State and Local Joint Engineering Laboratory for Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, PR China.
Dalton Trans. 2018 Jul 10;47(27):9103-9113. doi: 10.1039/c8dt01685b.
A bifunctional cationic metal-organic framework {Cu9(OH)6Cl2(itp)6(1,4-bdc)32(OH)2·20H2O}n (1-NO3-OH·20H2O) was synthesized and characterized (itp = 1-imidazol-1-yl-3-(1,2,4-triazol-4-yl)propane, 1,4-bdc = 1,4-benzenedicarboxylate). In 1-NO3-OH·20H2O, three [Cu3(μ3-OH)(μ2-OH)] trimeric clusters are bridged by two μ3-Cl and form a [Cu9(μ3-OH)3(μ2-OH)3(μ3-Cl)2] cluster. Such a nonanuclear copper(ii) cluster [Cu9(μ3-OH)3(μ2-OH)3(μ3-Cl)2] has not been reported till now, at least to the best of our knowledge. 1-NO3-OH·20H2O showed a 6-connected 2D 36-hxl net based on a nonanuclear copper(ii) cluster [Cu9(μ3-OH)3(μ2-OH)3(μ3-Cl)2]. 1-NO3-OH·20H2O is also the first 2D 36-hxl net-based nonanuclear cluster. 1-NO3-OH (guest-free phase) showed fast and highly efficient Cr2O72- and CrO42- trapping, and good recyclability for capturing Cr2O72- and CrO42-. The adsorption capacities of 1-NO3-OH to capture Cr2O72- and CrO42- were 1.762 mol mol-1 (154.8 mg g-1) and 1.896 mol mol-1 (89.5 mg g-1), respectively, at a molar ratio of 1 : 2 (1-NO3-OH to 2.5 × 10-3 mol L-1 Cr2O72- or CrO42-). 1-NO3-OH exhibited the selective sorption of Cr2O72- or CrO42- from a solution containing a mixture of Cr2O72- or CrO42- and a ten-fold molar amount of ClO4-, NO3-, Cl-, BF4- or a five-fold molar amount of mol L-1 SO42-. 1-NO3-OH could capture 87.9% dilute Cr2O72- or 91.8% dilute CrO42- at an equimolar 1-NO3-OH to 20 ppm Cr2O72- or CrO42-. 1-NO3-OH·20H2O exhibited a highly efficient photocatalytic degradation of the cationic organic dyes methylene blue (MB) and rhodamine B (RhB) under visible light irradiation, and was shown to be a good photocatalyst for photocatalytic degradation of the cationic organic dyes.
一种双功能阳离子金属-有机骨架{Cu9(OH)6Cl2(itp)6(1,4-bdc)32(OH)2·20H2O}n(1-NO3-OH·20H2O)被合成并进行了表征（itp=1-咪唑-1-基-3-(1,2,4-三唑-4-基)丙烷，1,4-bdc=1,4-苯二甲酸酯）。在 1-NO3-OH·20H2O 中，三个[Cu3(μ3-OH)(μ2-OH)]三聚体簇由两个μ3-Cl 桥接，形成一个[Cu9(μ3-OH)3(μ2-OH)3(μ3-Cl)2]簇。这样的九核铜(ii)簇[Cu9(μ3-OH)3(μ2-OH)3(μ3-Cl)2]目前尚未报道，至少据我们所知是这样。1-NO3-OH·20H2O 基于九核铜(ii)簇[Cu9(μ3-OH)3(μ2-OH)3(μ3-Cl)2]显示了一个 6 连接的 2D 36-hxl 网络。1-NO3-OH·20H2O 也是第一个基于 2D 36-hxl 网络的九核簇。1-NO3-OH（无客体相）对 Cr2O72-和 CrO42-具有快速高效的捕获能力，对捕获 Cr2O72-和 CrO42-具有良好的可回收性。1-NO3-OH 对 Cr2O72-和 CrO42-的吸附容量分别为 1.762 mol mol-1(154.8 mg g-1)和 1.896 mol mol-1(89.5 mg g-1)，摩尔比为 1:2（1-NO3-OH 与 2.5×10-3 mol L-1 Cr2O72-或 CrO42-）。1-NO3-OH 对 Cr2O72-或 CrO42-的吸附具有选择性，可从含有 Cr2O72-或 CrO42-和十倍摩尔量的 ClO4-、NO3-、Cl-、BF4-或五倍摩尔量的 SO42-的混合溶液中进行吸附。1-NO3-OH 可以在等摩尔 1-NO3-OH 与 20 ppm Cr2O72-或 CrO42-的条件下，捕获 87.9%稀 Cr2O72-或 91.8%稀 CrO42-。1-NO3-OH·20H2O 在可见光照射下对阳离子有机染料亚甲基蓝（MB）和罗丹明 B（RhB）表现出高效的光催化降解性能，是一种用于光催化降解阳离子有机染料的良好光催化剂。
