Journal Pre-proofs

A reductive strategy with ultrahigh selectivity for sequential recovery of ura‐

nium from radioactive wastewater

Jianzhang Gao, Jiaqi Chen, Huitao Lv, Xingan Feng, Shitao Liao, Zhidong
Wen, Yongde Yan, Yun Xue, Fuqiu Ma

PII: S1385-8947(24)00527-8
DOI: https://doi.org/10.1016/j.cej.2024.149042
Reference: CEJ 149042

To appear in: Chemical Engineering Journal

Received Date: 15 October 2023

Revised Date: 18 January 2024
Accepted Date: 22 January 2024

Please cite this article as: J. Gao, J. Chen, H. Lv, X. Feng, S. Liao, Z. Wen, Y. Yan, Y. Xue, F. Ma, A reductive
strategy with ultrahigh selectivity for sequential recovery of uranium from radioactive wastewater, Chemical
Engineering Journal (2024), doi: https://doi.org/10.1016/j.cej.2024.149042

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover
page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version
will undergo additional copyediting, typesetting and review before it is published in its final form, but we are
providing this version to give early visibility of the article. Please note that, during the production process, errors
may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2024 Published by Elsevier B.V.

1 A reductive strategy with ultrahigh selectivity for
2 sequential recovery of uranium from radioactive
3 wastewater
4 Jianzhang Gao, 1 Jiaqi Chen, 1 Huitao Lv, 1 Xingan Feng,21 Shitao Liao, 1 Zhidong
5 Wen, 3 Yongde Yan, 1,2 Yun Xue, 1,2, z, Fuqiu Ma 1,2,z

6 1
Fundamental Science on Nuclear Safety and Simulation Technology
7 Laboratory, College of nuclear science and technology, Harbin Engineering
8 University, Harbin 150001, China

9 2 Yantai Research Institute, Harbin Engineering University, Yantai

10 264006, China

11 3Yantai
Growth Drivers Conversion Research Institute and Yantai
12 Science and Technology Achievement Transfer and Transformation Demonstration
13 Base

14 Abstract

15 Uranium is valuable metal, and it is of great significance to develop the

16 simultaneous separation process of uranium and cesium from radioactive wastewater.
17 Herein, a process was designed to separate sequentially uranium and cesium from
18 wastewater. By comparing the limiting ability of OH- and CO32- to Co2+, Cd2+, and
19 Sr2+ ions, it was found that CO32- could effectively limit the above ions to the solid
20 phase. The result of X-ray photoelectron spectroscopy (XPS) and species analysis
21 revealed that the restriction was achieved through complexation. Through this
22 property, more than 99.9% of cobalt and cadmium were limited in the solid phase, and
23 U-Cs co-separation was realized. Furthermore, the results of cyclic voltammetry and
24 XPS indicated that U(VI) could be reduced in the solid phase, but Cs(I) could not,
25 which was the basis for uranium and cesium separation. And more than 99.5% of
26 uranium was separated from cesium by the electrochemical separation process.
27 Simultaneously, effective separation of uranium and cesium under different pHs has
28 been achieved via selective uranium leaching using carbonate. The co-separation

zCorresponding author.
E-mail address: xueyun@hrbeu.edu.cn (Y. Xue)
Telephone number：86-13359518908；
zCorresponding author.

E-mail address: mafuqiu@hrbeu.edu.cn (F. Ma)

Telephone number：86- 18504615879；
1
29 combined with electrochemical separation realized the recovery of pure uranium
30 products, indicating a large potential for realizing uranium resources in wastewater.

31 Keywords: Co-separation; Electrochemical separation; Uranium; Cesium;

32 Wastewater

33 1. Introduction

34 Nuclear power has attracted significant attention as a clean energy in the context of
35 reducing carbon emissions, which is gradually becoming the main force in dealing
36 with global climate issues. The large-scale development of nuclear power will
37 invariably face the problem of nuclear waste disposal, and the disposal of radioactive
38 wastewater is a critical component of such a problem [1]. Uranium and cesium are
39 distributed in radioactive wastewater. One of the most common types of wastewaters
40 containing uranium and cesium ions is radioactive wastewater from reprocessing
41 processes [2]. For example, in the Carbex Process, uranium and cesium are mainly
42 included in the solution after the dissolution of spent fuel [3]. The Fukushima nuclear
43 accident also resulted in the occurrence of both uranium and cesium in some waters
44 [4, 5]. Cesium has a high solubility in solution, which readily diffuses in the
45 environment and can be transported through cell membranes to the human body,
46 leading to human toxicity. Uranyl ions are chemically and radiotoxically toxic, and
47 excess uranium can cause various health problems through oxidative stress, metabolic
48 disorders, protein interactions, inflammation, and cell death [6, 7]. The treatment of
49 uranium and cesium in radioactive wastewater is of great significance to both the
50 environment and human health safety. In addition, the recovery of uranium from
51 radioactive wastewater was beneficial to improve the utilization of uranium resources.

52 The investigation of separation of uranium and cesium is still a bottleneck problem.

53 In recent years, phytoremediation techniques have been employed for uranium and
54 cesium removal. Yang [8] conducted laboratory-scale inter-root filtration
55 experiments, which revealed that during 72 h of root filtration, bean roots
56 accumulated 317-1019 times higher concentrations of uranium and cesium than the
57 initial concentrations, and the laboratory-scale continuous decontamination system
58 reduced uranium concentrations in 56 h from 240 μg/L to less than 10 μg/L. However,
59 the technique was strongly influenced by the pH. A suitable pH is the key to
60 achieving efficient removal of uranium and cesium, which is detrimental to the
61 practical application of the technique. Solid-phase adsorption is a more widely
62 developed technique, and the development of adsorbents is a crucial factor affecting
63 the application of adsorption technology. Zhou [9] developed a dual ion imprinting
64 strategy based on multiple interactions to achieve the simultaneous selective
65 adsorption of uranium and cesium in high-salt environments. The prepared adsorbent
66 could reach the equilibrium of uranium and cesium within 1h and the maximum
67 capacity could reach 221.7 mg U g-1 and 34.5 mg Cs g-1. The adsorption mechanism
68 demonstrated that the highly reactive phenolic hydroxyl groups of the imprinted
69 cavity could achieve selective separation of uranium and cesium through various
2
70 interactions such as coulombic attraction, redox, ion exchange, and complexation.
71 Although this technology achieved the co-separation of uranium and cesium to a
72 certain extent, the recovered uranium and cesium exist in a coexisting state, and direct
73 reuse of uranium cannot be realized. Therefore, the development of a strategy that
74 enables the resourceful reuse of uranium is essential for the recycling and reuse of
75 uranium.

76 To date, electrochemical methods have been widely used in pollution control due to
77 their efficient reaction rate, controllability, high treatment capacity, broad range of
78 application, and ease of operation. There are three main published methods for
79 removing uranium using electrochemical systems: (1) the first one was realized by the
80 in situ generation of co-deposition agents, such as the use of electro-flocculation
81 technology [10], which allowed the iron anode to generate free divalent iron ions to
82 co-deposit with uranium in the wastewater; (2) the second one was the electro-
83 adsorption method, which is to form an electrostatic field between the electrodes by
84 applying a voltage. The charged particles were forced to move towards the electrode
85 plate with opposite charges due to the electrostatic force. The charged particles were
86 adsorbed and temporarily stored in the double electric layer formed on the surface of
87 the electrode plate [11-15]; (3) the third method was the direct electrochemical
88 reduction method, which reduced the hexavalent uranium to pentavalent uranium and
89 tetravalent uranium by applying an electric field to achieve the immobilization of
90 hexavalent uranium in wastewater [16-18]. The third method has the following
91 advantages over the first two methods: (1) the electrode requirements could be reused,
92 lowering the cost significantly; (2) this method did not introduce pollutants, avoiding
93 secondary pollution; (3) this technology could directly convert uranyl ions in solution
94 into solid uranium oxide products that could be used in the nuclear fuel cycle, laying
95 the groundwork for the reuse of uranium resources in wastewater.

96 The electrochemical reduction process entails the diffusion of cations to the cathode
97 under the action of an electric field. The negatively charged coordinated ions are first
98 dissociated by polarization into uranyl ions. The reduced uranium is eventually
99 deposited as a solid on the electrode surface. This technique is currently being used
100 extensively for uranium target preparation [19], source preparation [20, 21], detector
101 device preparation [22], and semiconductor material preparation [23]. However, all of
102 the preceding applications were carried out in a more homogeneous environment
103 (pure uranyl solution), whereas real radioactive wastewater systems are more complex
104 and contain a large number of metal ions in addition to uranium. For example,
105 uranium wastewater contains certain concentrations of alkali metal ions (Na+, Cs+),
106 alkaline earth metal ions (Sr2+), and transition metal ions (Co2+, Cd2+) in addition to
107 UO22+ [24-28]. Realizing the separation of uranium from these ions can effectively
108 improve the utilization of uranium resources. However, the existing technology has
109 two difficult problems: (1) it is difficult to separate uranyl ions and cesium ions; (2)
110 transition metal ions could be reduced to metal monomers or metal oxides during
111 electrodeposition, resulting in a lower purity of the recovered uranium oxide.

3
112 Therefore, the method for separating uranium and cesium from radioactive
113 wastewater while recovering high purity uranium oxide is urgently needed.

114 In this work, a process for separating uranium and cesium from complex
115 radioactive wastewater was developed. The separation of uranium and cesium has
116 been realized by taking advantage of the property that UO22+ can be electrochemically
117 reduced while Cs+ cannot be electrochemically reduced. The application of this
118 method enabled us to successfully recover high purity uranium oxide from simulated
119 radioactive wastewater. The method included U-Cs co-separation and electrochemical
120 separation of uranium and cesium. The effects of various systems on uranium-cesium
121 co-separation, as well as the electrochemical separation of uranium and cesium, were
122 investigated to select the best separation system. X-ray photoelectron spectroscopy
123 (XPS) and species analysis were used to determine the uranium-cesium co-separation
124 process by analyzing the oxidation states of the elements in the separated solid phase.
125 The cyclic voltammetry was used to investigate the electrochemical separation
126 process of uranium and cesium. The leaching of solid-phase uranium was investigated
127 to improve uranium recovery and broaden the applicability of this method to different
128 pH ranges. The effect of different carbonate concentrations on uranium leaching and
129 separation was also investigated to optimize the uranium leaching process.
130 Furthermore, the feasibility of the strategy was evaluated in simulated wastewater
131 conditions for different initial ion concentrations to broaden the application of this
132 method.

133 2. Experimental section

134 2.1 Reagents

135 Uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) was purchased from Hubei Chu
136 Enterprise Chemical Co., Ltd. Cesium chloride (CsCl) and cadmium nitrate
137 (Cd(NO3)2) were purchased from Sinopharm Chemical Reagent Co., Ltd. and were of
138 AR grade. Strontium chloride (SrCl2) and cobalt chloride (CoCl2) were purchased
139 from Aladdin Reagent Co., Ltd. and were of AR grade. All the solutions were
140 prepared using ultrapure water (Milli-Q, Millipore, 18.2 MΩ·cm).

141 2.2 The building and optimization of process

142 This method consists of three processes: co-separation of uranium-cesium,

143 electrochemical separation of uranium and cesium, and solid-phase uranium leaching
144 and recovery (Fig. 1). Sodium carbonate or sodium hydroxide was added to the mixed
145 solution under stirring conditions so that the final concentration of sodium carbonate
146 or sodium hydroxide reached 0.05 M. The well-mixed solution was filtered using a
147 filter. The filter membrane used was an aqueous membrane of 0.45 μm. The filter
148 could be reused. The optimal system was determined by comparing the separation
149 effects of sodium carbonate and sodium hydroxide. A three-electrode system with a
150 titanium plate serving as the cathode, a platinum wire serving as the anode, and a
4
151 saturated calomel electrode serving as the reference electrode was then used to
152 electrochemically purify the uranium in the separated solution. To determine the
153 viability of the electrochemical separation of uranium and cesium, the electrochemical
154 method was employed to separate uranium from the separated solution in different
155 systems. The potential used was -1.5 V. And the working electrode could be reused.
156 Besides, a large amount of uranium was converted into solid phase at neutral pH, and
157 part of uranium entered solid phase at basic pH due to coprecipitation. To improve the
158 recovery rate of uranium and expand the application in different pH conditions, the
159 uranium in the solid phase was leached using carbonate solution and then recovered
160 via electrochemical method. Moreover, different carbonate concentrations (0.01-0.3
161 M) were used in order to compare the impact on uranium recovery and choose the
162 best leaching concentration.

163 2.3 Characterization analysis

164 The solid phase was separated after the addition of the separation system, and the
165 separated solid phase was dried. After the solid-liquid separation, the species
166 composition in the solid phase was determined using XPS. Inductively coupled
167 plasma mass spectrometry (ICP-MS) was used to determine the concentrations of
168 UO22+, Co2+, Sr2+, Cs+, and Cd2+ in the solution before and after separation. And the
169 samples underwent 2% nitric acid pretreatment prior. Cyclic voltammetry curve was
170 measured on a PGSTAT 302N electrochemical workstation with a three-electrode
171 system using a titanium sheet with an area of 1 cm2 as working electrode, a saturated
172 calomel electrode as reference electrode, and a platinum as counter electrode.

173

174 Fig. 1. Schematic diagram of uranium and cesium recovery and separation from
175 simulated wastewater

5
176 3. Results and discussion

177 3.1 The uranium-cesium co-separation

178 3.1.1 Separation system

179 The influence of transition metal ions and alkaline earth metal ions must be taken
180 into consideration to accomplish effective recovery of uranium and cesium. In this
181 investigation, the simulated mixed solution (0.84 mM) was treated with carbonate and
182 sodium hydroxide. As shown in Fig. S1a, the sodium hydroxide had a high removal
183 rate of Co2+ and Cd2+, up to 99.9%. However, the removal efficiency of this system
184 for Sr2+ was only 60%. The presence of large amounts of Sr2+ was detrimental to the
185 recovery of uranium and cesium. Furthermore, its ability to remove uranyl ions
186 resulted in an inability to retain uranyl in solution (Fig. S1a). Less than 10% of the
187 uranium was left in the liquid phase. Ultimately the system did not achieve uranium-
188 cesium co-separation.

189 In contrast, the removal effect of carbonate for various ions exhibited some very
190 intriguing phenomena. On the one hand, carbonate had a very pleasant removal effect
191 for both Co2+ and Cd2+ with a removal rate of over 99.9%, and its removal efficiency
192 for Sr2+ was also up to approximately 95%. The experimental results showed that only
193 0.184 g of waste was generated per liter of wastewater treated. On the other hand, the
194 majority of the uranium and cesium was kept in solution. This facilitated the co-
195 separation of uranium-cesium. This may be due to the different solubilization
196 capacities of the various complexes. The process of uranium-cesium co-separation in
197 the carbonate system should be further investigated below.

198 Moreover, a study on the electrochemical separation of uranium and cesium was
199 conducted after the separation with the sodium hydroxide and carbonate. The results
200 implied that effective electrochemical separation of uranium and cesium in the
201 solution could be achieved after the separation with the carbonate and sodium
202 hydroxide. Fig. S1b showed that more than 95% of the uranium in the sodium
203 hydroxide separation solution was electrochemically separated at 180 min, while
204 nearly 100% of the cesium ions were retained in the solution (as shown in Fig. S2).
205 The present work has a very good separation compared to previous studies (Table S1).
206 And the separation of uranium and cesium in the carbonate solution was more
207 effective. More than 92% and 99.6% of the uranium had been electrochemically
208 separated after 90 min and 180 min. And approximately 100% of the cesium ions in
209 the separation solution were still retained (Fig. S2). The carbonate is unquestionably
210 the best option since it combines the ability to remove impurities with the ability to
211 separate uranium and cesium. In addition, the cesium-uranium mass ratio in the
212 solution after separation of uranium-caesium by traditional separation methods such
213 as adsorption was as low as 4 × 10-8, while the cesium-uranium mass ratio after
214 separation by the present method was close to 0 (as shown in table S1).

6
215 3.1.2 Separation process

216 Fig. S3 was the thermodynamically modelled solubility diagram of different ions in
217 the sodium hydroxide system, the simulation results also revealed that the
218 concentrations of Co2+ and Cd2+ were reduced to less than 1μM (Fig. S3a and Fig.
219 S3b). The simulation results also indicated that due to the strong complexation of
220 OH-, Co2+ and Cd2+ were transformed into Co(OH)2 and Cd(OH)2. Their low
221 solubility resulted in high removal rates of Co2+ and Cd2+. However, OH- had no
222 obvious complexation with Sr2+ and Cs+, which still existed in the sodium hydroxide
223 solution (Fig. S3c and Fig. S3d). UO22+ could be complex with OH- to form uranium
224 hydroxide (Fig. S3e). The poor solubility of uranium hydroxide led to a low retention
225 of uranium in the sodium hydroxide system. These are the reasons why the sodium
226 hydroxide system cannot achieve uranium-cesium co-separation.

227 Meanwhile, species simulation analysis of different ions was performed to establish
228 the separation process of uranium and cesium in the carbonate system (Fig. 2a-c and
229 Fig. S4). The simulation results demonstrated that Cd2+, Co2+, and Sr2+ had a high
230 complexing ability with CO32-, resulting in solid phases that included CdCO3, CoCO3,
231 and SrCO3. Among them, Co2+ was unique in that it also produced Co(OH)2 through a
232 hydrolysis reaction. In contrast, Cs+ was not complex with CO32- or undergo
233 hydrolysis reactions, and it remained in the liquid phase as an ion (Fig. S4a). UO22+
234 also existed in the liquid phase. Unlike Cs+, it could be complex with CO32-, and the
235 complex product UO2(CO3)34- existed in the liquid phase because of its strong
236 solubility. To further verify the results of simulation analysis, the XPS was used to
237 analyze the oxidation state of the products obtained after the separation of different
238 ions to establish the separation process of uranium and cesium from impurity ions.
239 The existence of cadmium carbonate was evidenced by the main peak of 405.10 eV
240 (Fig. 2d), which was assigned to cadmium carbonate species [29]. The presence of
241 cadmium carbonate indicated that the cadmium ion entered the solid phase as a
242 complex of carbonate and cadmium ions in the carbonate solution. Co 2p could be
243 split into a main peak at 786.00 eV, which could be assigned to Co(II) (Fig. 2e). The
244 product was identified as alkaline cobalt carbonate through a combination of
245 hydrolysis and complexation reactions when combined with product color analysis.
246 The Sr 3d spectrum exhibited two contributions, 3d5/2 and 3d3/2, caused by the spin–
247 orbit splitting, located at respectively 133.20 and 135.00 eV, which could be assigned
248 to strontium carbonate (Fig. 2f) [30]. Based on the simulation and XPS results, the
249 uranium and cesium co-separation process has been established. As shown in Fig. 2g,
250 the solid in the separation process was primarily generated by the complexation of
251 impurity ions with carbonate and the hydrolysis of impurity ions, while the uranium
252 and cesium were mainly presented in the liquid phase. Among them, cesium ions had
253 poor complexation ability with carbonate and they were mainly presented in the liquid
254 phase as Cs+ [31]. In contrast, although uranyl ions could complex with carbonate at
255 high pH, the complex UO2(CO3)34- was more soluble and could be retained in the
256 liquid phase [18]. Therefore, uranium and cesium were successfully co-separated

7
257 from the mixed solution with the carbonate system.

258

259 Fig. 2. Thermodynamically modelled solubility diagram of (a) Cd2+, (b) Co2+, and
260 (c) Sr2+ species present in the carbonate system as a function of pH (d) XPS spectra of
261 species formed by Cd2+, (e) Co2+, and (f) Sr2+ at pH 10.5 (g) Schematic diagram of U-
262 Cs co-separation process.

263 3.2 The electrochemical separation process

264 3.2.1 The establishment of electrochemical separation process

265 Fig. S5 was the cyclic voltammograms of uranyl and cesium ions in carbonate
266 solutions with a scanning rate of 0.1 V/s. There is a reduction peak Ⅰc’ in the cyclic
267 voltammogram curve of the cesium ions. Combined with the reduction peak shown in
268 Fig S6, this reduction peak was consistent with that in the background curve, which
269 indicated that no reduction reaction of Cs+ occurred in the carbonate solution. Unlike
270 the cesium ions, the presence of the apparent reduction peak Ⅰc was direct evidence
271 that the uranyl ion could be effectively reduced in the carbonate system, which
8
272 corresponded to U(VI) to U(V). And U(V) readily disproportionated to form U(VI)
273 and U(IV) [32]. U (Ⅳ) has poor solubility in alkaline solutions and was finally
274 separated from the solution in the form of solid phase. Based on these, uranyl and
275 cesium ions could be separated and purified by electrochemical methods. To verify
276 the feasibility of the carbonate system coupled with electrochemistry for the
277 separation and purification of uranium and cesium, cyclic voltammetry curves of the
278 mixed solution of Co-Cd-Sr-Cs-U were measured before and after the addition of
279 carbonate. As shown in Fig. S7a, the cyclic voltammogram curve of the mixed
280 solution demonstrated the presence of multiple reduction peaks, which were due to the
281 reduction of multiple ions. The extraction of high-purity uranium could not be
282 achieved under such conditions. In contrast, after the addition of carbonate to the
283 mixed solution, only one reduction peak was present in the cyclic voltammogram
284 curve, which was related to the reduction of uranium U(VI) (Fig. S7b) to U(V). The
285 addition of carbonate strongly inhibited the reduction of impurity ions. It proved that
286 the recovery of high-purity uranium could not be directly achieved in the mixed
287 solution, but could be easily completed after adding carbonate.

288 To further verify the above conclusions, the sediment was analyzed by XPS. The
289 fitting results of Cd 3d, Co 2p, Sr 3d, Cs 3d, and U 4f spectra reflected (in Fig. 3) that
290 when the electroreduction experiment was carried out in the solution without
291 separation treatment, the sediment contained Cd (405.11 eV) [33], CoO (780.60 eV)
292 [34], SrCO3 (133.5 eV) [35], U6+, and U5+ [36]. The formation of complex products
293 indicated that complex reactions occurred in the solution without separation, which
294 was consistent with the results in Fig. S7a. Among them, the presence of Cd and U5+
295 was due to the electrochemical reduction of Cd2+ and U6+, respectively. CuO was the
296 result of Cu2+ complexing with OH- during electrolysis. The existence of SrCO3 was
297 caused by its adhesion to the electrode during electroreduction. Such a complex
298 reaction was unfavorable for the separation of uranium and cesium. However, only
299 U6+ and U5+ were found in the electrodeposition substance obtained from the
300 separated solution with the adding of the carbonate. The existence of U5+ also proved
301 the occurrence of single-electron transfer process. And there was no compound
302 related to Cd, Co, Cs, or Sr. This indicated that: (1) the separation in advance is
303 beneficial to the separation of uranium and cesium, effectively avoiding the influence
304 of impurity ions; (2) there is no reduction reaction of Cs+, and the electrochemical
305 separation of uranium and cesium is feasible.

9
306

307 Fig. 3. Cd 3d, Co 2p, Sr 3d, Cs 3d, and U 4f spectra of electrodeposition

308 compounds in mixed solution before and after U-Cs co-separation

309 3.2.2 The influence factors

310 The impact of various parameters on the electrochemical separation of uranium and
311 cesium was examined. The increase in temperature was advantageous for the
312 electrochemical separation of uranium, as illustrated in Fig. 4a. It only took 180 min
313 to finish the separation of more than 99% of uranium when the temperature was
314 higher than 303.15 K. This was because that the increase in temperature promoted the
315 transfer of electrons and the diffusion of uranyl ions [32]. The addition of excess
316 carbonate was detrimental to the electrochemical separation of uranium (Fig. 4b). The
317 addition of carbonate introduced additional cations and the conductivity increased
318 with the increase in carbonate concentration (Fig. S8). Unexpectedly, the increase in
319 conductivity did not lead to an increase in the electrochemical separation rate of
320 uranium. The electrochemical separation rate of uranium did not increase when the
321 concentration of carbonate was higher than 0.1 M. Additionally, when the
322 electrodeposition was conducted at high carbonate concentration, the concentration of
323 uranium did not continually decrease, suggesting that the deposited uranium oxide
324 was dissolved once more. This was because that large amounts of oxygen were
325 created at the anode due to the increase in carbonate concentration. This oxygen was
326 then reduced at the cathode due to the proximity of the two electrodes, and the
327 following reaction took place [37]：

328 O2 +2e-⇌O2-
2 (1)

329 while the uranium oxide was dissolved by the combined effect of O22- and high
330 concentration of CO32-, and the reaction was as follows [38, 39]:

2-2x-2y
331 UO2 + xO2- 2-
2 +yCO3 →UO2(O2)x(CO3)y + 2e- (2)

332 The resulting ternary complex UO2(O2)x(CO3)y2-2x-2y had a high solubility [38, 39].

10
333 The gradual change of the solution from pale yellow to orange during
334 electrodeposition likewise proved this point [38]. The above dissolution processes
335 seriously affected the electrochemical separation of uranium. This ultimately resulted
336 in the inability to achieve effective separation of uranium and cesium. In addition, the
337 cation type and concentration are also important factors affecting the separation effect
338 of uranium, and related studies were carried out. Due to the low concentration of iron
339 and vanadium ions at pH 10.5, only sodium, potassium and ammonium ions were
340 studied in this study. As shown in Fig. 4c, the results showed that the influence of
341 different cations on uranium electrochemical separation rate was ranked as follows:
342 K+>Na+>NH4+. Among them, the presence of NH4+ did not have any effect on the
343 electrochemical separation rate of uranium, while K+ and Na+ had a significant
344 promotion effect on that of uranium. And the promotion effect of K+ was slightly
345 stronger than that of Na+. However, Na+, K+, and NH4+ had no effect on the
346 electrochemical separation efficiency of uranium. In Fig. 4d, there was no dissolution
347 occurred within the selected cation concentration range, which could be attributed to
348 the lower carbonate concentration resulting in slower uranium oxide dissolution, and
349 the dissolution was not the primary influencing factor. The conductivity of the
350 solution was increased by the increase in cation concentration, which promoted the
351 electrochemical separation of uranium (Fig. S9). However, there was no obvious
352 pattern between different cation concentrations and the electrochemical separation
353 rate of uranium. The promotion effect of different concentrations of cations on the
354 electrochemical separation rate of uranium has no obvious difference. And the
355 electrochemical separation efficiency of uranium under different concentrations of
356 cations is the same. In general, the cation concentration has little effect on the
357 electrochemical separation of uranium.

11
358

359 Fig. 4. (a) Time dependence curve of the proportion of uranium remaining during the
360 electrochemical separation at different temperatures, (b) sodium carbonate
361 concentrations, (c) types of cations, (d) and cation concentrations (NaCl)

362 3.3 Solid-phase uranium leaching and electrochemical separation of uranium

363 According to the results revealed in Fig. S4b, pH had a significant effect on
364 uranium retention. A large amount of uranium was converted into solid phase at low
365 pH, and coprecipitation at high pH resulted in some uranium entering into solid phase.
366 How to realize the recovery of solid uranium was crucial to expand the application of
367 this method to different pHs. Therefore, leaching of solid-phase uranium generated
368 during different pH separations was investigated to further improve the recovery of
369 uranium resources. Fig. 5a reflected that the uranium in the solid phase could be
370 redissolved efficiently. The leaching concentration of uranium in the solid phase
371 separated by pH 6.0 was the highest. Excitingly, the concentrations of Co2+, Cd2+,
372 Cs+, and Sr2+ in the leachate were much lower than those of uranyl ions. This
373 indicated that the leaching process could selectively recover uranyl ions, which had a
374 very beneficial effect on the subsequent electrochemical separation of uranyl. Fig. 5b
375 depicted a graph of the remaining percentage of uranium in the leachate during
376 electrochemical separation process, and the leachate was obtained by leaching for the
377 solid phase generated after separation by different pHs. The results illustrated that
378 uranium in different leachates could be separated electrochemically. Meanwhile, the
379 Cs+ concentration did not change during the electrochemical separation (Fig. S10),
12
380 and it was well retained in the liquid phase, resulting in effective uranium and cesium
381 separation. Combining the two processes of liquid-phase uranium separation and
382 solid-phase uranium separation can greatly improve the recovery of uranium at all pH
383 conditions, greatly expanding the application of this method. To further optimize the
384 leaching of solid-phase uranium, different carbonate concentrations were employed
385 (Fig. 5c), and effective uranyl leaching was achieved for all of the different carbonate
386 concentrations. The concentration of uranium in the leaching solution gradually
387 increased with time, and 0.1 M carbonate had the fastest leaching rate and the greatest
388 leaching capacity. Fig. 5d showed that the variation in carbonate concentration had no
389 effect on Sr2+ and Cs+ leaching but had a significant effect on Co2+ and Cd2+ leaching.
390 The leaching capability of Co2+ and Cd2+ in the leach solution was improved
391 progressively with an increase in carbonate concentration, and it soared when the
392 carbonate concentration reached 0.3 M. In order to increase the mass percentage of
393 uranium in the leach solution, it is advantageous to properly reduce the carbonate
394 concentration. The comparison of the Cs+ concentration in the leach solution before
395 and after electrochemical separation (Fig. S11) revealed that Cs+ was kept in the
396 liquid phase, which was beneficial for achieving separation with uranium. In general,
397 the low carbonate concentration was more conducive to the selective recovery of
398 uranium.

399

400 Fig. 5 (a) Plots of different ion concentrations in the leachate obtained by leaching

13
401 solid-phase uranium separated under different pH (b) Plots of the proportion of
402 remaining uranium in the leachate during electrochemical separation of uranium with
403 time (c) Variation of uranium concentration in the leaching solution with time in the
404 process of leaching solid uranium with different sodium carbonate concentrations (d)
405 The concentration of various ions in the solution after leaching solid uranium with
406 different carbonate concentrations

407 3.4 Extension of the method

408 An initial concentration of 4.2 mM was used to further validate the feasibility of
409 this strategy at a high initial concentration. In Fig. 6a, uranium in the liquid phase
410 after separation could be effectively separated electrochemically, and more than
411 99.5% of the uranium was electrochemically separated at 180 minutes. The ratio of
412 ion concentration in the solution before and after electrochemical separation revealed
413 that the concentration of Cs+ remained nearly unchanged and was well retained in the
414 liquid phase (Fig. S12). Furthermore, 99.8% of the uranium was electrochemically
415 separated from the liquid phase, effectively separating uranium and cesium. And Cs+
416 in the liquid phase can be effectively treated by simple electro-sorption, adsorption,
417 and ion exchange methods for the purpose of final geological disposal [40-42]. This
418 implied that even at high initial concentrations, uranium and cesium could be
419 effectively separated. The results of recovering solid-phase uranium with various
420 carbonate concentrations demonstrated that effective uranium recovery was possible
421 with various carbonate concentrations (Fig. 6b). Strontium, cobalt, and cadmium
422 leaching capacity gradually increased with the increase in carbonate concentration, as
423 it did with low initial concentrations (Fig. 5d). Similarly, cobalt and cadmium
424 leaching capacities spiked in 0.3 M carbonate solution. As a result, the low carbonate
425 concentration allowed for selective uranium leaching. Furthermore, the
426 electrochemical separation ability of uranium in leachates derived from various
427 carbonate concentrations was investigated. The results in Fig. 6c indicated that
428 uranium could be separated electrochemically more efficiently in leachates with low
429 carbonate concentrations. Uranium and cesium could be effectively separated when
430 the results in Fig. 6d were combined. Overall, the method could extract uranium and
431 cesium with high purity from wastewater containing a high ion concentration. In
432 addition, iron ions are a common impurity ion in uranium-containing wastewater. For
433 this reason, the feasibility of the process in the presence of iron ions was verified. The
434 results of the experiments showed that, even in the presence of iron ions, the retention
435 rate of uranium in the solution was still more than 70 %, and that of cesium ions was
436 also more than 85%. More than 99% of the iron was converted to solid phase. This
437 indicates that the presence of iron ions has small effect on the co-separation of
438 uranium and cesium. Afterwards, an electrochemical separation study of uranium and
439 cesium was carried out. More than 99% of uranyl was transformed into solid phase
440 after separation, while nearly 100% of cesium ions were retained in the liquid phase.
441 The results showed that the presence of iron ions has small effect on the process of
442 uranium-cesium co-separation and electrochemical separation of uranium and cesium.

14
443

444 Fig. 6 (a) The remaining proportion of uranium in the U-Cs co-separation solution
445 with electrochemical separation time (b) Different ion concentrations in the solution
446 after leaching with different carbonate concentrations (c) The remaining proportion of
447 uranium in the solution after 90 min electrochemical separation with different
448 concentrations of leaching (d) Ratio of cesium ion concentration after
449 electrodeposition to cesium ion concentration before electrodeposition in leaching
450 solution with different concentrations of sodium carbonate

451 4. Conclusion

452 To summarize, the process based on electrochemical technology has realized the
453 separation of uranium and cesium in complex radioactive wastewater. The results
454 indicated that the solubility of the complex of OH- and UO22+ ions is low, making co-
455 separation of uranium and cesium impossible. However, CO32- could be complex with
456 Co2+, Sr2+, and Cd2+ and be limited in the solid phase to eliminate its influence on the
457 co-separation of U-Cs. Through the co-separation of U-Cs, the concentrations of Co2+
458 and Cd2+ in the liquid phase were less than 0.1% of the initial concentration, while
459 more than 90% of UO22+ and Cs+ were retained in the liquid phase. The separation of
460 uranium and cesium was realized by electrochemical technology. XPS results
461 indicated that after the co-separation of U-Cs and electrochemical separation, the solid
462 phase products only contained uranium. This proved that the co-separation process
15
463 effectively eliminated the influence of Co2+, Sr2+, and Cd2+, and the electrochemical
464 separation process realized the separation of uranium and cesium. And the selective
465 leaching of solid uranium could be achieved even if the solid uranium was separated
466 at different pH, which effectively expand the application scope of this method. And
467 the optimization of the leaching solution revealed that low concentration carbonate
468 was beneficial to the selective recovery of uranium and the subsequent
469 electrochemical separation of uranium and cesium. Surprisingly, this method still
470 achieved effective recovery and separation of uranium and cesium when it was used
471 in simulated wastewater with a high initial concentration. The proposed method
472 provided a potential scheme for the resource utilization of uranium in radioactive
473 wastewater.

474

475 ACKNOWLEDGMENT

476 This work was financially supported by the Fundamental Research Funds for the
477 Central Universities (3072022JC2703), the National Isotope Engineering Technology
478 Research Center (GJTWSGCZX-202301), the Yantai Growth Drivers Conversion
479 Research Institute and Yantai Science and Technology Achievement Transfer and
480 Transformation Demonstration Base (KXDNY2023-3). The authors are grateful for
481 all your support.

16
482 References

483 [1] S. Zhou, X. Zhang, Nuclear energy development in China: A study of opportunities and challenges,
484 Energy, 35 (2010) 4282-4288.

485 [2] D. Kadadou, E.A. Said, R. Ajaj, S.W. Hasan, Research advances in nuclear wastewater treatment
486 using conventional and hybrid technologies: Towards sustainable wastewater reuse and recovery,
487 Journal of Water Process Engineering, 52 (2023) 103604.

488 [3] A.M. Chekmarev, A.V. Boyarintsev, S.I. Stepanov, A.Y. Tsivadze, Physicochemical principles of
489 preparation of U(VI) carbonate solutions for extraction reprocessing in the Carbex process,
490 Radiochemistry, 59 (2017) 345-350.

491 [4] T.-W. Kang, Y.-U. Han, E.H. Na, B.-J. Koo, W.-P. Park, Deposition of Fukushima nuclear power plant
492 accident-derived radiocesium in the soils of Jeju Island, Korea, and evidence for long- and short-lived
493 radionuclides in rainwater, Chemosphere, 264 (2021) 128457.

494 [5] K. Buesseler, M. Aoyama, M. Fukasawa, Impacts of the Fukushima Nuclear Power Plants on Marine
495 Radioactivity, Environmental Science & Technology, 45 (2011) 9931-9935.

496 [6] M. Ma, R. Wang, L. Xu, M. Xu, S. Liu, Emerging health risks and underlying toxicological
497 mechanisms of uranium contamination: Lessons from the past two decades, Environment
498 International, 145 (2020) 106107.

499 [7] N. Gao, Z. Huang, H. Liu, J. Hou, X. Liu, Advances on the toxicity of uranium to different organisms,
500 Chemosphere, 237 (2019) 124548.

501 [8] M. Yang, J.W. Jawitz, M. Lee, Uranium and cesium accumulation in bean (Phaseolus vulgaris L. var.
502 vulgaris) and its potential for uranium rhizofiltration, Journal of Environmental Radioactivity, 140
503 (2015) 42-49.

504 [9] L. Zhou, M. Xu, J. Yin, R. Shui, S. Yang, D. Hua, Dual Ion-Imprinted Mesoporous Silica for Selective
505 Adsorption of U(VI) and Cs(I) through Multiple Interactions, ACS Applied Materials & Interfaces, 13
506 (2021) 6322-6330.

507 [10] N.K. Shammas, M.-F. Pouet, A. Grasmick, Wastewater Treatment by Electrocoagulation-Flotation,
508 in: L.K. Wang, N.K. Shammas, W.A. Selke (Eds.) Flotation Technology: Volume 12, Humana Press,
509 Totowa, NJ, 2010, pp. 199-220.

510 [11] J. Zhou, H. Zhou, Y. Zhang, J. Wu, H. Zhang, G. Wang, J. Li, Pseudocapacitive deionization of
511 uranium(VI) with WO3/C electrode, Chemical Engineering Journal, 398 (2020) 125460.

512 [12] M. Pan, C. Cui, W. Tang, Z. Guo, D. Zhang, X. Xu, J. Li, Carbon cloth as an important electrode
513 support for the high selective electrosorption of uranium from acidic uranium mine wastewater,
514 Separation and Purification Technology, 281 (2022) 119843.

515 [13] J. Huang, Z. Liu, D. Huang, T. Jin, Y. Qian, Efficient removal of uranium (VI) with a phytic acid-
17
516 doped polypyrrole/ carbon felt electrode using double potential step technique, Journal of Hazardous
517 Materials, 433 (2022) 128775.

518 [14] H. Ye, T.-H. Li, Y.-Q. Huang, J.-M. Jin, J.-Y. Fei, M.-B. Wu, J. Yao, Amyloid-like coatings decorated
519 electrodes boost the uranium electro-adsorption from seawater, Chemical Engineering Journal, 451
520 (2023) 138615.

521 [15] S. Yang, G. Wu, J. Song, B. Hu, Preparation of chitosan-based asymmetric electrodes by co-
522 imprinting technology for simultaneous electro-adsorption of multi-radionuclides, Separation and
523 Purification Technology, 297 (2022) 121568.

524 [16] T. Liu, J. Yuan, B. Zhang, W. Liu, L. Lin, Y. Meng, S. Yin, C. Liu, F. Luan, Removal and Recovery of
525 Uranium from Groundwater Using Direct Electrochemical Reduction Method: Performance and
526 Implications, Environmental Science & Technology, 53 (2019) 14612-14619.

527 [17] L. Lin, T. Liu, Y. Qie, W. Liu, Y. Meng, Q. Yuan, F. Luan, Electrocatalytic Removal of Low-
528 Concentration Uranium Using TiO2 Nanotube Arrays/Ti Mesh Electrodes, Environmental Science &
529 Technology, 56 (2022) 13327-13337.

530 [18] J. Gao, J. Wang, J. Chen, S. Liao, M. Cao, F. Ma, Y. Xue, Y. Yan, Valence regulation investigation of
531 key factors on the electrochemical immobilization uranyl from wastewater, Science of The Total
532 Environment, 836 (2022) 155609.

533 [19] S. He, J. He, Q. Chen, Y. Dang, H. Song, Characterization of electrodeposited uranium targets,
534 Journal of Radioanalytical and Nuclear Chemistry, 295 (2013) 1769-1774.

535 [20] Y.G. Ko, Preparation and characterization of electrodeposited layers as alpha sources for alpha-
536 particle spectrometry, Journal of Radioanalytical and Nuclear Chemistry, 326 (2020) 861-877.

537 [21] O.A. Dumitru, R.C. Begy, D.C. Nita, L.D. Bobos, C. Cosma, Uranium electrodeposition for alpha
538 spectrometric source preparation, Journal of Radioanalytical and Nuclear Chemistry, 298 (2013) 1335-
539 1339.

540 [22] H. Salar Amoli, J. Barker, A. Flowers, Electrodeposition and determination of nano-scale uranium
541 and plutonium using alpha-spectroscopy, Journal of Radioanalytical and Nuclear Chemistry, 268
542 (2006) 497-501.

543 [23] A.M. Adamska, E.L. Bright, J. Sutcliffe, W. Liu, O.D. Payton, L. Picco, T.B. Scott, Characterisation of
544 electrodeposited polycrystalline uranium dioxide thin films on nickel foil for industrial applications,
545 Thin Solid Films, 597 (2015) 57-64.

546 [24] Y. Cheng, P. He, F. Dong, X. Nie, C. Ding, S. Wang, Y. Zhang, H. Liu, S. Zhou, Polyamine and
547 amidoxime groups modified bifunctional polyacrylonitrile-based ion exchange fibers for highly
548 efficient extraction of U(VI) from real uranium mine water, Chemical Engineering Journal, 367 (2019)
549 198-207.

550 [25] J. Yu, C. Yu, W. Zhu, G. He, Y. Wei, J. Zhou, Hydrous titanium oxide and bayberry tannin co-
18
551 immobilized nano collagen fibrils for uranium extraction from seawater and recovery from nuclear
552 wastewater, Chemosphere, 286 (2022) 131626.

553 [26] E. Coelho, T.A. Reis, M. Cotrim, T.K. Mullan, B. Corrêa, Resistant fungi isolated from contaminated
554 uranium mine in Brazil shows a high capacity to uptake uranium from water, Chemosphere, 248
555 (2020) 126068.

556 [27] R.I. Foster, K.-W. Kim, M.-K. Oh, K.-Y. Lee, Effective removal of uranium via phosphate addition
557 for the treatment of uranium laden process effluents, Water Research, 158 (2019) 82-93.

558 [28] P. Li, B. Zhun, X. Wang, P. Liao, G. Wang, L. Wang, Y. Guo, W. Zhang, Highly Efficient Interception
559 and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with
560 Cooperative Chelation by Organic Ligands, Environmental Science & Technology, 51 (2017) 14368-
561 14378.

562 [29] S.W.G. J. S. Hammond, and Nicholas Winograd, X-Ray Photoelectron Spectroscopic Studies of
563 Cadmium- and Silver-Oxygen Surfaces, ANALYTICAL CHEMISTRY, 47 (1975).

564 [30] A.B. Christie, J. Lee, I. Sutherland, J.M. Walls, An XPS study of ion-induced compositional changes
565 with group II and group IV compounds, Applications of Surface Science, 15 (1983) 224-237.

566 [31] F. Lehmann, Cesium Carbonate (Cs2CO3), Synlett, 2004 (2004) 2447-2448.

567 [32] Y. Xue, J. Gao, Z. Ma, J. Wang, M. Cao, C. Guo, P. Liu, F. Ma, Y. Yan, M. Qiu, An Efficient System for
568 Uranyl Electrodeposition and Investigation of the Uranyl Electrochemical Behavior, Journal of The
569 Electrochemical Society, 168 (2021) 112508.

570 [33] C.J. Powell, Recommended Auger parameters for 42 elemental solids, Journal of Electron
571 Spectroscopy and Related Phenomena, 185 (2012) 1-3.

572 [34] T.J. Chuang, C.R. Brundle, D.W. Rice, Interpretation of the x-ray photoemission spectra of cobalt
573 oxides and cobalt oxide surfaces, Surface Science, 59 (1976) 413-429.

574 [35] M.I. Sosulnikov, and Yu A. Teterin. , X-ray photoelectron study of calcium, strontium, barium and
575 their oxides, Doklady Akademii Nauk SSSR 317.2, (1991) 418-421.

576 [36] K. Yuan, E.S. Ilton, M.R. Antonio, Z. Li, P.J. Cook, U. Becker, Electrochemical and Spectroscopic
577 Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite, Environmental Science &
578 Technology, 49 (2015) 6206-6213.

579 [37] P. Drogui, S. Elmaleh, M. Rumeau, C. Bernard, A. Rambaud, Hydrogen peroxide production by
580 water electrolysis: Application to disinfection, Journal of Applied Electrochemistry, 31 (2001) 877-882.

581 [38] S. Hickam, J. Breier, Y. Cripe, E. Cole, P.C. Burns, Effects of H2O2 Concentration on Formation of
582 Uranyl Peroxide Species Probed by Dissolution of Uranium Nitride and Uranium Dioxide, Inorganic
583 Chemistry, 58 (2019) 5858-5864.

19
584 [39] S.M. Peper, L.F. Brodnax, S.E. Field, R.A. Zehnder, S.N. Valdez, W.H. Runde, Kinetic Study of the
585 Oxidative Dissolution of UO2 in Aqueous Carbonate Media, Industrial & Engineering Chemistry
586 Research, 43 (2004) 8188-8193.

587 [40] W.-A. Li, Y.-C. Peng, W. Ma, X.-Y. Huang, M.-L. Feng, Rapid and selective removal of Cs+ and Sr2+
588 ions by two zeolite-type sulfides via ion exchange method, Chemical Engineering Journal, 442 (2022)
589 136377.

590 [41] H.H. Eom, H. Kim, D. Harbottle, J.W. Lee, Selective removal of Cs+ and Sr2+ by electrosorption
591 using intercalating titanosilicate, Separation and Purification Technology, 330 (2024) 125550.

592 [42] Z. Wei, W. Zhao, J. Hu, T.-L. Deng, N. Zhang, Engineering defect-rich Prussian blue analogs
593 composite for enhanced Cs+ removal performance, Chemical Communications, (2023).

594

595 Graphic for Table of Contents

596

597

598 1. The extraction of high purity uranium and cesium from wastewater was realized.

599 2. The sodium carbonate was beneficial for the co-separation of U-Cs.

600 3. The irreducible property of Cs was conducive to the separation of U and Cs.

601 4. The generation of O22- was not beneficial for the separation of U and Cs.

602

603 Declaration of interests

604
605 ☒ The authors declare that they have no known competing financial interests or personal
606 relationships that could have appeared to influence the work reported in this paper.
607
608 ☐ The authors declare the following financial interests/personal relationships which may be
20
609 considered as potential competing interests:
610

611
612
613
614
615

616

21