NANOREDOX: Carbon Based Nano-Hybrid Systems for Multi-Redox Electrocatalysis

PRIN [2019-2022]

Abstract

The NANO-REDOX project targets the synthesis of novel electrocatalytic nano-systems with composition, dimensionality and morphology controlled at the nanoscale and transferred onto electrodic surfaces for the multi-electron processing of vital redox couples including: H2O//O2; H2O//H2; O2//H2O2; CO2//CO CO2//HCOOH. The expected results are relevant for the urgent challenge of renewable energy vectors and feedstocks, while addressing the functional frontier of H2O splitting and selective CO2 reduction for a carbon-neutral circular economy. The multi-faceted composition and structural diversity of biological materials are key aspects that regulate multi-electron processes such as respiration (water-oxygen cycle) and metabolism (CO2 fixation) within living tissues. NANO-REDOX aims at new concepts in bio-inspired electroactive materials, overarching the natural benchmark with respect to robustness and versatility, and at the same time deciphering structure-activity descriptors to optimize performance within the artificial device. With this aim, NANO-REDOX materials and electrocatalytic interfaces will be shaped by a modular assembly of organic-inorganic building blocks with complementary properties including: molecular recognition and confinement phenomena, surface area, electron and proton transport, multi-site catalysis, stereo-electronic modulation of reactive intermediates, self-healing. NANO-REDOX scaffolds will be based on electron-conductive carbon nanostructures (CNS), i.e. nanotubes (CNTs), nanohorns (CNHs), nanocones (CNC), carbon nanodots (CND), and exfoliated graphene (G). Surface functionalities will be implemented by CNS covalent modification and/or by combination with organic-inorganic gels, polymeric blends and ionic liquid phases (ILs). Metal-metal oxide interfaces will be shaped on CNS by tailored synthetic protocols introducing metal-oxide nano-structures and coatings (TiO2, CeO2, ZnO, WO3) together with electro-active polyoxometalate clusters (POMs) and metal nano-particles (Pd, Pt, etc.). The envisioned NANO-REDOX multi-functionality will take further advantage of the geometry, spatial organization and hierarchical order of the merged sub-components, by controlling the inter-domain connectivity, size distribution, morphology and structural anisotropy (i.e. core-shell) of the resulting nano-structures. Moreover, electroactive surfaces based on NANO-REDOX building blocks and nano-composites will be fabricated using the layer-by-layer assembly (LbL) technique and Langmuir-Blodgett (LB) film deposition that allows a valuable control over both the interfacial adhesion and the dimensional organization of the material network, spanning several orders of magnitude (from Å to cm). Fundamental electrocatalysis studies will be used to probe the NANO-REDOX systems by evaluating their electrodic response for the Oxygen/Hydrogen evolution reaction (OER/HER), the CO2 reduction reactions (CO2-RR), in terms of overpotential, faradaic current and yield, selectivity and long-term performance. Structure-reactivity relationships will build on state-of-the-art microscopy imaging and nano-tomography of the electroactive materials and surfaces.


Durata del progetto

2019-2022


Unibo Team Leader

Dr. Valenti Giovanni


Responsabile Nazionale

Prof Maurizio Prato Università di Trieste

Partnership

Alma Mater Studiorum - Università di Bologna (Italy)
University of Trieste (Italy)

University of Padua (Italy)
University of SALENTO (Italy)

Consiglio Nazionale delle Ricerche (IMEM-Istituto dei Materiali per l' Elettronica ed il Magnetismo)

Finanziamento

euro 1.190.971