弯曲 Fe1-N4 单原子位点的前所未有的接力催化，可显着高效地生成 1O2,ACS Catalysis

当前位置： X-MOL 学术 › ACS Catal. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

弯曲 Fe1-N4 单原子位点的前所未有的接力催化，可显着高效地生成 1O2
ACS Catalysis ( IF 11.3 ) Pub Date : 2022-12-22 , DOI: 10.1021/acscatal.2c05409
Man Yang ₁ , Keying Wu ₁ , Shaodong Sun ₁ , Jianglin Duan ₂ , Xin Liu ₃ , Jie Cui ₁ , Shuhua Liang ₁ , Yujing Ren ₂

Affiliation

在氧化反应中高效和选择性地生成重要的单线态氧 ( ¹ O ₂ ) 活性物质的催化剂和催化工艺的设计仍然具有挑战性，尤其是在没有光电场或额外热条件的情况下利用丰富的环境 O _{2 。}在此，通过将孤立的 Fe 单原子结合到具有高曲率表面的纳米金刚石中，开发了弯曲的 Fe ₁ –N ₄单原子位点。它导致前所未有的中继催化路线，其中 O ₂的活化与过氧一硫酸盐 (PMS) 的活化相结合，以有效地生成¹ O ₂物种。_{详细地说，PMS 首先在弯曲的 Fe 1} –N ₄位点被激活，向 Fe 单原子提供电子，同时产生 1/2 当量的¹ O ₂。更重要的是，由于Fe 3d _z_²轨道能级较高的弯曲Fe ₁ –N _{4位点的压应变，具有电子电荷获取的弯曲Fe}₁ –N ₄位点可以直接将电子转移到O ₂分子和因此触发额外的 1 当量的¹ O _2的产生. 利用这一串联过程，实现了显着的效率和接近100%的¹ O ₂生成选择性，从而导致四环素氧化降解的超高金属催化效率为0.77 min ^–1和苯醇选择性氧化的出色催化性能。这项工作一方面开辟了一种在基于过氧化物的催化氧化中通过 O _{2活化生成}¹ O ₂的有效途径，另一方面开发了双功能 Fe ₁ –N ₄具有快速电子得失能力的单原子位点，这揭示了通过中继催化机制进一步提高单原子催化剂的催化性能。

"点击查看英文标题和摘要"

Unprecedented Relay Catalysis of Curved Fe1–N4 Single-Atom Site for Remarkably Efficient 1O2 Generation

The design of catalysts and catalytic processes for high efficiency and selectivity of important singlet oxygen (¹O₂) active species generation in oxidation reactions is still challenging, especially utilizing abundant and environmental O₂ without photoelectric field or extra thermal condition. Herein, a curved Fe₁–N₄ single-atom site is developed by incorporating isolated Fe single atom into nanodiamond with high-curvature surface. It leads to an unprecedented relay catalysis route, in which the activation of O₂ is coupled with peroxymonosulfate (PMS) activation, to efficiently generate ¹O₂ species. In detail, PMS is first activated on the curved Fe₁–N₄ site with electron donation to Fe single atom, accompanied by 1/2 equiv of ¹O₂ production. More importantly, due to the compressive strain of the curved Fe₁–N₄ site with a higher energy level of Fe 3d_z² orbital, the curved Fe₁–N₄ site with electron charge acquisition can directly transfer electron to O₂ molecule and consequently trigger the generation of additional 1 equiv of ¹O₂. Taking advantage of this tandem process, remarkable efficiency and near 100% selectivity of ¹O₂ generation are achieved, which leads to an ultrahigh metal catalytic efficiency of 0.77 min^–1 for tetracycline oxidative degradation and an outstanding catalytic performance for benzene alcohol selective oxidation. This work, on the one hand, opens up an efficient way to generate ¹O₂ by O₂ activation in peroxide-based catalytic oxidations, and on the other hand, develops a bifunctional Fe₁–N₄ single-atom site with rapid electron gain and loss ability, which sheds light on further improving catalytic performance in single-atom catalysts via relay catalysis mechanism.

更新日期：2022-12-22

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南