在 Co-N/S 协调框架中,格子应力诱导的旋转调节增强了氧降低反应
Liu Lin1,2, Youxuan Ni1, Long Shang1
1State Key Laboratory of Advanced Chemical Power Sources, Frontiers Science Center for New Organic Matter, Haihe Laboratory of Sustainable Chemical Transformations, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin, 300071, P.R. China.
Angewandte Chemie (International ed. in English)
|February 23, 2024
概括
金属协调聚合物中受控的格子应变显著增强了氧降解反应 (ORR) 活性. 一种新的温度-压力方法在Co-DABDT中实现了2%的格子压缩,提高了更好的电池和燃料电池的ORR性能.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 催化剂是一种催化剂.
背景情况:
- 氧降解反应 (ORR) 对金属空气电池和燃料电池至关重要,但在动力学上是有限的.
- 应变工程是一种有前途的策略,可以调整催化剂特性并增强ORR活动.
- 在材料中实现受控的格子应变仍然是一个重大挑战.
研究的目的:
- 开发一种温度-压力诱导的策略,用于金属协调聚合物中可控的格子应变.
- 调查格子应变对Co-DABDT催化剂ORR性能的影响.
- 阐明连接应变,电子结构和ORR活动的原子层次机制.
主要方法:
- 使用温度-压力诱导策略制造金属协调聚合物.
- 对受控格子应变对ORR活动的影响进行系统研究.
- 理论分析包括自旋电荷密度和键相互作用.
主要成果:
- 在Co-DABDT (2,5-diaminobenzene-1,4-dithiol) 中的2%格子压缩导致ORR的0.81 V的优越半波电位.
- 在Co-DABDT中,格子菌株被证明可以改变Co-DABDT中硫原子周围的自旋电荷密度.
- 压力诱导的电子结构变化与与中间体增强的键相互作用相关.
结论:
- 开发的温度-压力方法使得可控的晶格应变为催化剂优化.
- 在Co-DABDT中的晶格菌株通过改变电子特性和中间相互作用,有效地增强ORR活动.
- 这项研究提供了关于压力对原子水平上催化机制的影响的基本见解.
相关概念视频
01:17Spin–Spin Coupling: One-Bond Coupling
973
Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
973
02:42Valence Bond Theory
8.6K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.6K
02:34Structural Isomerism
19.2K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
19.2K
01:08Spin–Spin Coupling Constant: Overview
923
In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
923
02:54Trends in Lattice Energy: Ion Size and Charge
23.9K
An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
23.9K
03:02Colors and Magnetism
11.7K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
11.7K