CNR ExploRA

Articolo in rivista, 2021, ENG, 10.3390/polym13020243

Nanocellulose/fullerene hybrid films assembled at the air/water interface as promising functional materials for photo-electrocatalysis

Milano F.; Guascito M.R.; Semeraro P.; Sawalha S.; Da Ros T.; Operamolla A.; Giotta L.; Prato M.; Valli L.

Istituto di Scienze delle Produzioni Alimentari (ISPA), Consiglio Nazionale delle Ricerche (CNR), S.P. Lecce-Monteroni, Ecotekne, Lecce, 73100; Dipartimento di Scienze e Tecnologie Biologiche e Ambientali, Università del Salento, S.P. Lecce-Monteroni, Lecce, 73100, Dipartimento di Scienze e Tecnologie Biologiche e Ambientali, Università del Salento, S.P. Lecce-Monteroni, 73100, Lecce, Italy;, , Italy; Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Unità di Lecce, S.P. Lecce-Monteroni, Lecce, 73100, Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), Unità di Lecce, S.P. Lecce-Monteroni, 73100, Lecce, Italy, , Italy; Dipartimento di Ingegneria dell'Innovazione, Università del Salento, S.P. Lecce-Monteroni, Lecce, 73100; Department of Chemical Engineering, An-Najah National University, P.O. Box 7, Nablus, 00970, Department of Chemical Engineering, An-Najah National University, P.O. Box 7, Nablus, 00970, Palestine, , Palestine; Center of Excellence for Nanostructured Materials (CENMAT) and INSTM, Unit of Trieste, Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, via Giorgieri 1, Trieste, 34127, Italy; Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Giuseppe Moruzzi 13, Pisa, 56124, Italy, , Italy; Center for Cooperative Research in Biomaterials (CIC biomaGUNE), Basque Research and Technology Alliance (BRTA), Paseo de Miramón 182, Donostia San Sebastián, 20014, Spain; Basque Foundation for Science, Ikerbasque, Bilbao, 48013, Basque Foundation for Science, Ikerbasque, 48013, Bilbao, Spain, Spain

Cellulose nanomaterials have been widely investigated in the last decade, unveiling attractive properties for emerging applications. The ability of sulfated cellulose nanocrystals (CNCs) to guide the supramolecular organization of amphiphilic fullerene derivatives at the air/water interface has been recently highlighted. Here, we further investigated the assembly of Langmuir hybrid films that are based on the electrostatic interaction between cationic fulleropyrrolidines deposited at the air/water interface and anionic CNCs dispersed in the subphase, assessing the influence of additional negatively charged species that are dissolved in the water phase. By means of isotherm acquisition and spectroscopic measurements, we demonstrated that a tetra-sulfonated porphyrin, which was introduced in the subphase as anionic competitor, strongly inhibited the binding of CNCs to the floating fullerene layer. Nevertheless, despite the strong inhibition by anionic molecules, the mutual interaction between fulleropyrrolidines at the interface and the CNCs led to the assembly of robust hybrid films, which could be efficiently transferred onto solid substrates. Interestingly, ITO-electrodes that were modified with five-layer hybrid films exhibited enhanced electrical capacitance and produced anodic photocurrents at 0.4 V vs Ag/AgCl, whose intensity (230 nA/cm) proved to be four times higher than the one that was observed with the sole fullerene derivative (60 nA/cm).

Polymers (Basel) 13 , pp. 1–17