具有UV探测灵敏性、稳定性和重复利用性的层状铀酰配位聚合物研究

doi:10.15541/jim20200139

摘要/Abstract

摘要：

灵敏的UV探测对于工业生产和个人防护非常重要, 本研究旨在开发新型UV探测材料。一般而言, 铀酰单元具有相对高的UV吸收效率和荧光强度。本课题组成功地在水热条件下制备了一例铀酰配位聚合物[(TEA)₂(UO₂)₅(PhPC)₆] (TEA = 四乙基胺离子, PhPC = (2-羧基乙基)苯膦酸, 标记为UPhPC-1)。基于单晶XRD数据的结构分析表明UPhPC-1中有三个不同的铀酰中心, 其中两个铀酰单元为五角双锥构型, 而第三个铀酰单元为四角双锥构型。全部三个铀酰中心与配体在[bc]平面配位形成无限的铀酰层。通过氢键网格和π-π相互作用, 这些铀酰层堆积成整体的层状结构。此化合物具有很好的热稳定性、水稳定性和高抗辐照能力。UV辐照实验结果表明UPhPC-1的本征荧光强度对365 nm的UV辐射高度敏感, 检测下限低且响应速率快, 而发光强度与UV辐照剂量呈负相关。电子顺磁共振谱分析证实在UV光照射下, UPhPC-1中极有可能产生自由基, 造成铀酰荧光部分淬灭。进一步, 被淬灭样品中的自由基能够在加热后被去除, 从而实现UPhPC-1发光强度的快捷恢复。目前的结果表明UPhPC-1在UV辐照的定量探测领域具有一定的发展潜力。

关键词: 铀酰配位化合物, 荧光光谱, UV探测, 结构化学

Abstract:

The sensitive detection of UV light is critical in industrial production and for personal protection, and the aim of this research is to develop novel UV detection materials. The uranyl unit generally exhibits relatively high UV absorption efficiency and strong fluorescence intensity. Hence in this work, a uranyl coordination polymer compound [(TEA)₂(UO₂)₅(PhPC)₆] (TEA = tetraethylammonium ion, PhPC = (2-carboxyethyl)phenylphosphinic acid, denoted as UPhPC-1) was successfully synthesized via the hydrothermal method. The structural analysis of UPhPC-1 based on the single crystal XRD data elucidates that there are three crystallographically unique uranyl centers. Two uranyl units are in the pentagonal bipyramidal geometry, while the third one is in the tetragonal bipyramidal geometry. All three uranyl units are connected by the ligands to form infinite uranyl layers in the [bc] plane, which are packed via hydrogen bonding networks and π-π interactions to yield the overall layered structure. The stability test results of UPhPC-1 demonstrate that the compound exhibits good thermal and hydrolytic stability with high radiation resistance. Moreover, results of the UV irradiation experiments show that the intrinsic luminescence of UPhPC-1 is highly sensitive to 365 nm UV irradiation with a low detection limit and a fast response rate. A negative correlation between the emission intensity and the UV irradiation dosage was then established. The electron paramagnetic resonance data analysis strongly supports the production of radicals in UPhPC-1 under UV radiation, which leads to the partial quenching of the uranyl fluorescence. Furthermore, the radicals in the quenched sample can be readily eliminated by heating, resulting in the recovery of the photoluminescence intensity of UPhPC-1. The current results suggest suitable application potential of UPhPC-1 in the field of quantitative UV detection.

Key words: uranyl coordination polymer, luminescence spectroscopy, UV detection, structural chemistry

中图分类号:

TQ174

陈磊, 陈兰花, 张瑜港, 谢健, 第五娟. 具有UV探测灵敏性、稳定性和重复利用性的层状铀酰配位聚合物研究[J]. 无机材料学报, 2020, 35(12): 1391-1397.

CHEN Lei, CHEN Lanhua, ZHANG Yugang, XIE Jian, DIWU Juan. A Layered Uranyl Coordination Polymer with UV Detection Sensitivity, Stability, and Reusability[J]. Journal of Inorganic Materials, 2020, 35(12): 1391-1397.

图/表 10

Fig. 1 Structural depiction of UPhPC-1 (a) View of the layer topology in the [bc] plane; (b) View of the stacking mode of the uranyl layers

Table S1 Crystallographic data of UPhPC-1 (CCDC No. 1978001)

Formula	[N(C₂H₅)₄]₂(UO₂)₅[C₆H₅PO₂C₂COO]₆
Mr/(g?mol^-1)	2883.45
Color and habit	Yellow, block
Crystal system	Triclinic
Space group	$P \overline 1$
a/nm	1.0802(4)
b/nm	1.2288(5)
c/nm	1.7544(5)
α/(°)	86.856(13)
β/(°)	78.009(10)
γ/(°)	86.530(18)
V/nm³	2.2714(15)
Z	1
ρ calcd/(g?cm^-3)	2.108
T/K	298
R(F) for F_o² > 2σ(F_o²)^a	0.0322
R_w(F_o²)^b	0.0816
^aR(F)= ∑\|\| F_o\| - \|F_c\|\|/∑\|F_o\|	^bR_w(F_o²)=[∑[w(F_o² - F_c²)²]/∑wF_o⁴]^1/2

Table S2 The elemental analyses of UPhPC-1

	Content/%	Peak area	Daily factor
N	0.0832	929	0.9751
C	28.68	20169	0.9846
H	3.409	6670	0.9800

Fig. S1 FT-IR spectra of the pristine UPhPC-1 (a), and UPhPC-1 after UV irradiation and 100 Gy X-ray irradiation (b)

Fig. S2 Photoluminescent spectra of UPhPC-1 (λex = 365 nm) and UO2(NO3)2·6H2O

Fig. S3 UV-Vis absorption spectrum of UPhPC-1 at 298 K

Fig. 2 Luminescence spectra (a) of UPhPC-1 with increasing doses of UV radiation, correlation between the quenching ratio and the UV radiation dose (b) (measured at 516 nm), and corresponding photographs (c) of the single crystal under continuous UV irradiation The inset is the linear fitting of the point data in the low dose range (0-0.028 mJ)

Fig. 3 Photoluminescence spectra (a) of UPhPC-1 before and after X-ray irradiation, EPR spectra (b) of UPhPC-1 before and after UV and X-ray irradiation, luminescence intensities (c) of UPhPC-1 before and after UV irradiation, and after the heating recovery process

Fig. S4 PXRD patterns of samples irradiated by UV and X-ray radiation and soaking in HNO3/NaOH aqueous solutions at pH range from 5 to 12 for 24 h

Fig. S5 Thermogravimetric analysis curve of UPhPC-1

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