Atom transfer radical polymerization; Carbon dots; Photocatalysis; Catalysis; Chemistry (all)
Abstract :
[en] We herein report the use of carbon dots (CDs) in photoinduced atom transfer radical polymerizations (ATRP) as green metal-free sensitizers. In particular, the production of a polymethacrylate (poly-METAC, METAC = 2-(methacryloyloxy)ethyl]trimethylammonium chloride) by using cheap and easily affordable CDs made from citric acid and diethylenetriamine, under both ultraviolet (UV, λ = 365 nm) and visible light was studied. Different solvent systems have been tested and a CuII complex was used as catalyst. Under the best conditions a polymer in 89% conversion and with a narrow dispersity (1.4) was obtained. The first order kinetics and the “on-off” experiments gave further evidence of the constant concentration of radicals and of the controlled mechanism of the polymerization.
Disciplines :
Chemistry
Author, co-author :
Campalani, Carlotta ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Integrated Technology and Organic Synthesis ; Department of Molecular Sciences and Nanosystems, Università Ca’ Foscari di Venezia, Venezia, Italy
Bragato, Nicola; Department of Molecular Sciences and Nanosystems, Università Ca’ Foscari di Venezia, Venezia, Italy
Morandini, Andrea; Department of Molecular Sciences and Nanosystems, Università Ca’ Foscari di Venezia, Venezia, Italy
Selva, Maurizio; Department of Molecular Sciences and Nanosystems, Università Ca’ Foscari di Venezia, Venezia, Italy
Fiorani, Giulia; Department of Molecular Sciences and Nanosystems, Università Ca’ Foscari di Venezia, Venezia, Italy
Perosa, Alvise ; Department of Molecular Sciences and Nanosystems, Università Ca’ Foscari di Venezia, Venezia, Italy
Language :
English
Title :
Carbon dots as green photocatalysts for atom transfer radical polymerization of methacrylates
Cariplo Foundation for Scientific Research Fondazione Cariverona
Funding text :
This work was supported by: Nuova Ompi – Stevanato for funding AM’s research, Fondazione Cariverona for the project “Valorizzazione di scarti agroalimentari per nuovi cosmetici green” ID n° 1174 – Cod . SIME n° 2019.0428 and Fondazione Cariplo for the project “Photo- and Mechano-Chemistry for the Upgrading of Agro- and Sea-food Waste to advanced polymers and nanocarbon materials”, CUBWAM , n° 2021-0751 .Giorgia Minello is kindly acknowledged for her help during the experimental part of this project. Nuova Ompi – Stevanato is gratefully acknowledged for supporting AM’s research. Fondazione Cariverona is gratefully acknowledged for funding the project “Valorizzazione di scarti agroalimentari per nuovi cosmetici green” ID n° 1174 – Cod. SIME n° 2019.0428. We gratefully acknowledge the support from Fondazione Cariplo (Photo- and Mechano-Chemistry for the Upgrading of Agro- and Sea-food Waste to advanced polymers and nanocarbon materials, CUBWAM, project 2021–0751).This work was supported by: Nuova Ompi – Stevanato for funding AM's research, Fondazione Cariverona for the project “Valorizzazione di scarti agroalimentari per nuovi cosmetici green” ID n° 1174 – Cod. SIME n° 2019.0428 and Fondazione Cariplo for the project “Photo- and Mechano-Chemistry for the Upgrading of Agro- and Sea-food Waste to advanced polymers and nanocarbon materials”, CUBWAM, n° 2021-0751.
Wang, J.-S., Matyjaszewski, K., Controlled “Living ” radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 117 (1995), 5614–5615, 10.1021/ja00125a035.
Kato, M., Kamigaito, M., Sawamoto, M., Higashimura, T., Polymerization of methyl methacrylate with the carbon Tetrachloride/Dichlorotris(triphenylphosphine)ruthenium(II)/ methylaluminum Bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28 (1995), 1721–1723, 10.1021/ma00109a056.
Percec, V., Barboiu, B., “Living” radical polymerization of styrene initiated by arenesulfonyl chlorides and CuI(bpy)nCl. Macromolecules 28 (1995), 7970–7972, 10.1021/ma00127a057.
Dadashi-Silab, S., Tasdelen, M.A., Yagci, Y., Photoinitiated atom transfer radical polymerization: current status and future perspectives. Polym. Chem. 52 (2014), 2878–2888, 10.1002/pola.27327.
Di Lena, F., Matyjaszewski, K., Transition metal catalysts for controlled radical polymerization. Prog. Polym. Sci. 35 (2010), 959–1021, 10.1016/j.progpolymsci.2010.05.001.
Matyjaszewski, K., Jakubowski, W., Min, K., Tang, W., Huang, J., Braunecker, W.A., Tsarevsky, N.V., Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents. Proc. Natl. Acad. Sci. USA 103 (2006), 15309–15314, 10.1073/pnas.0602675103.
Magenau, A.J.D., Strandwitz, N.C., Gennaro, A., Matyjaszewski, K., Electrochemically mediated atom transfer radical polymerization. Science 332:2011 (1979), 81–84, 10.1017/cbo9781139167291.033.
Matyjaszewski, K., Tsarevsky, N.V., Braunecker, W.A., Dong, H., Huang, J., Jakubowski, W., Kwak, Y., Nicolay, R., Tang, W., Yoon, J.A., Role of Cu 0 in controlled/"living" radical polymerization. Macromolecules 40 (2007), 7795–7806, 10.1021/ma0717800.
Konkolewicz, D., Schröder, K., Buback, J., Bernhard, S., Matyjaszewski, K., Visible light and sunlight photoinduced ATRP with ppm of Cu catalyst. ACS Macro Lett. 1 (2012), 1219–1223, 10.1021/mz300457e.
Tasdelen, M.A., Uygun, M., Yagci, Y., Photoinduced controlled radical polymerization in methanol. Macromol. Chem. Phys. 211 (2010), 2271–2275, 10.1002/macp.201000445.
Tasdelen, M.A., Uygun, M., Yagci, Y., Studies on photoinduced ATRP in the presence of photoinitiator. Macromol. Chem. Phys. 212 (2011), 2036–2042, 10.1002/macp.201100267.
Ribelli, T.G., Konkolewicz, D., Bernhard, S., Matyjaszewski, K., How are radicals (re)generated in photochemical ATRP. J. Am. Chem. Soc. 136 (2014), 13303–13312, 10.1021/ja506379s.
Discekici, E.H., Anastasaki, A., Read De Alaniz, J., Hawker, C.J., Evolution and future directions of metal-free atom transfer radical polymerization. Macromolecules 51 (2018), 7421–7434, 10.1021/acs.macromol.8b01401.
Kütahya, C., Wang, P., Li, S., Liu, S., Li, J., Chen, Z., Strehmel, B., Carbon dots as a promising green photocatalyst for free radical and ATRP‐Based radical. Angew. Chem. - Int. Ed. 59 (2020), 3166–3171, 10.1002/anie.201912343.
Pan, X., Malhotra, N., Simakova, A., Wang, Z., Konkolewicz, D., Matyjaszewski, K., Photoinduced atom transfer radical polymerization with ppm-Level Cu catalyst by visible light in aqueous media. J. Am. Chem. Soc. 137 (2015), 15430–15433, 10.1021/jacs.5b11599.
Kütahya, C., Schmitz, C., Strehmel, V., Yagci, Y., Strehmel, B., Near-Infrared sensitized photoinduced atom-transfer radical polymerization (ATRP) with a Copper(II) catalyst concentration in the ppm range. Angew. Chem. - Int. Ed. 57 (2018), 7898–7902, 10.1002/anie.201802964.
Jiang, J., Ye, G., Wang, Z., Lu, Y., Chen, J., Matyjaszenski, K., Heteroatom‐Doped carbon dots CDs as a class of metal‐free photocatalysts for PET‐RAFT. Angew. Chem. 130 (2018), 12213–12218, 10.1002/anie.201807385.
Du, J., Xu, N., Fan, J., Sun, W., Peng, X., Carbon dots for in vivo bioimaging and theranostics. Small 15 (2019), 1–16, 10.1002/smll.201805087.
Cailotto, S., Amadio, E., Facchin, M., Selva, M., Pontoglio, E., Rizzolio, F., Riello, P., Toffoli, G., Benedetti, A., Perosa, A., Carbon-dots from sugars and ascorbic acid: role of the precursors on morphology, properties, toxicity and drug uptake. ACS Med. Chem. Lett. 9 (2018), 832–837, 10.1021/acsmedchemlett.8b00240.
Choi, H., Ko, S.J., Choi, Y., Joo, P., Kim, T., Lee, B.R., Jung, J.W., Choi, H.J., Cha, M., Jeong, J.R., Hwang, I.W., Song, M.H., Kim, B.S., Kim, J.Y., Versatile surface plasmon resonance of carbon-dot-supported silver nanoparticles in polymer optoelectronic devices. Nat. Photonics 7 (2013), 732–738, 10.1038/nphoton.2013.181.
Hutton, G.A.M., Martindale, B.C.M., Reisner, E., Carbon dots as photosensitisers for solar-driven catalysis. Chem. Soc. Rev. 46 (2017), 6111–6123, 10.1039/C7CS00235A.
Emanuele, A., Cailotto, S., Campalani, C., Branzi, L., Raviola, C., Ravelli, D., Cattaruzza, E., Trave, E., Benedetti, A., Selva, M., Perosa, A., Precursor-dependent photocatalytic activity of carbon dots. Molecules 25 (2019), 1–9, 10.3390/molecules25010101.
Cailotto, S., Negrato, M., Daniele, S., Luque, R., Selva, M., Amadio, E., Perosa, A., Carbon dots as photocatalysts for organic synthesis: Metal-free methylene-oxygen-bond photocleavage. Green. Chem. 22 (2020), 1145–1149, 10.1039/c9gc03811f.
Campalani, C., Cattaruzza, E., Zorzi, S., Vomiero, A., You, S., Matthews, L., Capron, M., Mondelli, C., Selva, M., Perosa, A., Biobased carbon dots: from fish scales to photocatalysis. Nanomaterials, 11, 2021, 524, 10.3390/nano11020524.
Yan, M., Zhu, F., Gu, W., Sun, L., Shi, W., Hua, Y., Construction of nitrogen-doped graphene quantum dots-BiVO4/g-C3N4 Z -scheme photocatalyst and enhanced photocatalytic degradation of antibiotics under visible light. RSC Adv. 6 (2016), 61162–61174, 10.1039/c6ra07589d.
Campalani, C., Petit, G., Selva, M., Perosa, A., Continuous flow photooxidative degradation of azo dyes with biomass-derived carbon dots. ChemPhotoChem, 2022, 10.1002/cptc.202200234.
Campalani, C., Causin, V., Selva, M., Perosa, A., Fish-waste-derived gelatin and carbon dots for biobased UV- blocking films. ACS Appl. Mater. Interfaces 14 (2022), 35148–35156, 10.1021/acsami.2c11749.
Cailotto, S., Massari, D., Gigli, M., Campalani, C., Bonini, M., You, S., Vomiero, A., Selva, M., Perosa, A., Crestini, C., N-Doped carbon dot hydrogels from brewing waste for photocatalytic wastewater treatment. ACS Omega 7 (2022), 4052–4061, 10.1021/acsomega.1c05403.
Hao, Q., Qiao, L., Shi, G., He, Y., Cui, Z., Fu, P., Liu, M., Qiao, X., Pang, X., Effect of nitrogen type on carbon dot photocatalysts for visible-light-induced atom transfer radical polymerization. Polym. Chem. 12 (2021), 3060–3066, 10.1039/d1py00148e.
Zhang, Z., Yi, G., Li, P., Zhang, X., Fan, H., Zhang, Y., Wang, X., Zhang, C., A minireview on doped carbon dots for photocatalytic and electrocatalytic applications. Nanoscale 12 (2020), 13899–13906, 10.1039/d0nr03163a.
Nguyen, K.G., Baragau, I.A., Gromicova, R., Nicolaev, A., Thomson, S.A.J., Rennie, A., Power, N.P., Sajjad, M.T., Kellici, S., Investigating the effect of N-doping on carbon quantum dots structure, optical properties and metal ion screening. Sci. Rep. 12 (2022), 1–12, 10.1038/s41598-022-16893-x.
Cailotto, S., Mazzaro, R., Enrichi, F., Vomiero, A., Cattaruzza, E., Cristofori, D., Amadio, E., Perosa, A., Design of carbon dots for metal-free photoredox catalysis. ACS Appl. Mater. Interfaces 10 (2018), 40560–40567, 10.1021/acsami.8b14188.
Soin, N., Sinha Roy, S., Roy, S., Hazra, K.S., Misra, D.S., Lim, T.H., Hetherington, C.J., McLaughlin, J.A., Enhanced and stable field emission from in situ nitrogen-doped few-layered graphene nanoflakes. J. Phys. Chem. C. 115 (2011), 5366–5372, 10.1021/jp110476m.
Matyjaszewski, K., Göbelt, B., Paik, H.J., Horwitz, C.P., Tridentate nitrogen-based ligands in Cu-based ATRP: a structure-activity study. Macromolecules 34 (2001), 430–440, 10.1021/ma001181s.
Stenzel, M.H., Barner-Kowollik, C., The living dead – common misconceptions about reversible deactivation radical polymerization. Mater. Horiz. 3 (2016), 471–477, 10.1039/c6mh00265j.
Tanan, W., Panichpakdee, J., Saengsuwan, S., Novel biodegradable hydrogel based on natural polymers: Synthesis, characterization, swelling/reswelling and biodegradability. Eur. Polym. J. 112 (2019), 678–687, 10.1016/j.eurpolymj.2018.10.033.
Roa, K., Tapiero, Y., Thotiyl, M.O., Sánchez, J., Hydrogels based on poly([2-(acryloxy)ethyl] trimethylammonium chloride) and nanocellulose applied to remove methyl orange dye from water. Polymer, 13, 2021, 10.3390/polym13142265.
Sánchez, J., Mendoza, N., Rivas, B.L., Basáez, L., Santiago-García, J.L., Preparation and characterization of water-soluble polymers and their utilization in chromium sorption. J. Appl. Polym. Sci. 134 (2017), 1–10, 10.1002/app.45355.
