Atomically dispersed metals maximize the number of catalytic sites and enhance their activity. However, their challenging synthesis and characterization strongly complicates their optimization. Here, the aim is to demonstrate that tuning the electronic environment of atomically dispersed metal catalysts through the modification of their edge coordination is an effective strategy to maximize their performance. This article focuses on optimizing nickel-based electrocatalysts toward alcohol electrooxidation in alkaline solution. A new organic framework with atomically dispersed nickel is first developed. The coordination environment of nickel within this framework is modified through the addition of carbonyl (CO) groups. The authors then demonstrate that such nickel-based organic frameworks, combined with carbon nanotubes, exhibit outstanding catalytic activity and durability toward the oxidation of methanol (CH₃OH), ethanol (CH₃CH₂OH), and benzyl alcohol (C₆H₅CH₂OH); the smaller molecule exhibits higher catalytic performance. These outstanding electrocatalytic activities for alcohol electrooxidation are attributed to the presence of the carbonyl group in the ligand chemical environment, which enhances the adsorption for alcohol, as revealed by density functional theory calculations. The work not only introduces a new atomically dispersed Ni-based catalyst, but also demonstrates a new strategy for designing and engineering high-performance catalysts through the tuning of their chemical environment.

中文翻译：

---

分子工程调节原子分散镍配体环境以实现高效醇电化学氧化

原子分散的金属最大限度地增加了催化位点的数量并提高了它们的活性。然而，它们具有挑战性的合成和表征使它们的优化变得非常复杂。在这里，目的是证明通过修改原子分散的金属催化剂的边缘配位来调整其电子环境是最大化其性能的有效策略。本文重点研究优化镍基电催化剂在碱性溶液中进行乙醇电氧化。首次开发了一种具有原子分散镍的新有机骨架。通过添加羰基（CO）基团来改变该框架内镍的配位环境。然后作者证明，这种镍基有机框架与碳纳米管相结合，₃ OH)、乙醇(CH ₃ CH ₂ OH)和苯甲醇(C ₆ H ₅ CH ₂ OH)；分子越小，催化性能越高。密度泛函理论计算表明，这些出色的醇电氧化电催化活性归因于配体化学环境中羰基的存在，这增强了对醇的吸附。这项工作不仅引入了一种新的原子分散的镍基催化剂，而且还展示了一种通过调节化学环境来设计和设计高性能催化剂的新策略。