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Functional Inorganic Materials and Devices
Trace detecting OPCWAs in wastewater and plant by a luminescent UIO-67(Hf) and evaluate bioaccumulation of OPCWAs Xiao Lian, and Bing Yan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 05 Apr 2018 Downloaded from http://pubs.acs.org on April 5, 2018
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ACS Applied Materials & Interfaces
Trace detecting OPCWAs in wastewater and plant by a luminescent UIO-67(Hf) and evaluate bioaccumulation of OPCWAs Xiao Lian and Bing Yan*
School of Chemical Science and Engineering, Tongji University, Siping Road 1239, Shanghai 200092, China
Keywords:
MOFs;
UIO-67(Hf);
OPCWAs;
lanthanide
functional;
methanephosphonic acid; bioaccumulation
Corresponding author: Prof. Dr. Bing Yan, Email:
[email protected] ACS Paragon Plus Environment
luminescence
sensing;
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Abstract OPCWAs are a group of organic pollutants characterized by high toxicity and chemical stability, and they are very difficult to be degraded. The trace quality of OPCWAs in water and food will cause great harm to the human body. Therefore, the detection of OPCWAs is a difficult challenge and research hotspots over the world. In this work, a Hf-based luminescent metal-organic framework (Eu@1) is prepared, and the reactivity of Hf12 result a MPA induced luminescence quenching, the charge transfer from MPA to Hf(Ⅳ) and generated exciplex is responsible for this quenching effect. The excellent performance for detecting MPA is encouraging it to apply in wasterwater detection, and with finer selectivity, high sensitivity (LOD = 0.4 ppm) and large linear range (10-7 – 10-3 M). Importantly, MPA is a pollutant that canbe absorbed by plants and causes bioaccumulation effect, thus the detection of MPA in real plant sample is a purposeful topic. Eu@1 also achieved satisfactory results in actual plants sample testing, and the bioaccumulation of MPA in onion, turnip and cabbage are demonstrated via our sensor. This fabricated detector provides a feasible path for the detection of ppm-level OPCWAs in complex environment, and it is favourable for human to avoid OPCWAs contaminated food.
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ACS Applied Materials & Interfaces
Introduction Organophosphorus chemical warfare agents (OPCWAs) are organophosphorus esters or acid with high toxicity applied in warfare, terrorism and pesticides. Due to their volatility, colourless and odourless, it could cause ground, air, surface, and water contaminated, and rapid absorption and action through inhalation.1-3 OPCWAs are extremely insidious and dangerous to effectively inhibit acetylcholine esterase, shutting down pulmonary muscle control and causing death by oxygen deprivation within minutes. Therefore, detection and neutralization of OPCWAs have received anticipated attention given the recent conflict and subsequent ISIS terrorist organization.4 The fast, sensitive and selective detection of OPCWAs is therefore critical to minimise exposure for both human and environment.5-7
In recent years, metal-organic frameworks (MOFs) as a class of crystalline materials with remarkably broad is emerged and rapidly developed.8-10 It is widely used in adsorbent and separation,11-12 catalytic degradation13-14 and luminescent sensing15-18 fields, especially for the organics and biomarkers sensing.19-22 The ultra-high surface area and large porosity make MOFs promising candidates for sorption of OPCWAs, while the metal-containing secondary building units present in MOFs can also function as Lewis-acidic catalytic sites for OPCWAs detoxification or detection.23-24 The flexibility of the ligand in MOFs also provides a feasible idea for the design of the sensor,25 just like post-synthesis modification (PSM) which includes covalent PSM, dative PSM and coordinate PSM.26 Among them, owing to the phosphoric acid products are strongly bound to the MOFs,27 the Zr-containing MOFs exhibit exceptional activity for detoxicating and detect OPCAWs, such as UIO,28 NU-100029 and PCN-222.30 While these MOFs exhibit excellent properties for OPCWAs destruction, explore novel MOFs with strong reactivity for OPCWAs is still a continuing mission for researchers. Hf-containing ACS Paragon Plus Environment
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cluster MOFs, are a kind of promising candidates for their unsaturated ligancy of Hf4+.31-32 According to the Hard-Soft-Acid-Base (HSAB) theory, Hf4+ is stronger hard acid than Zr4+, it is justified that Hf-containing cluster maybe has the same nature as Zr-containing cluster.
Herein, we chosen a dense hcp Hf12 cluster MOFs, as a subject to synthesize a luminescent sensor (Eu@1). The 1 is analogous to the condensation of coordination polyhedral and might show reactivity that similar with defective zeolites. The reactivity of Hf12 cluster and excellent luminescence of Eu3+ encouraged us to explore the sensing performance of Eu@1 for OPCWAs. The methanephosphonic acid (MPA) induced prominent fluorescence quenching effect was observed, and an exciplex mechanism was presented after detailed confirmation. This detection method is further verified in domestic wastewater and obtained a satisfactory outcome. The widely linear range (10-7 – 10-3 M), high sensitivity (LOD = 0.4 ppm) and outstanding selectivity among the complex component in wastewater demonstrated the preeminent performance of Eu@1. Moreover, MPA as a contaminant that is therefore difficult to degrade and can be enriched in plants via bioaccumulation,33 the assessment of the pollution level of MPA in plants was also conducted. These findings may pave the way for practical monitoring of OPCWAs in riverhead and food.
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ACS Applied Materials & Interfaces
Experimental Section Reagents and Instruments
EuCl3·6H2O and GdCl3·6H2O were prepared by dissolving the oxide (Eu2O3 or Gd2O3) into excess hydrochloric acid with continuous stirring, followed by evaporation and crystallization for several times. All the other reagents and solvents were commercially attainable and at least with analytical pure. Methanephosphonic acid (MPA, 98%), diisopropyl methanephosphonate (DIMP, 90%) and diethyl methylphosphonite (DEMP, 96%) were purchased from Acros Organics. Dimethyl methylphosphonate (DMMP, 98%), triethyl phosphate (TEP, 99%) and 2-chloroethyl ethyl sulfide (CEES, 97%) were purchased from Adamas-beta. Ethyl methylphosphonate (EMP, 98%) was purchased from Sigma-Aldrich. The wastewater used in experiment was taken from the domestic wastewater of Tongji University. All the plant samples used in experiment are purchased.
The powder X-ray diffraction (PXRD) patterns were recorded with a Bruker D8 Advance diffractometer using Cu Kα radiation with 40 mA and 40 Kv. Thermogravimetric (TG) analysis was measured using a Netzsch STA 449C system at a heating rate of 15 K min−1 under nitrogen protection. Nitrogen adsorption−desorption isotherms were measured at 77 K using a TriStar 3020 analyzer. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectra were recorded from 4000 to 400 cm−1 using a Nicolet IS10 infrared spectrophotometer with smart DuraSamplIR Diamond ATR accessory. X-ray photoelectron spectra (XPS) were recorded under ultrahigh vacuum (
