解开基于的金属有机框架的结构演变,以促进酸盐电还原到氨的结构演变
Zhi Wang1,2,3, Yanjun Han1,2,3, Depeng Wang1,2,3
1China-Belarus Belt and Road Joint Laboratory on Advanced Materials and Manufacturing, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, 130022, China.
Chemistry (Weinheim an der Bergstrasse, Germany)
|July 1, 2025
概括
金属有机框架 (MOFs) 在电催化过程中转化为氧化物 (Co(OH) 2,揭示了Co(OH) 2作为降解反应 (NO3RR) 到氨的活性场所.
科学领域:
- 电触媒溶解是一种电触媒.
- 材料科学 材料科学 材料科学
- 化学工程是化学工程的重要组成部分.
背景情况:
- 金属有机框架 (MOF) 是酸盐还原反应 (NO3RR) 的有希望的电催化剂.
- 了解MOF在催化过程中的结构演变对于设计高效的电催化剂至关重要.
- 由于结构转型,NO3RR在MOF中的活跃地点仍然存在争议.
研究的目的:
- 为了澄清在NO3RR期间的地质化伊米达框架-67 (ZIF-67) 和Co3 ((hexahydroxytriphenylene) 2 (Co-HHTP) 的结构演变.
- 为了确定负责生产氨的活性催化物种.
- 为基于MOF的电催化剂的合理设计提供见解.
主要方法:
- 对ZIF-67/碳纸 (CP) 和Co-HHTP/CP.的电化学表征
- 现场拉曼光谱和现场X射线衍射 (XRD) 来研究结构变化.
- 现场里叶变换红外光 (FTIR) 和微分电化学质谱 (DEMS) 分析反应中间体.
主要成果:
- 无论是ZIF-67/CP还是Co-HHTP/CP,都在一个广泛的潜能范围内实现了>95%的NH3法拉代效率 (-0.2到-1.0V与RHE相比).
- 在 -1.0 V 和 RHE 的情况下,NH3 的产率为 87.41 mg h-1 cm-2 (ZIF-67/CP) 和 79.11 mg h-1 cm-2 (Co-HHTP/CP).
- ZIF-67比Co-HHTP更快地转化为Co(OH) 2,Co(OH) 2被确定为化活性物种.
结论:
- 这项研究阐明了NO3RR期间ZIF-67和Co-HHTP的结构演变.
- 氧化 (Co(OH) 2) 被确定为从MOF转化中获得的关键活性物种.
- 这项工作为设计用于电化学反应的基于MOF的电催化剂提供了关键的理解.
更多相关视频
06:53Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
2.1K
10:57Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
18.4K
相关概念视频
02:34Structural Isomerism
19.7K
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...
19.7K
02:42Valence Bond Theory
9.7K
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...
9.7K
02:51Metal-Ligand Bonds
21.5K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
21.5K
02:58Crystal Field Theory - Octahedral Complexes
28.0K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
28.0K
03:45Formation of Complex Ions
24.0K
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
24.0K
02:54Coordination Compounds and Nomenclature
22.3K
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
22.3K