Evidence of the Core-Shell Structure of (Photo)magnetic CoFe Prussian Blue Analogue Nanoparticles and Peculiar Behavior of the Surface Species

被引：43
作者：
Bordage, Arnelie [1 ]
Moulin, Robinson [1 ]
Fonda, Emiliano [2 ]
Fornasieri, Giulia [1 ]
Riviere, Eric [1 ]
Bleuzen, Anne [1 ]
机构：
[1] Univ Paris Saclay, Univ Paris Sud, CNRS, Inst Chim Mol & Mat Orsay, F-91405 Orsay, France
[2] Synchrotron SOLEIL, BP 48, F-91192 Gif Sur Yvette, France
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 32期
关键词：
PHOTOINDUCED FERRIMAGNETIC SYSTEMS; SPIN TRANSITION; ELECTRON-TRANSFER; MAGNETIC-FIELD; ALKALI CATION; C-I; CROSSOVER; HEXACYANOFERRATE; TEMPERATURE; HETEROSTRUCTURES;
D O I：
10.1021/jacs.8b06147
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report on a comparative study of 5.5 nm (embedded in an ordered mesoporous silica matrix) and 100 nm (free) (photo)magnetic CoFe Prussian blue analogue (PBA) particles. Co and Fe K-edge X-ray absorption spectroscopy, X-ray diffraction, infrared spectroscopy, and magnetic measurements point out a core-shell structure of the particles in their ground states. In the 5.5 nm particles, the 11.5 angstrom thick shell is made of Fe(CN)(6) entities and Co-II-NC-Fe-III linkages departing from the geometry usually encountered in PBA, whatever the oxidation state ((CoFeIII)-Fe-II or (CoFeII)-Fe-III) of the CoFe pairs in the core. In the photomagnetic particles, the photomagnetic effect in the core of the particles is due to the same photoinduced Co-III(LS)Fe-II -> Co-II(HS)Fe-III electron transfer whatever the size of the particles. The shell of the nanoparticles exhibits a peculiar photoinduced structural rearrangement, and the nanoparticles in their photoexcited state exhibit a superparamagnetic behavior.
引用
收藏
页码：10332 / 10343
页数：12
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