A reliable hydrogen-based energy technology requires promising materials for safe storage and transport of hydrogen. Here, the storage of hydrogen in the organic polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is explored using density functional theory calculations. It is demonstrated that hydrogen chemisorption on PEDOT is feasible with the maximum gravimetric uptake of similar to 2.8 wt % in ambient condition, whereas physisorption is possible only at very low temperatures or at high pressure. The Gibbs absorption energies, electronic structure, and absorption spectra are calculated for the cases of chemisorption of a single hydrogen atom, a hydrogen pair, and hydrogen saturated chain for both neutral and oxidized PEDOT. Various experimental routes for PEDOT hydrogenations are discussed.
Organic semiconductors have recently emerged as promising catalytic materials for oxygen reduction to hydrogen peroxide, H2O2, a chemical of great importance in industry as well as biology. While examples of organic semiconductor-mediated photocatalytic and electrocatalytic processes for H2O2 production become more numerous and improve in performance, fundamental understanding of the reaction mechanisms at play have been explored far less. The aim of the present work is to computationally test hypotheses of how selective oxygen reduction to H2O2 generally occurs on carbonyl dyes and pigments. As an example material, we consider epindolidione (EPI), an industrial pigment with demonstrated semiconductor properties, which photocatalytic activity in oxygen reduction reaction (ORR) and thereby producing hydrogen peroxide (H2O2) in low pH environment has been recently experimentally demonstrated. In this work, the ability of the reduced form of EPI, viz. EPI-2H (which was formed after a photoinduced 2e(-)/2H(+) process), to reduce molecular triplet oxygen to peroxide and the possible mechanism of this reaction are computationally investigated using density functional theory. In the main reaction pathway, the reduction of O-2 to H2O2 reaction occurs via abstraction of one of the hydrogen atoms of EPI-2H by triplet dioxygen to produce an intermediate complex consisting of the radicals of hydrogen peroxide (HOW) and EPI-H at the initial stage. HOO center dot thus released can abstract another hydrogen atom from EPI-H-center dot to produce H2O2 and regenerates EPI; otherwise, it can enter another pathway to abstract hydrogen from a neighboring EPI-2H to form EPI-H-center dot and H2O2. EPI, after reduction, thus plays in ORR the role of hydrogen atom transfer (HAT) agent via its OH group, similar to anthraquinone in the industrial process, while HAT from its amino hydrogen is found unfavorable.