通过将DFT辅助的XAS分析和多变量曲线分辨率相结合,精确定位生物灵感MOF中的cu-coordination动机
Beatrice Garetto1, Ning Cao2,3, Valeria Finelli1,4
1Department of Chemistry, NIS and INSTM Reference Centre, Università di Torino, Via G. Quarello 15/A, I-10135, and Via P. Giuria 7, I-10125 Turin, Italy.
The journal of physical chemistry. C, Nanomaterials and interfaces
|February 26, 2025
概括
这项研究使用现场X射线吸收光谱学 (XAS) 进行先进分析,以揭示MOF催化剂中不同的铜物种. 它确定了催化剂结构内的特定Cu (II) 离子的优先氧化还原活性.
科学领域:
- 材料科学 材料科学 材料科学
- 催化剂是一种催化剂.
- 频谱学是一种光谱学.
背景情况:
- 射线吸收光谱 (XAS) 对于异质催化剂研究至关重要.
- 由于信号的平均化,解释来自现场/操作实验的XAS数据具有挑战性.
- 需要先进的分析方法来解决复杂的催化系统.
研究的目的:
- 为了监测不同铜 (Cu) 物种在化改性Cu-UiO-66金属有机框架 (MOF) 中的演变.
- 为了获得在催化反应过程中Cu活性位点的详细结构洞察力.
- 调查MOF内的不同Cu物种的氧化还原行为.
主要方法:
- 在现场的X射线吸收光谱 (XAS).
- 多变量曲线分辨率-交替最小平方 (MCR-ALS) 和波形变换 (WT) 分析.
- 密度函数理论 (DFT) 辅助的扩展X射线吸收细结构 (EXAFS) 配件.
主要成果:
- 成功地解决了在反应过程中演变的不同的Cu物种.
- 使用DFT-EXAFS.使用MCR衍生的Cu物种的局部结构量化精细化.
- 在有缺陷的Zr集群中协调的Cu (II) 离子的确定优先氧化还原活性.
结论:
- 结合的MCR-ALS,WT和DFT-EXAFS方法有效地解卷复杂的XAS信号.
- 在MOF中的特定Cu (II) 物种表现出明显的氧化还原行为,这对于催化活性至关重要.
- 这种方法提供了一个强大的工具,用于了解MOF催化剂中的活性位点.
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
1.9K
08:55Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
8.4K
相关概念视频
02:42Valence Bond Theory
8.4K
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...
8.4K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
41.2K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
41.2K
02:58Crystal Field Theory - Octahedral Complexes
26.0K
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...
26.0K
01:10X-ray Diffraction of Biological Samples
3.8K
X-ray diffraction or XRD is an analytical tool that utilizes X-rays to study ordered structures such as crystalline organic and inorganic samples, polycrystalline materials, proteins, carbohydrates, and drugs.
According to Bragg's law, when X-rays strike the sample positioned on a stage, the rays are scattered by the electron clouds around the sample atoms. The X-ray diffraction or scattering is caused by constructive interference of the X-ray waves that reflect off the internal...
According to Bragg's law, when X-rays strike the sample positioned on a stage, the rays are scattered by the electron clouds around the sample atoms. The X-ray diffraction or scattering is caused by constructive interference of the X-ray waves that reflect off the internal...
3.8K
03:02Colors and Magnetism
11.5K
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...
11.5K
01:182D NMR: Overview of Heteronuclear Correlation Techniques
143
Heteronuclear correlation spectroscopy is an analytical technique that investigates the coupling between different types of nuclei, often a proton and an X-nucleus, such as carbon-13 or nitrogen-15. This method is commonly used in nuclear magnetic resonance (NMR) spectroscopy to gain insights into complex chemical compounds' structural and compositional aspects. A typical heteronuclear correlation spectrum displays X-nucleus chemical shifts on one axis and a proton spectrum on the other...
143