Five novel Pb/Zn/Co metal-organic frameworks using 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene and carboxylate ligands: Synthesis, characterization, DFT calculation and catalytic PMS degradation of RhB

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2024-11-01 DOI:10.1016/j.molstruc.2024.140478

Nanhao Jin , Yuqi Liu , Tong Yan , Qi Wang , Xinying Wang , Yuebin Feng , Huilong Luo , Wei Li

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引用次数: 0

Abstract

Five new metal-organic frameworks (MOFs), namely {Pb(atpt)(3-bpd)_0.5}_n (1); {Co(cbz)₂(3-bpd)(H₂O)₂·2H₂O}_n (2); {Co(imdc)(3-bpd)(H₂O)·H₂O}_n (3); {Co(tdca)(3-bpd)(H₂O)₂·DMF}_n (4); {Zn(tdca)(3-bpd)(H₂O)₂·DMF}_n (5), were assembled with metal ions Pb²⁺, Zn²⁺, and Co²⁺ using 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (3-bpd) as the main ligand, combined with 2-aminoterephthalic acid (H₂atpt), 4-cyanobenzoic acid (Hcbz), 4,5-imidazoledicarboxylic acid (H₂imdc), and thiophene-2,5-dicarboxylic acid (H₂tdca) as auxiliary ligands via hydro/solvothermal methods. Their molecular structures were analyzed by single-crystal X-ray diffraction and characterized by FT-IR and PXRD. Complex 1 has a three-dimensional structure with a hepta-coordinated, semi-directed {PbNO₆} metal center. The central metal ions in complexes 2–5 exhibit a six-coordinated {MN₂O₄} (M = Co or Zn) octahedral geometry. In complex 2, the carboxylate ligand does not function as a bridging ligand, resulting in a 1D chain structure, while complexes 3- 5 extend into 2D layered structures. Thermogravimetric analysis indicates good thermal stability for complexes 1–5. Then, the prepared complexes were used as catalysts to degrade Rhodamine B (RhB) during the monopersulfate (PMS) activation. Complexes 3 and 4 demonstrated significant efficiency, achieving degradation rates of 93.61 % and 98.56 % within 10 min. Radical scavenging experiments and EPR analysis identified that the activation of PMS for dye degradation by the two catalysts occurs through both radical and non-radical pathways, with SO₄^•− and •OH radicals being the dominant species. Density functional theory (DFT) calculations explained the superior catalytic performance of complex 4 compared to complex 3.

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使用 1,4-双（3-吡啶基）-2,3-二氮杂-1,3-丁二烯和羧酸配体的五种新型铅/锌/钴金属有机框架：合成、表征、DFT 计算和催化 PMS 降解 RhB

五种新的金属有机框架（MOFs），即{Pb(atpt)(3-bpd)0.5}n (1)；{Co(cbz)2(3-bpd)(H2O)2-2H2O}n (2)；{Co(imdc)(3-bpd)(H2O)-H2O}n (3)；{Co(tdca)(3-bpd)(H2O)2-DMF}n (4)；以 1,4-双(3-吡啶基)-2,3-二氮杂-1,3-丁二烯（3-bpd）为主要配体，与 Pb²⁺、Zn²⁺ 和 Co²⁺ 等金属离子组装成{Zn(tdca)(3-bpd)(H2O)2-DMF}n (5)、结合 2-氨基对苯二甲酸 (H2atpt)、4-氰基苯甲酸 (Hcbz)、4,5-咪唑二羧酸 (H2imdc) 和噻吩-2,5-二羧酸 (H2tdca) 作为辅助配体。通过单晶 X 射线衍射分析了它们的分子结构，并用 FT-IR 和 PXRD 对其进行了表征。络合物 1 具有三维结构，其金属中心为七配位的半定向 {PbNO6}。络合物 2-5 中的中心金属离子呈现六配位的{MN2O4}（M = Co 或 Zn）八面体几何结构。在配合物 2 中，羧酸配体不作为桥接配体，形成一维链状结构，而配合物 3- 5 则延伸为二维层状结构。热重分析表明，1-5 复合物具有良好的热稳定性。然后，将制备的配合物用作催化剂，在单过硫酸盐（PMS）活化过程中降解罗丹明 B（RhB）。络合物 3 和 4 的降解效率非常高，在 10 分钟内分别达到 93.61% 和 98.56%。自由基清除实验和 EPR 分析表明，这两种催化剂通过自由基和非自由基两种途径活化 PMS 以降解染料，其中 SO4-- 和 -OH 自由基是主要物种。密度泛函理论（DFT）计算解释了复合物 4 比复合物 3 更优越的催化性能。

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

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