具有尺寸和电荷选择性多功能分子吸附能力的电荷可转变型金属-有机框架材料

doi:10.15541/jim20170163

摘要/Abstract

摘要：

通过研究具有两种轮桨状构筑基元和四种纳米笼子结构锌基金属-有机框架(Zn-MOF)的染料吸附特性和机理,发现其分子吸附的普适性, 以及尺寸和电荷的选择性。由于Zn-MOF孔道内漂浮着抗衡阴离子, 及框架上有可配位位点, 所以它能通过离子交换机理吸附阴性染料、框架上电荷转变机理吸附阳性染料、主客体相互作用吸附中性染料, 表现出优越的分子吸附多功能性。Zn-MOF内带电荷纳米笼的尺寸选择性和电荷选择性的共同作用为设计具有更高水平兼容性和识别性的优异多孔材料铺平了道路。

关键词: 金属-有机框架, 电荷转变, 分子吸附, 选择性

Abstract:

Highly size/charge-selective molecular inclusions by a charge-switchable zinc-based metal-organic framework (Zn-MOF) have been achieved, which comprises of two kinds of paddle-wheel building units and four kinds of nanocages. Featuring counter anions floating in the pore and accessible coordination sites on the skeleton, Zn-MOF represents exceptional versatility in taking up anionic dyes by ion-exchange, cationic dyes by charge switch of skeleton, and neutral organic dyes by host-guest interactions. Both size and charge selectivities in the molecular inclusion by the charged nanocages in Zn-MOF provide an efficient way in designing superior porous materials with an enhanced level of compatibility and recognition.

Key words: metal-organic framework, charge-switchability, molecular inclusion, selectivity

中图分类号:

TQ174

袁贝贝，周蓓蓓，章跃标，施剑林. 具有尺寸和电荷选择性多功能分子吸附能力的电荷可转变型金属-有机框架材料[J]. 无机材料学报, 2018, 33(3): 352-356.

YUAN Bei-Bei, ZHOU Bei-Bei, ZHANG Yue-Biao, SHI Jian-Lin. Charge-switchable Metal-organic Framework for Size/Charge-selective Molecular Inclusions[J]. Journal of Inorganic Materials, 2018, 33(3): 352-356.

图/表 11

Fig. S1 PXRD patterns of Zn-MOF and Co-MOF with simulation bar. All the PXRD were carried out with a few drop of DMF on the surface

Fig. S2 (a) The rhombicuboctahedral cage enclosed alternatively by eight Zn2(COO)3+ and six Zn2(COO)4 clusters; (b) The cuboctahedral cage enclosed by four Zn2(COO)3+ clusters; (c) The truncated octahedral cage enclosed by six Zn2(COO)4 clusters; (d) The square-bifrustum cage enclosed alternatively by four Zn2(COO)3+ clusters and four Zn2(COO)4 clusters.The open pores size of cages in (a), (b), (c) and (d) are (e) 0.40 × 0.60 nm, (f) 0.72 × 0.76 nm, (g) 1.04 × 0.34 nm and (h) 0.70 × 0.90 nm, respectively

Table S1 Structures and dimension of guest dye molecules with different charges

Fig. S3 The optical microscope images of the Zn-MOF crystals before (centered) and after (top and bottom) dye inclusion experiments. To confirm the uptake homogeneity of dyes, both the exterior and interior of dyes adsorbed MOF crystals were shown except those for AB-, OG2-, and NC3- with dyes penetrated only the outer part of the crystals

Fig. S4 PXRD patterns of Zn-MOF and dye@Zn-MOF samples compared with simulation All the PXRD were carried out with a few drop of DMF on the surface. It shows that the crystal structure is still maintained after adsorption of dyes

Table S2 The adsorption capacity of selected MOFs and Zn-MOF toward MLB and MO

MOFs	Absorption capacity/(mg•g^-1)		Metal	Framework charge	Ref.
MOFs	Cationic dye	Anionic dye	Metal	Framework charge	Ref.
MOF-5	Congo Red	NM	Zn	Neutral	[1]
MOF-5	Pyronin Y, Azure A	NM	Zn	Neutral	[2]
ZIF-8	9.2 (MLB)	~11.6 (MO)	Zn	Neutral	[3]
ZIF-8	5.4 (MLB)	22 (AB40)	Zn	Neutral	[4]
IFMC-2	MLB, CV	NA	Zn	Anionic	[5]
Compound 1	MLB, RhB	NA	Zn	Anionic	[6]
NENU-505	MLB, BR2	NA	Zn	Anionic	[7]
Zn-MOF	12.6 (MLB)	19 (MO)	Zn	Cationic	This work
ITC-4	NA	77.4 (OG)	In	Cationic	[8]
Compound 1	NA	183.5 (OG)	In	Cationic	[9]
MOF-235	252.0 (MLB)	477.0 (MO)	Fe	Cationic	[10]
MIL-100(Fe)	736.2 (MLB)	1045.2 (MO)	Fe	Cationic	[11]
MIL-100(Cr)	643.3 (MLB)	211.8 (MO)	Cr	Cationic	[11]
PCN-222	906 (MLB)	589 (MO)	Zr	Neutral	[12]

Fig. 1 (a) Dye adsorption kinetics of AO7- by Zn-MOF, which was immersed into a fresh AO7- solution at 30 h for second uptake, indicating that the concentration gradient potential served as the driving force for dye inclusion; (b) Release rates of AR88- (at λmax = 509 nm) salt out from AR88-@Zn-MOF in 0.18 mol/L methanol solution of NaCl and Et4N+BF4-, respectively

Fig. 2 (a) The time dependent UV-Vis spectra of the solutions of AB1- and TOO- in the ratio of 765∶1 for the competitive adsorption by Zn-MOF (λmax= 412 nm for TOO-, λmax= 630 nm for AB1-) with inset showing the colour of TOO-/AB1- solution before and after dye inclusion for 600 min, respectively; (b) The adsorption kinetics of AB1- and TOO- by Zn-MOF in the binary mixture solution

Fig. S5 The time dependent UV-Vis spectra of the solution of MLB+ for adsorption by Zn-MOF from 0 to 25 h

Fig. 3 Release profiles of MLB+ (at λmax = 648 nm) salt out from MLB+@Zn-MOF in saturated methanol solution of NaNO3 and NaCl, respectively

Fig. 4 (a) The time dependent UV-Vis spectra of the solutions of MLB+ and SY2 at the ratio of 1∶1 for the competitive adsorption by Zn-MOF from 0 to 31 h (λmax = 652 nm for MlB+, λmax = 406 nm for SY2); (b) The competitive adsorption rate of MIB+ and SY2 by the Zn-MOF

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