Metal-Free Pyrene-Based Conjugated Microporous Polymer Catalyst Bearing N- and S-Sites for Photoelectrochemical Oxygen Evolution Reaction

Abstract

The development of an efficient, sustainable, and inexpensive metal-free catalyst for oxygen evolution reaction (OER) via photoelectrochemical water splitting is very demanding for energy conversion processes such as green fuel generators, fuel cells, and metal-air batteries. Herein, we have developed a metal-free pyrene-based nitrogen and sulfur containing conjugated microporous polymer having a high Brunauer-Emmett-Teller surface area (761 m2 g−1) and a low bandgap of 2.09 eV for oxygen evolution reaction (OER) in alkaline solution. The π-conjugated as-synthesized porous organic material (PBTDZ) has been characterized by Fourier transform infrared spectroscopy (FT-IR), solid-state 13C (cross-polarization magic angle spinning-nuclear magnetic resonance) CP-MAS NMR, N2 adsorption/desorption analysis, field-emission scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) experiments. The material acts as an efficient catalyst for photoelectrochemical OER with a current density of 80 mA/cm2 at 0.8 V vs. Ag/AgCl and delivered 104 µmol of oxygen in a 2 h run. The presence of low bandgap energy, π-conjugated conducting polymeric skeleton bearing donor heteroatoms (N and S), and higher specific surface area associated with inherent microporosity are responsible for this admirable photoelectrocatalytic activity of PBTDZ catalyst.

An interfacially stacked covalent porous polymer on graphene favors electronic mobility: ensuring accelerated oxygen reduction reaction kinetics by an in situ study

“…S4 †) under acidic media to obtain the electrocatalyst, namely FePP@G mg/V/t (here mg, V and t denote the amount of FePP (mg), voltage (V) and time (t) used for the exfoliation). 31 The striking advantage of the underlying graphene support with the FePP material has been brought to the front by several experimental techniques, which was nally corroborated with the electrocatalytic performances of the catalysts, as discussed in the Results and discussion part.…”

Cobalt metal–organic framework microcrystalline particles with strong electrocatalytic activity: amine controlled morphology and OER activity

“…[15][16][17] Metal-organic frameworks (MOFs) which are constructed from metal-based nodes and organic linkers are considered as potential alternative materials for a wide range of applications including gas-storage and catalysis, owing to their inherent features such as large surface area, unique porosity and tailorable functionality. [18][19][20][21][22][23] Apart from offering abundant active metal centres, the MOFs provide accessible pores for guest molecules/solvents/reactants. The coordination environment of the metal centre significantly influences the electrocatalytic activity.…”

A Sensitive Photoelectrochemical Sensor for Levodopa Detection Using Benzothiadiazole-Based Conjugated Microporous Polymer-Coated Graphene Heterostructures

“…The spectrum showed two distinct peaks. The peak at 166 eV can be attributed to the emergence of oxygen−sulfur species due to the oxidation of sulfur species in the air, 49 whereas the peak at 165 eV can be attributed to N−S.…”

“…The spectrum showed two distinct peaks. The peak at 166 eV can be attributed to the emergence of oxygen−sulfur species due to the oxidation of sulfur species in the air,49 whereas the peak at 165 eV can be attributed to N−S.The porosity of CMP-rGO was studied using N 2 adsorption−desorption experiments. The N 2 adsorption− desorption isotherms of the CMP-rGO are shown in Figure3A.…”