Porphyrin-Conjugated Microporous Polymer Nanospheres as Electrocatalysts for Nitrobenzene Detection and Oxygen Evolution Reaction

Abstract

Using pyrrole and terephthalaldehyde as raw materials, porphyrin-conjugated microporous polymer (CMP) without metal centers in the porphyrin ring was synthesized directly via the one-step method. The polymer was carbonized at different temperatures to obtain a series of carbonaceous nanospheres C-CMP-x (x is the pyrolysis temperature), of which C-CMP-900 is a multifunctional electrochemical catalyst with excellent performance. Compared to the uncarbonized polymer, C-CMP-900 is more sensitive and efficient for the reduction of nitrobenzene and exhibits a lower limit of detection. There was a significant improvement in the performance of nitrobenzene reduction over nonmetallic catalysts described in the literature. Moreover, the catalyst also shows excellent oxygen evolution reaction (OER) electrocatalytic activity, with lower overpotential than commercial RuO 2 . Even after long cycling tests, the catalyst maintained good activity. The catalyst, with an ultralow detection limit for nitrobenzene reduction and excellent OER activity, may be attributed to its high specific surface area and special porous carbon structure based on the porphyrin skeleton.

Porphyrin-containing conjugated microporous polymers with gradient asymmetric design for efficient oxygen reduction

“…32,33 Meanwhile, the selected organic building block porphyrins with a delocalized p-electron system provide a rigid and planar structure, large surface area, and high-density activity, which facilitate intramolecular and intermolecular charge transfer on the polymer backbones. 34,35 For above considerations, three CMPs with different asymmetry degrees were prepared by using 4-[10,15,20-tris(4-aminophenyl)-21,24-dihydroporphyrin-5-yl] aniline as an organic linker, and uorene (BB), indenothiophene (BT), and boron nitrogen-containing units (BN) as building units via Buchwald Hartwig coupling reactions, [36][37][38] which were named PPA-BB, PPA-BT, and PPA-BN, respectively. As Fig.…”

Carbon-Based Single-Atom Nanocatalysts for Electrochemical Energy Applications

“…However, the extensive use of these materials is limited due to their high expense and rarity. 123 Consequently, it is paramount to devise nonprecious metalbased catalytic materials that are economical, effective, and long lasting, serving as viable alternatives to materials based on precious metals. Catalysts based on M−N−C, especially those incorporating widely available 3d transition metals, have emerged as viable options for EOER uses.…”

Study on naphthalene ring-linked metalloporphyrin-conjugated microporous polymers with enhanced visible photocatalytic activity

“…The conjugated microporous polymer (CMP) is a new type of porous material made only from covalent bonds and exhibits a rigid backbone, large surface area, and high stability. [5] Various organic building blocks have been used to synthesize the CMP, and the CMP plays an important role in applications such as gas storage, [6] catalysis, [7] and sensing, [8] etc. The incorporation of porphyrin into CMP reduces porphyrin aggregation, which in turn enhances its photocatalytic degradation performance.…”