铀酰与羧酸和肟基类配体相互作用的理论研究

doi:10.6023/A22010054

摘要/Abstract

深入了解各种功能基团与铀酰离子的络合行为有助于设计和开发高效海水提铀吸附剂. 本工作通过密度泛函理论(DFT)方法系统地研究了两种典型铀酰络合配体吡啶-2,6-二羧酸(H₂DPA)和戊二酰偕亚胺二肟(H₂A)与铀酰离子及碳酸根离子形成的配合物的结构、成键性质以及热力学稳定性. 研究结果表明, 所有配合物中, 配体与铀酰离子之间具有不同强度的共价相互作用. 由于H₂A配位时发生了质子重排, 而且配体的解离能较高, 使其更难与[UO₂(CO₃)₃]^4-发生取代反应, 因此H₂DPA配体是海水提铀中一种潜在的有效配体. 本工作的相关研究结果为海水提铀中高效吸附基团的设计和开发提供了理论线索.

关键词: 铀酰配合物, 碳酸铀酰, 密度泛函理论, 吡啶二羧酸, 戊二酰偕亚胺二肟

Uranium is the main raw material for nuclear reactor fuel. However, uranium resources on land are limited. According to the statistic, the total amount of proven about uranium ore in the world is about 7.64×10⁶ t. The uranium reserves in seawater are about 4.5×10⁹ t, which is abundant in seawater. It is expected to alleviate the shortage of uranium resources on land by extraction of uranium from seawater. An in-depth understanding of the complexation behavior of various functional groups with uranyl ions is helpful for the design and development of high-efficient seawater uranium adsorbents. Pyridine-2,6-dicarboxylic acid group (H₂DPA) and glutarimidedioxime group (H₂A) are two typical uranyl extractants with the same coordination pattern. In the present work, we have systematically studied the uranyl extraction complexes with these two ligands and carbonate ions by quasi-relativistic density functional theory (DFT) methods. The structures, bonding properties and thermodynamic stability of the 1∶1 (metal/ligand molar ratio) and 1∶2 type extraction complexes were investigated at the B3LYP/6-311G(d, p)/SDD level of theory. The results show that the covalent interaction strength between uranyl cations and these two ligands are different in the 1∶1 and 1∶2 type complexes. H₂DPA has a stronger coordination ability with uranyl in the 1∶1 type of complexes, while in the 1∶2 type complexes H₂A has a stronger coordination ability. For each complex, the covalent interaction between oxygen atom and uranyl ions is stronger than that of nitrogen atom. Due to the high proton rearrangement energy and dissociation energy of the H₂A ligand, the H₂DPA ligand is more likely to react with [UO₂(CO₃)₃]^4-. Therefore, the H₂DPA ligand is a potential effective ligand for uranium extraction from seawater. In addition, the presence of Ca²⁺ in seawater inhibits the complexation of uranyl cations and these ligands. The results of this work provide the theoretical clue for the design and development of highly effective adsorption groups in uranium extraction from seawater.

Key words: uranyl complex, uranyl carbonate, density functional theory, dipicolinic acid, glutarimidedioxime

引用此文

栾雪菲, 王聪芝, 夏良树, 石伟群. 铀酰与羧酸和肟基类配体相互作用的理论研究[J]. 化学学报, 2022, 80(6): 708-713.

Xuefei Luan, Congzhi Wang, Liangshu Xia, Weiqun Shi. Theoretical Studies on the Interaction of Uranyl with Carboxylic Acids and Oxime Ligands[J]. Acta Chimica Sinica, 2022, 80(6): 708-713.

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图/表 10

图1. H2DPA和H2A配体的结构

Figure 1. Structures of H2DPA and H2A ligands

图2. B3LYP方法优化的DPA2-和HA-配体的结构. (a)白、绿、蓝和红色分别代表H、C、N和O; (b) DPA2-和HA-配体的ESP图

Figure 2. Optimized structures of DPA2- and HA- ligands by the B3LYP method. (a) White, green, blue and red represent H, C, N and O, respectively; (b) ESP plots of DPA2- and HA- ligands

图3. B3LYP方法优化的铀酰配合物的结构. 白色、绿色、蓝色、红色和橙色分别代表H、C、N、O和U

Figure 3. Optimized structures of the uranyl complexes by the B3LYP method. White, green, blue, red and orange represent H, C, N, O and U, respectively

铀酰配合物	U=O_ax	U—N(L)	U—O(L)	U—O(CO₃^2-)	v_s	v_as
[UO₂(CO₃)₃]^4-	0.182			0.253	765.58	835.01
[UO₂(CO₃)(DPA)]^2-	0.180	0.265	0.247	0.231	826.61	893.72
[UO₂(CO₃)(HA)]^-	0.180	0.266	0.254	0.228	825.19	895.12
[UO₂(DPA)₂]^2-	0.178	0.276	0.248		848.10	929.87
UO₂(HA)₂	0.178	0.266	0.250		851.62	932.91

表1. B3LYP方法计算的铀酰配合物U=Oax、U—N(L)、U—O(L)和U—O(CO32-)键的平均键长(nm)以及U=Oax的对称和反对称拉伸振动频率(vs 和vas, cm-1)

Table 1. Average bond lengths (nm) for the U=Oax, U—N(L), U—O(L) and U—O(CO32-) bonds in uranyl complexes and the symmetrical and antisymmetrical stretching frequencies (vs and vas, cm-1) of U=Oax calculated by the B3LYP method

铀酰配合物	U—N(L)	U—O(L)	U—O(CO₃^2-)	Q(U)	ΔQ(L)	ΔQ(CO₃^2-)
[UO₂(CO₃)(DPA)]^2-	0.301	0.449	0.700	1.544	0.716	0.897
[UO₂(CO₃)(HA)]^-	0.281	0.401	0.749	1.554	0.647	0.958
[UO₂(DPA)₂]^2-	0.301	0.480		1.499	1.574
UO₂(HA)₂	0.335	0.475		1.471	1.593

表2. PBE方法计算的U—N和U—O键的WBIs、U原子上分布的自然电荷(Q(U), e)和配体到U原子的电荷转移量(ΔQ, e)

Table 2. WBIs of U—N and U—O bonds, natural charge of U atoms (Q(U), e), and charge transfer from ligands to U atoms (ΔQ, e) by the PBE method

图4. B3LYP方法计算的铀酰配合物中金属-配体的成键轨道(等值面值为0.01 a.u.)

Figure 4. The metal-ligand bonding MOs of the uranyl complexes calculated by the B3LYP method (The isosurface value is set as 0.01 a.u.)

图5. PBE方法计算的铀酰配合物中U—O和U—N键的NBO轨道(等值面值为0.02 a.u.)

Figure 5. NBO orbitals of the U—O bonds and U—N bonds in uranyl complexes by the PBE method (The isosurface value is set as 0.02 a.u.)

铀酰配合物	ΔE_Pauli	ΔE_elstat	ΔE_orb	ΔE_int	%ΔE_elstat	%ΔE_orb
[UO₂(CO₃)(DPA)]^2-	1017.7	–3837.3	–1385.6	–4205.1	73.47	26.53
[UO₂(CO₃)(HA)]^-	1035.6	–3311.6	–1403.1	–3679.0	70.24	29.76
[UO₂(DPA)₂]^2-	664.2	–3518.4	–1179.6	–4033.8	74.89	25.11
UO₂(HA)₂	705.9	–2563.6	–1187.1	–3044.8	68.35	31.65

表3. PBE/TZP/ZORA理论水平下铀酰配合物的能量分解分析(ΔE, kJ/mol)

Table 3. Energy decomposition analysis of uranyl complexes (ΔE, kJ/mol) at the PBE/TZP/ZORA level of theory

络合反应	ΔG_BE
[UO₂(H₂O)₅]²⁺+CO₃^2-+DPA^2-→[UO₂(CO₃)(DPA)]^2-+5H₂O	–452.1
[UO₂(H₂O)₅]²⁺+2DPA^2-→[UO₂(DPA)₂]^2-+5H₂O	–363.3
[UO₂(H₂O)₅]²⁺+CO₃^2-+HA^-→[UO₂(CO₃)(HA)]^-+5H₂O	–472.6
[UO₂(H₂O)₅]²⁺+2HA^-→UO₂(HA)₂+5H₂O	–446.6

表4. B3LYP方法计算的水溶液中铀酰配合物的金属-配体结合能(ΔGBE, kJ/mol)

Table 4. Metal-ligand binding energy (ΔGBE, kJ/mol) of the uranyl complexes in aqueous solution by the B3LYP method

取代反应	ΔG
[UO₂(CO₃)₃]^4-+H₂DPA→[UO₂(CO₃)(DPA)]^2-+2HCO₃^-	–103.0
[UO₂(CO₃)(DPA)]^2-+H₂DPA→[UO₂(DPA)₂]^2-+HCO₃^-+H⁺	41.4
[UO₂(CO₃)₃]^4-+2H₂DPA→[UO₂(DPA)₂]^2-+3HCO₃^-+H⁺	–61.1
[UO₂(CO₃)₃]^4-+H₂A→[UO₂(CO₃)(HA)]^-+HCO₃^-+CO₃^2-	137.3
[UO₂(CO₃)(HA)]^-+H₂A→UO₂(HA)₂+HCO₃^-	8.4
[UO₂(CO₃)₃]^4-+2H₂A→UO₂(HA)₂+2HCO₃^-+CO₃^2-	145.7

表5. B3LYP方法计算的水溶液中[UO2(CO3)3]4-和配体进行取代反应的反应能(ΔG, kJ/mol)

Table 5. Gibbs free energy changes (ΔG, kJ/mol) for the substitution reactions of [UO2(CO3)3]4- and ligands in aqueous solution by the B3LYP method

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