1,3,5‐Triphenylbenzene Based Porous Conjugated Polymers for Highly Efficient Photoreduction of Low‐Concentration CO₂ in the Gas‐Phase System

Abstract

Herein, three 1,3,5‐triphenylbenzene based porous conjugated polymers (PCPs) are designed for photochemical reduction of CO2 in simulated flue gas in the mild gas−solid reaction system. By tuning the nature of the comonomers, the PCPs present high surface areas, high CO2/N2 selectivity, and broad visible light absorptions with bandgaps of 1.81−2.07 eV. At 1 bar and 273 K, the CO2 uptake capacity of PCPs is enhanced from 1.28 to 2.18 mmol g−1, with an increase in CO2 adsorption heat from 21.8 to 28.3 KJ mol−1. In the presence of gaseous water, SO‐TPB demonstrates the highest CO production rate of 40.12 μmol h−1 g−1 and nearly 100% product selectivity without using organic sacrificial reagent and additional cocatalyst (>420 nm). Moreover, SO‐TPB can be recovered while well retaining the photocatalytic activity and reused at least five runs, indicating good recyclability.

Red‐Light‐Driven CO2Photoreduction into CH4and CO Enabled by Narrow‐Gap Conjugated Microporous Polymers

“…The characteristic peak at 90 ppm originated from alkyne carbons (C≡C) owning to the efficient coupling of the comonomers as indicated in our previous studies. [25] This can be further confirmed by FT-IR spectra, the stretching vibration of the C≡C could be observed around 2195 cm À1 . For P2 and P3, the peaks at 190.69 and 180.05 ppm in NMR spectra were accountable for the keto group (C═O) in the polymer backbone.…”

“…As reported in our previous studies, inductively coupled plasma-mass spectrometry (ICP-MS) analysis indicated the presence of 0.31-0.40 wt% Pd and 0.012-0.042 wt% Cu in the porous polymer due to residual catalyst. [19,25] The formation of polymer networks was verified by cross-polarization/magic angle spinning (CP/MAS) 13 C NMR spectra and Fourier transform infrared (FT-IR) spectra (Figure S2-S5, Supporting Information). The 13 C NMR spectra showed peaks at approximately 120-140 ppm for all polymers, which could be assigned to sp 2 hybridized carbons.…”

“…The stronger fluorescence of P2 compared to P1 and P3 could be ascribed to the unique packing of planar units, which is also found in the CMPs. [25,33,34] The time-resolved photoluminescence (TRPL) spectra of the polymers indicated an average lifetime of 1.41 ns for P1, 1.78 ns for P2, and 1.57 ns for P3 (Figure S10, Supporting Information). The electrochemical properties of resulting polymers were examined by cyclic voltammetry (CV) measurements (Figure S11, Supporting Information).…”

Synthesis of 3,3’‐(Ethane‐1,2‐diylidene)bis(indolin‐2‐one) Promoted by Thermally‐activated Electron Transfer and Photoreduction of CO2 to CH4 and CO

“…Organic functionalities pyrene, [3] triazine, [4] benzothiadiazole, [4] cyclotriphosphazene, [5–6] triphenylamine, [7] oxadiazole, [7] eosin Y, [8] carbazole, [9] naphthalenedimide, [10–11] fluorene [10] phenanthraquinone, [12] and 1,3,5‐triphenylbenzene [13] have been used to build cross‐linked or linear conjugated polymer catalysts (Scheme S1, Supporting Information). Among these polymeric photocatalysts, a pyrene‐based polymer gave a CO product rate ( R CO ) of 47.37 μmol g cat −1 (per gram of catalyst) h −1 (per hour), [3] and an N,O,P‐containing polymer afforded a CH 4 production rate ( R CH4 ) of 22.5 μmol g cat −1 h −1 [5] .…”

Thienothiophene and Triphenylbenzene Based Electroactive Conjugated Porous Polymer for Oxygen Reduction Reaction (ORR)

“…It is electron-rich with two sulfur heteroatoms and flat and has remarkable optic/electronic and electrochemical oxidation/reduction properties. − Another important building block is 1,3,5-triphenylbenzene (TPB), which is a photochemically and thermally stable chromophore with a π-extended structure. As in TTs, TPB has a useful core for various electronic areas such as OLED, water splitting, triplet–triplet annihilation photon upconversion, and CO 2 photoreduction. − Since addition of sulfur has a positive impact in catalyzing the ORR, − combining a porous structure with a thiophene-based backbone may help to enhance the ORR activity.…”