Electro-Polymerization of Hydrogen-Bonding Conductive Polymers As Metal-Free Electrocatalysts for Energy Conversion
Authors: Harada Yuya , Kaiwa Haruka , Huang Xin , Coskun Halime , Aljabour Abdalaziz , Stadler Philipp , Yoshida Tsukasa 
Published: May 2020

Electrocatalytic hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2RR) are the key reactions for conversion of renewable electricity into storable chemical energies. It is crucially important to develop active and stable electrocatalysts without relying on rare metal elements for sustainable energy systems. Recently, some metal-free conductive organic polymers such as polydopamine (PDA) and poly guanine (PGA) synthesized by oxidative chemical vapor deposition (oCVD) have been found to exhibit high catalytic activity and durability for HER and CO2RR1,2. In addition to their conductivity of the π-conjugated system of the main chain, these polymers contain heteroatoms such as N and O at high densities, which are believed to act as hydrogen bonding sites for stabilization of reaction intermediates. However, their exact structures and relationship to the catalytic activities are not fully grasped.
In this study, we employ electro-polymerization as the mean to obtain catalytic polymers. Taking polyaniline (PANI) as the host, hydrogen bonding monomers such as dopamine (DA), guanine (GA) and neutral red (NR) are to be introduced to obtain co-polymers with controlled structure and density of the hydrogen bonding sites. Comparison of their electrocatalytic activity to those of the respective homo-polymers should reveal the effective catalytic sites and its product selectivity, which should result in optimal design of the catalyst.
Electro-polymerization of PANI and PNR was carried out at an ITO glass substrate in an aqueous solution containing 50 mM ANI or NR and 0.1 M H2SO4 during 50 times potential cycling between -0.5 and +0.6 V vs. Ag/AgCl under the N2. Copolymers were obtained by mixing the monomers at appropriate ratios. The films were characterized by FT-IR spectra.
PANI, PNR and their copolymer appeared dark green, dark red and black, respectively. While CVs during electropolymerization of PANI continue to increase the redox peaks of PANI as typically expected, those for PNR show decrease of anodic current suggesting inactiveness of PNR for its redox (Figs. 1 a, b). When they are mixed together, a new redox peak in between those from PANI and another irreversible anodic peak close to +0.9 V appear, which indicate loading of NR in redox active form into PANI (Fig. 1c). The FTIR spectrum of the copolymer showed significant difference from the homo-polymers of PANI and PNR with intense absorption peaks between 800 and 1600 cm-1 (Fig. 1d). These peaks arise from infrared-activated vibrations (IRAV) due to the presence of polaron in the main chain, thus are indicative of its conductive nature. These results suggest improvement of conductivity by heterogeneity in copolymers. Its relevance to the catalytic property and optimal density of hydrogen bonding sites are to be further investigated.

References:

1. Coskun et al., Adv. 2017, 3, e1700686.
2. Coskun et al., adv mater interfaces, 2019, 1901364.

Figure 1