Effects of Fe doping on the structures and properties of hexagonal birnessites - Comparison with Co and Ni doping

doi:10.1016/j.gca.2013.04.020

IHEP OpenIR

	Effects of Fe doping on the structures and properties of hexagonal birnessites - Comparison with Co and Ni doping
	Yin, H; Liu, F; Feng, XH; Hu, TD; Zheng, LR; Qiu, GH; Koopal, LK; Tan, WF; 胡天斗;郑黎荣
	2013
发表期刊	GEOCHIMICA ET COSMOCHIMICA ACTA (IF:4.609[JCR-2016],4.847[5-Year])
ISSN	0016-7037
卷号	117 页码:1-15
摘要	Fe-doped hexagonal birnessite was synthesized by adding Fe3+ to the initial reactants, and the effects of Fe doping on the structures and properties of birnessite were investigated and compared with the effects of Co and Ni doping. The underlying mechanisms controlling the incorporation of transition metals (TMs) into the birnessite structure were proposed. Compared to the un-doped control, Fe-doped birnessite has weaker crystallinity, i.e., less stacking of the phyllomanganate sheets in the c direction, and larger surface area. Combination of X-ray photoelectron spectroscopy (XPS) and Mn K-edge XANES and EXAFS spectra demonstrates that Fe doping decreases the Mn average oxidation state (AOS) but has little effect on the basic layer structure and local Mn environments. Fe(III) located in the birnessite layers exhibits high-spin (HS) configuration whereas layer Mn(III) and Co(III) plausibly adopt low-spin (LS) state. The TMs decrease the thickness of birnessite plate crystals along the c axis and affect the unit cell parameter b in the order Fe > Ni > Co. Co and Fe incorporate into the birnessite layers by substitution for Mn(IV) while Ni substitutes for Mn(III). The substitution of TMs into the birnessite layers is governed by the coordination radius (CR), crystal field stabilization energy (CFSE) and oxidation state of the TMs. The variations in potassium contents in doped birnessites together with TM K-edge EXAFS data indicate that most of the Fe (similar to 81-82%) or Ni (similar to 66-76%) incorporated into the birnessite structure exists in the interlayer regions, while most of the Co (similar to 71-80%) occurs in the manganese layers. The compatibility of these TM ions in the birnessite layers is in the order Co > Ni > Fe. The smaller the difference between the CR of Fe, Co or Ni and Mn(IV) or Mn(III), the more dopants are compatible within the Mn layers. (C) 2013 Elsevier Ltd. All rights reserved.
学科领域	Geochemistry & Geophysics
DOI	10.1016/j.gca.2013.04.020
收录类别	SCI ; ADS
语种	英语
WOS记录号	WOS:000324035300001
ADS Bibcode	2013GeCoA.117....1Y
ADS URL	https://ui.adsabs.harvard.edu/abs/2013GeCoA.117....1Y
ADS引文	https://ui.adsabs.harvard.edu/abs/2013GeCoA.117....1Y/citations
引用统计	正在获取... 被引频次：81 [ADS]
文献类型	期刊论文
条目标识符	https://ir.ihep.ac.cn/handle/311005/223753
专题	中国科学院高能物理研究所
推荐引用方式 GB/T 7714	Yin, H,Liu, F,Feng, XH,et al. Effects of Fe doping on the structures and properties of hexagonal birnessites - Comparison with Co and Ni doping[J]. GEOCHIMICA ET COSMOCHIMICA ACTA,2013,117:1-15.
APA	Yin, H.,Liu, F.,Feng, XH.,Hu, TD.,Zheng, LR.,...&胡天斗；郑黎荣.(2013).Effects of Fe doping on the structures and properties of hexagonal birnessites - Comparison with Co and Ni doping.GEOCHIMICA ET COSMOCHIMICA ACTA,117,1-15.
MLA	Yin, H,et al."Effects of Fe doping on the structures and properties of hexagonal birnessites - Comparison with Co and Ni doping".GEOCHIMICA ET COSMOCHIMICA ACTA 117(2013):1-15.