Mechanochemical Formation of Protein Nanofibril: Graphene Nanoplatelet Hybrids and Their Thermoelectric Properties

Hybrids between biopolymeric materials and low-cost conductive carbon-based materials are interesting materials for applications in electronics, potentially reducing the need for materials that generate environmentally harmful electronic waste. Herein we investigate a scalable ball-milling method to form graphene nanoplatelets (GNPs) by milling graphite flakes with aqueous dispersions of proteins or protein nanofibrils (PNFs). Aqueous GNP dispersions with high concentrations (up to 3.2 mg mL–1) are obtained under appropriate conditions. The PNFs/proteins help to exfoliate graphite and stabilize the resulting GNP dispersions by electrostatic repulsion. PNFs are prepared from hen egg white lysozyme (HEWL) and β-lactoglobulin (BLG). The GNP dispersions can be processed into free-standing films having an electrical conductivity of up to 110 S m–1. Alternatively, the GNP dispersions can be drop-cast on PET substrates, resulting in mechanically flexible films having an electrical conductivity of up to 65 S m–1. The drop-cast films are investigated regarding their thermoelectric properties, having Seebeck coefficients of about 50 μV K–1. By annealing drop-cast films and thus carbonizing residual PNFs, an increase of electrical conductivity, coupled with a modest decrease in Seebeck coefficient, is obtained resulting in materials displaying power factors of up to 4.6 μW m–1 K–2.
A green method for preparation of graphene nanoplatelets is presented and the thermoelectric properties of the GNP materials are investigated.