二维共价有机框架(COFs)膜是一种理想的分离材料。以2,4,6-三羟基-1,3,5-苯三甲醛(Tp)和2,5-二氨基苯磺酸(Pa-SO3H)为构筑单体,通过原位溶剂热聚合方法,在多孔三氧化二铝(AAO)基底上快速制备出了一种二维COF膜TpPa-SO3H,并研究了所得膜材料对锂镁离子的分离性能。结果表明:膜表面光滑平整,具有较高的结晶度和一维纳米孔道。TpPa-SO3H上带负电荷的磺酸基团,不仅有利于提高膜的渗透通量,还能通过静电作用,提高两种离子的分离效率。该膜材料在LiCl(0.1mol/L)和MgCl2(0.1mol/L)的双组分混合体系中,对Li+/Mg2+的分离因子可达22。静电作用和氢键相互作用是Mg2+在纳米多孔膜中的主要扩散阻力和离子分离性能的主要影响因素。
Two-dimensional covalent organic frameworks (COFs) membranes are ideal materials for molecular separation.In this paper,a 2D COF membrane,TpPa-SO3H,was rapidly prepared on a porous aluminium oxide (AAO) substrate by in situ solvent-thermal polymerization using 2,4,6-trihydroxy-1,3,5-benzotricarboxaldehyde (Tp) and 2,5-diaminobenzenesulphonic acid (Pa-SO3H) as the building monomers,and the separation performance of the membrane for lithium (Li) and magnesium (Mg) ions was investigated.The results showed that the membrane surface was smooth and dense with high crystallinity and one-dimensional nanopores.The negatively charged sulfonic acid groups on TpPa-SO3H not only facilitated the improvement of the permeation flux of the membrane,but also enhanced the separation efficiency of the two ions through electrostatic interactions.The separation factor of this membrane for Li+/Mg2+ in a binary salt system of LiCl (0.1mol/L) and MgCl2 (0.1mol/L) was up to 22.Electrostatic and hydrogen bonding interactions were the main diffusion resistance of magnesium ions in COF membranes and the decisive influences on the ion separation properties.
[1] Liu Y B,Ma B Z,Lü Y W,et al.A review of lithium extraction from natural resources[J].International Journal of Minerals,Metallurgy and Materials,2023,30:209-224.
[2] Ding T,Zheng M P,Peng S P,et al.Lithium extraction from salt lakes with different hydrochemical types in the Tibet Plateau[J].Geoscience Frontiers,2023,14:101485.
[3] Li H F,Li L J,Ji L M,et al.Extraction of lithium from salt lake brine with high Mg/Li mass ratio by N523-DIBK extraction system[J].Journal of Sustainable Metallurgy,2023,9:1456-1465.
[4] Luo Q L,Dong M Z,Nie G L,et al.Extraction of lithium from Salt Lake brines by granulated adsorbents[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2021,628:127256.
[5] Qi D G,Jin D Y,Tu Y M,et al.Synthesis of lithium ion-imprinted polymers for selective recovery of lithium ions from Salt Lake brines[J].Separation and Purification Technology,2024,340:126661.
[6] Xu P,Hong J,Qian X M,et al.Materials for lithium recovery from Salt Lake brine[J].Journal of Materials Science,2021,56:16-63.
[7] Tang C,Bruening M L.Ion separations with membranes[J].Journal of Polymer Science,2020,58:2831-2856.
[8] Li Z,Fan J R,Wang L,et al.Two-dimensional lamellar stacking COF membrane with charge repulsion effect for ions separation[J].Journal of Membrane Science,2024,699:122645.
[9] Shen J,Cai Y C,Zhang C H,et al.Fast water transport and molecular sieving through ultrathin ordered conjugated-polymer-framework membranes[J].Nature Materials,2022,21:1183-1190.
[10] Bing S S,Xian W P,Chen S F,et al.Bio-inspired construction of ion conductive pathway in covalent organic framework membranes for efficient lithium extraction[J].Matter,2021,4:2027-2038.
[11] Niu B,Xin W W,Qian Y C,et al.Covalent organic frameworks embedded in polystyrene membranes for ion sieving[J].Chemical Communications,2022,58:5403-5406.
[12] Hou L X,Xian W P,Bing S S,et al.Understanding the ion transport behavior across nanofluidic membranes in response to the charge variations[J].Advanced Functional Materials,2021,31:2009970.
[13] Ren L,Chen J X,Han J,et al.Anti-scaling covalent organic framework membranes with custom-tailored nanochannels for efficient lithium extraction[J].Chemical Engineering Journal,2023,462:142112.
[14] Meng Q W,Wu D,Wang S,et al.Function-led design of covalent-organic-framework membranes for precise ion separation[J].Chemistry-a European Journal,2023,29:e202302460.
[15] Razmjou A,Asadnia M,Hosseini E,et al.Design principles of ion selective nanostructured membranes for the extraction of lithium ions[J].Nature Communications,2019,10:5793-5807.
[16] Sheng F M,Wu B,Li X Y,et al.Efficient ion sieving in covalent organic framework membranes with sub-2-nanometer channels[J].Advanced Materials,2021,33:2104404.
[17] Chandra S,Kandambeth S,Biswal B P,et al.Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination[J].Journal of the American Chemical Society,2013,135(47):17853-17861.
[18] Peng Y,Xu G,Hu Z,et al.Mechanoassisted synthesis of sulfonated covalent organic frameworks with high intrinsic proton conductivity[J].ACS Applied Materials & Interfaces,2016,8(28):18505-18512.
[19] Liu X,Wang J R,Shang Y X,et al.Ionic covalent organic framework-based membranes for selective and highly permeable molecular sieving[J].Journal of the American Chemical Society,2024,146(4):2313-2318.
[20] Zeng X J,Xu L,Deng T,et al.Anionic MOFs embedded in anion-exchange membranes for the separation of lithium/magnesium cations[J].ACS Sustainable Chemistry & Engineering,2023,11:12877-12887.
[21] Liao D C,Xu Z Q,Wei M J,et al.Interference mechanism of cations on transport of lithium and magnesium inside COF nanofiltration membranes[J].Molecular Simulation,2022,48:1369-1377.
[22] Yin C C,Liu M,Zhang Z,et al.Perpendicular alignment of covalent organic framework (COF) pore channels by solvent vapor annealing[J].Journal of the American Chemical Society,2023,145:11431-11439.
基金资助
青海省自然科学基金项目(2020-ZJ-742);国家自然科学基金(22164017)
PDF
