Efficient Removal of Anionic Radioactive Pollutant from Water Using

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Efficient Removal of Anionic Radioactive Pollutant from Water Using Ordered Urea-Functionalized Mesoporous Polymeric Nanoparticle Jian Shen, Wei Chai, Kaixuan Wang, and Fang Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b04325 • Publication Date (Web): 14 Jun 2017 Downloaded from http://pubs.acs.org on June 18, 2017

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ACS Applied Materials & Interfaces

Efficient Removal of Anionic Radioactive Pollutant from Water Using Ordered Urea-Functionalized Mesoporous Polymeric Nanoparticle Jian Shen , Wei Chai , Kaixuan Wang , Fang Zhang* †

†

‡

†

†

The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of

Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234, P. R. China ‡

Department of Chemical Engineering, Zaozhuang Vocational College, Shandong, China

*

(F. Z.) Email: [email protected]; Telephone: +86-21-64321673.

ACS Paragon Plus Environment


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ABSTRACT. A urea-functionalized ordered mesoporous polymeric nanoparticle for removing the perrhenate anion ReO4- as the surrogate of the particularly intractable anion radioactive pollutant TcO4- was demonstrated in the present study. This nanomaterial (denoted as urea-MPN) was produced for the first time by a surfactant-directed urea-phenol-formaldehyde resol oligomers self-assembly protocol under hydrothermal condition. The obtained urea-MPN possessed the uniform nanosized spherical morphology with 3D interconnected ordered cubic mesoporous structure. Also, the urea functional groups were succefully embedded in the polymer framework without the alteration of the molecular configuration. Meanwhile, it exhibited excellent β radiation-resistance up to 200 kGy dose. We employed the perrhenate anion ReO4- to test its potential for the removal of anionic radioactive pollutant TcO4- from water. Interestingly, the optimized urea-MPN naocomposite achieved the high removal efficiency at a low concentration of 0.25 mM within a short contact time of 30 min. The control experimental results revealed that the short nanoscale pore channels and the hydrophobic mesopore surface facilitated the hydrogen-bonding interaction between the charge-diffuse ReO4- tetrahedral oxoanion and the urea moieties in the framework of urea-MPN, accounting for the rapid and effective removal performance in pure water. Importantly, it can selectively capture ReO4- in the presence of different competitive anions including NO3-, CO32-, SO42- and PO43-. This attractive capability of this unique nanosized mesoporous polymeric sorbent will pave the way for the diverse applications in the decontamination of nuclear wastes in more economical and sustainable manner.

Keywords.

Nuclear waste, TcO4-, Adsorbent,

Mesoporous polymeric

Urea-functionalization


nanoparticle,

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1. Introduction The rapid world population growth and the fast economic development in developing countries bring the ever-increasing energy demand.1 However, the current major energy sources such as oil, coal and natural gas are finite and nonrenewable, which are difficult to fulfill mankind’s enormous energy needs.2 Meanwhile, the increase of CO2 content in the atmosphere associated with their combustion is considered as a major manmade cause of climate change.3 To solve this dilemma, our society has to develop renewable and environmentally clean alternative energy resources.4 Nuclear power is the only scalable and carbon neutral energy resource capable of replacing carbon-based fuels in the foreseeable future.5 Nevertheless, the massive toxic and radioactive waste that generated from nuclear fuel cycle is a serious threat to human health and the natural environment.6 Technetium-99 (99Tc) is a fission waste product of 235

U or

239

Pu in nuclear reactors with remarkable radioactivity. Owing to the high fission yield

(6.1%) and long half-life (2.13 x 105 years), it is believed as the significant concern for long-term disposal of radioactive waste. In addition, because of the readily accessible +7 oxidation state, 99Tc exists in the environment as the most stable chemical form of heptavalent pertechnetate anion (TcO4-), which is highly soluble, unreactive and high environmental mobility.7, 8 These intrinsic properties of TcO4- oxo-anion make it very difficult to adsorb by natural minerals or soils and therefore it is one of most dangerous radiation-derived contaminants in the surface and near-surface environments. To remediate

99

Tc nuclear waste,

the reduction of TcO4- anion to technetium(IV) oxides (TcO2 • nH2O) is an effective approach to immobilize TcO4- in the sediment due to the low solubility of TcO2, thereby impending its migration in the groundwater. However, TcO2 precipitation can be re-oxidized or complexated



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to dissolve back to the environment, leading to uncontrollable secondary pollution.9 Alternatively, the use of solid sorbents that trap and separate TcO4- anion from the environment has attracted much recent attention because of simple operation, low cost and energy consumption.10-12 To date, various natural and synthesized sorbents have been adopted for TcO4- anion sequestration, such as clay minerals, inorganic compounds, organic polymer, activated carbon.13-24 Unfortunately, most of these reported sorbents suffer from low efficiency under conditions encountered in actual

99

Tc nuclear contaminations with the extreme trace

TcO4- anion concentrations (70-300 kBq), which significantly limits their practical applications. This phenomenon was mainly related to the low surface area, small pore size, hydrophilic surface or weak adsorption of these solid sorbents.25 Recently, functionalized metal-organic frameworks and porous aromatic frameworks were also used for TcO4- similar surrogate anion removal. The elegant work reported by Thallapally group described that UiO-66-NH2 can efficiently adsorb ReO4- from an aqueous medium with very high uptake capacity of 159 mg/g, even in the presence of other competing anions, which was significantly higher than those of the traditional inorganic materials.26 But, the cost of MOF synthesis usually is higher than inorganic zeolites and layered double hydroxides. Also, they synthesized the NR3+X--functionalized hierarchical porous frameworks (PAF-1) for ReO4- removal. It displayed the highest adsorption capacity with 420 mg/g and meanwhile the uptake capacity was consistent because the number of ion-exchange sites per gram of PAF-1-F was very high. However, the adsorption selectivity with the competing anions still needs to improve.27 Therefore, the design and fabrication of the novel solid sorbent capable of rapid and efficient sequestration of TcO4- anion still remains an outstanding challenge.28


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Ordered mesoporous materials provide an ideal platform for the development of highly efficient solid sorbents in the separation processes of nuclear fuel cycle due to their large surface area, tunable pore size and easy functionalization of pore surface.29-31 Accordingly, many efforts have been made to fabricate mesoporous material-based sorbents for removing the actinides and fission product contaminants from liquid effluents such as 135

Cs, 99Tc,

129

234

U,

239

Pu,

232

Th,

I and 155Eu.32-39 However, the use of mesoporous solid sorbents for TcO4- anion

sequestration is quite limited and also their performances are unsatisfactory due to the aqueous diffusion resistance or the non-selective electrostatic bonding.40-42 In this work, we reported the synthesis of ordered urea-functionalized mesoporous polymeric nanoparticle (urea-MPN) for the first time by the surfactant-directed self-assembly process with the low-concentration urea-phenol-formaldehyde resol oligomers as the building blocks under hydrothermal conditions. This facile process allowed a low cost and scalable sorbent preparation without complicated synthesis and tedious post-functionalization. This novel nanomaterial showed the nanosized spherical morphology and 3D interconnected ordered cubic mesopore structure. Meanwhile, a detailed analysis by solid

13

C CP MAS NMR and XPS spectra confirmed the

molecular integrity of urea groups in the framework of this mesoporous polymer. Importantly, it can maintain the ordered mesoporous structure after 200 kGy dose β radiation. It was investigated for the sorption tests of the ReO4- anion as a chemically and structurally similar surrogate for the radioactive TcO4- anion and the results showed that urea-MPN can efficiently remove around 90% ReO4- anion from contaminated water after just 30 min of contact. The control studies demonstrated that the excellent performance could be attributed to the unique intrinsic features of the urea-MPN. Specially, the urea functional groups provided the effective



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hydrogen-bond bonding interaction for ReO4- tetrahedral anion while the short nanoscale pore channels and high surface area effectively decreased the diffusion resistance of ReO4- anion. Moreover, the hydrophobic pore surface of urea-MPN was also beneficial for removing the charge-diffuse ReO4- anion from water. These unique properties also led to the good selectivity for ReO4- in the presence of different interfering anionic species.

2. Experimental Section 2.1 Synthesis of ordered urea-functionalized mesoporous polymeric nanoparticle (urea-MPN). In a typical synthesis, 57 mg urea and 3.2 ml 37 wt% formaldehyde aqueous solution were mixed at 40oC and then allowed the mixture to reflux at 70oC for 0.5 h. Then, 0.80 g phenol and 15 ml 0.10 M NaOH aqueous solution were added into the mixture to maintain the molar ratio of 1: 10 (urea/(urea+phenol)) and the mixture was allowed to stir for 0.5 h. Then, 0.66 g of triblock copolymer Pluronic F127 dissolved in 15 ml H2O was introduced. The obtained mixture was continued to stir at 66°C with a stirring speed of 350 rpm for 2.0 h. Next, 50 ml water was added to dilute the solution and allowed to stir for another 18 h. In this process, the red precipitate was formed and then stopped the heating, resulting in urea-phenol-formaldehyde resin oligomer, denoted as urea-RO. Subsequently, 18 ml urea-RO solution was transferred into a 100 ml autoclave and diluted with 56 ml H2O and heated at 130°C for 24 h. The solid sample was collected by centrifugation and washed with distilled water for several times and dried at 60oC. The obtained powder was calcined in a tubular furnace at 380oC for 6.0 h in nitrogen atmosphere to remove F127 template, denoted as urea-MPN-3. In addition, urea-MPN-1, urea-MPN-2 and urea-MPN-4 with the same 10 mol%


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urea molar ratio (urea/(urea+phenol)) with urea-MPN-3 were prepared by using 0.60 g, 0.70 g and 0.90 g phenol in the initial mixture, respectively. Meanwhile, urea-MPN-5 and urea-MPN-6 samples with the corresponding 5.0 mol% and 20 mol% urea contents were also synthesized by using 28.5 mg and 114 mg urea with 0.80 g phenol, respectively. Also, the urea-MPN-3 sample with relatively large pore size was prepared by adding 0.13 g TMB into F127 aqueous solution, denoted as urea-MPN-3-TMB. 2.2 Characterization. The nitrogen amount was calculated by a Vario EL III Elemental analyzer. Fourier transform infrared (FT-IR) spectra were obtained on a Nicolet Magna 550 spectrometer. Solid 13C CP MAS nuclear magnetic resonance (NMR) spectrum was recorded on a Bruker DRX-400 spectrometer. The electronic state of nitrogen element was analyzed by X-ray photoelectron spectroscopy (XPS, Perkin-Elmer PHI 5000C ESCA). All the bonding energy value was calibrated by using C1S = 284.6 eV as a reference. X-ray powder diffraction (XRD) patterns were acquired on a Rigaku D/maxr B diffractometer using Cu Kα radiation. N2 adsorption-desorption isotherms were obtained on a Quantachrome NOVA 4000e analyzer. Specific surface areas (SBET) and average pore diameter (DP) are calculated by using BET and BJH models, respectively. The sample morphologies and mesoporous structures were observed by field emission scanning electron microscopy (FESEM, S-4800) and transmission electron microscopy (TEM, JEM 2011), respectively. Toluene and water vapour absorption measurements were carried out on an intelligent gravimetric analyse (Hiden Isochema IGA-002/3) by introducing a dosed amount of high-purity vapor directly into the sample chamber and recording the weight change after stable equilibrium pressure was reached.



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2.3 Perrhenate anion uptake experiment. In a typical run, 50 mg urea-MPN was added to a 50 mL 0.25 mM NaReO4 solution. The solution was then oscillated for 2.0 h at 25oC with an oscillation frequency of 150 rpm in a thermostat oscillator (SKY-100). The equilibrated solution was filtered, and the concentration of the resulting filtrate was measured using inductively coupled plasma-optical emission spectroscopy (ICP-OES, Varian VISTA-MPX). All the adsorption experiments were carried out in duplicate. The ReO4- anion removal efficiency (r, %) was calculated by the following equation: r = (C0 - Ce)/C0 x 100%, where C0 (mmol/L) and Ce (mmol/L) represent the initial and the equilibrium ReO4- concentrations, respectively. The amount of ReO4- adsorbed per unit mass of the adsorbent (qe, mmol/g) was evaluated by using the mass balance equation: qe = (C0 - Ce)V/W, where qe is the amount adsorbed per gram of adsorbent at the equilibrated time, V (L) is the initial volume of the ReO4solution and W is the mass of the adsorbent used (g). 2.4 Kinetic studies. ReO4- anion adsorption experiments under various adsorption times (10-180 min) were performed. For each experiment, 50 mg of urea-MPN-3 or urea-MP was weighted into a 250 mL flask, and a 50 mL 0.25 mM NaReO4 aqueous solution was added. In the settled time (10 min, 20 min, 30 min, 45 min, 60 min and 180 min), the suspensions were centrifuged and the resulting supernatant solutions were analyzed by ICP-OES to get their ReO4 contents. 2.5 Anion Competition Studies. The effect of NO3- was performed by adding 0.25 mM, 1.25 mM, 2.5 mM, 5.0 mM, or 25 mM NaNO3 solutions into a 0.25 mM ReO4- solution, respectively. The competing effects of other anions including SO42-, CO32- and PO43- were initially performed by adding 0.25 mM Na2SO4, Na2CO3, or NaH2PO4 solutions receptively into


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a 0.25 mM ReO4- solution. Then, the urea-MPN-3 sample was added in these above solutions. The concentrations of ReO4- after sorption in aqueous solution were determined by ICP-OES. 2.6 β Radiation Resistance Measurement. β irradiation experiment was conducted using electron beams (1.5 MeV) provided by an electron accelerator (Philips SL 18). The urea-MPN-3 sample was irradiated at a dose rate of 20 kGy/h for 200 kGy dose.

3. Results and Discussion

Scheme 1. Illustration of the synthetic route of urea-MPN.

Scheme 1 depicted the synthetic route of ordered urea-functionalized mesoporous phenol-formaldehyde polymeric nanoparticle (urea-MPN). Firstly, urea-containing phenolic resol oligomers (urea-ROs) were prepared through the base-catalyzed addition and



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condensation reactions. Next, these urea-functionalized resol oligomers assembled with triblock copolymer F127 micelles via hydrogen bonding interactions and subsequently the resulting oligomer/F127 composite monomicelles cross-linked and accumulated to spherical polymeric nanoparticles under the hydrothermal process.43 Finally, ordered urea-functionalized mesoporous phenol-formaldehyde polymeric nanoparticle can be easily obtained after removing F127 template by calcination.

Figure 1. FT-IR spectra of urea-MPN-3 before and after adsorption of ReO4- oxoanion.

Elemental analysis (Table S1) revealed that the nitrogen content in the series of urea-MPN samples was varied from 0.65 to 1.45 wt.%, confirming the presence of organic nitrogen species. Also, the ratios of C/N and H/N of all the urea-MPN samples were in the range of 75 to 120 and 6.0 to 11, respectively. These results indicated that the amine functional groups with


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different contents in these samples were well-dispersed in the organic polymer. The chemical composition of the representative urea-MPN-3 was further analyzed by FT-IR and solid state NMR spectroscopy. As shown in Figure 1, the strong band at 3450 cm-1 was attributed to the stretching vibration of phenolic OH groups and two peaks at 3014 and 2995 cm-1 could be assigned to C-H stretching vibration of the benzene ring in the urea-MPN-3 sample. A series of bands around 1250-1500 cm-1 were attributed to the benzene skeleton stretching, C-H out-of-plane bending and C-H in-plane bending vibrations of the benzene ring, respectively.44 Meanwhile, the band at 1610 cm-1 indicative of the C-C stretching vibration of 1,2,4- and 1,2,6-tri-substituted and phenyl alkyl ether-type substituted aromatic rings was observed. Furthermore, the peak at 760 cm-1 could be attributed to the wag vibration of the urea bond.45 All these results demonstrated the formation of urea-phenol-formaldehyde resin framework. Furthermore,

13

C CP MAS NMR of urea-MPN-3 (Figure 2a) showed two major peaks around

150 and 127 ppm, which were attributed to the substituted and unsubstituted phenolic ring carbons, respectively. Interestingly, two characteristic peaks at 55.4 and 47.7 ppm indicative of the methylene carbon in the urea units (-NH-CH2-NH-) and the methylene carbon between urea and phenolic rings (-Ph-CH2-NH-) were observed in urea-MPN-3.46 This result clearly demonstrated that the urea functional groups were successfully incorporated in the framework of urea-MPN. Furthermore, N 1s XPS spectrum (Figure 2b) of the urea-MPN-3 sample showed that only one peak was found at bonding energy 399.8 eV assigned to the nitrogen atoms in the urea moieties,47 suggesting the chemical configuration of urea could be well retained after the polymerization, assembly and calcination processes. SEM images (Figure 3) showed that urea-MPN-1, urea-MPN-2, urea-MPN-3 and urea-MPN-4 samples have the similar spherical



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Figure 2. 13C CP MAS (a) and N 1s XPS (b) spectra of urea-MPN-3.

morphologies in large domains. Meanwhile, the particle sizes of urea-MPN samples were gradually increased with the increasing amount of phenol in the initial mixture for urea-MPN series samples. Noted that the distributions of their particle sizes were uniform and the average particle sizes of urea-MPN-1, urea-MPN-2, urea-MPN-3 and urea-MPN-4 were around 150 nm, 200 nm, 300 nm and 400 nm, respectively. The remarkable color changed from the starting red-purple color urea-containing resol oligomer/F127 composite aqueous clear solution to the final yellow color solid-liquid mixture indicated the tremendous change of urea-containing resol oligomer/F127 composite under hydrothermal treatment (Figure S1a). Then, we monitored the particle growth process by observing the morphology change of the resol oligomer/F127 monomicelles of the typical urea-MPN-3 during different time periods. As shown in Figure S1b, SEM image showed that the resol oligomer/F127 monomicelle was disordered aggregate after 15 min, and then the phase separation occurred, which caused this aggregate gradually transferred to undivided globular clusters after 1.0 h (Figure S1c-d). After 2.0 h, the clusters


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was separated into incomplete spheres and the further filling process resulted in the individual round spheres in the extended period of time (Figure S1e-h). This dramatic morphology transformation confirmed that the high-temperature treatment drived the urea-containing resol oligomer/F127 monomicelles to polymerize, separate and accumulate, resulting in the formation of spherical structure. Based on this observation, the gradually increasing particle sizes of the series urea-MPN sample with the increasing starting concentrations of phenol could be attributed to the increasing molecular weights of the initial urea-containing resol oligomers.48

Figure 3. SEM images of urea-MPN-1 (a), urea-MPN-2 (b), urea-MPN-3 (c) and urea-MPN-4 (d) samples.



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Small-angle XRD pattern of urea-MPN-3 displayed one intense diffraction peak and two weak peaks at the 2θ range of 0.5 to 2.0o (Figure S2). Since the d-spacing value ratio of three peaks was about 1: 1/√2: 1/√3, these peaks can be indexed as (110), (200) and (211) reflections associated with body-centered 3D cubic Im3m mesostructure.49 The urea-MPN-1 and urea-MPN-2 samples exhibited the similar XRD patterns with urea-MPN-3. However, the decrease of the peak intensity of (110) reflection and the disappearance of (200) and (211) reflections of urea-MPN-4 implied that the high molecular weight of resol oligomer was unfavorable to assemble with triblock copolymer F127, leading to the decreased ordered degree of the mesostructure during the hydrothermal treatment. The same phenomenon was also found in urea-MPN-6 with the highest urea content, which indicated that more urea units in the precursor disturbed the hydrogen-bonding driving assembly between F127 and the hydrophilic phenolic -OH groups.50 TEM pictures (Figure 4) of the representative urea-MPN-3 exhibited the uniform isolated spheres with diameters of approximately 260 nm, which corresponded well with SEM results. Meanwhile, all the TEM images showed the obviously highly ordered mesoporous structure. These images viewed along [110], [100] and [111] directions further confirmed the body-centered cubic mesostructure with space-group Im3m symmetry. The pore structural information of these urea-MPN samples was further characterized using nitrogen sorption experiments. All the urea-MPN samples exhibited the type IV isotherms with H1 hysteresis loop characteristic of mesoporous structure (Figure S3). In the region of low relative pressure, the adsorption and desorption branches could not have a complete closure due to the intrinsic properties of polymer materials.51 The BET surface areas, average pore size and pore volume of urea-MPN samples were summarized in Table S1. The BET surface areas of these


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Figure 4. TEM images viewed along [110] (a), [100] (b) and [111] (c) directions of urea-MPN-3 sample.

urea-MPN spheres were in the range of 210-485 m2/g. The pore sizes were calculated to be 2.4-3.0 nm and the pore volume was varied from to 0.18-0.34 cm3/g. The increases of both phenol and urea amounts in the initial reaction conditions caused the decrease of specific surface area, pore size and pore volume in the corresponding urea-MPN-4 and urea-MPN-6 samples, which was attributed to the partial damages of their mesoporous structures. Furthermore, we tried to add the pore-expanding agent trimethylbenzene (TMB) to the F127 aqueous solution to obtain the urea-MPN-3-TMB with larger pore size.52 As expected, the pore size increased from 2.6 nm to 3.2 nm. This phenomenon was attributed to the increased hydrophobic part of the F127/TMB component. However, the surface area decreased in comparison with urea-MPN-3. Moreover, TEM image (Figure S4) showed that the



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urea-MPN-3-TMB sample displayed the disordered worm-like mesopores, which was maybe due to the addition of TMB disturbed the self-assembly process between the urea-containing resol oligomer and F127 surfactant.

Table 1. Adsorption performances of different urea-functionalized samplesa

a

Entry

Sample

Ce (mg/L)

qe (mg/g)

r (%)

1

urea-MPN-1

25.0

37.5

60

2

urea-MPN-2

17.5

45.0

72

3

urea-MPN-3

7.55

55.0

88

4

urea-MPN-4

30.0

32.5

52

5

urea-MPN-5

12.5

50.0

80

6

urea-MPN-6

15.0

47.5

76

7

urea-MP

31.3

31.3

50

8

urea-MPN-3-TMB

27.5

35.0

56

50 mL 0.25 mM NaReO4 aqueous solution, 50 mg adsorbent, pH = 7.0, 150 rpm, 25oC.

Rhenium (Re) which is placed in the VIIB group together with Tc, is a good chemical surrogate of Tc owing to their similar electronic configuration and stereochemistry and thermodynamic properties.53, 54 Accordingly, we employed the perrhenate anion (ReO4-) to test the adsorption performances of urea-MPN sample for the application of anionic radionuclide sequestration. As shown in Table 1, all the urea-MPN samples could effectively adsorb ReO4-


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anion with moderate to excellent removal efficiencies in pure water. Specially, urea-MPN-3 displayed the highest adsorption capability with 88% removal percentage. However,

Figure 5. ReO4- anion adsorption capacity and removal efficiency as functions over urea-MPN-3 and urea-MP with different contact time (initial concentration 2.5 x 10-4 mmol/1, solution volume 50 mL, adsorbent 50 mg, pH = 7.0, 150 rpm, 25oC).

urea-MPN-4 showed the lowest adsorption capability with 52% removal percentage. Also, urea-MPN-3-TMB with the larger pore size displayed the adsorption capability with 56% removal percentage. It could be explained by the decreased ordered degree of urea-MPN-4 and urea-MPN-3-TMB mesostructure, which was unfavorable for the interactions between urea chelated groups and ReO4- anion due to the increased diffusion resistance.55 This phenomenon could be further confirmed by the adsorption efficiency of urea-MPN-6 even with the highest urea content, which exhibited the inferior removal percentage of 76%. Moreover, the low urea



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content of urea-MPN-5 also showed the inferior adsorption capability due to the reduced coordinated sites. Furthermore, the kinetic of ReO4- anion adsorption by urea-MPN-3 was studied and the result was shown in Figure 5. Noted that it achieved the high removal efficiency at a low concentration of 0.25 mM within a very short contact time of 30 min, which was the fastest adsorption rate of any sorbents reported in the literature for weakly basic tetrahedral oxoanions.

Figure 6. XRD pattern (a), TEM images (b-c) and SEM picture (d) of urea-MP sample.


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To further demonstrate the advantage of urea-MPN-3, the control ordered mesoporous sorbent urea-MP with the irregular morphology was synthesized by evaporation-induced self-assembly approach.56 It had the similar urea content (1.0 wt.%) with urea-MPN-3 (Table 1). XRD pattern and TEM image confirmed that it displayed ordered mesoporous structure with two-dimensional hexagonal arrangement of one-dimensional channels (Figure 6a-c).57 Meanwhile, according to N2 adsorption-desorption isotherm (Figure S5), it had the large surface area (380 m2/g), pore size (3.5 nm) and pore volume (0.40 cm3/g) (Table 1). The significant difference was that it displayed a very irregular morphology with average particle diameters greater than 2.0 µm (Figure 6d). Nevertheless, urea-MP sample only achieved 50% removal efficiency and much slower adsorption kinetics (Figure 5). It could be attributed to much longer pore channel length, which caused the enhanced diffusion limitation for ReO4anion. This result confirmed the merit of the nanosized mesoporous structure. On the basis of these results, the fast kinetics and excellent adsorption ability to remove ReO4- anion to trace level could be attributed to nanospherical morphology with short pore channels and open mesoporous structure of urea-MPN-3, which allowed easy access of ReO4- anion to the hydrogen-bonding urea functional groups.58-60 This coordination effect was also confirmed by FI-IR analysis (Figure 1). Comparing with the pristine urea-MPN-3, the arise of a new peak at 879 cm-1 indicative of ReO4- oxoanion confirmed the efficient uptake of ReO4- in the urea-MPN-3 sample after the adsorption treatment and meanwhile the peak of the urea vibration shifted to 780 cm-1, indicating the existence of interaction between the ReO4oxoanion and the urea functional groups (Figure 1).61 Moreover, the hydrophobic surface property of urea-MPN-3 was also beneficial for the adsorption ReO4- anion due to its



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Table 2. Comparison of the uptake capacity of ReO4- by urea-MPN-3, Mg-Al LDH, NDTB-1 and MOFs. Samples

ReO4- concentration (mg/L)

Uptake capacity (mg/g)

urea-MPN-3

62.5

55.0

Mg-Al-LDH

48.0

10.1

NDTB-1

48.0

18.8

Purolite A532E

28

28

SLUG-21

340

413

UIO-66-NH3+Cl-

150

159

MIL-101-F

100

376

MIL-101

100

312

PAF-1

100

420

charge-diffuse nature in water. To gain better insight into the surface property of urea-MPN-3, both toluene and water vapor absorption tests were performed to test its intrinsic hydrophobicity. As shown in Figure S6, all isotherms showed type V behavior, indicating a weak adsorbent-adsorbate interaction. The maximum adsorption capacity of urea-MPN-3 for toluene (27.3 wt.%) was much higher than that for water (19.0 wt.%). Moreover, the adsorption speed for toluene in the low pressure portion (P/P0 < 0.2) was significant faster than that of water adsorbate. These results demonstrated that the surface of urea-MPN-3 is rather hydrophobic, resulting in the efficient adsorption of ReO4- anion from water.62 In comparison with these perilously reported materials (Table 2),26, 27, 63, 64 the uptake capacity of ReO4- by urea-MPN-3 was higher than hydrotalcite/LDHs (Mg-Al-LDH), ion-exchange resin (Purolite


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A532E) and cationic framework material (NDTB-1). However, it showed the lower capacity than those of MOFs (UIO-66-NH3+Cl-, MIL-101, SLUG-21 and PAF-1) since these MOFs had the much larger surface area. But, the MOFs usually are not very stable in aqueous solution due to their coordination bonding mode compared to the resin materials.65 Furthermore, the interfering anionic species including nitrate, carbonate, sulfate and phosphate were chosen to investigate the adsorption selectivity.66 Because the concentration of nitrate ion is very high in the nuclear waste solution, we firstly conducted the competing ion adsorption experiments of ReO4- (0.25 mM) by using the representative urea-MPN-3 with the different amounts of NO3-. Specially, the effect of NO3- was executed by adding 0.25 mM, 1.25 mM, 2.5 mM, 5.0 mM, or 25 mM NaNO3 solutions into a 0.25 mM ReO4- solution, respectively. As shown in Figure 7, the removal percentage of ReO4- was 77 % when n = 1 (n is the molar ratio between NO3- and ReO4-). With the increasing amounts of NO3-, the removal percentage accordingly slowly decreased. However, even with the large excess of NO3- when n=100, removal percentage of ReO4- was 43 %, indicating that urea-MPN-3 exhibited the good selectivity toward ReO4- with the competitive nitrate anion (Table S2). Furthermore, the uptake capacity of urea-MPN-3 in the presence of CO32-, SO42- and PO43- was also investigated. The competing effects of other anions were performed by adding 0.25 mM Na2SO4, Na2CO3 or NaH2PO4 solution into a 0.25 mM ReO4- solution with 50 mg urea-MPN-3 sample, receptively. As shown in Table S3, the results showed that urea-MPN-3 exhibited the negligible decrease in the uptake capability with the competitive CO32- ion. Also, it still can absorb ReO4- with the dibasic anion SO42- and tribasic anion PO43- with higher charge densities, indicating the good selectivity with these competing anions.



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Figure 7. Effect of the competing nitrate ions on the ReO4- oxoanion adsorption by urea-MPN-3. Meanwhile, we tested the radiolytical stability of the urea-MPN-3 by β radiation up to 200 kGy with a dose rate of 20 kGy/h. As shown in Figure S7a, small angle XRD pattern of urea-MPN-3 after β irradiation displayed an intense (100) diffraction peak, indicating that it still had the typical 2D p6mm hexagonal mesoporous structure. The pore structure was further characterized by using nitrogen sorption experiment. Figure S7b showed that it exhibited type IV isotherms with H1 hysteresis loop characteristic of mesopores. Also, the surface area, average pore size and pore volume were 399 m2/g, 2.5 nm and 0.20 cm3/g, respectively, which were almost similar with the pristine urea-MPN-3. These results clearly demonstrated that urea-MPN-3 had the good radiolytic stability.


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4. Conclusion In summary, we have demonstrated the synthesis of ordered urea-functionalized mesoporous polymeric nanoparticle by a facile surfactant-directed urea-phenol-formaldehyde resol oligomers self-assembly approach under hydrothermal condition. This novel material is highly efficient sorbent for perrhenate anion (ReO4-), which is believed as the good chemical surrogate of the particularly intractable nuclear waste (TcO4-). It possessed rapid sorption kinetics and exceeded all previously reported solid sorbent in anionic radionuclide removal. This can be ascribed to the short nanosized pore channels and the hydrophobic pore surface, which was beneficial for the hydrogen-bonding interactions between tetrahedral oxoanions and the urea functional groups in the framework of mesoporous polymer. This unique effect also resulted in the good selectivity for ReO4- in the presence of different interfering anionic species. More importantly, it exhibited excellent β radiation-resistance up to 200 kGy dose. This novel synthetic strategy has great promise for the fabrication of highly robust solid sorbents for a wide range of challenging radioactive water treatment.

Acknowledgements This work was supported by the Natural Science Foundation of China (21677098), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning (TP2016034) and PCSIRT (IRT-16R49). Supporting Information Available. Elemental analysis and structural parameters of urea-containing samples, adsorption experimental data, SEM images, XRD patterns, N2 sorption isotherms and toluene and water vapor absorption tests of urea-MPN and urea-MP samples. This information is available free of charge via the Internet at http://pubs.acs.org/.



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