在Ru协调的异核双金属原子催化剂上促进氨酸电氧化
Zhengfeng Zhang1, Zhonghui Gao1,2, Yanqin Liang1,2,3
1School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China. wcxu@tju.edu.cn.
Physical chemistry chemical physics : PCCP
|October 9, 2025
概括
开发用于氧化反应 (HzOR) 的高效电催化剂是低能生产的关键. 像RuCo@N6C和RuCu@N6C这样的双金属原子催化剂显示出高活性和稳定性.
科学领域:
- 电化学 电化学 电化学
- 材料科学 材料科学 材料科学
- 计算化学计算化学
背景情况:
- 氧化演化反应 (OER) 对于生产来说是能源密集型的.
- 水氧化反应 (HzOR) 提供了一个低能耗的替代方案.
- 有效的电催化剂对于推进HzOR至关重要.
研究的目的:
- 为了计算选双金属原子催化剂 (DACs) 的氧化反应 (HzOR).
- 为了确定高活性和稳定的DAC,以有效生产气.
- 阐明有前途的DAC的电子结构和反应机制.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 评估了各种Ru-M@N6C (M = 3d-5d过渡金属) DACs的催化活性.
- 分析包括电子转移,晶体轨道哈密尔顿数和电子定位函数.
主要成果:
- RuCo@N6C和RuCu@N6C对HzOR具有较低的限制电位 (-0.13V和0.00V,分别) 的高催化活性.
- 发现中度金属协调可以减少*N2H3中间体的强吸附.
- RuCo@N6C和RuCu@N6C表现出极好的热力学稳定性.
结论:
- 电子转移在HzOR机制中起着至关重要的作用.
- 与Ru协调的异质核DAC对可持续的气生产有希望.
- 这些发现有助于开发用于清洁能源技术的先进催化剂.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.8K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.8K
Catalysis
30.1K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
30.1K
Nitriles to Amines: LiAlH4 Reduction
4.6K
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
4.6K
Reduction of Alkenes: Catalytic Hydrogenation
13.9K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
13.9K
Regioselectivity and Stereochemistry of Hydroboration
9.4K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
9.4K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
12.6K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
12.6K


