美国橡树岭国家实验室Sheng Dai团队报道了基于基于低温离子热方法制备高全氟共价三嗪骨架增强CO2电还原。相关研究成果发表在2021年9月28日出版的《德国应用化学》。
全氟共价三嗪骨架(F-CTF)在分离和催化方面显示出独特的特性和诱人的性能。然而,由于氯化物(一种路易斯碱)诱导的C-F键断裂和恶劣条件(400-700℃),通过ZnCl2促进程序合成的最先进的F-CTF具有相当低的氟含量。制备高氟含量(>30 wt%)的F-CTF仍然具有挑战性。
该文中,研究人员提出了一种低温离子热方法(275°C)来制备F-CTF,该方法是通过在Lewis超强酸(例如三氟酰亚胺锌[Zn(NTf 2)2])上聚合四氟对苯二甲酸(TFPN)实现的,无副反应。在低催化剂负载量(等摩尔)下,F-CTF具有高氟含量(31 wt%),表面积高达367 m2 g-1,微孔约为1.1 nm。高疏水性F-CTF-1表现出良好的促进CO 2电还原为CO的能力,在0.8 V下法拉第效率为95.7%,电流密度(141 mA cm-2)高,超过大多数无金属电催化剂。
附:英文原文
Title: Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction
Author: Xian Suo, Fengtao Zhang, Zhenzhen Yang, Hao Chen, Tao Wang, Zongyu Wang, Takeshi Kobayashi, Chi-Linh Do-Thanh, Dmitry Maltsev, Zhimin Liu, Sheng Dai
Issue&Volume: 2021-09-28
Abstract: Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-art F-CTFs synthesized via the ZnCl 2 -promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400-700 °C). Fabricating F-CTFs with high fluorine contents (> 30 wt%) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf 2 ) 2 ] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt%), surface area up to 367 m 2 g -1 , and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO 2 to CO, with faradaic efficiency of 95.7% at 0.8 V and high current density (141 mA cm -2 ) surpassing most of the metal-free electrocatalysts.
DOI: 10.1002/anie.202109342
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202109342
Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx