在Cu2V2O7上共享角的四面体协调的W-V双活性位点,用于光电化学水氧化
Zheng-Yi Huang1,2, Yi-Ying Chen2, Le-Yang Hao2
1School of Chemistry and Chemical Engineering/Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province/Key Laboratory of Electrochemical Energy Storage and Light Energy Conversion Materials of Haikou, Hainan Normal University, Haikou, 571158, China.
Small (Weinheim an der Bergstrasse, Germany)
|October 9, 2023
概括
这项研究引入了W-doped Cu2V2O7,用于增强光电化学水分解. 该材料优化了活性部位,显著提高了氧气演变反应,以有效生产气.
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:
- 氧气演化反应 (OER) 对于光电化学水分裂至关重要,但受到缓慢动力学的限制.
- 优化氧结合的活性位点和促进*O转换为*OOH是提高开放式氧化物效率的关键.
研究的目的:
- 开发一种高效的光电极材料,用于用 (W) 化Cu2V2O7进行水分裂.
- 研究W-doping在创建双活性位点和改善氧进化反应中的作用.
主要方法:
- 合成W-doped Cu2V2O7 (CVO) 材料的合成.
- 一个W修改的CVO光电极的制造.
- 电化学表征,包括在1.23V与RHE的光电流测量.
- 理论计算 (例如,DFT) 以了解电子结构和反应机制.
主要成果:
- W-doped CVO形成了四面体共享的四面体协调的 W-V 双重活性位点,创造了缺电子中心.
- 修改为W的CVO光电极在1.23V与RHE时实现了0.97mA cm-2的光电流,性能优于未使用CVO的CVO.
- 实验和理论数据表明,W和V之间有协同效应,电荷迁移距离缩短,光生成载体寿命延长.
- 电子结构的调整降低了限制速度的*O到*OOH转换步骤的能量障碍.
结论:
- 在Cu2V2O7中W-doping有效地创建了协同作用的双活性位点,增强了氧气演化反应的水分裂.
- 性能提升归因于优化的电子结构,高效的电荷载体动力学和便利的中间转换.
- 这项工作为设计用于高效太阳能燃料生产的先进光电极材料提出了一个有前途的策略.
相关概念视频
01:26Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
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
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
2.4K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.4K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
42.7K
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,...
42.7K
01:34Woodward–Hoffmann Selection Rules and Microscopic Reversibility
3.1K
Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
3.1K
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.1K