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. 2024 Apr 10;9(16):18429–18437. doi: 10.1021/acsomega.4c00431

A Bifunctional Three-Dimensional Zn(II) Metal–Organic Framework with Strong Luminescence and Adsorption Cr(VI) Properties

Yufeng Chen †,‡, Shixiong Li †,‡,*, Yubing Liu †, Ping Shi †, Shihua Xu †,‡,*, Yuejing Bin †,‡,§,*
PMCID: PMC11044258  PMID: 38680302

Abstract

graphic file with name ao4c00431_0007.jpg

The mixed ligand 3-amino-1,2,4-triazole (Hatz) and terephthalic acid (H2pta) reacted with Zn(NO3)2·6H2O to synthesize a three-dimensional binuclear Zn(II) metal–organic framework: {[Zn2·(atz)2·(pta)]·3H2O}n (3D-Zn-MOF). This 3D-Zn-MOF has two different types of pores (4.5 × 4.5 Å2, 5.7 × 5.7 Å2). The crystalline 3D-Zn-MOF could be prepared into nanomaterials (3D-N-Zn-MOF) with particles of approximately 100 nm by a cell fragmentation apparatus. Compared with the solid-state luminescence of Hatz and H2pta, it was found that 3D-N-Zn-MOF exhibited strong luminescence performance and significant red-shift phenomenon. Due to the decrease in electronegativity and rigidity of ligands, as well as the effect of ligand metal charge transfer (LMCT), the fluorescence lifetime and quantum yield of 3D-ZN-N-MOF were 2.7241 ns and 3.02%, respectively. The maximum experimental adsorption capacity of 3D-N-Zn-MOF could reach 125.52 mg/g, which was superior to the majority of MOF adsorbents under the optimal adsorption conditions (25 °C, pH = 7, and the adsorbent concentration is 0.2000 g/L). The thermodynamic analysis of adsorption showed that the adsorption of Cr(VI) by 3D-N-Zn-MOF was a spontaneous (△G < 0) and exothermic (△H < 0) process. It could be found that 3D-N-Zn-MOF was a bifunctional material with potential applications by comprehensive analysis of the fluorescence and adsorption Cr(VI) performance.

1. Introduction

Multifunctional materials can integrate multiple properties and functions, thereby demonstrating excellent performance in various aspects.1−3 Developing multifunctional materials can provide more efficient and flexible solutions to energy and complex problems1 and promote innovation and development in science and technology. This is of great significance for promoting sustainable development, improving the quality of life, and addressing major challenges.

Metal–organic frameworks (MOFs) are crystal structured materials composed of metal ions or metal clusters and organic ligands through coordination chemical reactions.4 The basic structure of MOFs consists of metal ions (usually transition metals such as copper, zinc, and nickel) as centers, connecting multiple organic ligands (usually electron-rich organic acid molecules) to form a three-dimensional network.5−7 The organic ligands of MOFs can form spatial configurations of different shapes and sizes through coordination with metal ions, which are called pores.8 The pore structure of MOFs can be designed and regulated according to specific requirements, enabling MOFs to have highly adjustable functions such as adsorption,9,10 separation,11,12 photocatalysis,13−15 and energy storage.16−18 In addition, MOFs have many characteristics and advantages,8−18 including high adjustability, large pore volume and surface area, porous structure, low density, and high chemical stability. These characteristics make MOFs have broad application potential in fields such as fluorescence,19 adsorption,20 gas separation,12 catalytic reactions,13−15 energy storage,16−18 and sensing.21−23 For example, fluorescent MOFs can achieve different fluorescence characteristics (optoelectronic devices, biological imaging, sensors) by selecting appropriate metal ions (Zn2+, Cd2+, Ag+, and rare earth metal ions) and designing organic ligands. So, significant progress has been made in the research and development of MOFs, which have attracted widespread attention in various fields. They are considered the next generation of functional materials, providing new possibilities for addressing major challenges in fields such as energy, environment, and chemistry. Therefore, developing multifunctional metal–organic frameworks enables us to obtain materials with better performance and functionality, which can meet the needs of different fields. The development of this material will have extensive applications and promote scientific and technological progress in fields such as energy, environment, and medicine.

In this paper, a three-dimensional binuclear Zn(II) metal organic framework: {[Zn2·(atz)2·(pta)]·3H2O}n (3D-Zn-MOF), was synthesized by mixed ligands 3-amino-1,2,4-triazole (Hatz) and terephthalic acid (H2pta) reacted with Zn(NO3)2·6H2O. The structure of 3D-Zn-MOF was characterized by Fourier transform infrared (IR), elemental analysis, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and single crystal X-ray single crystal diffraction. The solid-state luminescence of the 3D-Zn-MOF nanomaterial (3D-N-Zn-MOF) and the effects of adsorbent dosage, pH, and temperature on the adsorption performance of Cr(VI) were studied. The results showed that 3D-N-Zn-MOF exhibited a strong performance of luminescence and adsorption of Cr(VI).

2. Experimental Section

2.1. Synthesis of {[Zn2·(atz)2·(pta)]·3H2O}n (3D-Zn-MOF)

The Hatz (0.0841 g, 1.0 mmol), H2pta (0.1661 g, 0.5 mmol), and Zn(NO3)2·6H2O (0.2975 g, 1.0 mmol) were mixed in the solution of 8 mL N,N-dimethylformamide (DMF) and 2 mL water. The mixed solution was dispersed under ultrasound at room temperature. Then, it was transferred into a 23 mL polytetrafluoroethylene reactor liner. Finally, the mixed solution was heated in a 150 °C blast drying oven for 72 h. The mixed solution was naturally cooled to room temperature after the reaction heating was completed. Colorless block crystals of 3D-Zn-MOF were obtained. Yield: 98.53%. (based on Zn2+). Anal. Calcd for C6H8O3.5N4Zn: C, 27.96; H, 3.11; N, 21.74. Found: C, 28.01; H, 3.08; N, 21.77. IR (cm–1) (Figure S1): 3416s, 3331m, 3233w, 2924w, 1665m, 1632w, 1586s, 1534w, 1397s, 1291m, 1284m, 1233s, 1154w, 1062s, 1016s, 892m, 839s, 747s, 749m, 576m, 498m.

2.2. X-Ray Diffraction

Diffraction data for 3D-Zn-MOF were collected on a Bruker SMART CCD diffractometer (Mo Kα radiation, λ = 0.71073 Å) in Φ and ω scan modes. The anisotropic displacement parameters were applied to all non-hydrogen atoms in full-matrix least-squares refinements based on F2, which was performed by SHELXL-2013. The structure was solved by direct methods using Olex2 program.24 The guest molecules were removed through SQUEEZE in structure refinement due to disorder. Anisotropic thermal parameters were assigned to all non-hydrogen atoms. The hydrogen atoms were placed at calculated positions and refined as riding atoms with isotropic displacement parameters. Crystallographic data and structure processing parameters for 3D-Zn-MOF are summarized in Table S1. Selected bond lengths and bond angles for 3D-Zn-MOF are listed in Table S2. The hydrogen bonds of 3D-Zn-MOF are listed in Table S3, CCDC:2313254, 3D-Zn-MOF.

2.3. Preparation of Nanoparticles (3D-N-Zn-MOF)

0.1000 g of 3D-Zn-MOF (0.1000 g) was added to a 250 mL beaker. Next, added 100 mL of deionized water to the beaker. Shook the suspension solution in the beaker for 15 min by the cell crusher. Then, collected the solid powder precipitates by a high-speed centrifuge at 10 000 r/pm. Finally, the collected solid powder precipitates were placed in a 120 °C blast drying oven and heated for 12 h to obtain 3D-N-Zn-MOF.

3. Results and Discussion

3.1. Structure of 3D-Zn-MOF

The elemental and valence state composition of 3D-Zn-MOF was characterized and analyzed by X-ray photoelectron spectroscopy (XPS). The XPS of 3D-Zn-MOF (Figure 1a) indicated that it was mainly composed of C, N, O, and Zn elements. The characteristic orbital peaks of C(1s), N(1s), and O(1s) were found at 284.8 eV (Figure 1b), 399.9 eV (Figure 1b), and 531.6 eV (Figure 1d), respectively. The characteristic orbital peak of Zn(2p) was observed at 1022.2 and 1045.3 eV (Figure 1e), which indicated that the zinc ions in 3D-Zn-MOF were all Zn(II). The positions of these characteristic orbital peaks were all within the range reported in the literature.19 However, XPS had not yet determined the structure of 3D-Zn-MOF. Therefore, this requires the use of X-ray single crystal diffraction to determine its structure.

Figure 1.

Figure 1

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XPS of 3D-Zn-MOF: (a) Survey; (b) C(1s); (c) N(1s); (d) O(1s); (e) Zn(2p).

The structure of 3D-Zn-MOF was analyzed by single-crystal X-ray single crystal diffraction. The results (Table S1) indicated that 3D-Zn-MOF belonged to the tetragonal crystal system and P4/nnc space group, with a = 12.5961(5) Å, b = 12.5961(5) Å, c = 25.4618(12) Å, α = β = γ = 90.00°, V = 4039.8(4) Å3. The elemental and thermogravimetric analyses (Figure S2) showed the presence of solvent molecules in 3D-Zn-MOF. The SQUEEZE analyses also revealed the presence of solvent molecules in crystal cells. A solvent mask was calculated, and 244 electrons were found in a volume of 1214 Å3 in 2 voids per unit cell. This was consistent with the presence of 1.5[H2O] per Formula Unit, which accounts for 240 electrons per unit cell. As a result,there was a single formula unit in the asymmetric unit, which was represented by the reported sum formula. In other words: Z was 16 and Z’ was 1. The moiety formula was C6H5N4O2Zn,1.5[H2O]. So, it was consisted of two Zn(II) ions, two atz– anions, and one pta2– anion in the structure of 3D-Zn-MOF after removing solvent molecules (Figure 2a). In 3D-Zn-MOF, each Zn(II) ion (Figure 2b) coordinated with three N atoms (the N1A, N2, N3B were from different atz– anions), and two O atoms (the O1 and O2 were from pta2– anion). Therefore, the coordination between Zn(II) and coordinating atoms in 3D-Zn-MOF formed a ZnN3O2 square cone geometry (Figure S3a). Among them, the bond length range of Zn–N was 1.970(9)–2.042(9) Å (Zn(1)–N(1) = 1.970(9) Å, Zn(1)–N(3)A = 2.029(9) Å, Zn(1)–N(2)B = 2.042(9) Å, Zn(2)–N(5) = 1.982(9) Å, Zn(2)–N(7)C = 2.059(9) Å, Zn(2)–N(6)D = 2.019(9) Å). The two Zn–O bond lengths were Zn(1)–O(1) = 1.916(9) Å and Zn(2)–O(3) = 1.930 (9) Å, respectively. These bond lengths and bond angles were within the range of bond lengths and bond angles reported in literature for Zn complexes.25−28 It is worth noting that a two-dimensional Zn-atz layer was formed by the atz– took μ3-η1:η1:η1 to coordinated with three Zn(II) atoms (Figure S3b). The adjacent Zn-atz two-dimensional layers were connected by pta2– to form a three-dimensional structure (Figure 2c) with two different pores types of apertures (4.5 × 4.5 Å2, 5.7 × 5.7 Å2). The porosity of 3D-Zn-MOF was calculated to be 27.5% by Platon software. According to topology analysis, the structure of the entire 3D-Zn-MOF could be described as a (3,4)-three-dimensional skeleton by simplifying the Zn(II) element into a single node. It was interesting that there were a large number of carboxyl O atoms on the surface of the stacked structure of 3D-Zn-MOF (Figure 2d), and these O functional groups could effectively affect the adsorption sites and performance.

Figure 2.

Figure 2

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(a) Minimum independent structural unit of 3D-Zn-MOF; (b) the coordination mode of Zn (II) in 3D-Zn-MOF; (c) a 3D pore structure formed by ligand bridging; (d) 3D stacked structure.

3.2. Preparation and Physicochemical Properties of 3D-N-Zn-MOF

The crystalline 3D-Zn-MOF could been prepared into nanomaterials (3D-N-Zn-MOF) with particles of approximately 100 nm (Figure S4a–d) by a cell fragmentation apparatus. The specific surface area, pore volume, and pore size distribution of 3D-N-Zn-MOF were analyzed by N2 adsorption/desorption experiments. The results (Figure S5, Table 1) indicated that it was a typical S-type adsorption isotherm. The BET surface area, pore volume, and pore size of the 3D-N-Zn-MOF were 192.22 m2/g, 0.47 cm3/g, and 9.97 nm, respectively.

Table 1. N2 Adsorption/Desorption Isotherms of 3D-N-Zn-MOF.

parameter value parameter value
single point surface area 188.57 m2/g BET surface area 192.22 m2/g
t-plot micropore area 120.70 m2/g t-plot external surface area 71.51 m2/g
pore volume 0.47 cm3/g pore size 9.97 nm
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3.3. Fluorescence Performance of 3D-N-Zn-MOF

3.3.1. Solid State Luminescence of Ligands and 3D-N-Zn-MOF

The luminescent properties of Hatz and H2PTA were tested at room temperature. The results (Figure 3a,b) indicated that the fluorescence intensities of these two ligands were relatively weak. Hatz was excited at 340 nm in the ultraviolet region, and it had a strong emission spectrum at 400 nm (Figure 3a). When H2PTA was excited in the ultraviolet region at 350 nm, its emission spectrum reached its maximum peak at 430 nm (Figure 3b).

Figure 3.

Figure 3

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(a) The fluorescence of Hatz; (b) the fluorescence of H2PTA; (c) the fluorescence of 3D-N-Zn-MOF; (d) the fluorescence lifetime of 3D-N-Zn-MOF.

The above single-crystal X-ray diffraction analysis proved that Zn(II) had undergone a coordination reaction with ligands Hatz and H2PTA, and 3D-Zn-MOF was generated. Thus, some lone pair electrons on atz– and PTA2– were transferred to Zn(II) with empty orbitals. The XPS also proved that the zinc ions in 3D-Zn-MOF were all Zn(II). The arrangement of extranuclear electrons in Zn(II) was 3d10. And literature29 had also proven that Zn(II) complexes with a 3d10 arrangement typically exhibited good fluorescence performance. The solid-state fluorescence performance of 3D-N-Zn-MOF was tested at room temperature. The results (Figure 3c) indicated that it had a strong emission spectrum at 451 nm when excited at 340 nm. By comparing the fluorescence properties with Hatz and H2PTA, it was found that 3D-N-Zn-MOF exhibited strong fluorescence intensity. In addition, 3D-N-Zn-MOF showed a significant red-shift phenomenon. This was due to the transfer of electrons from the ligand (atz– and PTA2–) to central coordination Zn(II) in 3D-Zn-MOF. At room temperature (298 K), 3D-N-Zn-MOF was excited at 340 nm to measure its fluorescence lifetime. The results (Figure 3d) indicated that the fluorescence lifetime of 3D-N-Zn-MOF was 2.7241 ns. This fluorescence lifetime was longer than most reported Zn(II) complexes in literature.29 This may be because it was a binuclear Zn(II) MOF, and each Zn(II) in 3D-N-Zn-MOF coordinated with the N atoms in atz– and the O atoms in PTA2–. This led to the electron being transferred from atz– and PTA2– to Zn(II), reducing the electronegativity and rigidity of the ligand aromatic ring. Resulting in a longer fluorescence lifetime of 3D-N-Zn-MOF.

3.3.2. Quantum Yield of 3D-N-Zn-MOF

At room temperature (298 K), the 3D-N-Zn-MOF was excited at 340 nm, and its quantum yield was measured between 320 and 700 nm. The results (Figure S6) indicated that the quantum yield of 3D-N-Zn-MOF was 3.02%, which was higher than the similar Zn(II) complexes reported in most literature.19 This may be because the 3D-N-Zn-MOF could provide a stable coordination architecture and suitable coordinate substrate for Zn(II), which could effectively reduce nonradiative energy transfer and loss, thereby improving quantum yield. Moreover, there was a small energy gap between the 4s and 3d orbital levels of Zn(II) in 3D-N-Zn-MOF, making the charge transfer process easier. Zn(II) could promote electron transfer from ligands to central metal ions (LMCT), thereby improving the lifetime and yield of excited states.

3.4. Adsorption Performance of 3D-N-Zn-MOF

Herein, the performance of 3D-N-Zn-MOF in adsorbing Cr(VI) was studied. The concentration of the inorganic pollutant Cr(VI) was 40 mg/L, with a dosage of 100 mL each time. The effects of 3D-N-Zn-MOF dosage (0.0100 g–0.0500 g), different pH (5.00–8.00), and temperature (25–45 °C) on the adsorption of Cr(VI) were studied.

3.4.1. Effect of Dosage on Adsorption Performance

Accurately 0.0100 0.0200, 0.0300, 0.0400, and 0.0500 g of 3D-N-Zn-MOF was weighed into 100 mL of Cr(VI) solution with a concentration of 40 mg/L at 25 °C, and pH = 7. The adsorption capacity (mg/g) of Cr(VI) adsorbed at different times was calculated by the adsorption capacity calculation formula q = (C0–Ct) · V/W. The adsorption experiment results (Figure 4) indicated that the adsorption capacity of 3D-N-Zn-MOF for Cr(VI) increased continuously with time. The adsorption equilibrium was reached after adsorption for 150 min by 3D-N-Zn-MOF (Figure 4a,b). At this time, the adsorption capacities of 0.0100–0.0500 g of 3D-N-Zn-MOF (Figure 4c) were 108.41 125.52, 101.41, 88.56, and 70.34 mg/g, respectively. So, the adsorption capacity was the best when the concentration of adsorbent 3D-N-Zn-MOF was 0.2000 g/L, which could reach 125.52 mg/g. By comparison of the performance of some MOFs adsorbents in adsorbing Cr(VI) (Table 2), it could be found that the 3D-N-Zn-MOF had better performance in adsorbing Cr(VI) than the vast majority of MOFs adsorbents. The performance of 3D-N-Zn-MOF in adsorbing Cr(VI) was analyzed by the quasi first order adsorption kinetics equation qt = qe – qee–k1t. It was found that they have a good linear relationship (R2 > 0.97) (Table S4). In addition, the quasi first order adsorption kinetics analysis also proved that the optimal concentration of the adsorbent was 0.2000 g/L, and the theoretical calculated maximum adsorption capacity at this time can reach 174.42 mg/g (Table S4), which was higher than the actual experimental adsorption capacity of 125.52 mg/g. This indicated that due to interference from experimental conditions such as solution purity and instrument precision, the experimental adsorption capacity was lower than the theoretical calculated adsorption capacity.

Figure 4.

Figure 4

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(a)–(c) Experimental adsorption curves under different dosages; (d) adsorption curve fitted by quasi first order adsorption kinetics.

Table 2. Cr(VI) Adsorption Performance of some Reported MOFs.
entry MOF adsorbate adsorption capacity (mg/g) refs
1 ABT-(ClO4)2 Cr(VI) 271 (30)
2 ZJU Cr(VI) 245 (30)
3 MONT-1 Cr(VI) 211.8 (30)
4 TMU-30 Cr(VI) 145 (30)
5 NiCo-LDH Cr(VI) 99.9 (30)
6 UPC-50 Cr(VI) 56.8 (30)
7 UIO-66-NH2 Cr(VI) 32.4 (30)
8 PAN/chitosan/UiO-66-NH2 Cr(VI) 372.6 (31)
9 ACS Omega Cr(VI) 145.0 (32)
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3.4.2. Effect of pH on Adsorption Performance

The above experimental results had shown that the optimal concentration of 3D-N-Zn-MOF was 0.2000 g/L. So, in order to study the effect of pH on the adsorption performance of 3D-N-Zn-MOF for Cr(VI),the pH of Cr(VI) solution was adjusted to 5, 6, and 8 by 0.100 mol/L HCl and NaOH at 25 °C. The experimental results (Figure S7a,b) indicated that the 3D-N-Zn-MOF could reach adsorption equilibrium in solutions with pH 5, 6, and 8 after 150 min. At this point, their maximum equilibrium adsorption capacities (Figure S7c) were 91.77, 111.11, and 100.01 mg/g, respectively. They were all lower than the adsorption capacity at pH = 7. So, the optimal pH for 3D-N-Zn-MOF to adsorb Cr(VI) was 7. It could been found that the 3D-N-Zn-MOF had a wide pH adaptability for the adsorption of Cr(VI) by analyzing the performance at different pH. It was also found (Figure S7d) that they had a good linear relationship (R2 > 0.95) (Table S5) by the quasi first-order adsorption kinetics equation to analyze the effect of pH on the adsorption of Cr(VI) by 3D-N-Zn-MOF. The quasi first-order adsorption kinetics calculation analysis showed that the maximum equilibrium adsorption capacity could reach 232.29 mg/g at pH 5, which was only lower than the reported PAN/chitosan/UiO-66-NH2 and ABT-(ClO4) 2 adsorbents in literature.31

3.4.3. Effect of Temperature on Adsorption Performance

The above research results indicated that the optimal dosage concentration of 3D-N-Zn-MOF was 0.2000 g/L, and the optimal pH was 7. Therefore, in a Cr(VI) solution with a pH of 7, the 3D-N-Zn-MOF (0.0200 g) was added to study the effect of the temperature (25–45 °C) on adsorption. The experimental results (Figure 5a,b) indicated that 3D-N-Zn-MOF could adsorb Cr(VI) for 150 min and reach adsorption equilibrium. However, as the temperature increased, the amount of Cr(VI) adsorbed by 3D-N-Zn-MOF significantly decreased (Figure 5a,b). The maximum equilibrium adsorption capacities at 25–45 °C were 125.52 106.74, 87.95, 69.14, and 50.33 mg/g, respectively. A quasi first order kinetic analysis was conducted on the adsorption behavior at these temperatures, indicated a good linear relationship (R2 > 0.95) (Table S6), and also demonstrated the maximum experimental and theoretical adsorption capacity at 25 °C. The adsorption thermodynamic data of 3D-N-Zn-MOF for Cr(VI) adsorption process were fitted and analyzed by the Van’t Hoff equation (Table S7). The analysis results indicated that the adsorption of Cr(VI) by 3D-N-Zn-MOF at 25–45 °C was a spontaneous (△G < 0) and exothermic (△H < 0) process.

Figure 5.

Figure 5

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(a)–(c) Experimental adsorption curves under different temperatures; (d) adsorption curve fitted by quasi first order adsorption kinetics.

3.5. Adsorbent Regeneration and Cycling Experiments

The X-ray powder diffraction was used to characterize and analyze the collected solid adsorbent after the desorption and regeneration of the adsorbent. The test results showed that the diffraction peaks of the collected solid adsorbent (Figure S8) were consistent with the theoretical simulation of 3D-N-Zn-MOF. This clearly demonstrates that the 3D-N-Zn-MOF could be repeatedly regenerated, and it was a very pure material. In addition, XPS (Figure S9) also indicated that the 3D-N-Zn-MOF after adsorption regeneration was composed of elements such as Zn, C, N, and O. As a result, the 3D-N-Zn-MOF had the characteristics of regeneration and reuse.

The cyclic experimental results (Figures 6and S10) indicated that the efficiency of 3D-N-Zn-MOF could reach 100% after one cycle. Even though its efficiency had decreased after five cycles, it still maintains 98.26%. It could be seen that the 3D-N-Zn-MOF had efficient adsorption performance for Cr(VI).

Figure 6.

Figure 6

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Maximum equilibrium adsorption capacity of the cycle experiment.

4. Conclusion

In summary, a three-dimensional Zn(II) metal organic framework {[Zn2·(atz)2·(pta)]·3H2O}n (3D-Zn-MOF) with strong luminescence and Cr(VI) adsorption properties was synthesized and fully characterized. In addition, its nanomaterials (3D-N-Zn-MOF) with particles of approximately 100 nm were prepared by a cell fragmentation apparatus. The fluorescence lifetime and quantum yield of 3D-N-Zn-MOF were 2.7241 ns and 3.02%, respectively. The maximum experimental adsorption capacity of 3D-N-Zn-MOF for Cr(VI) could reach 125.52 mg/g, which was superior to the majority of MOF adsorbents. Furthermore, at 25 °C–45 °C, the adsorption of Cr(VI) by 3D-N-Zn-MOF was a spontaneous (△G < 0) and exothermic (△G < 0) process. This study provides an example for studying bifunctional materials with fluorescence and Cr(VI) adsorption properties.

Acknowledgments

This work was supported by the Guangxi University Young and Middle-aged Teachers’ Basic Scientific Research Ability Improvement Project (no. 2020KY17021), Guangxi Natural Science Foundation, China (no. 2023JJA120079), Science and Technology Project of WuZhou (202302049), Central Government Funds for Guiding Local Scientific and Technological Development (2021ZYZX2089), School level scientific research project of Wuzhou University (no. 2021B002), and National College Student Entrepreneurship Training Program (no. 202111354318).

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.4c00431.

  • Chemicals and instruments, adsorption experiment, adsorbent regeneration experiment, IR of 3D-Zn-MOF, TGA of 3D-N-Zn-MOF, the geometric configuration of Zn(II), and the atz– take μ3-η1:η1:η1 to coordinates with three Zn(II) ions, SEM of 3D-N-Zn-MOF, the N2 adsorption/desorption isotherms of 3D-N-Zn-MOF, quantum yield of 3D-N-Zn-MOF, experimental adsorption curves under different pH, XRD of 3D-N-Zn-MOF, XPS of 3D-N-Zn-MOF after adsorption and regeneration, circular experiment (Figure S1–S8), crystal parameters of 3D-N-Zn-MOF, partial bond length (Å) and bond angle (deg) of 3D-N-Zn-MOF, hydrogen bond of 3D-Zn-MOF, quasi first order kinetic equation under the influence of dosage, pH, and temperature, and adsorption thermodynamic parameters of adsorbents at different temperatures (Tables S1–S7) (PDF)

  • data_lsx-1 (CIF)

Author Contributions

Y.C. contributed to writing–original draft. S.L. contributed to funding acquisition and writing–review and editing. Y.L. contributed to data curation. P.S. contributed to data curation. S.X. contributed to funding acquisition. Y.B. contributed to funding acquisition and writing–review and editing.

The authors declare no competing financial interest.

Supplementary Material

ao4c00431_si_001.pdf (1MB, pdf)
ao4c00431_si_002.cif (421.2KB, cif)

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