Exploiting selective isotope exchange of amino–phenolic networks for boron-10 isotopologue separation
Nanjiong Pang , Yunxiang He , Mingyao Wang , Xiaoling Wang , Junling Guo , Xuepin Liao , Bi Shi
The isotope of boron-10 (10B) performs an effective neutron shielding property due to the relatively higher adsorption cross section for thermal neutrons (3800 barns) than boron-11 isotope (11B) (0.005 barns). This promotes the nuclear power plants to provide base-load electricity on a large-scale with low-carbon generation and high-energy density sources [1-3]. In addition, 10B is also one of the most important nuclides used in neutron capture therapy of cancer [4, 5]. As the low natural abundance of 10B (18%−20%) compared with the principal 11B (80%−82%), a great demand for the separation and enrichment of 10B has arisen in the very early stage of the nuclear era (in the 1930s) (Fig. 1A) [6]. However, the separation of 10B isotope is one of the most challenging tasks, primarily due to the very similar relative atomic mass between 10B (Ar = 10.012) and 11B (Ar = 11.009) (Fig. S1 in Supporting information) [7, 8]. Despite the significant efforts made in nearly a hundred years, the chemical exchange distillation between boron trifluoride and its complexes is the only known and successfully-realized practical method for 10B isotopologue separation with a single-stage separation factor (S) of 1.028 (Fig. 1A) [9-11]. Though ion-exchange resins have also been explored for enriching 10B, they present an S value lower than 1.03 (in the range between 1.010 to 1.028) [12-24]. Based on the currently-highest S value, extremely high energy and large-scale separation facilities are still needed to obtain a sufficient amount of 10B in a wide range of application needs.
Herein, we provide an unprecedented adsorption-desorption separation method of 10B isotopologue without significant energy expenditure based on an amino–galloyl synergistic materials (referred to as AGSM). Specifically, the AGSM is prepared from the integration of natural polyphenol (black wattle tannin, BWT) and polyethyleneimine (PEI) on collagen matrix by means of a polyphenol-based surface functionalization method (Figs. S2 and S3 in Supporting information) [25]. Natural polyphenols, as sustainable plant-based biomass resources, contain abundant of dihydroxyphenyl (catechol) or trihydroxyphenyl (galloyl) groups and could bind boron by the oxygen in these phenolic hydroxyl groups, forming dynamic B–O covalent bonds that result in a tetrahedral coordination structure with the protonation of amino groups of PEI [26-28]. The essence of our mechanism in the adsorption-desorption system of AGSM is to promote the isotope exchange between 11B in tetrahedral complexes with phenolic hydroxyl groups and 10B in B(OH)3, leading to the amplification of their B–O bond energy differences to induce the efficient separation of 10B isotopologue [29]. Furthermore, the collagen matrix, a byproduct of leather industry, exhibits low mass transfer resistance to liquid flow as adsorbents due to the unique hierarchical structure and good hydrophilic property [30]. Experimental results obtained from 11B magic angle spinning nuclear magnetic resonance (11B MAS NMR) revealed that the galloyl groups of AGSM exhibit inherent high affinity to B(OH)4– (forming tetrahedral sp3 B–galloyl complexes) coupled with the protonation of amino groups [31-34]. Moreover, density functional theory (DFT) calculations provided insights that the relatively higher 10B–O bond energy of 10B–galloyl complexes facilitates the isotope exchange reaction between 11B in B–galloyl complexes and 10B in B(OH)3. Our results demonstrated that, for the first time in the past 100 year, AGSM performed a record-high S value of 1.048 in an absorption-desorption separation with the abundance of 10B up to 21.42%. This facile, efficient, and recyclable approach holds a great promise for a sustainable and eco-efficient 10B isotopologue separation for the use in diverse applications of nuclear energy and biomedical research.
In AGSM, the fractions of PEI and polyphenol of AGSM were 18% and 13%, respectively. AGSM exhibited relatively enhanced absorbance in the 280 nm range of ultraviolet-visible (UV–vis) diffuse reflectance spectra (Fig. S4 in Supporting information) due to the presence of aromatic rings of galloyl groups in BWT molecules. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectra further confirmed the presence of amino and galloyl groups in AGSM (Figs. S5 and S6 in Supporting information). The 10B isotopologue separation based on AGSM could be described briefly (Fig. 1B). 11B–O dynamic covalent bond can be formed in the 11B–galloyl groups, in which the trigonal sp2 hybridized 11B(OH)3 transforms to tetrahedral sp3 complexes [35-41]. In our design, the generated protons can be neutralized by the abundant number of amino groups in AGSM to facilitate the formation of B–galloyl complexes [42]. The 11B in B–galloyl complexes can be subsequently exchanged with the 10B in B(OH)3, resulting in the isotopologues separation and enrichment of 10B in B–galloyl complexes in AGSM. Finally, the enrichment of 10B(OH)3 is achieved by desorption through acidic elution due to the disassembly of B–galloyl complexes.
We first conducted the static 10B(OH)3 separation starting from natural abundance (Fig. 2A). After the adsorption, a significant signal appeared in the XPS B 1s spectra of AGSM, with the peak displaying an asymmetric shape with a shoulder, suggesting the formation of new bond on the surface of AGSM (Fig. 2B) [43]. Additionally, the XPS B 1s spectra of AGSM after adsorption could be fitted into two peaks at 191.6 eV and 192.5 eV, corresponding to B–OH and B–OC bonds, respectively [44]. The XPS O 1s spectra of AGSM was fitted into two peaks before the adsorption, and three peaks could be observed after the adsorption by means of least squares curve fitting (Fig. 2C). Two binding energy peaks at 532.3 eV and 531.3 eV were attributed to the C–O and C=O of AGSM, respectively [45]. After the adsorption, a new peak appeared at 533.1 eV in the O 1s spectra, representing the formation of B–O bond (Fig. 2C) [46]. These results indicated that B was successfully adsorbed in AGSM by forming B–O dynamic covalent bonds in the B–galloyl complexes. Scanning electron microscopy (SEM) images and surface area analysis confirmed that AGSM maintained the hierarchical structure possessed by collagen matrix (Fig. 2D and Figs. S7−S9 in Supporting information), which was in favor of efficient mass transfer [30]. Energy dispersive spectroscopy (EDS) elemental mapping analysis showed highly-distributed B in AGSM (Fig. 2D). The B adsorption capacity (q) of AGSM increased and reached a maximum (4.6 mg/g) when the pH increased from 5 to 7 (Fig. S10 in Supporting information). When the pH of solution was higher than 7.0, the phenolic hydroxyl groups of polyphenol would be oxidized into quinone groups, and the collagen matrix was also hydrolyzed into collagen molecules [47, 48].
In addition, the reaction between the B(OH)3 and phenolic hydroxyl groups of AGSM was hindered in acidic condition, because low pH would lead to protonation of phenolic hydroxyl functional groups [49]. The precise measurement of 10B abundance in B(OH)3 solutions before and after separation was performed using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS), coupled with the accurate determination of B concentration in the same solutions using an inductively coupled plasma optical emission spectrometer (ICP-OES), which further supported the calculation of 10B abundance in AGSM. In comparison with the abundance of 10B (20.05%) in the initial B(OH)3 solution, the abundance of 10B in AGSM increased to 20.50%−20.70% with the increase of pH values (from 5 to 9) and temperatures (from 283 K to 323 K) (Figs. 2E and F). For analyzing the thermodynamic processes related to boron isotope exchange, the temperatures range in the experiment of static 10B isotopologue separation was divided into two parts, and the plots of lnS versus 1/T (Fig. S11 in Supporting information) were obtained and the values of ΔH0 and ΔS0 were calculated from the slope and intercept of fitted lines [50]. The thermodynamics parameters were summarized in Table S1 (Supporting information). The negative value of ΔG0 indicated that the isotope exchange reaction was spontaneous with the increase of temperatures (from 283 K to 323 K). With the temperatures increasing from 283 K to 303 K, the B(OH)3 was mainly adsorbed by polyphenol through the endothermic progress of forming B–O dynamic chemical bonds in B-galloyl complexes [51]. These dynamic chemical bonds could significantly improve the isotope exchange between the 11B-galloyl complexes and 10B(OH)3 in aqueous solution, thus resulting in effective separation performance and high S. Meanwhile, the positive values of ΔH0 and ΔS0 indicated that the isotope exchange reaction was endothermic and the disorder increased. While, when the temperature further increased to 323 K, the values of ΔH0 and ΔS0 were negative, that suggested that boron isotope exchange reaction on the AGSM became exothermic with decreasing disorder. Thus, the boron isotope exchange reaction was limited with increasing temperatures from 303 K to 323 K, and the corresponding S became decreased, which was consistent with the previous research by Tsukamoto et al. [16]. And it had also been proven that the equilibrium differences in chemical properties of isotope (for the isotopes of all elements other than hydrogen) decreased with the increasing temperatures by Bigeleisen [52]. For AGSM, the results indicated that amino-phenolic networks of AGSM played a synergetic role in boron isotope separation, while the deep mechanism for explaining the boron isotope separation still needed to be further explored. Remarkably, based on the highest 10B abundance of 20.70% in AGSM at pH 7 with the temperature at 303 K, the highest S value of 1.048 was calculated according to the equation used by Kakihana and Kanzaki [12, 53].
To gain insights into the adsorption process, the experimental data from the adsorption isotherm test was fitted using Langmuir [54] and Freundlich [55] isotherm models (Figs. S12 and S13 in Supporting information). The correlation coefficient of the Langmuir model was higher than 0.99, indicating that the Langmuir model could better describe the adsorption of AGSM. This suggested that the adsorption likely occurred on the monomolecular layer on the AGSM due to the forming of B–O dynamic covalent bond. Furthermore, the adsorption kinetic data was fitted using pseudo-first-order [56] and pseudo-second-order kinetic models (Figs. S14 and S15 in Supporting information) [57]. Among them, the pseudo-second-order model had higher correlation coefficients, indicating that the interaction between B(OH)3 and galloyl groups in AGSM was the rate-limiting step during adsorption. Moreover, the desorption of B(OH)3 from absorbent was critically important for the enrichment of 10B(OH)3 and their practical applications. The adsorption-desorption recycling performance of AGSM was further investigated. After 10 cycles of regeneration, the B adsorption capacity of AGSM maintained 83% of the initial adsorption capacity (Fig. S16 in Supporting information). This indicated that AGSM was recyclable with high separation ability due to the breakdown of covalently cross-linking between galloyl groups and B(OH)3.
To investigate the mechanism of 10B isotopologue separation by AGSM, 11B MAS NMR showed five peaks in the spectra of AGSM after B(OH)3 adsorption (δ = 2.3, 7.9, 12.2, 14.1, and 17.1 ppm) ascribed to the B–galloyl complexes (Fig. 3A). Specifically, the two peaks in the spectra with chemical shifts at 7.9 ppm and 12.2 ppm were assigned to the monochelate and bischelate of B–galloyl complexes, respectively [58]. To further reveal the molecular interactions in the B–galloyl complexation, robinetinidol (containing a single galloyl group) was used to calculate the free energies (FE) and binding energies (BE) with B(OH)3 by DFT calculations. The complexation process of B(OH)3 and robinetinidol was carried out in two main steps (Fig. 3B), each of which was followed by the nucleophilic attack of the galloyl groups on the vacant orbital of the planar triangular B(OH)3, followed immediately by the proton transfer, and at which pointed it became a transition state and finally lose the H2O molecule [59]. In the first step of the reaction, the FE change of the transition state formed by 10B(OH)3 (29.3 kcal/mol) was slightly smaller than that of 11B(OH)3 (29.4 kcal/mol). While in the formation of second transition state, the FE of the transition state formed by 11B(OH)3 (30.9 kcal/mol) was significantly smaller than that of 10B(OH)3 (33.4 kcal/mol). These DFT calculations suggested that 11B was a more preferable species in B–galloyl complexes during the adsorption. The difference of thermodynamic stability of B–galloyl complexes could further promote the isotope exchange between 11B in 11B–galloyl complexes with 10B in 10B(OH)3. We noticed that in both monochelate and bischelate, the BE of 10B–galloyl complexes was higher than that of 11B–galloyl complexes (Fig. 3C). Meanwhile, the BE of the bischelate was much smaller than that of monochelate, indicating that the monochelate had favorable interactions with another galloyl group to form bischelate, which was in accordance with the experimental results of 11B MAS NMR.
In addition, the value of reaction free energy (ΔrG) for isotope exchange reaction between 11B–galloyl complexes and 10B(OH)3 was negative (ΔrG < 0), which indicated that the reaction was spontaneous (Fig. S17 in Supporting information) [60]. The corresponding calculated single-stage separation factor S values (Scal) of B–galloyl monochelate and B–galloyl bischelate were obtained through the Van't Hoff isotherm equation (Fig. 3D) [61, 62]. The Scal value of B–galloyl bischelate was 1.0522, which was higher than that of B–galloyl monochelate (Scal = 1.0510). This suggested that the formation of B–galloyl bischelate could be in favor of isotope exchange reaction, thus promoting the enrichment of 10B. Collectively, our experimental and computational results generated the mechanistic details of the three key steps: (1) During the absorption process, 11B(OH)3 could form dynamic covalent bond with the galloyl groups of AGSM, (2) the trigonal sp2 hybridized B(OH)3 transited to tetrahedral sp3 B–galloyl complexes with the protonation of amino groups, and (3) finally, the 11B of B–galloyl complexes in AGSM was able to exchange with the 10B of free B(OH)3 in solution and formed stable monochelate and bischelate complexes, resulting in the enrichment of 10B in AGSM.
We also revealed that the amino groups play a synergetic role with the galloyl groups for 10B isotopologue separation. At the pH < 7, trigonal B(OH)3 was the dominant state (Fig. S18 in Supporting information). While at pH > 7, the trigonal B(OH)3 changed to the ionic state B(OH)4–, which presented relatively higher reactive activity to form B–galloyl complexes [63]. However, the accumulation of released H+ ions could inhibit B–galloyl complexation (q = ~0.1 mg/g) (Fig. S19 in Supporting Information). Our results showed that the introduction of amino groups could increase the proton uptake capacity and synergistically enhanced the adsorption capacity of AGSM (q = ~5.0 mg/g) (Figs. S20 and S21 in Supporting information).
To demonstrate the feasibility and potential of large-scale deployment of AGSM in real-world, the performance of flowthrough separation of 10B isotopologue from B(OH)3 solution was evaluated in fixed-bed settings including the band method and the breakthrough and reverse-breakthrough (BT&RBT) methods, respectively. For the band method, B(OH)3 solution (5 mL, B concentration: 1080 mg/L) was added, and then the HCl solution (pH 1.5) was followed through the whole fixed-bed. The electronic conductivity and pH values of the effluents were monitored in real time (Fig. 4A). When the pH values were reduced from 7.0 to 4.5 and finally maintained at 4.5, the electronic conductivity was reduced to 20 µS/cm, due to the proton uptake capacity of amino groups on AGSM. Following the end point, the values of electronic conductivity and pH changed greatly in a short time due to the fully protonated amino groups.
The B concentration and 10B/11B isotope ratio were obtained from band method of column chromatography (Fig. 4B). Compared to the initial 10B/11B isotope ratio of 0.2508, a significant difference could be observed in the front part (0.1421) and rear part (0.2726) of the effluents, indicating a decrease in the abundance of 10B to 12.44% in the front part and an increase to 21.42% in the rear part. This indicated an enrichment fraction (ζ10B) range from –433‰ to 87‰ for B isotopes in the effluents (Fig. S22 in Supporting information). To further evaluate the 10B isotopologue separation performance of AGSM in the column operation of band method, enrichment factor was used as the key performance factor. Our results showed that the front part had an enrichment factor (10αf) of 0.666, while the rear part (10αr) was 1.096. To the best of our knowledge, these values of enrichment factor were the highest in the comparison of all the reported literature (Table S2 in Supporting information).
For the BT&RBT methods, B(OH)3 solution (1000 mL, 108 mg/L) was used as the feed solution and the HCl solution (pH 1.5) was also used as the eluent for the enrichment of 10B(OH)3. Similar to the band method, the electronic conductivity and pH values of the effluents were reduced greatly in a short time due to the fully protonated amino groups of AGSM and the completed desorption of B(OH)3 (Fig. 4C).
The B concentration and 10B/11B isotope ratio obtained from BT&RBT methods were also shown in Fig. 4D. When the volume of effluents was up to 560 mL, the B concentration reached the concentration of the feed B(OH)3 solution (B concentration: 108 mg/L), indicating the B(OH)3 breakthrough. Similar to the band method, there was a significant difference in the 10B/11B isotope ratio in the front part (0.1927) and the rear part (0.2675) of the effluents, revealing a decrease in 10B abundance to 16.16% in the front part and an increase to 21.11% in the rear part. An enrichment factor range (ζ10B) from −232‰ to 67‰ was observed from the BT&RBT process (Fig. S23 in Supporting information). The enrichment factor of the front part (10αf) was 0.971, whereas the rear part (10αr) was 1.039. In addition, the breakthrough curve had neglected change after the regeneration (Fig. S24 in Supporting information), indicating the recyclability of AGSM.
In summary, we designed a bio-derived and economical method to effectively separate 10B isotopologue based on a designed adsorption and isotope exchange mechanism. A record-high single-stage separation factor S of 1.048 and 10B abundance of 21.42% could be achieved. The 11B MAS NMR results and DFT calculations revealed that the 11B(OH)3 could form 11B–galloyl complexes in the AGSM. Importantly, the 11B of B–galloyl complexes could preferentially exchange with the 10B of B(OH)3 due to the relatively higher stability of 10B–galloyl complexes, allowing the enrichment of 10B–galloyl complexes in AGSM. Our strategy demonstrates efficient distinguishing among B isotopologues, offering a sustainable route to improve the key single-stage separation factor at room temperature, and paving the way for the nuclear energy and biomedical research.
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Nanjiong Pang: Writing – original draft, Visualization, Methodology, Investigation. Yunxiang He: Writing – review & editing, Data curation. Mingyao Wang: Methodology, Investigation. Xiaoling Wang: Writing – review & editing, Visualization, Validation, Supervision. Junling Guo: Writing – review & editing, Supervision, Project administration, Conceptualization. Xuepin Liao: Supervision, Project administration, Conceptualization. Bi Shi: Project administration, Conceptualization.
This work was supported by the National Natural Science Foundation of China (Nos. 22108181, 22178233), the Fund of Science and Technology on Reactor Fuel and Materials Laboratory (No. 6142A06190601), the National Excellent Young Scientists Fund (No. 00308054A1045), the National Key R&D Program of China (No. 2022YFA0912800), the Talents Program of Sichuan Province, Double First Class University Plan of Sichuan University, the State Key Laboratory of Polymer Materials Engineering (No. sklpme 2020–03–01), the Tianfu Emei Program of Sichuan Province (No. 2022-EC02–00073-CG), and Ministry of Education Key Laboratory of Leather Chemistry and Engineering (Sichuan University). We acknowledge Z. H. Dong at the College of Life Sciences of Sichuan University for data processing and useful discussions, and we also would like to thank M. Zhou and X. He at the College of Biomass Science and Engineering of Sichuan University for characterization assistance. We also appreciate H. Wang from the Analytical & Testing Center of Sichuan University for help with scanning electron microscopy characterizations.
Supplementary material associated with this article can be found, in the online version, at doi:
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Figure 1 (A) The technical critical points of distillation and extraction methods occurred in 1958 and 2018, respectively, while this work suggests a technical critical point in the development of the ion exchange method. (B) The proposed schematic of the synergetic interactions of 10B(OH)3 and 11B(OH)3 adsorption, B isotope exchange, and 10B(OH)3 desorption. The relatively higher binding energy of 10B–galloyl complexes facilitates the isotope exchange reaction.
Figure 2 (A) Schematic diagram of the static separation performance of AGSM for 10B isotopologue from B(OH)3 solution (B concentration: 100 mg/L). (B) High resolution XPS B 1s spectra of the B(OH)3 and AGSM before/after adsorption. (C) High resolution XPS O 1s spectra of the AGSM before and after B(OH)3 adsorption. (D) SEM images of AGSM before and after B(OH)3 adsorption, and the EDS elemental mapping analysis of AGSM after B(OH)3 adsorption. (E) Effect of B(OH)3 solution with different pH values (5−9) on 10B isotopologue separation efficiency of AGSM. (F) Effect of different temperatures (283−323 K) on 10B isotopologue separation efficiency of AGSM.
Figure 3 (A) 11B MAS NMR of B(OH)3 solution (B concentration: 1080 mg/L) and AGSM after the B(OH)3 adsorption at different pH (pH 6−9). (B) Calculated FE of reactants, intermediates, products, and the corresponding transition states of the complexes between robinetinidol and B(OH)3. (C) Optimized structures and corresponding calculated BE of the complexes between robinetinidol and B(OH)3. (D) Calculated single-stage separation factor S values (Scal) of robinetinidol from forming monochelate and bischelate with 10B(OH)3 and 11B(OH)3.
Figure 4 (A) Changes of electronic conductivity and pH values with increased volume of effluents in the column operation of band method. (B) Profiles of B concentration and 10B/11B isotope ratio with increased volume of effluents using the band method. (C) Changes of electronic conductivity and pH values with increased volume of effluents in the column operation of the BT&RBT methods. (D) Profiles of B concentration and 10B/11B isotope ratio with increased volume of effluents using BT&RBT methods.
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