 12, 1044-1050, Dec. 1, 2012.
doi:10.1038/nmat3454
14. Honda, M., Y. Kumamoto, A. Taguchi, Y. Saito, and S. Kawata, "Plasmon-enhanced UV photocatalysis," Applied Physics Letters, Vol. 104, No. 6, 2014.
doi:10.1063/1.4864395
15. Knight, M. W., N. S. King, L. Liu, H. O. Everitt, P. Nordlander, and N. J. Halas, "Aluminum for plasmonics," ACS Nano, Vol. 8, No. 1, 834-840, Jan. 28, 2014.
doi:10.1021/nn405495q
16. Wu, H., X. Cheng, S. Xie, Y. Huang, R. A. Janjua, X. Liu, and S. He, "Aluminum quantum dots with surface controlled blue-UV photoluminescence," The Journal of Physical Chemistry C, Vol. 127, No. 5, 2687-2693, Feb. 9, 2023.
doi:10.1021/acs.jpcc.2c08441
17. Douglas-Gallardo, O. A., G. J. Soldano, M. M. Mariscal, and C. G. Snchez, "Effects of oxidation on the plasmonic properties of aluminum nanoclusters," Nanoscale, Vol. 9, No. 44, 17471-17480, 2017.
doi:10.1039/C7NR04904H
18. Makula, P., M. Pacia, and W. Macyk, "How to correctly determine the band gap energy of modified semiconductor photocatalysts based on UV-Vis spectra," The Journal of Physical Chemistry Letters, Vol. 9, No. 23, 6814-6817, Dec. 6, 2018.
doi:10.1021/acs.jpclett.8b02892
19. Schaaff, T. G., G. Knight, M. N. Shafigullin, R. F. Borkman, and R. L. Whetten, "Isolation and selected properties of a 10.4 kDa Gold: Glutathione cluster compound," The Journal of Physical Chemistry B, Vol. 102, No. 52, 10643-10646, Dec. 1, 1998.
doi:10.1021/jp9830528
20. Kasha, M., "Characterization of electronic transitions in complex molecules," Discussions of the Faraday Society, Vol. 9, No. 0, 14-19, 1950.
doi:10.1039/df9500900014
21. Diez, I., R. H. A. Ras, M. I. Kanyuk, and A. P. Demchenko, "On heterogeneity in fluorescent few-atom silver nanoclusters," Physical Chemistry Chemical Physics, Vol. 15, No. 3, 979-985, 2013.
doi:10.1039/C2CP43045B
22. Zhou, M., S. Long, X. Wan, Y. Li, Y. Niu, Q. Guo, Q.-M. Wang, and A. Xia, "Ultrafast relaxation dynamics of phosphine-protected, rod-shaped Au20 clusters: interplay between solvation and surface trapping," Physical Chemistry Chemical Physics, Vol. 16, No. 34, 18288-18293, 2014.
doi:10.1039/C4CP02336F
23. Wen, X., P. Yu, Y.-R. Toh, X. Ma, S. Huang, and J. Tang, "Fluorescence origin and spectral broadening mechanism in atomically precise Au8 nanoclusters," Nanoscale, Vol. 5, No. 21, 10251-10257, 2013.
doi:10.1039/c3nr03015f
24. Zhou, M. and R. Jin, "Optical properties and excited-state dynamics of atomically precise gold nanoclusters," Annual Review of Physical Chemistry, Vol. 72, No. 1, 121-142, Apr. 20, 2021.
doi:10.1146/annurev-physchem-090419-104921
25. Ning, J., et al., "Synthesis and structural properties of AlCNO composite thin films," Thin Solid Films, Vol. 385, No. 1, 55-60, Apr. 2, 2001.
26. Ricci, M., M. Trinquecoste, F. Auguste, R. Canet, P. Delhaes, C. Guimon, G. Pfister-Guillouzo, B. Nysten, and J. P. Issi, "Relationship between the structural organization and the physical properties of PECVD nitrogenated carbons," Journal of Materials Research, Vol. 8, No. 3, 480-488, Mar. 1, 1993.
doi:10.1557/JMR.1993.0480
27. Liu, Z., X. Jing, S. Zhang, and Y. Tian, "A copper nanocluster-based fluorescent probe for real- time imaging and ratiometric biosensing of calcium ions in neurons," Analytical Chemistry, Vol. 91, No. 3, 2488-2497, Feb. 5, 2019.
doi:10.1021/acs.analchem.8b05360
28. Panayotov, D. A. and J. R. Morris, "Thermal decomposition of a chemical warfare agent simulant (DMMP) on TiO2: Adsorbate reactions with lattice oxygen as studied by infrared spectroscopy," The Journal of Physical Chemistry C, Vol. 113, No. 35, 15684-15691, Sep. 3, 2009.
doi:10.1021/jp9036233
29. Abuelela, A. M., T. A. Mohamed, and O. V. Prezhdo, "DFT simulation and vibrational analysis of the IR and raman spectra of a CdSe quantum dot capped by methylamine and trimethylphosphine oxide ligands," The Journal of Physical Chemistry C, Vol. , No. , {, Vol. 116, No. 27, 14674-14681, Jul. 12, 2012.
doi:10.1021/jp303275v
30. Koninti, R. K., S. Satpathi, and P. Hazra, "Ultrafast fluorescence dynamics of highly stable copper nanoclusters synthesized inside the aqueous nanopool of reverse micelles," The Journal of Physical Chemistry C, Vol. 122, No. 10, 5742-5752, Mar. 15, 2018.
doi:10.1021/acs.jpcc.7b11457
31. Zhou, M. and Y. Song, "Origins of visible and near-infrared emissions in [Au25(SR)18]-nanoclusters," The Journal of Physical Chemistry Letters, Vol. 12, No. 5, 1514-1519, Feb. 11, 2021.
doi:10.1021/acs.jpclett.1c00120
32. Mills, A., J. Johnston, and C. O'Rourke, "Photocatalyst activity indicator inks, paiis, for assessing self-cleaning films," Accounts of Materials Research, Vol. 3, No. 1, 67-77, Jan. 28, 2022.
doi:10.1021/accountsmr.1c00196
33. Krishnamoorthy, K., R. Mohan, and S. J. Kim, "Graphene oxide as a photocatalytic material," Applied Physics Letters, Vol. 98, No. 24, 244101, 2011.
doi:10.1063/1.3599453