Theoretical Studies on the Interaction of Uranyl with Carboxylic Acids and Oxime Ligands

doi:10.6023/A22010054

Abstract

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

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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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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

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

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

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

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

铀酰与羧酸和肟基类配体相互作用的理论研究