烯烃连接的三嗪共轭多孔聚合物的合成及其可见光催化产氢性能

doi:10.6023/A21030121

摘要/Abstract

近年来, 多孔有机光催化材料因其结构和能带易调控、比表面积大和密度小等优点而备受关注. 本工作以Horner-Wadsworth-Emmons (HWE)反应为基础, 使用有机碱(t-BuOK)作为催化剂, 在室温下制备了两例C=C连接的三嗪共轭多孔聚合物, 分别是由双取代的苯环和三甲基三嗪通过C=C键连接的结构(TB-CPN)和由三苯胺和三甲基三嗪通过C=C键连接的结构(TT-CPN）, 将其用于光降解水产氢. 通过固体核磁和红外等结构表征, 证明C=C的存在, 说明结构的正确性. 然后, 在300 W氙灯光源下分别将两个聚合物作为光催化剂进行裂解水产氢研究, 其中, TT-CPN的产氢速率达到了913.3 μmol•h ^-1•g^-1, 相同条件下, TB-CPN的产氢速率为TT-CPN的86%. 此外, TT-CPN在连续照射反应25 h后, 其光催化活性几乎没有降低, 表现出良好的光化学稳定性和可重复性. 本工作采用了一种低温、短反应时间的方法来合成C=C连接的共轭多孔聚合物, 用于可见光照射下光催化分解水制氢, 期望为多孔聚合物的设计合成提供新的方案.

关键词: 低温合成, 烯烃连接, 多孔聚合物, 光催化, 析氢

Global energy storage and environmental pollution have received increasing attention, and finding sustainable clean energy to replace fossil fuels has become an urgent issue. Visible-light-driven photocatalytic water splitting can not only obtain clean hydrogen energy, but also can store solar energy. Therefore, great efforts have been put into research and it has consequently developed rapidly. In recent years, different types of photocatalysts, such as inorganic materials, metal complexes, organic dyes and porous organic networks, have been extensively explored. Among these photocatalysts, conjugated porous networks (CPNs) have attracted much attention due to their adjustable structures, high specific surface area and high structural stability. The band gap and the specific surface area of materials is significant to photocatalytic performance. Hence, exploring appropriate band gap and porosity of materials is the main challenge, which can be achieved by changing the reaction methods and reactants to adjust the materials structure. In this article, unsubstituted olefin-linked (C=C) CPNs through Horner-Wadsworth-Emmons (HWE) reaction have been designed, which are the structure of disubstituted benzene and trimethyltriazine connected by C=C bond (TB-CPN) and the structure of triphenylamine and trimethyltriazine connected by C=C bond (TT-CPN) respectively. In this method, organic base (t-BuOK) was used as a catalyst, and finished the reaction at room temperature, which cost less energy. The entire synthesis procedure takes relatively short time, compared with other polymeric means costing 72 h or 48 h. Firstly, the formation of olefin (C=C) bonds was characterized by Fourier transform infrared (FT-IR) spectroscopy. Next, the structure of the polymers was further confirmed by solid-state nuclear magnetic resonance. Nitrogen adsorption-desorption measurement was applied to examine the porosity of the polymers, it showed that TT-CPN has a larger specific surface area than TB-CPN. The band gap of TT-CPN and TB-CPN obtained by UV-Vis diffuse reflection spectra is 2.22 and 2.30 eV, respectively. After that, the two polymers were used as photocatalysts to investigate the visible-light-driven hydrogen evolution by water splitting. Of these, the porous polymer TT-CPN reveals a better photocatalytic behavior with a hydrogen evolution rate of 913.3 μmol•h ^-1•g^-1. Under the same testing condition, the hydrogen evolution rate of TB-CPN was only 86% of TT-CPN. Besides, after TT-CPN was continuously irradiated under visible light for 25 h, its photocatalytic activity barely decreased, showing good photochemical stability and repeatability. In a word, in this article, a method with low-temperature and short reaction time was developed to synthesize C=C bond connected conjugated porous networks, and the polymers were used for efficient photocatalytic water splitting to produce hydrogen under visible light irradiation. This method may provide a new choice for the design and synthesis of porous polymers as photocatalysts.

Key words: low-temperature synthesis, olefin-linkage, conjugated porous networks, photocatalysis, hydrogen evolution

引用此文

麻旺坪, 贺彦彦, 刘洪来. 烯烃连接的三嗪共轭多孔聚合物的合成及其可见光催化产氢性能[J]. 化学学报, 2021, 79(7): 914-919.

Wangping Ma, Yanyan He, Honglai Liu. Olefin-linked Conjugated Porous Networks and Their Visible-Light-Driven Hydrogen Evolution Performance[J]. Acta Chimica Sinica, 2021, 79(7): 914-919.

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图/表 9

图1. TB-CPN和TT-CPN合成示意图

Figure 1. Synthesis schematic diagram of TB-CPN and TT-CPN

图2. TB-CPN和TT-CPN的(a) ss13C NMR谱图, (b) 傅里叶变换红外光谱图, (c) C 1s X射线光电子能谱和(d) 粉末X射线衍射光谱

Figure 2. (a) ss NMR spectra, (b) FT-IR spectra, (c) C 1s XPS spectra and (d) PXRD spectra of TB-CPN and TT-CPN

图3. TB-CPN和TT-CPN的热重分析图

Figure 3. Thermogravimetric analysis of TB-CPN and TT-CPN

图4. TB-CPN (a)和TT-CPN (c)的SEM图; TB-CPN (b)和TT-CPN (d)的TEM图

Figure 4. SEM images of (a) TB-CPN and (c) TT-CPN; TEM images of (b) TB-CPN and (d) TT-CPN

图5. (a) TB-CPN和(b) TT-CPN的N2吸附-解吸等温曲线; (c) TB-CPN和(d) TT-CPN的孔径分布图

Figure 5. Nitrogen adsorption and desorption isotherm curves of (a) TB-CPN and (b) TT-CPN; and pore size distribution diagrams of (c) TB-CPN and (d) TT-CPN

图6. TB-CPN和TT-CPN的(a) 紫外-可见吸收光谱, (b)由Kubelka-Munk变换的反射光谱确定的聚合物带隙, (c)稳态荧光光谱和(d) 时间分辨瞬态光致发光衰减

Figure 6. (a) UV-Vis absorption spectra, (b) band gaps of the polymers determined from the Kubelka-Munk transformed reflectance spectra, (c) photoluminescence spectra and (d) time-resolved transient photoluminescence decay of TB-CPN and TT-CPN

图7. (a) TB-CPN和(b) TT-CPN的紫外光电子能谱图

Figure 7. UPS spectra of (a) TB-CPN and (b) TT-CPN

Sample	S_BET^a/ (m²•g^-1)	E_opt^b/ eV	E_v^c/E_c^d (V vs. SHE)	HER_vis^e/ (μmol•h^-1•g^-1)
TB-CPN	103	2.30	4.75/2.45	792.2
TT-CPN	620	2.22	5.12/2.90	913.3

表1. 聚合物的孔隙率数据和光学性能

Table 1. Porosity data and electrochemical properties of the polymers

图8. TB-CPN和TT-CPN的(a) 光催化水分解产氢速率, (b) 光催化水分解产氢量与时间的关系, (c) TT-CPN的光催化产氢稳定性测试, (d) TT-CPN在不同波长下(λ=420、475和578 nm)的光催化表观量子产率和紫外漫反射光谱对比

Figure 8. (a) Photocatalytic H2 evolution rates, (b) time course of H2 evolution from water by the TB-CPN and TT-CPN, (c) stability and reusability tests using TT-CPN as a photocatalyst under visible-light irradiation, (d) wavelength-dependent AQY and DRS spectrum of TT-CPN (λ=420, 475 and 578 nm)

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