在N2大气层中通过光谱阐明局部质子合电子转移环从氨基基团到基团通过Au表面
1School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, P. R. China.
Analytical chemistry
|November 12, 2024
概括
这项研究揭示了如何在固体-气体界面上发生质子合电子转移 (PCET),使用表面增强的拉曼光谱学. 研究人员确定了电子转移中间体,这对于理解表面反应至关重要.
科学领域:
- 表面化学 表面化学
- 频谱学是一种光谱学.
- 催化剂是一种催化剂.
背景情况:
- 质子合电子转移 (PCET) 对化学反应至关重要.
- 在固体-气体界面上识别PCET中间体是具有挑战性的.
- 等离子体介导反应为表面化学研究提供了新的途径.
研究的目的:
- 在金/ (Au/N2) 接口上研究和描述PCET.
- 为了阐明由等离子体介导的p-aminothiophenol (PATP) 转化为p,p'-dimercaptoazobenzene的机制.
- 在反应过程中识别电子和质子转移中间体.
主要方法:
- 使用了可变温度表面增强拉曼光谱法 (VT-SERS).
- 激光波长和功率密度被用来控制PCET.
- 为了分析,进行了密度函数理论 (DFT) 模拟.
主要成果:
- 在PATP和PNTP的拉曼波段中特有的蓝色和红色转移表明了电子转移.
- DFT模拟证实了AU表面上存在充电的PATP和PNTP中间体.
- 观察到PCET依赖于激光,并且仅在热循环下不会发生.
结论:
- 证明了局部PCET循环,涉及与Au的电子转移和分子间质子转移.
- 强调了黄金表面在促进PCET电子转移方面的重要性.
- 提供了固体气相PCET反应中电子转移中间体的直接证据.
相关概念视频
NMR Spectroscopy Of Amines
8.5K
In proton NMR spectroscopy, primary amines and secondary amines showcase their N–H protons as a broad signal in the chemical shift range between δ 0.5 and 5 ppm. The exact position in this range depends on several factors, including sample concentration, hydrogen bonding, and the type of solvent used. Since amine protons undergo fast proton exchange in solution, the protons are labile and therefore do not participate in any splitting with adjacent protons. Thus, the observed peak is...
8.5K
¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)
1.0K
When proton-coupled carbon-13 spectra are simplified by a broadband proton decoupling technique, structural information about the coupled protons is lost. Distortionless enhancement by polarization transfer (DEPT) is a technique that provides information on the number of hydrogens attached to each carbon in a molecule. While the DEPT experiment utilizes complex pulse sequences, the pulse delay and flip angle are specifically manipulated. The resulting signals have different phases depending on...
1.0K
Mass Spectrometry of Amines
4.1K
In mass spectroscopy, amines undergo fragmentation to give parent ions with odd molecule weights. This observed mass spectrum follows the nitrogen rule: a molecule with an odd number of nitrogen atoms produces a parent ion with an odd molecular weight. The remaining fragments have an even mass.
Amines undergo fragmentation through α cleavage, producing nitrogen-containing cations—iminium ions—and alkyl radicals. Mass spectra of aromatic and cyclic aliphatic amines exhibit...
Amines undergo fragmentation through α cleavage, producing nitrogen-containing cations—iminium ions—and alkyl radicals. Mass spectra of aromatic and cyclic aliphatic amines exhibit...
4.1K
Electrophilic Aromatic Substitution: Nitration of Benzene
5.7K
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.
5.7K
Nuclear Overhauser Enhancement (NOE)
641
Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. This phenomenon, called the Nuclear Overhauser Enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring...
641
¹H NMR: Complex Splitting
1.2K
A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
1.2K


