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Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-03-08 , DOI: 10.1021/jacs.2c10233 Ting He 1 , Zhanfeng Zhao 2, 3 , Ruoyang Liu 4 , Xinyan Liu 5 , Bing Ni 6 , Yanping Wei 7 , Yinglong Wu 1 , Wei Yuan 1 , Hongjie Peng 5 , Zhongyi Jiang 2, 3, 8 , Yanli Zhao 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-03-08 , DOI: 10.1021/jacs.2c10233 Ting He 1 , Zhanfeng Zhao 2, 3 , Ruoyang Liu 4 , Xinyan Liu 5 , Bing Ni 6 , Yanping Wei 7 , Yinglong Wu 1 , Wei Yuan 1 , Hongjie Peng 5 , Zhongyi Jiang 2, 3, 8 , Yanli Zhao 1
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The development of efficient photocatalysts for N2 fixation to produce NH3 under ambient conditions remains a great challenge. Since covalent organic frameworks (COFs) possess predesignable chemical structures, good crystallinity, and high porosity, it is highly significant to explore their potential for photocatalytic nitrogen conversion. Herein, we report a series of isostructural porphyrin-based COFs loaded with Au single atoms (COFX–Au, X = 1–5) for photocatalytic N2 fixation. The porphyrin building blocks act as the docking sites to immobilize Au single atoms as well as light-harvesting antennae. The microenvironment of the Au catalytic center is precisely tuned by controlling the functional groups at the proximal and distal positions of porphyrin units. As a result, COF1–Au decorated with strong electron-withdrawing groups exhibits a high activity toward NH3 production with rates of 333.0 ± 22.4 μmol g–1 h–1 and 37.0 ± 2.5 mmol gAu–1 h–1, which are 2.8- and 171-fold higher than that of COF4–Au decorated with electron-donating functional groups and a porphyrin–Au molecular catalyst, respectively. The NH3 production rates could be further increased to 427.9 ± 18.7 μmol g–1 h–1 and 61.1 ± 2.7 mmol gAu–1 h–1 under the catalysis of COF5–Au featuring two different kinds of strong electron-withdrawing groups. The structure–activity relationship analysis reveals that the introduction of electron-withdrawing groups facilitates the separation and transportation of photogenerated electrons within the entire framework. This work manifests that the structures and optoelectronic properties of COF-based photocatalysts can be finely tuned through a rational predesign at the molecular level, thus leading to superior NH3 evolution.
中文翻译：
卟啉基共价有机骨架锚定金单原子用于光催化固氮
开发用于在环境条件下固定 N 2以产生 NH 3的高效光催化剂仍然是一个巨大的挑战。由于共价有机框架（COFs）具有可预先设计的化学结构、良好的结晶度和高孔隙率，因此探索它们在光催化氮转化中的潜力具有重要意义。在此，我们报告了一系列负载 Au 单原子（COFX–Au，X = 1–5）的同构卟啉基 COF，用于光催化 N 2定影。卟啉结构单元充当固定 Au 单个原子和光捕获天线的停靠点。Au催化中心的微环境是通过控制卟啉单元近端和远端位置的官能团来精确调节的。因此，装饰有强吸电子基团的 COF1–Au 对 NH 3生产表现出高活性，速率分别为 333.0 ± 22.4 μmol g –1 h –1和 37.0 ± 2.5 mmol g Au –1 h –1，这是分别比装饰有供电子官能团和卟啉-Au 分子催化剂的 COF4-Au 高 2.8 倍和 171 倍。NH 3在具有两种不同强吸电子基团的 COF5-Au 催化下，产率可进一步提高至 427.9 ± 18.7 μmol g –1 h –1和 61.1 ± 2.7 mmol g Au –1 h –1 。构效关系分析表明，吸电子基团的引入促进了光生电子在整个框架内的分离和传输。这项工作表明，COF 基光催化剂的结构和光电性能可以通过分子水平的合理预设计进行微调，从而导致优异的 NH 3释放。
更新日期：2023-03-08
中文翻译：
卟啉基共价有机骨架锚定金单原子用于光催化固氮
开发用于在环境条件下固定 N 2以产生 NH 3的高效光催化剂仍然是一个巨大的挑战。由于共价有机框架（COFs）具有可预先设计的化学结构、良好的结晶度和高孔隙率，因此探索它们在光催化氮转化中的潜力具有重要意义。在此，我们报告了一系列负载 Au 单原子（COFX–Au，X = 1–5）的同构卟啉基 COF，用于光催化 N 2定影。卟啉结构单元充当固定 Au 单个原子和光捕获天线的停靠点。Au催化中心的微环境是通过控制卟啉单元近端和远端位置的官能团来精确调节的。因此，装饰有强吸电子基团的 COF1–Au 对 NH 3生产表现出高活性，速率分别为 333.0 ± 22.4 μmol g –1 h –1和 37.0 ± 2.5 mmol g Au –1 h –1，这是分别比装饰有供电子官能团和卟啉-Au 分子催化剂的 COF4-Au 高 2.8 倍和 171 倍。NH 3在具有两种不同强吸电子基团的 COF5-Au 催化下，产率可进一步提高至 427.9 ± 18.7 μmol g –1 h –1和 61.1 ± 2.7 mmol g Au –1 h –1 。构效关系分析表明，吸电子基团的引入促进了光生电子在整个框架内的分离和传输。这项工作表明，COF 基光催化剂的结构和光电性能可以通过分子水平的合理预设计进行微调，从而导致优异的 NH 3释放。
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