文献类型：期刊文献

英文题名：High spin Fe3+-related bonding strength and electron transfer for sensitive and stable SERS detection

作者：Zheng, Xinlu;Wu, Xiao;Zhang, Letian;Kang, Jianjian;Zhou, Man;Zhong, Yang;Zhang, Jinlong;Wang, Lingzhi[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai Engn Res Ctr Multimedia Environm Catalys, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China; East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Inst Fine Chem,Joint Int Res Lab Precis Chem & Mo, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2022

卷号：13

期号：42

起止页码：12560

外文期刊名：CHEMICAL SCIENCE

收录：;EI(收录号：20224513074564);WOS:【SCI-EXPANDED(收录号:WOS:000870315900001)】；

基金：This study was supported by the National Key R&D Program of China (2021YFC2103500), the National Natural Science Foundation of China (No. 21972040, 21822603, and 21773062), Shanghai Municipal Science and Technology (No. 21ZR1417900, 2018SHZDZX03, 17520711500, and 20DZ2250400), the Innovation Program of Shanghai Municipal Education Commission, the Program of Introducing Talents of Discipline to Universities (No. B16017 and B20031), and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Aromatic compounds - Electronic states - Photoelectron spectroscopy - Precious metals - Spin dynamics - Substrates - X ray absorption

摘要：The intrinsic electronic states of transition metal-containing SERS substrates, especially the effect of spin state on the detection sensitivity, still remain unknown. Herein, we propose a simple co-precipitation approach to form trimetallic MIL-101(FeNiTi) with high-spin (HS) Fe3+ as a result of geometric distortion of the octahedral symmetry. Using methylene blue as a demonstration, the trimetallic MIL-101(FeNiTi) shows a high enhancement factor (EF) of 6.1 x 10(6), a low detection limit of 10(-9) M and excellent detection stability after long-term preservation. X-ray absorption fine structure and photoelectron spectra demonstrate that coupling between high-spin Fe3+ and aliovalent transition metals Ni2+ and Ti4+ with different filling degree of 3d e(g)-orbitals results in electron delocalization. The DFT calculation suggests that MIL-101(FeNiTi) with high-spin Fe3+ favors molecular adsorption and the charge transfer from the molecule to MIL-101(FeNiTi) is promoted, benefitting from the enhanced electron delocalization, which both contribute to the distinguished SERS performance of MIL-101(FeNiTi). This finding provides in-depth mechanistic understanding of the effect of the spin state of transition metals on mediating SERS activity, which is expected to efficiently promote the development of SERS platforms based on non-noble metals.