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Nano Research 2023, 16(4): 5909-5918 https://doi.org/10.1007/s12274-022-5167-8
Research Article | Issue | Published: 04 November 2022

Cascading electron transfer and photophysics in a donor-π-acceptor graphene nanoconjugate

Show Author's Information Lulu Fu1,  Hui Li1,  Yan Fang1,  Zihao Guan1,  Zhiyuan Wei1,  Naying Shan1,  Fang Liu1,  Yang Zhao1,  Mingfei Zhang1,  Zhipeng Huang1,  Mark G. Humphrey2,  Chi Zhang1( )
China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia
Keywords:
graphene, nonlinear optics, nanoconjugate, donor-π-acceptor (D-π-A), cascading charge separation
Topics:
Synthesis
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Fu L, Li H, Fang Y, et al. Cascading electron transfer and photophysics in a donor-π-acceptor graphene nanoconjugate. Nano Research, 2023, 16(4): 5909-5918. https://doi.org/10.1007/s12274-022-5167-8
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Abstract Full text Electronic supplementary material About this article

Electron-donating porphyrins (Por), electron-accepting phthalocyanines (Pcs), and reduced graphene oxide (RGO) were integrated into a multicomponent nanoconjugate (Por-RGO-Pc). The donor-π-acceptor nanoconjugate Por-RGO-Pc was characterized using Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and ultraviolet–visible (UV–Vis) spectroscopy. Photoinduced cascading electron/charge transfer from Por to RGO and from RGO to Pc was established from fluorescence, electrochemical, and femtosecond transient absorption (fs-TA) spectroscopy studies. The increased distance between the electron donors and acceptors of the Por-RGO-Pc nanoconjugate compared to the parent materials and the intermediate RGO-Pc results in long-lived charge separation, and an enhancement in nonlinear optical (NLO) absorption (a large NLO coefficient of about 827.44 cm/GW) towards nanosecond laser irradiation at 532 nm.


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Electronic supplementary material
About this article

Cascading electron transfer and photophysics in a donor-π-acceptor graphene nanoconjugate

Show Author's information Lulu Fu1, Hui Li1, Yan Fang1, Zihao Guan1, Zhiyuan Wei1, Naying Shan1, Fang Liu1, Yang Zhao1, Mingfei Zhang1, Zhipeng Huang1, Mark G. Humphrey2, Chi Zhang1( )
China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China
Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia

Abstract

Electron-donating porphyrins (Por), electron-accepting phthalocyanines (Pcs), and reduced graphene oxide (RGO) were integrated into a multicomponent nanoconjugate (Por-RGO-Pc). The donor-π-acceptor nanoconjugate Por-RGO-Pc was characterized using Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and ultraviolet–visible (UV–Vis) spectroscopy. Photoinduced cascading electron/charge transfer from Por to RGO and from RGO to Pc was established from fluorescence, electrochemical, and femtosecond transient absorption (fs-TA) spectroscopy studies. The increased distance between the electron donors and acceptors of the Por-RGO-Pc nanoconjugate compared to the parent materials and the intermediate RGO-Pc results in long-lived charge separation, and an enhancement in nonlinear optical (NLO) absorption (a large NLO coefficient of about 827.44 cm/GW) towards nanosecond laser irradiation at 532 nm.

Keywords: graphene, nonlinear optics, nanoconjugate, donor-π-acceptor (D-π-A), cascading charge separation

References(59)

[1]

Novoselov, K. S.; Geim A. K.; Morozov S. V.; Jiang D.; Zhang Y.; Dubonos S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666–669.
DOI Google Scholar
[2]

Geim, A. K.; Novoselov, K. S. The rise of graphene. Nat. Mater. 2007, 6, 183–191.
DOI Google Scholar
[3]

Park, S.; Ruoff, R. S. Chemical methods for the production of graphenes. Nat. Nanotechnol. 2009, 44, 217–224.
DOI Google Scholar
[4]

Waissman, J.; Anderson, L. E.; Talanov, A. V.; Yan, Z. Y.; Shin, Y. J.; Najafabadi, D. H.; Rezaee, M.; Feng, X. W.; Nocera, D. G.; Taniguchi, T. et al. Electronic thermal transport measurement in low-dimensional materials with graphene non-local noise thermometry. Nat. Nanotechnol. 2022, 17, 166–173.
DOI Google Scholar
[5]

Bae, S.; Kim, H.; Lee, Y.; Xu, X. F.; Park, J. S.; Zheng, Y; Balakrishnan, J.; Lei, T.; Kim, H. R.; Song, Y. I. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 2010, 5, 574–578.
DOI Google Scholar
[6]

Luo, B.; Fang, Y.; Wang, B.; Zhou, J. S.; Song, H. H.; Zhi, L. J. Two dimensional graphene-SnS2 hybrids with superior rate capability for lithium ion storage. Energy Environ. Sci. 2012, 5, 5226–5230.
DOI Google Scholar
[7]

Bottari, G.; Herranz, M. Á.; Wibmer, L.; Volland, M.; Rodríguez-Pérez, L.; Guldi, D. M.; Hirsch, A.; Martín, N.; D’Souza, F.; Torres, T. Chemical functionalization and characterization of graphene-based materials. Chem. Soc. Rev. 2017, 46, 4464–4500.
DOI Google Scholar
[8]

Chen, L. P.; Wang, L. J.; Shuai, Z. G.; Beljonne, D. Energy level alignment and charge carrier mobility in noncovalently functionalized graphene. J. Phys. Chem. Lett. 2013, 4, 2158–2165.
DOI Google Scholar
[9]

Muruganathan, M.; Sun, J.; Imamura, T.; Mizuta, H. Electrically tunable van der Waals interaction in Graphene-molecule complex. Nano Lett. 2015, 15, 8176–8180.
DOI Google Scholar
[10]

Woomer, A. H.; Druffel, D. L.; Sundberg, J. D.; Pawlik, J. T.; Warren, S. C. Bonding in 2D donor–acceptor heterostructures. J. Am. Chem. Soc. 2019, 141, 10300–10308.
DOI Google Scholar
[11]

Chen, Y.; Bai, T.; Dong, N. N.; Fan, F.; Zhang, S. F.; Zhuang, X. D.; Sun, J.; Zhang, B.; Zhang, X. Y.; Wang, J. et al. Graphene and its derivatives for laser protection. Prog. Mater. Sci. 2016, 84, 118–157.
DOI Google Scholar
[12]
Fu, L. L.; Fang, Y.; Guan, Z. H.; Wei, Z. Y.; Yang, R.; Shan, N. Y.; Liu, F.; Zhao, Y.; Zhang,M. F.; Huang, Z. P. et al. Dramatic femto second nonlinear absorption at a strongly coupled porphyrin-graphene nanoconjugate. Nano Res., in press, https://doi.org/10.1007/s12274-022-5155-z.
[13]

Xu, T.; Zhao, S. J.; Lin, C. W.; Zheng, X. L.; Lan, M. H. Recent advances in nanomaterials for sonodynamic therapy. Nano Res. 2020, 13, 2898–2908.
DOI Google Scholar
[14]

Kim, H.; Solak, K.; Han, Y.; Cho, Y. W.; Koo, K. M.; Kim, C. D.; Luo, Z. T.; Son, H.; Kim, H. R.; Mavi, A. et al. Electrically controlled mRNA delivery using a polypyrrole-graphene oxide hybrid film to promote osteogenic differentiation of human mesenchymal stem cells. Nano Res. 2022, 15, 9253–9263.
DOI Google Scholar
[15]

Behura, S. K.; Wang, C.; Wen, Y.; Berry, V. Graphene-semiconductor heterojunction sheds light on emerging photovoltaics. Nat. Photonics 2019, 13, 312–318.
DOI Google Scholar
[16]

Xu, H.; Zhang, L.; Ding, Z. C.; Hu, J. L.; Liu, J.; Liu, Y. C. Edge-functionalized graphene quantum dots as a thickness-insensitive cathode interlayer for polymer solar cells. Nano Res. 2018, 11, 4293–4301.
DOI Google Scholar
[17]

Gu, H. L.; Zhong, L. X.; Shi, G. S.; Li, J. Q.; Yu, K.; Li, J.; Zhang, S.; Zhu, C. Y.; Chen, S. H.; Yang, C. L. et al. Graphdiyne/graphene heterostructure: A universal 2d scaffold anchoring monodispersed transition-metal phthalocyanines for selective and durable CO2 electroreduction. J. Am. Chem. Soc. 2021, 143, 8679–8688.
DOI Google Scholar
[18]

Tian, S. F.; Chen, S. D.; Ren, X. T.; Hu, Y. Q.; Hu, H. Y.; Sun, J. J.; Bai, F. An efficient visible-light photocatalyst for CO2 reduction fabricated by cobalt porphyrin and graphitic carbon nitride via covalent bonding. Nano Res. 2020, 13, 2665–2672.
DOI Google Scholar
[19]

Wang, A. J.; Ye, J.; Humphrey, M. G.; Zhang, C. Graphene and carbon-nanotube nanohybrids covalently functionalized by porphyrins and phthalocyanines for optoelectronic properties. Adv. Mater. 2018, 30, 1705704.
DOI Google Scholar
[20]

Dissanayake, D. M. A. S.; Cifuentes, M. P.; Humphrey, M. G. Optical limiting properties of (reduced) graphene oxide covalently functionalized by coordination complexes. Coord. Chem. Rev. 2018, 375, 489–513.
DOI Google Scholar
[21]

Stergiou, A.; Cantón-Vitoria, R.; Psarrou, M. N.; Economopoulos, S. P.; Tagmatarchis, N. Functionalized graphene and targeted applications-Highlighting the road from chemistry to applications. Prog. Mater Sci. 2020, 114, 100683.
DOI Google Scholar
[22]

Miraftab, R.; Ramezanzadeh, B.; Bahlakeh, G.; Mahdavian, M. An advanced approach for fabricating a reduced graphene oxide-AZO dye/polyurethane composite with enhanced ultraviolet (UV) shielding properties: Experimental and first-principles QM modeling. Chem. Eng. J. 2017, 321, 159–174.
DOI Google Scholar
[23]

Bottari, G.; de la Torre, G.; Torres, T. Phthalocyanine-nanocarbon ensembles: From discrete molecular and supramolecular systems to hybrid nanomaterials. Acc. Chem. Res. 2015, 48, 900–910.
DOI Google Scholar
[24]
Chen, Y.; EI-Khouly, M. E.; Doyle, J. J.; Lin, Y.; Liu, Y.; Notaras, E.; Blau, W. J.; O’Flaherty, S. M. Phthalocyanines and related compounds: Nonlinear optical response and photoinduced electron transfer process. In Handbook of Organic Electronics and Photonics. Nalwa, H. S., Ed.; American Scientific Publishers: USA, 2008; pp 151−181.
[25]

Wang, A. J.; Yu, W.; Xiao, Z. G.; Song, Y. L.; Long, L. L.; Cifuentes, M. P.; Humphrey, M. G.; Zhang, C. A 1,3-dipolar cycloaddition protocol to porphyrin-functionalized reduced graphene oxide with a push–pull motif. Nano Res. 2015, 8, 870–886.
DOI Google Scholar
[26]

Balapanuru, J.; Yang, J. X.; Xiao, S.; Bao, Q. L.; Jahan, M.; Polavarapu, L.; Wei, J.; Xu, Q. H.; Loh, K. P. A graphene oxide-organic dye ionic complex with DNA-sensing and optical-limiting properties. Angew. Chem., Int. Ed. 2010, 49, 6549–6553.
DOI Google Scholar
[27]

Xu, Y. F.; Liu, Z. B.; Zhang, X. L.; Wang, Y.; Tian, J. G.; Huang, Y.; Ma, Y. F.; Zhang, X. Y.; Chen. Y. S. A graphene hybrid material covalently functionalized with porphyrin: Synthesis and optical limiting property. Adv. Mater. 2009, 21, 1275–1279.
DOI Google Scholar
[28]

Li, D. J.; Li, Q. H.; Wang, Z. R.; Ma, Z. Z.; Gu, Z. G.; Zhang, J. Interpenetrated metal-porphyrinic framework for enhanced nonlinear optical limiting. J. Am. Chem. Soc. 2021, 143, 17162–17169.
DOI Google Scholar
[29]

Luo, C.; Guldi, D. M.; Imahori, H.; Tamaki, K.; Sakata, Y. Sequential energy and electron transfer in an artificial reaction center: Formation of a long-lived charge-separated state. J. Am. Chem. Soc. 2000, 122, 6535–6551.
DOI Google Scholar
[30]

Kirner, S. V.; Henkel, C.; Guldi, D. M.; Megiatto, J. D. Jr.; Schuster, D. I. Multistep energy and electron transfer processes in novel rotaxane donor–acceptor hybrids generating microsecond-lived charge separated states. Chem. Sci. 2015, 6, 7293–7304.
DOI Google Scholar
[31]

Kaur, R.; Possanza, F.; Limosani, F.; Bauroth, S.; Zanoni, R.; Clark, T.; Arrigoni, G.; Tagliatesta, P.; Guldi, D. M. Understanding and controlling short- and long-range electron/charge-transfer processes in electron donor–acceptor conjugates. J. Am. Chem. Soc. 2020, 142, 7898–7911.
DOI Google Scholar
[32]

Limosani, F.; Kaur, R.; Cataldo, A.; Bellucci, S.; Micciulla, F.; Zanoni, R.; Lembo, A.; Wang, B. Z.; Pizzoferrato, R.; Guldi, D. M. et al. Designing cascades of electron transfer processes in multicomponent graphene conjugates. Angew. Chem., Int. Ed. 2020, 59, 23706–23715.
DOI Google Scholar
[33]

Liu, L. L.; Niu, Z. Q.; Zhang, L.; Zhou, W. Y.; Chen, X. D.; Xie, S. S. Nanostructured graphene composite papers for highly flexible and foldable supercapacitors. Adv. Mater. 2014, 26, 4855–4862.
DOI Google Scholar
[34]

Sheik-Bahae, M.; Said, A. A.; Wei, T. H.; Hagan, D. J.; Van Stryland, E. W. Sensitive measurement of optical nonlinearities using a single beam. IEEE J. Quantum Electron. 1990, 26, 760–769.
DOI Google Scholar
[35]

Feng, W.; Liu, K.; Zang, J. Y.; Wang, G.; Miao, R.; Ding, L. P.; Liu, T. H.; Kong, J. L.; Fang, Y. Flexible and transparent oligothiophene-o-carborane-containing hybrid films for nonlinear optical limiting based on efficient two-photon absorption. ACS Appl. Mater. Interfaces 2021, 13, 28985–28995.
DOI Google Scholar
[36]

Rusanova, J.; Pilkington, M.; Decurtins, S. A novel fully conjugated phenanthroline-appended phthalocyanine: Synthesis and characterisation. Chem. Commun. 2002, 2236–2237.
DOI Google Scholar
[37]

Wibmer, L.; Lourenco, L. M. O.; Roth, A.; Katsukis, G.; Neves, M. G. P. M. S.; Cavaleiro, J. A. S.; Tomé, J. P. C.; Torres, T.; Guldi, D. M. Decorating graphene nanosheets with electron accepting pyridyl-phthalocyanines. Nanoscale 2015, 7, 5674–5682.
DOI Google Scholar
[38]

Chen, Y.; Araki, Y.; Fujitsuka, M.; Hanack, M.; Ito, O.; O’Flaherty, S. M.; Blau, W. J. Photophysical studies on axially substituted indium and gallium phthalocyanines upon UV–Vis laser irradiation. Solid State Commun. 2004, 131, 773–778.
DOI Google Scholar
[39]

O’Flaherty, S. M.; Hold, S. V.; Cook, M. J.; Torres, T.; Chen, Y.; Hanack, M.; Blau, W. J. Molecular engineering of peripherally and axially modified phthalocyanines for optical limiting and nonlinear optics. Adv. Mater. 2003, 15, 19–32.
DOI Google Scholar
[40]

Chen, Y; Hanack, M; Araki, Y; Ito, O. Axially modified gallium phthalocyanines and naphthalocyanines for optical limiting. Chem. Soc. Rev. 2005, 34, 517–529.
DOI Google Scholar
[41]

Konarev, D. V.; Khasanov, S. S.; Lyubovskaya, R. N. Fullerene complexes with coordination assemblies of metalloporphyrins and metal phthalocyanines. Coord. Chem. Rev. 2014, 262, 16–36.
DOI Google Scholar
[42]

Fu, L. L.; Ye, J.; Li, H.; Huang, Z. P.; Humphrey, M. G.; Zhang, C. Strong near-infrared and ultrafast femtosecond nonlinearities of a covalently-linked triply-fused porphyrin dimer-SWCNT nanohybrid. Nano Res. 2022, 15, 1355–1365.
DOI Google Scholar
[43]

Ragoussi, M. E.; Malig, J.; Katsukis, G.; Butz, B.; Spiecker, E.; de la Torre, G.; Torres, T.; Guldi, D. M. Linking photo- and redoxactive phthalocyanines covalently to graphene. Angew. Chem., Int. Ed. 2012, 51, 6421–6425.
DOI Google Scholar
[44]
Xu, H. J.; Cai, H. Z.; Cui, L. X.; Yu, L. M.; Gao, R.; Shi, C. Molecular modulating of cobalt phthalocyanines on amino functionalized carbon nanotubes for enhanced electrocatalytic CO2 conversion. Nano Res., in press, https://doi.org/10.1007/s12274-022-4578-x.
[45]

Goswami, P.; Das, S.; Jain, P.; Chakma, B. Aptamer-graphene oxide for highly sensitive dual electrochemical detection of Plasmodium lactate dehydrogenase. Anal. Biochem. 2016, 514, 32–37.
DOI Google Scholar
[46]

Kotsyubynsky, V. O.; Boychuk, V. M.; Budzulyak, I. M.; Rachiy, B. I.; Hodlevska, M. A.; Kachmar, A. I.; Hodlevsky, M. A. Graphene oxide synthesis using modified Tour method. Adv. Nat. Sci.: Nanosci. Nanotechnol. 2021, 12, 035006.
DOI Google Scholar
[47]

Dasler, D.; Schäfer, R. A.; Minameyer, M. B.; Hitzenberger, J. F.; Hauke, F.; Drewello, T.; Hirsch, A. Direct covalent coupling of porphyrins to graphene. J. Am. Chem. Soc. 2017, 139, 11760–11765.
DOI Google Scholar
[48]
Ahmadianyazdi, A.; Nguyen, N. H. L.; Xu, J.; Berry, V. Glucose measurement via Raman spectroscopy of graphene: Principles and operation. Nano Res. 2022, 15, 8697–8704.
[49]

Guo, Z.; Du, F.; Ren, D. M.; Chen, Y. S.; Zheng, J. Y.; Liu, Z. B.; Tian, J. G. Covalently porphyrin-functionalized single-walled carbon nanotubes: A novel photoactive and optical limiting donor–acceptor nanohybrid. J. Mater. Chem. 2006, 16, 3021–3030.
DOI Google Scholar
[50]

Tomaszewicz, E.; Kurzawa, M. Use of XPS method in determination of chemical environment and oxidation state of sulfur and silver atoms in Ag6S3O4 and Ag8S4O4 compounds. J. Mater. Sci. 2004, 39, 2183–2185.
DOI Google Scholar
[51]

Hoenig, E.; Strong, S. E.; Wang, M. Z.; Radhakrishnan, J. M.; Zaluzec, N. J.; Skinner, J. L.; Liu, C. Controlling the structure of MoS2 membranes via covalent functionalization with molecular spacers. Nano Lett. 2020, 20, 7844–7851.
DOI Google Scholar
[52]

Pellegrino, G.; Alberti, A.; Condorelli, G. G.; Giannazzo, F.; La Magna, A.; Paoletti, A. M.; Pennesi, G.; Rossi, G.; Zanotti, G. Study of the anchoring process of tethered unsymmetrical Zn-phthalocyanines on TiO2 nanostructured thin films. J. Phys. Chem. C 2013, 117, 11176–11185.
DOI Google Scholar
[53]

Xiao, Y. H.; Gu, Z. G.; Zhang, J. Vapor-assisted epitaxial growth of porphyrin-based MOF thin film for nonlinear optical limiting. Sci. China Chem. 2020, 63, 1059–1065.
DOI Google Scholar
[54]

Tian, Y. B.; Vankova, N.; Weidler, P.; Kuc, A.; Heine, T.; Wöll, C.; Gu, Z. G.; Zhang, J. Oriented growth of in-oxo chain based metal-porphyrin framework thin film for high-sensitive photodetector. Adv. Sci. 2021, 8, 2100548.
DOI Google Scholar
[55]

Xiao, Y. H.; Zhang, Y. X.; Zhai, R.; Gu, Z. G.; Zhang, J. Helical copper-porphyrinic framework nanoarrays for highly efficient CO2 electroreduction. Sci. China Mater. 2022, 65, 1269–1275.
DOI Google Scholar
[56]

Rauch, F.; Krebs, J.; Günther, J.; Friedrich, A.; Hähnel, M.; Krummenacher, I.; Braunschweig, H.; Finze, M.; Marder, T. B. Electronically driven regioselective iridium-catalyzed C-H borylation of donor-π-acceptor chromophores containing triarylboron acceptors. Chem. —Eur. J. 2020, 26, 10626–10633.
DOI Google Scholar
[57]

Arpacay, P.; Maity, P.; El-Zohry, A. M.; Meindl, A.; Akca, S.; Plunkett, S.; Senge, M. O.; Blau, W. J.; Mohammed, O. F. Controllable charge-transfer mechanism at push–pull porphyrin/nanocarbon interfaces. J. Phys. Chem. C 2019, 123, 14283–14291.
DOI Google Scholar
[58]

Wang, A. J.; Yu, W.; Huang, Z. P.; Zhou, F.; Song, J. B.; Song, Y. L.; Long, L. L.; Cifuentes, M. P.; Humphrey, M. G.; Zhang, L. et al. Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance. Sci. Rep. 2016, 6, 23325.
DOI Google Scholar
[59]

Fu, L. L.; Humphrey, M. G.; Zhang, C. Covalent edge-functionalization of graphene oxide with porphyrins for highly efficient photoinduced electron/energy transfer and enhanced nonlinear optical performance. Nano Res. 2023, 16, 25–32.
DOI Google Scholar
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Acknowledgements

Publication history

Received: 03 September 2022
Revised: 29 September 2022
Accepted: 03 October 2022
Published: 04 November 2022
Issue date: April 2023

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© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

Financial support from the National Natural Science Foundation of China (No. 51432006), the Ministry of Science and Technology of China for the International Science Linkages Program (No. 2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (No. IRT14R23), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (No. B13025), and the Innovation Program of Shanghai Municipal Education Commission are gratefully acknowledged. M.G.H thanks the Australian Research Council (No. DP170100411) for support.

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