A Doubly Interpenetrated Zn4O-based MOF for CO2 Chemical

Subscriber access provided by Nottingham Trent University

Article

A Doubly Interpenetrated Zn4O-based MOF for CO2 Chemical Transformation and Antibiotic Sensing Hongming He, Qian-Qian Zhu, Mei-Tong Guo, Qiao-Shu Zhou, Jing Chen, Cheng-Peng Li, and Miao Du Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00621 • Publication Date (Web): 12 Aug 2019 Downloaded from pubs.acs.org on August 13, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

A Doubly Interpenetrated Zn4O-based MOF for CO2 Chemical Transformation and Antibiotic Sensing Hongming He, Qian-Qian Zhu, Mei-Tong Guo, Qiao-Shu Zhou, Jing Chen, Cheng-Peng Li and Miao Du* Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of Inorganic–Organic Hybrid Functional Material Chemistry, College of Chemistry, Tianjin Normal University, Tianjin 300387, P. R. China

ABSTRACT

A

double

interlacing

metal–organic

framework

(MOF),

formula

as

[(Zn4O)2(PDDA)6(H2O)2]·10DMF (1), with pcu-topology has been successfully assembled by Zn4O inorganic clusters and a V-shaped ligand 4,4’-(pyridine-2,6-diyl) dibenzoic acid (denoted as H2PDDA) under solvothermal condition. Benefitting from its internal porosity with available Lewis basic sites and open metal centers, 1 shows excellent performances on CO2 transformation with epoxides and also selective luminescence sensing for nitrofuran antibiotics. Therefore, 1 can be used as an efficient bifunctional platform on both catalyst for CO2 cycloaddition reaction and sensor for antibiotic detection.

1 ACS Paragon Plus Environment

Crystal Growth & Design 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 27

INTRODUCTION CO2 is the base of greenhouse gases, leading to exponentially serious environment and energy issues in a global context.1 Therefore, it is in urgent need of developing efficient approaches to sequentially catch and convert CO2 into available chemicals, to distinctly improve environmental quality and accelerate sustainable development. As we know, CO2 is also an avirulent, abundant and cheap C1 source to synthesize dimethyl carbonate, cyclic carbonate, N,N’-disubstituted urea and others.2-5 Among them, the CO2 cycloaddition reaction with epoxide is viewed as the greatest effective route to make full use of CO2 as starting materials to afford carbonates for polycarbonates, electrolytes and aprotic polar solvents. On the other hand, harmful substances from factory, agriculture and mining severely affect the human health and living environment in our daily life. Antibiotics are diffusely employed in various fields, such as treatment of human bacterial interference and food additives for livestock. In this context, nitrofurans are common antibiotics containing five-membered nitrofuran nucleus, which are detected in many places to trigger a sequence of environmental and health issues.6 Bearing the above points in mind, it is significantly critical to design and synthesize multifunctional materials for both CO2 chemical transformation and antibiotic sensing. Currently, metal–organic frameworks (MOFs)7-9 have received continuous concerns as a rising type of porous crystalline materials, not only by reason of their potential employments in multiple aspects, for example, gas selective sorption or separation,10-13 sensing,14-18 catalysis,19-23 and photoluminescence,24-26 but also because of their unique modular nature, which can be rationally constructed via bottom-up synthesis from organic ligands and metal centers.27-29 Up to now, a variety of extended ligands have been explored to assemble with different metal centers to create newfangled MOFs with extremely high surface areas and relative larger apertures.30 Nevertheless,


Page 3 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


most MOFs are tend to destroy after dislodging free solvent molecules in their pores because of superabundant empty space and thin-wall construction. Interpenetration always occurs in porous MOFs to reduce the empty voids and also improve the stability of frameworks.31,32 Although interpenetration phenomenon may significantly reduce the inherent porosity of MOFs, the resultant network solids may generate peculiar properties, suchlike multi-step sorption, guest-solvent responsive structural transformation, luminescent alteration etc.33-42 Nevertheless, there is no report about multifunctional interpenetrated MOFs for both chemical transformation of CO2 and luminescence sensing towards antibiotics. Inspired by the favorable designability of framework structures for MOFs, we postulate that if the metal and ligand moieties are both considered as the functional sites, the resultant MOFs will possess the individual properties of diverse components. Among the polytypic inorganic clusters in MOFs, the tetranuclear [Zn4( 4-O)(COO)6] unit has been extensively used to construct porous MOFs. This cluster can not only be rationally pre-designed, but also act as Lewis acid centers to catalyze the CO2 cycloaddition reaction. For example, Ma’s group has shown an interpenetrating MOF based on Zn4O clusters for CO2 selective uptake and chemical transformation.39 In addition, the aromatic ditopic ligands are readily to extend the [Zn4( 4-O)(COO)6] clusters to afford MOFs with luminescent properties based on ligand-centered emissions. For instance, Zhu and coworkers have designed and synthesized a doubly interpenetrated Zn4O-based MOF with unique luminescence for nitro-explosive detection.33 In this work, a V-shaped aromatic ligand H2PDDA is selected and used as a luminescent linker to assemble with [Zn4( 4-O)(COO)6] clusters, affording a 2-fold interpenetrated three-dimensional (3D) framework [(Zn4O)2(PDDA)6(H2O)2]·10DMF (1) with primitive cubic (pcu) topology. 1 represents the first interpenetrated MOF as a bifunctional material for both CO2 chemical transformation and antibiotic sensing, as shown in Scheme 1.



Page 4 of 27

Scheme 1. Diagrammatic drawing of constructing bifunctional MOFs for sensing and catalysis.

Experimental Section Methods and Materials. The used H2PDDA linker was successfully prepared based on a reported approach and analyzed by 1H NMR (Figure S1) on a Bruker AV 400 spectrometer machine.43 All applied chemicals were achieved from commercial source. Powder X-ray diffraction (PXRD) results were achieved on a Scintag X1 diffractometer. Thermogravimetric (TGA) data were performed in air on a Perkin-Elmer thermogravimetric analyser. Elemental analyses were taken on a Perkin-Elmer 240 analyzer. Fourier-transform infrared (FTIR) spectra were recorded on a Nicolet Impact 410 FTIR spectrometer. All gas sorption tests were performed on ASAP 2020. Gas chromatographic results were obtained on Agilent 7890A. Cary Eclipse fluorescence spectrophotometer was utilized to collect all luminescent data. UV-Vis adsorption spectra were recorded on Mapada V-1200. Preparation of [(Zn4O)2(PDDA)6(H2O)2]·10DMF (1). Zn(NO3)2 6H2O (20 mg, 0.067 mmol) and H2PDDA linker (10 mg, 0.03 mmol) were dissolved in 4 mL DMF and putted into a auto-


Page 5 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


clave. The mixture was heated at 90 °C and retained 3 days. Colorless block single crystals can be generated after cooling to room temperature with a yield of 71% (based on H2PDDA). Anal. Calcd of C, H, and N (%) for C144H140O38N16Zn8: C, 53.66; H, 4.35; N, 6.96. Experimental: C, 53.96; H, 4.11; N, 7.12. Selected FTIR data (cm–1): 3477 (m), 2364 (s), 2337 (s), 1581 (s), 1547 (s), 1408 (s), 1163 (s), 1014 (s), 872 (s), 771 (s), 675 (s), 501 (s) (Figure S2). Catalytic Reaction. The as-synthesized 1 was dried before a catalytic reaction. In each catalytic experiment, epoxide (1 mmol) and n-tetrabutyl ammonium bromide (TBABr, 0.01 mmol) were putted into a 10 mL glass bottle with 2 mL acetonitrile. Catalyst 1 (50 mg) was added and slowly stirred at 80 °C with CO2 purged. The yield of product was determined by GC with n-dodecane as standard. Recyclable Experiment of Catalysis. 1 can be regained by centrifugation and the reused sample was washed by acetonitrile after a catalytic trial, which is further used again. Luminescence Sensing Experiment. 0.3 mg of as-synthesized 1 was well dispersed in DMF (3 mL) solution of different antibiotics at 1.0 × 10–5 mol L–1. The luminescence data were achieved after 2 min and repeated three times in parallel. Luminescence Titration. 0.3 mg of as-synthesized 1 was putted in 3 mL of DMF solution in a quartz cell. The titration experiments were taken by increasingly adding analyte of nitrofurantoin (NFT) or nitrofurazone (NFZ) in DMF at 1 × 10–3 mol L–1. In addition, each measurement was repeated three times in parallel. Recyclable Experiment of Sensing. The recyclability of 1 was explored after the quenching trial. 1 can be regained by fast centrifugation, washed by DMF, and then, reused in the next trials.



Page 6 of 27

Single Crystal X-ray Diffraction. Single crystal data were taken on a Bruker SMART APEX II CCD based on the Mo-K radiation. The diffracted absorption can be gathered by SADABS program.44 Crystal structure was resolved by the direct approach and refined using SHELXL-2015.45 All non-hydrogen atoms were directly determined from Fourier maps. The disorganized solvents were treated by PLATON/SQUEEZE route,46,47 and confirmed by TGA and elemental analyses. Table 1 shows the crystallographic data and Table S1 summarizes the bond angles and distances. Table 1. Crystal Structure Data for As-synthesized 1. Chemical formula Formula mass Crystal system Space group a (Å) b (Å) c (Å) V (Å3) Z –3 calc (g cm ) –1 (mm ) Nref F(000) Rint GOF R1 / wR2 values (I > 2 (I)) R1 / wR2 values (all data)

C144H140O38N16Zn8 3220 Trigonal R c 19.655(3) 19.655(3) 78.66(2) 26317(12) 12 0.945 1.123 6068 7560 0.0488 1.066 0.0553 / 0.1751 0.0687 / 0.1875

RESULTS AND DISCUSSION Structural Description. 1 crystallizes in the trigonal crystal system and R c space group. Figure S3 illustrates the asymmetrical unit with one deprotonated PDDA2– ligand, one Zn1 plus 1/3 Zn2 centers, 1/3

2– 4-O

anion, and 1/3 terminated H2O ligand. Each PDDA2– ligand serves as a two-

connected linker to bind with two classical Zn4O clusters (Figure 1a), with the distance between two neighboring

4-O

atoms of ca. 17.34 Å. In fact, only one Zn center has a terminal coordinat-


Page 7 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ed H2O molecule in the Zn4O cluster (Figure 1b). Notably, the pyridyl N atom in PDDA2– can be intactly reserved to serve as the Lewis basic site. Figure 1c shows a single coordination network in 1, just like that found in MOF-5,48 UMCM-1,49 JUC-135,33 and JLU-Liu33.34 Because the adjacent benzene and pyridyl rings in PDDA2– from different nets present the – stacking interactions (~3.56 Å) and the PDDA2– ligand has a long length (Figure S4), a two-fold interpenetrating network is fabricated to reduce the pore space for structural stability (Figures 1d and 1e). In view of net topology, each classical Zn4O inorganic cluster can be regarded as a six-connected linker with octahedral configuration, while the bridging ligand is simplified as a rod-like linker. Thus, each 3D network exhibits a classical pcu topology (Figure 1f).



Page 8 of 27

Figure 1. Crystal structure of 1 (Zn: green; N: blue; C: gray; O: red): coordinated mode of ligand (a); Zn4O inorganic cluster (b); a single 3D net (c); doubly interpenetrated structure (d and e); and simplified pcu topology (f). FTIR, PXRD and Thermal Analysis. The free H2PDDA ligand exhibits a strong signal at 1679 cm–1 of carbonyl asymmetric stretching band of –COOH group in the FTIR spectrum. However, this characteristic vibration completely disappears in the FTIR spectrum of 1, because two –COOH groups of the bridging linker are fully deprotonated. Instead, two characteristic peaks of the symmetric and asymmetric bands for the


Page 9 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


deprotonated –COO– appear at 1581 and 1407 cm–1 (Figure S2). The PXRD plot of fresh 1 (Figure S5) is identical to the simulated data, suggesting the phase purity of crystalline product. The TGA curve (Figure S6) shows that the as-synthesized 1 suffers a weight loss of ~23.80% before 220 °C, due to the removal of both guest and coordinated solvents (calculated result: ~23.82%). The residual skeleton will sharply decompose in the temperature range from 450 to 500 °C. Gas Sorption. Gas sorption properties of 1 were performed to estimate its porous texture. The fresh sample was further desolvated at 0–10 °C using supercritical CO2 drying method. PXRD result of the evacuated sample is essentially similar to the original material (Figure S7), indicating that the 3D host skeleton is still remained after the activation process. 1 shows an interesting two-step N2 adsorption isotherm (Figure 2a). At the relative lower pressures, almost no adsorption is observed for 1. Subsequently, a sharply vast N2 absorption is observed at the gate opening pressure (P/P0 = 0.04) and the saturated N2 uptake rapidly enhances to 330 cm3 g–1. Such a behavior is similar to those reported interpenetrated MOFs,34,35 where the gating opening effect may be triggered by the shift of interpenetrated networks.50 Further, CO2 sorption of 1 was taken at different testing temperatures. Figure 2b exhibits that the maximal CO2 uptake can reach up to 55 cm3 g–1 (2.46 mmol g–1) at 273 K and 1 atm pressure, and sharply increases to 31 cm3 g–1 (1.38 mmol g–1) at 298 K and 1 atm pressure. Gas adsorption enthalpy (Qst) is estimated by sorption data at 273 and 298 K with the virial method.51 At zero cover loading, the maximal CO2 Qst value is ~31.7 kJ mol–1, due to the existence of interaction forces between exposed Zn(II) and N sites in the framework and CO2 molecules (Figure S8).



Page 10 of 27

Figure 2. N2 (at 77 K) (a) and CO2 (at 273 and 298 K) (b) sorption isotherms on activated 1.

Catalytic Properties. In virtue of the open metal site, permanent porosity, functional pyridyl group, and CO2-adsorbing capacity of 1, its potential for CO2 cycloaddition with epoxides has been explored. First, the CO2 cycloaddition reaction with epibromohydrin was investigated to indicate the catalytic ability of 1 under 1 bar CO2 and 80 °C. As seen in Table 2, the conversation of epibromohydrin will almost not proceed in the absence of 1 or TBABr (entries 1 and 2). Nevertheless, 1 possesses an excellent catalytic performance in the presence of TBABr with a yield of >99% after 12 h. This result illustrates that both 1 and TBAB are essential to play a critical role in this cycloaddition reaction (entry 3). Actually, TBABr can be seemed as a co-catalyst in CO2 cycloaddition to facilitate this reaction.2-5 Encouraged by the excellent catalytic ability of 1, epoxides with different substituents, including electron withdrawing substituent (–Cl), electron donating substituent (–C2H5) and benzene group, have been further evaluated, with corresponding catalytic yields of >99%, 65% and 93% (entries 3, 4, and 5). The relatively lower yield of 1,2-epoxybutane may be attributed to the presence of electron donating substituent (–C2H5), which will increase the electron cloud density of C–O bond, and thus result in its lower reactivity. In view of the high stability, 1 is easily recy-


Page 11 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


cled and reused by centrifugation and further washing by acetonitrile, which shows excellent catalytic performance after four times of cycles (entry 6). PXRD pattern for reused material reveals its structural integrity (Figure S9). Based on the previous reports and the crystal structure of 1, a plausible catalytic mechanism for CO2 cycloaddition reaction is proposed in Figure 3.52-55 First, the oxygen atom of epoxide can be initiated by Zn4O cluster as Lewis acidic site to excite epoxide. Second, Br– nucleophilic reagent of TBABr will assault the C atom of epoxide to unfold the epoxy ring. Then, the CO2 molecules, enriched by the porous framework of 1, can readily interact with the resultant O anion from opened epoxy ring to generate alkycarbonate anion. Finally, the targeting cyclic carbonate will be successfully obtained via the cyclization step. Meanwhile, the catalyst 1 can be regenerated for the next catalytic process. Notably, the synergistic effect of Lewis acid metal site, free pyridyl nitrogen, and porosity for CO2 uptake can enhance the catalytic performance of 1.56-58 Table 2. Reactions of CO2 and Various Epoxides under Different Catalytic Conditions.a O O

+ CO2

catalysis

O

O

1 bar, 80

R

R

Entry

Catalyst

1

TBABr

Epoxide O

O

Cl

1

17

O O

Cl

2

Yield%b

Product

O

O

2

O

Cl Cl

O



3

Page 12 of 27

O

1 + TBABr

O

Cl Cl

4

O

O

1 + TBABr

>99

O

O

65

O O

5

O

1 + TBABr

O

93

O O

6

a

Recycled 1 + TBABr

O

O

>99

O

Cl Cl

O

Reaction conditions: 1 mmol epoxide, 50 mg 1, 0.01 mmol TBABr, 2 mL CH3CN, 1

bar CO2, 80 °C and 12 h. b Confirmed by GC.

Figure 3. Proposed catalytic mechanism of 1 for CO2 cycloaddition with epoxides. Fluorescence Properties. Luminescent spectrum of free H2PDDA ligand shows an emission aiguille at 354 nm ( nm, Figure S10). As-synthesized 1 exhibits a similar characteristic peak at 366 nm (

ex

ex

= 331

= 340 nm,


Page 13 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 4a), revealing its ligand-based luminescence. At present, only several examples have been reported to use luminescent MOFs as sensors for antibiotic detection.59-72 Here, the luminescence sensing ability of 1 has been explored with eight frequently-used antibiotics as models, including ronidazole (RDZ), thiamphenicol (THI), metronidazole (MDZ), ornidazole (ODZ), chloramphenicol (CAP), nitrofurantoin (NFT), sulfamethazine (SMZ), and nitrofurazone (NFZ). Figure 4b exhibits the emission intensity of 1 in different antibiotics solutions at 1.0 × 10–5 mol L–1. Obviously, 1 shows significant luminescence quenching toward NFZ or NFT. The quenching order is NFT > NFZ > ODZ > MDZ > RDZ > SMZ > THI > CAP. After adding NFZ and NFT (1.0 × 10–5 and 6.0 × 10–5 mol L–1), the corresponding luminescent intensity will instantaneously weaken and reach the minimum values after 75 seconds (Figures 4c and 4d).

Figure 4. Excitation (black) and emission (red) spectra of as-synthesized 1 (a); the emission intensity of 1 in various antibiotic solutions at room temperature (b); and the response rates at different time intervals in solution of NFZ (c) or NFT (d).



Page 14 of 27

To reveal the detection capability in detail, titration experiments were taken via monitoring the luminescent signals of MOF 1 after adding NFZ or NFT at different concentrations. Significantly, the luminescent intensity gradually decreases with a gradual increase of NFZ or NFT (Figures 5a, 5b and S11). In general, the quenching efficiency is estimated by Ksv values, calculated based on I0/I = 1 + Ksv[Q], where I0 and I are the luminescent intensity without and with antibiotics, [Q] is on behalf of the molar concentration (M–1) of analyte, and Ksv is the Stern-Volmer constant. The Ksv value could be determined when [Q] and I0/I are nearly linear. Consequently, Ksv values are calculated to be ~6.08 × 104 M–1 (R2 = 0.9965) for NFZ and ~1.16 × 105 M–1 (R2 = 0.997) for NFT in lower concentration range, which are higher than most known luminescent MOFs (Table S2). The results further show that 1 is an efficient luminescent sensor for NFT and NFZ. Notably, the recyclability is also a critical aspect for sensing materials. The recycled 1 can be readily obtained by centrifuged at 7000 r min–1 for 3 min and washed by DMF (5 mL) three times. The reused samples basically retain the original luminescence sensing ability after four cycles (Figures 5c and 5d). The PXRD result of recycled 1 also reveals the integrity of MOF framework after the sensing experiment (Figures S12 and S13), revealing that the sensing ability of 1 is not caused by the collapse of skeleton. Additionally, the rapid luminescence quenching phenomenon illustrates that the detectability is not trigged by adsorption of guest molecules into the host framework of 1. It is readily found that a large overlap occurs between the luminescent emission of 1 and UV-Vis absorption spectrum of NFZ or NFT (Figure S14). Thus, the sensing capacity may be a result of energy competition between 1 and NFZ or NFT, just like that observed in previous reports.59-72


Page 15 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 5. Stern-Volmer plots and emission spectra of 1 titrated with NFZ (a) and NFT (b); and reproducibility of 1 in 1.0 × 10–4 M solution of NFZ (c) or NFT (d).

CONCLUSION In this work, we have designed and constructed a double interlacing MOF material which can act as a high-efficiency heterogeneous catalyst toward CO2 transformation to cyclic carbonate under mild condition. Moreover, it illustrates an excellent luminescence detectability for NFZ with Ksv value of 6.08 × 104 M–1 or NFT with Ksv value of 1.16 × 105 M–1 with good reproducibility. This contribution provides additional insights into the rational fabrication of bifunctional MOFs with targeting properties and further understanding of the structure-performance relationship therein. ASSOCIATED CONTENT



Page 16 of 27

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 1H

NMR spectrum, FTIR spectra, structural figures, PXRD patterns, TGA plot, Qst curve, UV-

vis and fluorescence spectra, and tables (PDF). AUTHOR INFORMATION Corresponding Author * E-mail:

[email protected]

Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We are grateful to the financial support from the National Natural Science Foundation of China (no. 21801187), the Program for Innovative Research Team in University of Tianjin (no. TD135074), Tianjin Natural Science Foundation (no. 17JCYBJC22800), and Tianjin Science & Technology Fund Project for High Education (no. 2017KJ127). REFERENCES [1]

Shakun, J. D.; Clark, P. U.; He, F.; Marcott, S. A.; Mix, A. C.; Liu, Z. Y.; Otto-Bliesner, B.; Schmittner, A.; Bard, E. Global Warming Preceded by Increasing Carbon Dioxide Concentrations During the Last Deglaciation. Nature 2012, 484, 49–54.

[2]

Ding, M.; Flaig, R. W.; Jiang, H.-L.; Yaghi, O. M. Carbon Capture and Conversion using Metal–Organic Frameworks and MOF-Based Materials. Chem. Soc. Rev. 2019, 48, 2783– 2828.


Page 17 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


[3]

He, H.; Sun, Q.; Gao, W.; Perman, J. A.; Sun, F.; Zhu, G.; Aguila, B.; Forrest, K.; Space B.; Ma, S. A Stable Metal–Organic Framework Featuring Local Buffer Environment for Carbon Dioxide Fixation. Angew. Chem., Int. Ed. 2018, 57, 4657–4662.

[4]

Cao, C.-S.; Shi, Y.; Xu, H.; Zhao, B. A Multifunctional MOF as a Recyclable Catalyst for the Fixation of CO2 with Aziridines or Epoxides and as a Luminescent Probe of Cr(VI). Dalton Trans. 2018, 47, 4545–4553.

[5]

He, H.; Perman, J. A.; Zhu, G.; Ma, S. Metal–Organic Frameworks for CO2 Chemical Transformations. Small 2016, 12, 6309–6324.

[6]

Edhlund, B. L.; Arnold, W. A.; McNeill, K. Aquatic Photochemistry of Nitrofuran Antibiotics. Environ. Sci. Technol. 2006, 40, 5422–5427.

[7]

Yang, H.; Guo, F.; Lama, P.; Gao, W.-Y.; Wu, H.; Barbour, L. J.; Zhou, W.; Zhang, J.; Aguila, B.; Ma, S. Visualizing Structural Transformation and Guest Binding in a Flexible Metal–Organic Framework under High Pressure and Room Temperature. ACS Cent. Sci. 2018, 4, 1194–1200.

[8]

Zhou, W.; Huang, D. D.; Wu, Y. P.; Zhao, J.; Wu, T.; Zhang, J.; Li, D. S.; Sun, C.; Feng, P.; Bu, X. Stable Bimetal–Organic Hierarchical Nanostructures as High-Performance Electrocatalysts for Oxygen Evolution Reaction. Angew. Chem., Int. Ed. 2019, 58, 4227–4231.

[9]

Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to Metal–Organic Frameworks. Chem. Rev. 2012, 112, 673–674.

[10] Luebke, R.; Eubank, J. F.; Caims, A. J.; Belmabkhout, Y.; Wojtas, L.; Eddaoudi, M. The Unique rht-MOF Platform, Ideal for Pinpointing the Functionalization and CO2 Adsorption Relationship. Chem. Commun. 2012, 48, 1455–1457.



Page 18 of 27

[11] Zhang, Y.; Li, B.; Krishna, R.; Wu, Z.; Ma, D.; Shi, Z.; Pham, T.; Forrest, K.; Space, B.; Ma, S. Highly Selective Adsorption of Ethylene over Ethane in a MOF Featuring the Combination of Open Metal Site and pi-Complexation. Chem. Commun. 2015, 51, 2714– 2717. [12] Chen, D.-M.; Liu, X.-H.; Tian, J.-Y.; Zhang, J.-H.; Liu, C.-S.; Du, M. Microporous Cobalt(II)–Organic Framework with Open O-Donor Sites for Effective C2H2 Storage and C2H2/CO2 Separation at Room Temperature. Inorg. Chem. 2017, 56, 14767–14770. [13] Zhao, Y.; Wang, L.; Fan, N. N.; Han, M. L.; Yang, G. P.; Ma, L. F. Porous Zn(II)-Based Metal–Organic Frameworks Decorated with Carboxylate Groups Exhibiting High Gas Adsorption and Separation of Organic Dyes. Cryst. Growth Des. 2018, 18, 7114–7121. [14] Huang, J.-J.; Yu, J.-H.; Bai, F.-Q.; Xu, J.-Q. White-Light-Emitting Materials and Highly Sensitive Detection of Fe3+ and Polychlorinated Benzenes Based on Ln-Metal–Organic Frameworks. Cryst. Growth Des. 2018, 18, 5353–5364. [15] Tan, J.; Chen, L.; Jiang, F.; Yang, Y.; Zhou, K.; Yu, M.; Cao, Z.; Li, S.; Hong, M. Fabrication of a Robust Lanthanide Metal–Organic Framework as a Multifunctional Material for Fe(III) Detection, CO2 Capture, and Utilization. Cryst. Growth Des. 2018, 18, 2956–2963. [16] Wu, X.-X.; Fu, H.-R.; Han, M.-L.; Zhou, Z.; Ma, L.-F. Tetraphenylethylene Immobilized Metal–Organic Frameworks: Highly Sensitive Fluorescent Sensor for the Detection of Cr2O72– and Nitroaromatic Explosives. Cryst. Growth Des. 2017, 17, 6041–6048. [17] Li, J.; Luo, X.; Zhou, Y.; Zhang, L.; Huo, Q.; Liu, Y. Two Metal–Organic Frameworks with Structural Varieties Derived from cis-trans Isomerism Nodes and Effective Detection of Nitroaromatic Explosives. Cryst. Growth Des. 2018, 18, 1857–1863.


Page 19 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


[18] Chen, D.-M.; Tian, J.-Y.; Wang, Z.-W.; Liu, C.-S.; Chen, M.; Du, M. An Anionic Na(I)– Organic Framework Platform: Separation of Organic Dyes and Post-Modification for Highly Sensitive Detection of Picric Acid. Chem. Commun. 2017, 53, 10668–10671. [19] Xiao, J.-D.; Jiang, H.-L. Metal–Organic Frameworks for Photocatalysis and Photothermal Catalysis. Acc. Chem. Res. 2019, 52, 356–366. [20] Wang, X. K.; Liu, J.; Zhang, L.; Dong, L. Z.; Li, S. L.; Kan, Y. H.; Li, D. S.; Lan, Y. Q. Monometallic Catalytic Models Hosted in Stable Metal–Organic Frameworks Tunable CO2 Photoreduction. ACS Catal. 2019, 9, 1726–1732. [21] Jiao, L.; Jiang, H.-L. Metal–Organic–Framework-Based Single-Atom Catalysts for Energy Applications. Chem 2019, 5, 786–804. [22] Shi, D.; Zheng, R.; Sun, M.-J.; Cao, X.; Sun, C.-X.; Cui, C.-J.; Liu, C.-S.; Zhao, J.; Du, M. Semiconductive Copper(I)–Organic Frameworks for Efficient Light-Driven Hydrogen Generation without Additional Photosensitizers and Cocatalysts. Angew. Chem., Int. Ed. 2017, 56, 14637–14641. [23] Zhao, Y.; Deng, D. S.; Ma, L. F.; Ji, B. M.; Wang, L. Y. A New Copper-Based Metal– Organic Framework as a Promising Heterogeneous Catalyst for Chemo- and RegioSelective Enamination of -Ketoesters. Chem. Commun. 2013, 49, 10299–10301. [24] Zhao, Y.; Yang, X. G.; Lu, X. M.; Yang, C. D.; Fan, N. N.; Yang, Z. T.; Wang, L. Y.; Ma, L. F. {Zn6} Cluster Based Metal–Organic Framework with Enhanced Room-Temperature Phosphorescence and Optoelectronic Performances. Inorg. Chem. 2019, 58, 6215–6221. [25] Zhang, X.-J.; Su, F.-Z.; Chen, D.-M.; Peng, Y.; Guo, W.-Y.; Liu, C.-S.; Du, M. A WaterStable EuIII-Based MOF as a Dual-Emission Luminescent Sensor for Discriminative Detection of Nitroaromatic Pollutants. Dalton Trans. 2019, 48, 1843–1849.



Page 20 of 27

[26] He, H.; Sun, F.; Borjigin, T.; Zhao, N.; Zhu, G. Tunable Colors and White-Light Emission Based on a Microporous Luminescent Zn(II)-MOF. Dalton Trans. 2014, 43, 3716–3721. [27] Chen, F.; Shen, K.; Chen, J.; Yang, X.; Cui, J.; Li, Y. General Immobilization of Ultrafine Alloyed Nanoparticles within Metal–Organic Frameworks with High Loadings for Advanced Synergetic Catalysis. ACS Cent. Sci. 2019, 5, 176–185. [28] Yang, G.-P.; Hou, L.; Ma, L.-F.; Wang, Y.-Y. Investigation on the Prime Factors Influencing the Formation of Entangled Metal–Organic Frameworks. CrystEngComm 2013, 15, 2561–2578. [29] Du, M.; Wang, X.; Chen, M.; Li, C.-P.; Tian, J.-Y.; Wang, Z.-W.; Liu, C.-S. Ligand Symmetry Modulation for Designing a Mesoporous Metal–Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization. Chem. Eur. J. 2015, 21, 9713–9719. [30] Deng, H.; Grunder, S.; Cordova, K. E.; Valente, C.; Furukawa, H.; Hmadeh, M.; Gándara, F.; Whalley, A. C.; Liu, Z.; Asahina, S.; Kazumori, H.; O’Keeffe, M.; Terasaki, O.; Stoddart, J. F.; Yaghi, O. M. Large-Pore Apertures in a Series of Metal–Organic Frameworks. Science 2012, 336, 1018–1023. [31] Park, Y. K.; Choi, S. B.; Kim, H.; Kim, K.; Won, B.-H.; Choi, K.; Choi, J.-S.; Ahn, W.-S.; Won, N.; Kim, S.; Jung, D. H.; Choi, S.-H.; Kim, G.-H.; Cha, S.-S.; Jhon, Y. H.; Yang, J. K.; Kim, J. Crystal Structure and Guest Uptake of a Mesoporous Metal–Organic Framework Containing Cages of 3.9 and 4.7 nm in Diameter. Angew. Chem., Int. Ed. 2007, 46, 8230–8233. [32] Lin, X.; Telepeni, I.; Blake, A. J.; Dailly, A.; Brown, C. M.; Simmons, J. M.; Zoppi, M.; Walker, G. S.; Thomas, K. M.; Mays, T. J.; Hubberstey, P.; Champness, N. R.; Schröder,


Page 21 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


M. High Capacity Hydrogen Adsorption in Cu(II) Tetracarboxylate Framework Materials: The Role of Pore Size, Ligand Functionalization, and Exposed Metal Sites. J. Am. Chem. Soc. 2009, 131, 2159–2171. [33] He, H.; Song, Y.; Sun, F.; Bian, Z.; Gao, L.; Zhu, G. A Porous Metal–Organic Framework Formed by a V-Shaped Ligand and Zn(II) Ion with Highly Selective Sensing for Nitroaromatic Explosives. J. Mater. Chem. A 2015, 3, 16598–16603. [34] Sun, X.; Yao, S.; Li, G.; Zhang, L.; Huo, Q.; Liu, Y. A Flexible Doubly Interpenetrated Metal–Organic Framework with Breathing Behavior and Tunable Gate Opening Effect by Introducing Co2+ into Zn4O Clusters. Inorg. Chem. 2017, 56, 6645–6651. [35] Sun, X.; Ma, Y.; Zhao, J.; Li, D.-S.; Li, G.; Zhang, L.; Liu, Y. Tuning the Gate Opening Pressure of a Flexible Doubly Interpenetrated Metal–Organic Framework through Ligand Functionalization. Dalton Trans. 2018, 47, 13158–13163. [36] Nijem, N.; Wu, H.; Canepa, P.; Marti, A.; Balkus, K. J.; Thonhauser, T.; Li, J.; Chabal, Y. J. Tuning the Gate Opening Pressure of Metal–Organic Frameworks (MOFs) for the Selective Separation of Hydrocarbons. J. Am. Chem. Soc. 2012, 134, 15201–15204. [37] Choi, S. B.; Furukawa, H.; Nam, H. J.; Jung, D.-Y.; Jhon, Y. H.; Walton, A.; Book, D.; O’Keeffe, M.; Yaghi, O. M.; Kim, J. Reversible Interpenetration in a Metal–Organic Framework Triggered by Ligand Removal and Addition. Angew. Chem., Int. Ed. 2012, 51, 8791–8795. [38] Yang, S.; Lin, X.; Lewis, W.; Suyetin, M.; Bichoutskaia, E.; Parker, J. E.; Tang, C. C.; Allan, D. R.; Rizkallah, P. J.; Hubberstey, P.; Champness, N. R.; Thomas, K. M.; Blake, A. J.; Schröder, M. A Partially Interpenetrated Metal–Organic Framework for Selective Hysteretic Sorption of Carbon Dioxide. Nat. Mater. 2012, 11, 710–716.



Page 22 of 27

[39] Gao, W.-Y.; Tsai, C.-Y.; Wojtas, L.; Thiounn, T.; Lin, C.-C.; Ma, S. An Interpenetrating Metal–Metalloporphyrin Framework for Selective CO2 Uptake and Chemical Transformation of CO2. Inorg. Chem. 2016, 55, 7291–7294. [40] Yang, H.-Y.; Li, Y.-Z.; Jiang, C.-Y.; Wang, H.-H.; Hou, L.; Wang, Y.-Y.; Zhu, Z. An Interpenetrated Pillar-Layered Metal–Organic Framework with Novel Clusters: Reversible Structural Transformation and Selective Gate-Opening Adsorption. Cryst. Growth Des. 2018, 18, 3044–3050. [41] Liu, L.; Yao, Z.; Ye, Y.; Lin, Q.; Chen, S.; Zhang, Z.; Xiang, S. Enhanced Intrinsic Proton Conductivity of Metal–Organic Frameworks by Tuning the Degree of Interpenetration. Cryst. Growth Des. 2018, 18, 3724–3728. [42] Liu, C.-S.; Zhang, Z.-H.; Chen, M.; Zhao, H.; Duan, F.-H.; Chen, D.-M.; Wang, M.-H.; Zhang, S.; Du, M. Pore Modulation of Zirconium–Organic Frameworks for HighEfficiency Detection of Trace Proteins. Chem. Commun. 2017, 53, 3941–3944. [43] Li, J.-R.; Zhou, H.-C. Metal–Organic Hendecahedra Assembled from Dinuclear Paddlewheel Nodes and Mixtures of Ditopic Linkers with 120 and 90° Bend Angles. Angew. Chem., Int. Ed. 2009, 48, 8465–8468. [44] Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction for Area Detector Data. University of Gottingen, Gottingen, Germany, 1996. [45] Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Cryst. C 2015, 71, 3–8. [46] Spek, A. L. Single-Crystal Structure Validation with the Program PLATON. J. Appl. Cryst. 2003, 36, 7–13. [47] Spek, A. L. PLATON, A Multipurpose Crystallographic Tool. Utrecht University, The Netherlands, 2001.


Page 23 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


[48] Choi, J.-S.; Son, W.-J.; Kim, J.; Ahn, W.-S. Metal–Organic Framework MOF-5 Prepared by Microwave Heating: Factors to be Considered. Microporous Mesoporous Mater. 2008, 116, 727–731. [49] Mu, B.; Walton, P. M.; Walton, K. S. Gas Adsorption Study on Mesoporous Metal– Organic Framework UMCM-1. J. Phys. Chem. C 2010, 114, 6464–6471. [50] Schneemann, A.; Schwedler, V. B. I.; Senkovska, I.; Kaskel, S.; Fischer R. A. Flexible Metal–Organic Frameworks. Chem. Soc. Rev. 2014, 43, 6062–6096. [51] Czepirski, L.; Jagiello, J. Virial-Type Thermal Equation of Gas-Solid Adsorption. Chem. Eng. Sci. 1989, 44, 797–801. [52] Li, P.-Z.; Wang, X.-J.; Liu, J.; Phang, H.-S.; Li, Y.; Zhao, Y. Highly Effective Carbon Fixation via Catalytic Conversion of CO2 by an Acylamide-Containing Metal–Organic Framework. Chem. Mater. 2017, 29, 9256–9261. [53] Zhou, H.-F.; Liu, B.; Hou, L.; Zhang, W.-Y.; Wang, Y.-Y. Rational Construction of a Stable Zn4O-Based MOF for Highly Efficient CO2 Capture and Conversion. Chem. Commun. 2018, 54, 456–459. [54] Ugale, B.; Dhankhar, S. S.; Nagaraja, C. M. Exceptionally Stable and 20-Connected Lanthanide Metal–Organic Frameworks for Selective CO2 Capture and Conversion at Atmospheric Pressure. Cryst. Growth Des. 2018, 18, 2432–2440. [55] Gao, W.-Y.; Chen, Y.; Niu, Y.; Williams, K.; Cash, L.; Perez, P. J.; Wojtas, L.; Cai, J.; Chen, Y.-S.; Ma, S. Crystal Engineering of an nbo Topology MOF for Chemical Fixation of CO2 under Ambient Conditions. Angew Chem., Int. Ed. 2014, 53, 2615–2619.



Page 24 of 27

[56] Kumar, S.; Verma, G.; Gao, W.-Y.; Niu, Z.; Wojtas, L.; Ma, S. Anionic Metal–Organic Framework for Selective Dye Removal and CO2 Fixation. Eur. J. Inorg. Chem. 2016, 4373–4377. [57] Li, J.; Li, W.-J.; Xu, S.-C.; Li, B.; Tang, Y.; Lin, Z.-F. Porous Metal–Organic Framework with Lewis Acid–Base Bifunctional Sites for High Efficient CO2 Adsorption and Catalytic Conversion to Cyclic Carbonates. Inorg. Chem. Commun. 2019, 102, 256–261. [58] Cui, W.-G.; Zhang, G.-Y.; Hu, T.-L.; Bu, X.-H. Metal–Organic Framework-Based Heterogeneous Catalysts for the Conversion of C1 Chemistry: CO, CO2 and CH4. Coord. Chem. Rev. 2019, 387, 79–120. [59] Zhang, Q.; Lei, M.; Yan, H.; Wang, J.; Shi, Y. A Water-Stable 3D Luminescent Metal– Organic Framework Based on Heterometallic [EuIII6ZnII] Clusters Showing Highly Sensitive, Selective, and Reversible Detection of Ronidazole. Inorg. Chem. 2017, 56, 7610– 7614. [60] Qin, Z.-S.; Dong, W.-W.; Zhao, J.; Wu, Y.-P.; Zhang, Q.; Li, D.-S. A Water-Stable Tb(III)-Based Metal–Organic Gel (MOG) for Detection of Antibiotics and Explosives. Inorg. Chem. Front. 2018, 5, 120–126. [61] Hou, S.-L.; Dong, J.; Jiang, X.-L.; Jiao, Z.-H.; Wang, C.-M.; Zhao, B. InterpenetrationDependent Luminescent Probe in Indium–Organic Frameworks for Selectively Detecting Nitrofurazone in Water. Anal. Chem. 2018, 90, 1516–1519. [62] Pan, H.; Wang, S.; Dao, X.; Ni, Y. Fluorescent Zn-PDC/Tb3+ Coordination Polymer Nanostructure: A Candidate for Highly Selective Detections of Cefixime Antibiotic and Acetone in Aqueous System. Inorg. Chem. 2018, 57, 1417–1425.


Page 25 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


[63] Zhu, X.-D.; Zhang, K.; Wang, Y.; Long, W.-W.; Sa, R.-J.; Liu, T.-F.; Lü, J. Fluorescent Metal–Organic Framework (MOF) as a Highly Sensitive and Quickly Responsive Chemical Sensor for the Detection of Antibiotics in Simulated Wastewater. Inorg. Chem. 2018, 57, 1060–1065. [64] Han, M.-L.; Wen, G.-X.; Dong, W.-W.; Zhou, Z.-H.; Wu, Y.-P.; Zhao, J.; Li, D.-S.; Ma, L.-F.; Bu, X. A Heterometallic Sodium–Europium-Cluster-Based Metal–Organic Framework as a Versatile and Water-Stable Chemosensor for Antibiotics and Explosives. J. Mater. Chem. C 2017, 5, 8469–8474. [65] Wang, B.; Lv, X.-L.; Feng, D.; Xie, L.-H.; Zhang, J.; Li, M.; Xie, Y.; Li, J.-R.; Zhou, H.-C. Highly Stable Zr(IV)-Based Metal–Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water. J. Am. Chem. Soc. 2016, 138, 6204–6216. [66] Zhang, F.; Yao, H.; Chu, T.; Zhang, G.; Wang, Y.; Yang, Y. A Lanthanide MOF ThinFilm Fixed with Co3O4 Nano-Anchors as a Highly Efficient Luminescent Sensor for Nitrofuran Antibiotics. Chem. Eur. J. 2017, 23, 10293–10300. [67] Zhou, Z.; Han, M.-L.; Fu, H.-R.; Ma, L.-F.; Luo, F.; Li, D.-S. Engineering Design toward Exploring the Functional Group Substitution in 1D Channels of Zn–Organic Frameworks upon Nitro Explosives and Antibiotics Detection. Dalton Trans. 2018, 47, 5359–5365. [68] Liu, X.; Liu, B.; Li, G.; Liu, Y. Two Anthracene-Based Metal–Organic Frameworks for Highly Effective Photodegradation and Luminescent Detection in Water. J. Mater. Chem. A 2018, 6, 17177–17185. [69] He, H.; Zhu, Q.-Q.; Sun, F.; Zhu, G. Two 3D Metal–Organic Frameworks Based on CoII and ZnII Clusters for Knoevenagel Condensation Reaction and Highly Selective Luminescence Sensing. Cryst. Growth Des. 2018, 18, 5573–5581.



Page 26 of 27

[70] Liu, G.-N.; Zhao, R.-Y.; Xu, R.-D.; Zhang, X.; Tang, X.-N.; Dan, Q.-J.; Wei, Y.-W.; Tu, Y.-Y.; Bo, Q.-B.; Li, C. A Novel Tetranuclear Copper(I) Iodide Metal–Organic Cluster [Cu4I4(Ligand)5] with Highly Selective Luminescence Detection of Antibiotic. Cryst. Growth Des. 2018, 18, 5441–5448. [71] Zhao, D.; Liu, X.-H.; Zhao, Y.; Wang, P.; Liu, Y.; Azam, M.; Al-Resayes, S. L.; Lu, Y.; Sun, W.-Y. Luminescent Cd(II)–Organic Frameworks with Chelating NH2 Sites for Selective Detection of Fe(III) and Antibiotics. J. Mater. Chem. A 2017, 5, 15797–15807. [72] He, H.; Xue, Y.-Q.; Wang, S.-Q.; Zhu, Q.-Q.; Chen, J.; Li, C.-P.; Du, M. A Double-Walled Bimetal Organic Framework for Antibiotics Sensing and Size-Selective Catalysis. Inorg. Chem. 2018, 57, 15062–15068.


Page 27 of 27 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


For Table of Contents Use Only

A Doubly Interpenetrated Zn4O-based MOF for CO2 Chemical Transformation and Antibiotic Sensing

Hongming He, Qian-Qian Zhu, Mei-Tong Guo, Qiao-Shu Zhou, Jing Chen, Cheng-Peng Li and Miao Du*

A doubly interpenetrated Zn4O cluster-based MOF has been rationally designed and prepared, which exhibits excellent performances on chemical transformation of CO2 and luminescence sensing of nitrofuran antibiotics.


A Doubly Interpenetrated Zn4O-based MOF for CO2 Chemical

Recommend Documents