Rapid Synthesis of Hierarchical Porous MetalâOrganic Frameworks

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Rapid synthesis of hierarchical porous MOFs and the simulation of growth Hang Zhang, Jinhao Huo, Feier Li, Chongxiong Duan, and Hongxia Xi Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 09 Oct 2018 Downloaded from http://pubs.acs.org on October 9, 2018

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Crystal Growth & Design

Rapid synthesis of hierarchical porous MOFs and the simulation of growth Hang Zhang, † # Jinhao Huo,† # Feier Li, † Chongxiong Duan,†* and Hongxia Xi†, ‡ * †

School of Chemistry and Chemical Engineering, South China University of Technology,

Guangzhou 510640, PR China ‡

Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control,

Guangzhou Higher Education Mega Centre, Guangzhou 510006, P. R. China

ABSTRACT: Hierarchically porous metal-organic frameworks (HP-MOFs) have been successfully synthesized under mild conditions within 60 s using an anionic surfactant in a (Cu, Zn) hydroxyl double salt (HDS) solution. The anionic surfactant served as a template for the construction of mesopores and macropores and the (Cu, Zn) HDS accelerated crystal nucleation. Importantly, the growth of the HP-MOFs was monitored by attenuated total-reflectance Fouriertransform infrared (ATR-FTIR) spectroscopy and the mechanism of synthesis was explored using mesodynamics (MesoDyn) simulations. The introduction of larger pores into conventional MOFs aided the diffusion of bulky molecules into the active center and enhanced the catalytic activity of the MOFs.

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Introduction Hierarchically porous metal-organic frameworks (HP-MOFs), self-assembled structures produced from metal nodes and organic ligands, are mesoporous and microporous (or macroporous, mesoporous, and microporous) crystalline hybrid materials where the atomic periodicity extends to the multimodal pores and channels.1-3 HP-MOFs possess fascinating physical and chemical properties, including various structural topologies, high specific surface areas, permanent porosities, rich chemical functionalities, and outstanding active site accessibilities.4 Compared with conventional microporous MOFs (M-MOFs), HP-MOFs exhibit enhanced mass transfer and diffusion rates, allowing guest molecules to freely and rapidly reach the reactive sites within the micropores via the large pore channels.5,

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Moreover, the faster

molecular diffusion in HP-MOFs than in M-MOFs has also been proven by theoretical calculations.6, 7 It has been reported that more active sites are exposed in HP-MOFs than in MMOFs, thereby resulting in the observed enhanced reactivity.8 Furthermore, compared to conventional porous solids like hierarchical zeolites, mesoporous silica, and activated carbon, precise design and modification of HP-MOF framework structures and tailoring of their pore environments at the molecular and atomic levels are possible.9, 10 Consequently, application of HP-MOFs is particularly attractive in various fields involving both small and large guest molecules, including adsorption,11 separation,12 drug delivery,13 photoelectronics,13 and catalysis.14, 15 Therefore, large-scale preparation of HP-MOFs is of importance in the context of practical industrial applications. To date, extensive efforts have been devoted to the development of HP-MOFs, and novel approaches such as ligand extension method,16 crystal defect method,17 post-modification method,18 mechanochemical synthesis,19 and spray-drying technologies,20 have been reported.


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However, issues relating to ligand costs, small mesopore sizes ( 12 h) and high temperatures and pressures to yield the desired HP-MOF products,13, 32, 33 leading to high energy consumption and low production rate (space-time yields (STYs) < 300 kg·m−3·d−1).34, 35 The main focus of both academia and industry to date has been the use of different templates to prepare HP-MOFs,36, 37 while the growth mechanism for the templating synthesis of HP-MOFs has received no attention from a mesoscopic perspective. In this context, although Parsons et al.38 developed a facile method for the rapid (within 1 min) roomtemperature synthesis of MOFs with high STYs (3.6 × 104 kg·m−3·d−1), the resultant products were M-MOFs rather than HP-MOFs. Herein, the above issues have been addressed, including an investigation into the HP-MOF growth mechanism. More specifically, the development of a novel method for the design and synthesis of HP-MOFs under mild conditions has been reported. In this system, anionic surfactants have been used as templates to give the desired hierarchical porosity, while a (Cu, Zn)


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hydroxy double salt (HDS) solution has been used as an accelerator for the rapid formation of Cu-BTC crystals. The micro-, meso-, and macroporous structures of the products have been examined, and rational tuning of the porosity has been studied by varying the quantity and type of surfactants employed. The STY of HP-MOFs was as high as > 1.94 × 104 kg·m−3·d−1, leading to production on the ton scale. Furthermore, the growth of HP-MOF crystals has been monitored by attenuated total-reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy. Moreover, mesodynamics (MesoDyn) simulations have been employed to investigate the phase behavior of the mixture system to aid in the verification of our synthetic mechanism. Finally, the activities of the prepared HP-MOFs have been compared to those of microporous MOFs in reactions containing large molecules. Experimental and simulation details Rapid synthesis of hierarchically porous Cu-BTC using anionic surfactant as template at room temperature and pressure In a typically procedure,38,

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firstly, 0.293 g of zinc oxide (ZnO) was dispersed in 8 mL

deionized water (H2O) and 8 mL N, N-dimethylmethanamide (DMF) using sonication for 30 min to form suspension (denoted as solution A). Secondly, 4.5 mmol of copper nitrate trihydrate (Cu(NO3)2·3H2O) was added to 15 mL of H2O (denoted as solution B). Next, n (n = 4.5, 2.25, 1.125, 0.45) mmol of template (sodium benzene sulfonate, SBS) and 2.5 mmol of 1, 3, 5benzenetricarboxylic acid (H3BTC) were added to 15 mL of ethanol (denoted as solution C). Then, solution A and solution B were mixed and still stirred for 15 min, and then solution C was added to mixture under fast magnetic stirring. After stirring for 60 s, the blue product was subsequently filtered and washed by methanol (25 mL, 4 times), and then dried in an oven at


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120 °C for 12 h. The resulting products synthesized with different template/Cu2+ molar ratio are denoted as H-Cu-BTC_AX (X = 1, 2, 3, 4, where X represents the molar ratio of template/Cu2+, X = 1 for n = 4.5, X = 2 for n = 2.25, X = 3 for n = 1.125, X = 4 for n = 0.45). Similarly, hierarchically porous Cu-BTC synthesized using other surfactants as templates are denoted as Cu-BTC_Y2 (Y = B, C, D, where Y represents the type of surfactants, B: sodium 4hydroxybenzenesulfonate

dihydrate;

C:

sodium

p-toluenesulfonate;

D:

sodium

dodecylbenzenesulfonate; and the molar ratio of template/Cu2+ = 0.5). For comparison, solvothermal synthesis of conventional Cu-BTC at 120 oC for 12 h following a previous report,40 which is denoted as C-Cu-BTC. Results and discussion The powder X-ray diffraction (XRD) patterns of the prepared H-Cu-BTC_AX (X = 1, 2, 3, 4) and C-Cu-BTC are shown in Figure 1a, along with the simulated Cu-BTC patterns obtained from the Materials Studio Package 5.0 (CCDC-112954).41 As indicated, the XRD patterns of H-CuBTC_AX showed sharp diffraction peaks, similar to those of C-Cu-BTC and simulated result, thereby confirming that this rapid synthetic route produced highly crystalline Cu-BTC. However, a few additional peaks (2θ = 12.8°) were observed in the XRD pattern of H-Cu-BTC_A2, attributed to either the presence of other unidentified phases or an abundance of lattice defects.42 The crystal structures of the samples were further investigated by Fourier transform infrared (FTIR) spectroscopy. Figure 1b shows that the FTIR spectra of all the H-Cu-BTC_AX species were consistent with that of C-Cu-BTC (with major peaks at ~1650, 1450, 1375, 1112, 757, and 729 cm−1),43 again confirming the formation of crystalline Cu-BTC. It should be noted that no characteristic diffraction peaks or infrared stretching vibrations corresponding to ZnO or SBS surfactant were observed in the XRD patterns (Figure S2a) and the FTIR spectra (Figure S2b) of


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the obtained HP-MOFs,44 respectively. These results confirm that the introduced ZnO and SBS did not bond to the organic ligands (H3BTC) or to Cu2+ to form other crystals.32, 45

Figure 1. (a) Powder XRD patterns of H-Cu-BTC_AX (X = 1, 2, 3, 4), C-Cu-BTC, and the simulated Cu-BTC pattern (Bragg conditions: 2θ: 5–50°; step size: 0.020644°; 1/dhkl: 0.056628 Å−1 (min) and 0.548655 Å−1 (max)); (b) FTIR spectra of H-Cu-BTC_AX (X = 1, 2, 3, 4) and CCu-BTC. The mesostructures of the H-Cu-BTC_AX samples were investigated using the N2 adsorption– desorption method at 77 K.46 As shown in the N2 adsorption-desorption isotherms (Figure 2a), all the H-Cu-BTC_AX samples exhibit a combination of type I and type IV isotherms with small hysteresis loops, confirming the presence of mesopores and micropores.37 However, C-Cu-BTC exhibits a type I isotherm, confirming its previously reported microporous structure.40 Furthermore, the pore size distribution curves of H-Cu-BTC_AX, calculated using the nonlocal density functional theory (NLDFT) (Figure 2b), showed broad pore size distributions of 8– 100 nm for H-Cu-BTC_AX (with the exception of intrinsic micropores of diameter ~0.86 nm). Moreover, the existence of macropores in HP-MOFs was confirmed using mercury intrusion porosimetry (Figure S3). These results indicate the presence of mesoporous and macroporous


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regions, which were absent from C-Cu-BTC.40 Interestingly, H-Cu-BTC_A2 appears to contain well-ordered mesopores with diameters centered at 10 nm, which may be attributed to the formation of uniform columnar micelles (10 nm) by SBS at this concentration (2.25 mmol).26 More information regarding the porosity properties and STYs of the reported H-Cu-BTC_AX samples are summarized in Table S2. We also found that the as-synthesized H-Cu-BTC_AX materials displayed significantly higher Smeso/Smicro and mesopore volumes (Vmeso) than the reported values of conventional Cu-BTC,32 further verifying the formation of mesostructures. The textural properties of the HP-MOFs (e.g., Brunauer–Emmett–Teller (BET) surface area and pore volume) were found to depend on the amount of template employed, thereby allowing easy tailoring of the porosity. Moreover, the STYs of the prepared HP-MOFs ranged from 1.94 × 104 to 2.90 × 104 kg·m−3·d−1 (Table S2), comparable to the corresponding values for Al-MOF, which are currently produced on the ton scale.47

Figure 2 (a) The N2 adsorption–desorption isotherms and (b) pore size distributions of the assynthesized H-Cu-BTC_AX (X = 1, 2, 3, 4) HP-MOFs and C-Cu-BTC samples. The crystal morphologies of the prepared samples were examined using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). As shown in Figures 3a–3b,


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both C-Cu-BTC and H-Cu-BTC_A2 exhibited typical octahedral structures. However, their particle sizes, surface properties, and internal structures differed significantly. More specifically, the average particle size of H-Cu-BTC_A2 (~400 nm) was significantly smaller than that of CCu-BTC (~10 µm), attributed to the formed (Cu, Zn) HDS exhibiting high rate of anion exchange, thereby resulting in the rapid growth of Cu-BTC frameworks and formation of small crystals.38, 48 In addition, C-Cu-BTC exhibited a smooth surface (Figures 3a, 3c), while H-CuBTC_A2 had obvious lattice defects and abundant pore voids on the crystal surface (Figure 3b, 3d), consistent with the XRD result with additional peaks (2θ = 12.8°) (Figure 1a). Furthermore, the formed mesopores of H-Cu-BTC_A2 produced a three-dimensional (3D) penetrative network structure instead of surface pores (the light gray area represents large pores), as confirmed by TEM observations (Figure 3d). However, H-Cu-BTC_AX (X = 1, 3, or 4) exhibited interparticle voids due to random stacking of crystals, as shown in Figure S4. Moreover, elemental mapping of H-Cu-BTC_A2 obviously reveals a uniform distribution of C, O, and Cu in the HP-MOF crystal (Figure S5), whereas the absence of Zn indicates that other MOFs such as Zn-BTC were not formed.49 The thermal stabilities of the samples were examined using thermogravimetric analysis (TGA). The TGA curves (Figure S6a) of the H-Cu-BTC_AX samples synthesized using four different template concentrations are similar, indicating that the amount of template employed has no influence on the stability of the HP-MOFs. We also found that the structural decomposition of H-Cu-BTC_AX occurred at 330 °C, consistent with the decomposition of CCu-BTC under identical conditions. These results indicate that the introduction of large pores does not reduce the thermal stability of these materials. In addition, H-Cu-BTC_A2 remained stable after immersion in nitromethane and toluene for 3 days, as confirmed by TGA (Figure S6b). These results indicate that the HP-MOFs obtained by room-temperature rapid synthesis


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have excellent stability. Compared with the conventional template method for solvothermal synthesis of HP-MOFs,50 which typically requires harsh conditions (high temperature and pressure), in the technique described herein, stable HP-MOFs could be synthesized rapidly at room temperature and pressure by the simultaneous addition of ZnO and a template, and the resulting mesoporous properties renders the HP-MOFs promising materials for a range of applications.

Figure 3. SEM and TEM images of (a, c) C-Cu-BTC and (b, d) H-Cu-BTC_A2 samples. To investigate bond formation and ion−ligand exchange during HP-MOF growth, ATR-FTIR spectroscopy was adopted to monitor the growth process of H-Cu-BTC_A2. Figure 4 shows the obtained time-resolved ATR-FTIR spectra for the rapid formation of HP-MOF crystals (the absorption bands of the ν(NO3−), ν(C=C), and ν(OCO−) were recorded automatically at 15 s intervals; detailed test process given in the SI), in which the bands at 1420 and 1360 cm−1,


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corresponding to NO3−, were observed for the (Cu, Zn) HDS.51, 52 As shown in Figure 4a, the intensity of the ν(NO3−) peak first increased sharply, followed by a plateau, thereby confirming the rapid formation of the (Cu, Zn) HDS from ZnO particles, which is consistent with a previous report.53 The absorption peak at 1588 cm−1 corresponding to ν(C=C) was attributed to the aromatic ring of BTC3−,52 while the ν(OCO−) peak at 1647 cm−1 originated from the symmetric and asymmetric stretching modes of the carboxylate groups in Cu-BTC.38 As shown in Figure 4b, the intensities of the ν(OCO−) and ν(C=C) peaks increased rapidly, then remained relatively constant, indicating rapid formation of Cu-BTC crystals, which can be attributed to the selfassembly of the Cu2+ ions of (Cu, Zn) HDS with BTC3− to form Cu-BTC crystals due to the high rate of anion exchange.26, 38 Moreover, the fact that no variations were observed for the ν(C=C) signal was attributed to the excess H3BTC employed in the reaction. These analyses verify the fast formation of Cu-BTC crystals within 60 s at room temperature and pressure. Similar conclusions were drawn in earlier works of the Parsons group.38, 52 In addition, a powder XRD pattern was recorded for the HP-MOF product (denoted as H-Cu-BTC_A2R) prepared by filtering the damp sample without activation. As shown in Figure S7, the main diffraction peaks of H-Cu-BTC_A2R agreed well with those of H-Cu-BTC_A2 and C-Cu-BTC, as well as simulated results, confirming that the HP-MOFs were synthesized within 60 s at room temperature instead of during the subsequent activation process at high temperature.


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Figure 4. Variation in peak intensity of time-resolved ATR-FTIR spectra with time: (a) ν(NO3−) at 1360 and 1420 cm-1, (b) ν(OCO−) at 1647 cm-1 and ν(C C) at 1588 cm-1. Investigation of the formation mechanism of HP-MOFs is necessary to produce designable and controllable synthetic procedures, but remains an ongoing challenge.36,

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Since theoretical

calculations can offer valuable insight into mechanical behavior on a molecular or atomic level,55 mesoscopic dynamics (MesoDyn) simulations, based on the density functional theory (DFT) calculations,56 was employed herein to elucidate the phase behavior of the surfactant and explore structural control during synthesis.57, 58 The curve of the system free energy and snapshots of the surfactant system are presented in Figure 5. The system energy reflects not only the stability of the system but also any changes in the microphase structure in solution.59 It is a comprehensive embodiment of the system phase separation and the degree of compatibility of each component, which reflects the phase separation process of the system.60 The free energy can be defined as per equation (1):

E

(1)


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(where R is the gas constant, T refers to the system temperature, and refers to the volume of grid). As shown in Figure 5a, the formation of mesoscopic HP-MOFs phases can be divided into three stages. In stage I, the free energy decreases gradually, indicating micelle formation,61 corresponding to the synergistic assembly of the SBS surfactant with Cu2+ and BTC3− to form spherical micelles (Figure 5b, T = 0.15 ms). In stage II, the addition of a steady shear along the x-axis rapidly increases the free energy, followed by an immediate decrease, correlated with the conversion of spherical micelles into columnar micelles (Figure 5b, T = 0.3 ms). In stage III, the free energy remains relatively constant, indicating the stability of the cylindrical micelles, and confirming that the synergistic assembly of SBS and Cu-BTC into the HP-MOF mesoscopic phase has reached equilibrium (Figure 5b, T = 1.0 ms).62

Figure 5. (a) The change in free energy density with simulation time; and (b) the snapshots of the system at 0.0 ms, 0.15 ms, 0.3 ms, and 1.0 ms. Figure 6 shows the cross-sectional representations of the SBS surfactant/MOF precursors. As shown in Figure 6a, the introduced surfactants self-assembled into columnar micelles when the SBS concentration exceeded the critical micellization concentration (CMC).63 Moreover, the cross-section of the MOF precursor appeared identical to that of the surfactant (Figure 6b),


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indicating that the Cu-BTC crystal grows synergistically with micelles to form supramolecular micelles (Figure 6c).

Figure 6. (a) Cross-section of the SBS surfactant, (b) Cu-BTC precursors, and (c) surfactant/CuBTC precursors (where green bead and yellow bead representative benzene and sodium sulfonate, red for the benzene and blue for the carboxyl group in H3BTC, respectively). Figure 7 compares the density heat maps with the SEM and TEM images, where the different density distributions (i.e., regions I, II, and III) are apparent. The internal heat density (III) is significantly higher than that of the edge (I), indicating that the majority of Cu-BTC grows inside the micelles, mainly occupying region I. Furthermore, the internal density shows an uneven distribution, i.e. the density of the local area (II) is lower than that of the surrounding area (III), indicating that these areas are occupied by the template. Following template removal, the hierarchical porous system was obtained. These simulation results are consistent with the experimental data, as confirmed by the SEM and TEM observations.


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Figure 7. Density heat maps of hierarchical porous Cu-BTC. To further highlight the synergy between the surfactant and ZnO, three control experiments were performed: (1) solvothermal synthesis of hierarchical porous Cu-BTC without ZnO (denoted as Cu-BTC_S), (2) room-temperature synthesis of Cu-BTC in the presence of SBS, (3) rapid synthesis of Cu-BTC with (Cu, Zn) HDS at room temperature and pressure (denoted as CuBTC_ZnO). The obtained crystal diffraction peaks of Cu-BTC_S corresponded with the simulated pattern for Cu-BTC (Figure S8), confirming the crystalline nature of the Cu-BTC product. The sorption isotherm of Cu-BTC_S showed a type IV curve, indicating that the obtained product contained a micro- and mesoporous structure (Figure S9). These results indicate that the introduced SBS surfactant can act as a template for the construction of the mesostructure. However, in room-temperature synthesis of Cu-BTC in the presence of SBS, no precipitate was obtained even after a reaction time of 30 min, indicating that the template alone cannot accelerate the reaction. Furthermore, XRD measurements of Cu-BTC_ZnO confirmed the successful synthesis of Cu-BTC crystal within 60 s (Figure S10); however, a type I sorption isotherm (Figure S11a) was obtained and the pore size distributions (Figure S11b) were concentrated in the microporous region, indicating that the obtained product possessed


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micropores only. These results confirm that the (Cu, Zn) HDS obtained from the ZnO particles can accelerate the nucleation of MOF crystals, but cannot generate large pores, similar to the observation by Parsons et al.38 As such, combination of these control experiments with the previous experimental results indicate that the simultaneous introduction of the SBS surfactant and the ZnO particles produced a synergetic effect, where the SBS surfactant served as the templates to fabricate mesopores and macropores, while ZnO accelerated the growth of the MOF crystals. Based on the experimental and simulation results, a feasible mechanism for the synthesis of hierarchical porous Cu-BTC was proposed (Scheme 1). First, the introduced ZnO combines with Cu(NO3)2 to form (Cu, Zn) HDS with a high of anion exchange.53 Meanwhile, the added anionic surfactant (SBS) forms columnar micelles via self-assembly in the ligand solution.36 Upon addition of (Cu, Zn) HDS to the ligand/micelle mixture, Cu2+ and BTC3- undergo rapid selfassembly on the micelles surface to form MOF frameworks due to the high anion exchange rate,26, 38 and the electrostatic attraction present between the MOF precursors and the template micelles.36, 64, 65 Mesopores and macropores are generated following template removal via simple activation and drying, where the mesopore and macropore walls are constructed by the crystalline microporous framework.26, 65


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Scheme 1. Schematic showing the mechanism of the rapid room-temperature synthesis of HPMOFs using a supramolecular template strategy. Recently, some MOFs (e.g., [{Cu(L1)(DMF)}·DMF·H2O]n) were reported to catalyze the Henry reaction efficiently.66-68 Thus, the Henry reaction was selected as a model catalytic reaction to evaluate the diffusion and mass transfer of large molecules in the HP-MOFs. As shown in Figure 8, the lowest rate of 4-nitrobenzaldehyde conversion was observed using the CCu-BTC catalyst, indicating that the reaction takes place on the catalyst surface.69 Interestingly, similar conversions were observed for the H-Cu-BTC_AX (X = 1, 3, or 4) samples; for the H-CuBTC_A4 catalyst, the conversion reached 20.3%. These results indicate that the effects of interparticle meso- or macropores are small. In contrast, for the H-Cu-BTC_A2 catalyst, the conversion reached 28.8%, which was attributed to the presence of intra-crystal mesopores. As confirmed in Figure 7, the (I) and (II) regions are rich in mesopore channels, which allow 4nitrobenzaldehyde to enter the active center and assist in the expulsion of 1-(4-nitrophenyl)-2nitroethanol. These results indicate that intra-crystal mesopores are keys to improving the catalytic activity. Inductively coupled plasma optical emission spectroscopy measurements revealed that the Cu content concentration in the solution after the reaction was less than 10.6 ppm (Table S3). Moreover, the as-synthesized HP-MOFs (H-Cu-BTC_A2) displayed excellent


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recyclability and stability after three catalytic reaction cycles (Figure S12). Furthermore, under alkaline conditions (pH = 8.5), the HP-MOFs exhibited high catalytic activity, as shown in Figure S13. In addition, HP-MOFs are expected to be an attractive adsorbent for the capture and removal of target species such as volatile organic compounds.70 Here, we tested the HP-MOFs for the adsorption of large molecules such as toluene. As shown in Figure S14, the HP-MOFs showed significantly higher toluene saturation uptake (681 mg·g−1) than C-Cu-BTC (408 mg·g−1) owing to the presence of mesopores and macropores.70 These results indicate that the introduction of 3D penetrative pores into MOFs is beneficial to their application.

Figure 8. The conversion rate of 4-nitrobenzaldehyde catalyzed by H-Cu-BTC_AX (X = 1, 2, 3, 4) and C-Cu-BTC, respectively. To determine the versatility of the synthetic mechanism reported herein, three other anionic surfactants were chosen as templates for the rapid synthesis of HP-MOFs (denoted as H-CuBTC_Y2 (Y = B, C, D); see SI for details). The XRD patterns of H-Cu-BTC_Y2 (Y = B, C, D) and the simulated Cu-BTC (Figure S15) show that the crystalline diffraction peaks of H-CuBTC_Y2 correlated with those of the simulated Cu-BTC, confirming that these products are


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highly crystalline. The N2 adsorption-desorption isotherms and the pore size distributions indicate the existence of micro-, meso-, and macropores (Figure 16). Moreover, the porosity properties of H-Cu-BTC_Y2 further verify the presence of mesostructures (Table S2). Notably, the porosity of the HP-MOFs depended on the template employed. Therefore, these results confirm that our synthetic method can be considered versatile. Conclusion In summary, a facile and versatile method was developed herein for the rapid preparation of stable hierarchically porous metal-organic frameworks (HP-MOFs) under mild conditions, through the simultaneous introduction of an anionic surfactant and a (Cu, Zn) hydroxide double salt (HDS) solution. The surfactant served as a template for the construction of meso- and macropores, while the (Cu, Zn) HDS accelerated crystal nucleation. The mechanism for the cooperative templating synthesis of HP-MOFs was elucidated based on a combination of experimental data and mesodynamics (MesoDyn) simulations. The obtained HP-MOFs exhibited excellent catalytic performances and adsorption capacities compared to microporous MOFs for reactions involving large molecules. These results are of importance because the facile preparation of HP-MOFs is necessary for their potential application in various fields involving both large and small guest molecules, such as adsorption, separation, and drug delivery. ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. More detail for the synthesis and Figure S1 to S16, Table S1 to S3 (PDF)


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AUTHOR INFORMATION Corresponding Author Chongxiong Duan and Hongxia Xi *

E-mail addresses: [email protected] (C. Duan), [email protected] (H. Xi)

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. # These authors contributed equally. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 21576094), SRFDP (No.20130172110012), Guangdong Natural Science Foundation, and the Fundamental Research Funds for the Central Universities, SCUT (2015ZM046). ABBREVIATIONS SBS, sodium benzene sulfonate; HDS, hydroxy double salt; ATR-FTIR, attenuated total-reflectance Fourier-transform infrared spectroscopy; MesoDyn, mesodynamics simulation; STY, space–time yield; CMC, critical micelle concentration;


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For Table of Contents Use Only Rapid synthesis of hierarchical porous MOFs and the simulation of growth Hang Zhang, † # Jinhao Huo,† # Feier Li, † Chongxiong Duan†*, and Hongxia Xi†, ‡ * SYNOPSIS TOC

A simple and facile method to rapidly synthesize hierarchically porous metal-organic frameworks (HP-MOFs) within 60 s by using an anionic surfactant in a (Cu, Zn) hydroxyl double salt (HDS) solution, where the surfactant served as a template for the construction of meso- and macropores and the (Cu, Zn) HDS accelerated crystal nucleation.


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Rapid Synthesis of Hierarchical Porous MetalâOrganic Frameworks

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