Ag掺杂氟磷酸盐和磺磷酸盐玻璃的光学性质的结构来源,The Journal of Physical Chemistry B

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Ag掺杂氟磷酸盐和磺磷酸盐玻璃的光学性质的结构来源
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2021-01-11 , DOI: 10.1021/acs.jpcb.0c09375
Ru Zhou ₁ , Courtney Calahoo ₁ , Yicong Ding ₁ , Xu Yang ₁ , Carl P. Romao ₂ , Lothar Wondraczek ₁

Affiliation

考虑到使用银化合物进行功能化的玻璃配方的普遍性，孤立的银阳离子与玻璃网络之间的电子相互作用值得更多关注。在这里，我们报告了由氟磷酸盐（PF）和磺基磷酸盐（PS）玻璃中的银掺杂产生的光学特性的结构起源。为此，将固态核磁共振（NMR）光谱和密度泛函理论（DFT）与光谱分析和物理性质测量相结合。比较掺杂玻璃和大量Ag ^+的玻璃的³¹ P NMR，²⁷ Al 1d NMR和²⁷ Al多量子幻角旋转NMR此外，我们推断出这些混合阴离子铝磷酸盐玻璃中银的键合偏好。我们表明，这种理解为在PF和PS玻璃中观察到的Ag ⁺的大斯托克斯位移提供了解释，这与离子Ag ⁺ ··· ^– O–P物种的吸收以及更共价的内激发能的转移有关键合Ag ₂ O样簇。DFT计算证实了这一点，DFT计算表明相应晶体中的Ag ⁺ ·· ^– O-P和Ag ⁺ ·· ^– O–S键大部分为离子键。在晶体结构中引入更多的银离子会导致Ag ⁺之间更多的共价键结合和磷酸盐基质。

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Structural Origin of the Optical Properties of Ag-Doped Fluorophosphate and Sulfophosphate Glasses

Given the ubiquity of glass formulations that are functionalized with silver compounds, the electronic interaction between isolated silver cations and the glass network deserves more attention. Here, we report the structural origin of the optical properties that result from silver doping in fluorophosphate (PF) and sulfophosphate (PS) glasses. To achieve this, solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) are combined with optical spectroscopic analysis and physical property measurements. Comparing the ³¹P NMR, ²⁷Al 1d NMR, and ²⁷Al multi-quantum magic-angle spinning NMR of doped glasses and glasses with large amounts of Ag⁺ added, we deduce silver’s bonding preference in these mixed-anion aluminophosphate glasses. We show that such understanding provides an explanation for the large Stokes shift observed for Ag⁺ in PF and PS glasses, which is related to absorption by the ionic Ag⁺···^–O–P species and transfer of the excitation energy within more covalently bonded Ag₂O-like clusters. This is corroborated by DFT calculations, which show that the Ag⁺···^–O–P and Ag⁺···^–O–S bonds in corresponding crystals are mostly ionic. The introduction of more silver ions into the crystal structure results in more covalent bonding between Ag⁺ and the phosphate matrix.

更新日期：2021-01-21

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