A Dual-Purpose 3D Pillared MetalâOrganic Framework with Excellent

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Energy, Environmental, and Catalysis Applications

A Dual-Purpose 3D Pillared Metal–Organic Framework with Excellent Properties for Catalysis of Oxidative Desulfurization and Energy Storage in Asymmetric Supercapacitor Reza Abazari, Soheila Sanati, Ali Morsali, Alexandra M. Z. Slawin, and Cameron L. Carpenter-Warren ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b00415 • Publication Date (Web): 29 Mar 2019 Downloaded from http://pubs.acs.org on March 29, 2019

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ACS Applied Materials & Interfaces

A Dual-Purpose 3D Pillared Metal–Organic Framework with Excellent Properties for Catalysis of Oxidative Desulfurization and Energy Storage in Asymmetric Supercapacitor

Reza Abazari,† Soheila Sanati,† Ali Morsali,*† Alexandra M. Z. Slawin‡ and Cameron L. CarpenterWarren‡ † Department ‡ EaStCHEM,

of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran

School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, Scotland, UK

1 ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 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

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ABSTRACT: This study proposes an approach for improving catalysis of oxidative desulfurization (ODS) of diesel fuel under mild reaction conditions and enhancing supercapacitor (SC) properties for storage of a high amount of charge. Our approach takes advantage of a novel dual-purpose cobalt(II)based metal organic framework, [Co(2-ATA)2(4-bpdb)4]n (2-ATA: 2-aminoterephthalic acid and 4-bpdb: N,N-bis-pyridin-4-ylmethylene-hydrazine as the pillar spacer), that is called NH2-TMU-53. Due to the stability of the used compound, we decided to evaluate the capability of this compound as a novel electrode material for storing energy in supercapacitors, and also to investigate its catalytic capabilities. It is demonstrated that addition of H2O2 as an oxidant enhances the efficiency of sulfur removal, which indicates that NH2-TMU-53 can efficiently catalyze the ODS reaction. According to the kinetics results, the catalyzed process follows pseudo-first-order kinetics and exhibits 15.57 kJ mol-1 activation energy. Moreover, with respect to the radical scavenging evaluations, the process is governed by direct catalytic oxidation rather than indirect oxidative attack of radicals. Further, the NH2-TMU-53 was applied as an electrode material for energy storage in SCs. This material used in three electrode system and shows specific capacitance as 325 Fg-1 at 5 Ag-1 current density. The asymmetric supercapacitor of NH2-TMU53//AC evaluate for the further electrochemical activity in real applications, delivers the high power density (2.31 kWkg−1), high energy density (50.30 Wh kg−1), and long cycle life after 6000 cycles (90.7%). Also, the asymmetric supercapacitor practical application was demonstrated by a glowing red LED and driving a mini-rotating motor. These results demonstrate that the fabricated device presents a good capacity of energy storage without pyrolyzing the MOF structures. These findings can guide development of high performance SCs towards a new direction to improve their practical applications and motivate application of MOFs without pyrolysis or calcination.

KEYWORDS: Metal–organic framework, without pyrolysis, Oxidative desulfurization, Cyclic stability, Electrode material, Asymmetric supercapacitor.


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1. INTRODUCTION One of the industrial problems that can be solved to alleviate air pollution is related to the presence of undesirable organosulfur compounds in petroleum products.1-3 The corresponding environmental issue is so critical that the Environmental Protection Agency (EPA) and EU Euro V standards have announced that the permitted level of sulfur in diesel fuel should be below 15 and 10 ppm, respectively.4, 5 Consequently, it is essential to decrease the sulfur content of transportation fuels. In addition to sulfur level reduction, environmental pollution can be decreased by shifting from fossil fuels to clean and reliable sources of energy, such as batteries and electrochemical supercapacitors (SCs).6-8 In this respect, many researchers have attempted to propose new materials and solve the energy and environmental issues of the world with less cost and energy consumption at a lower working temperature. Though different researchers have acquired great achievements in the fields of energy and environmental pollutions, the challenge of developing multipurpose materials has not been answered properly. Therefore, more materials should be examined to find an appropriate option with suitable pores, high specific surface area, low cost, good cycling performances, low internal electrical resistance and diverse potentials, such as high catalytic activity.9-11 Some of the outlined properties can be addressed by using metal organic frameworks (MOFs), which present high porosity, tunable structure, great surface area, low density and versatile functionalities and have been applied for gas storage and separation, sensing, catalysis and drug delivery purposes.12, 13 Despite the noticeable body of literature on MOFs, few studies have used pure MOFs for desulfurization and electrochemical energy storage, particularly without MOF pyrolysis. As the advantages of MOFs are promising, this study considers the applications of a new MOF for catalysis and energy storage. For storage of energy, the studied MOF is used to fabricate a SC. Since SCs provide long life cycle, high power density and great discharge efficiency and MOFs facilitate charge transport, particle diffusion and electrochemical reactions by their large internal surface areas and porosities.14-16 There have already been several studies investigating the electrochemical application of



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MOFs.17-19 However, a limited number of studies have used MOFs as the electrode material of an electrochemical system, due to the non-conductive nature of MOFs.20-22 Conductivity of MOFs can be improved through carbonization.23-25 However, this method requires temperatures over 800 ℃, resulting in a high cost and an extremely low level of wettability.26, 27 MOFs have also been used as a precursor and sacrificial template for the preparation of metallic oxides/hydroxides/sulfides.28-30 These proceedures involve prolonged, multi-step processes that require a great amount of energy.31 Therefore, it is a tough challenge to fabricate a highly efficient energy storage device based on pure MOFs to reduce costs. To overcome the conductivity problem of pure MOFs, X-MOFs (X= Fe, Ni or Co) can be used.32-34 X-MOFs have conjugate π bonds, low steric hindrance and excellent electrolyte penetrability, to permit fast transfer of electrons and electrolyte diffusion in electrochemical reactions. For instance, a Co-MOF with 206.76 F g-1 specific capacitance at a rate of 0.6 A g-1 and a Ni-MOF with enhanced supercapacitive performance (55.8 Wh/kg and 7000 W/kg) have been reported.35,

36

However, the importance of cobalt-based

compounds has become more evident in SCs than other metals in recent years, and many researchers have done a lot of efforts in recent years to improve the performance of cobalt-based SCs.37-40 As mentioned, this study aims to apply a MOF to both energy storage and desulfurization catalysis. In general, elimination of refractory sulfur species from diesel fuels is possible using conventional hydrodesulfurization (HDS) and oxidative desulfurization (ODS).41, 42 HDS is not appropriate for deep desulfurization of fuels since its operating conditions are harsh and it wastes a great deal of energy.43, 44 Also, it cannot efficiently remove aromatic sulfur compounds, such as dibenzothiophene (DBT) due to steric hindrance, which inhibits the interaction between sulfur atoms and catalysts.45, 46 On the other hand, ODS is suitable and highly efficient for deep desulfurization at mild temperatures and pressures, lowers operational costs and excludes the need for the use of costly hydrogen.47 However, appropriate catalysts should be used to promote the activity and efficiency of ODS processes. The ODS catalysts can be porous materials with high surface areas, such as MOFs.48 To date, a few reports are available on using MOFs for ODS catalysis.49-54 For example, we reported a Co-MOF that can act as a remarkable heterogeneous


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catalyst for improving ODS.55 However, it is still a challenge to develop effective heterogeneous catalysts, giving high yields at low temperatures, for catalysis of the ODS reaction. To confront this challenge and take a step forward for a cleaner environment, herein we introduce a dual-purpose pillar-layered Co-MOF, which can demonstrate high activity and stability for applications in both ODS and electrochemical energy storage. The results confirm that the MOF is highly efficient for elimination of DBT from a model oil (a biphasic organic system) using H2O2 as an oxidant and without adding any surfactant, in addition to acting as an efficient SC without performing any pyrolysis process. To the best of our knowledge, no study has reported synthesis of any pillar-layered MOF for lowtemperature oxidation of DBT and fabrication of a non-calcined SC electrode.

2. EXPERIMENTAL SECTION The reaction of Co(NO3)2.6H2O with 4-bpdb and 2-ATA in DMF at 115 ℃ gave the orange blockshaped crystals of NH2-TMU-53 (TMU stands for Tarbiat Modares University). The optical microscopy image of the obtained crystals is shown in Figure S1 of the Supporting Information (SI). The crystals are monoclinic and belong to the C2/c space group with lattice parameters: a = 15.6250(4) Å, b = 16.6264(3) Å, c = 18.7807(4) Å and β = 104.289(2) (see CCDC No. 1825324 for detailed conditions) (Tables S1 to S3, Figures 1 to 3, and Figures S2 to S7). The asymmetric unit of NH2-TMU-53, along with its labelling scheme, is shown in Figure S2 and a thermal ellipsoid plot is illustrated in Figure S3. Both of these diagrams show that the asymmetric unit consists of a Cobalt atom, one 4-bpdb linker and one 2-ATA unit, disordered over two different orientations resulting in the amino substituent being disordered over C6 and C7 (equaling one full amine group per 2-ATA unit). Figure 1 shows that the Cobalt atoms adopt a pseudo-octahedral environment surrounded by 2 trans nitrogen donors from the 4-bpdb linkers, which run down the b axis, and 4 planar carboxylate oxygens from 3 different 2-ATA units, which all lie in the bc plane. Pairs of Cobalt centers are linked together by two 2-ATA units to form 8-membered rings.



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Figure 1. A schematic of NH2-TMU-53 showing the Co environments including the 8-membered ring holding pairs of Co centers together. All H atoms and the disordered components are omitted for clarity. The amino groups of the 2-ATA units are modelled as disordered over two sites with occupancies equaling 1 per unit.

Figure 2. (a) Polyhedral representation of the three-dimensional NH2-TMU-53 structure along the z-axis, (b) perspective view of the NH2-TMU-53 structure along the x-axis, and (c) space-filling view of NH2TMU-53 along the z-axis. All disordered guest molecules and hydrogen atoms are omitted for clarity.


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The concept of analyzing MOF structures by their topology requires the breaking down of the structure into secondary building units (SBUs), Figure 3(c) shows the inorganic SBUs as pink polyhedra, being linked together by the organic SBUs. The structural ‘net’ can then be simplified by taking the center of each of these SBUs in turn and reducing that unit to said central point, whilst maintaining the overall connectivity of the structure (Figure 3(b)). This process revealed that the NH2-TMU-53 structure is interpenetrated (Figure 3(a)). The extended structure forms a 3D interpenetrated array with square like channels (Figure 3a). The cross-section of these channels is 6.8 × 5.7 Å (including the van der Waals radii), which allows NH2-TMU-53 to be considered as a microporous material. This feature is advantageous since hierarchically porous structures facilitate accessibility of the active catalyst sites and diffusion of the reactants and products.56-58 Elemental microanalysis and single-crystal XRD analysis determined that NH2-TMU-53 has the formula of [Co(2-ATA)2(4-bpdb)4]n.



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Figure 3. Topological representation of the 2-fold interpenetrating network of NH2-TMU-53 (a), the simplified net of NH2-TMU-53 as viewed down the b axis, showing the topology of the structure and the relationship of the different SBUs to one another. The inorganic Cobalt centered units are shown in purple, the 2-ATA units shown in red and the 4-bpdb linkers (parallel to the b axis) shown in blue (b), and 3D extended structure of NH2-TMU-53 along the z-axis showing polyhedrons of Co/O/N inorganic clusters (c).


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3. RESULTS AND DISCUSSION Powder X-ray diffraction (PXRD) spectroscopy was employed to identify any phase impurities. The simulated and recorded PXRD patterns of NH2-TMU-53 before and after activation are displayed in Figure S8 and confirm that no impurities are present. Figure S9 shows the FT-IR spectra of NH2-TMU53, Figure S10 presents the corresponding thermal gravimetric analysis (TGA) curves and Figure S11 shows the related N2 adsorption-desorption isotherms. According to the TGA results, NH2-TMU-53 is stable up to 360 ℃ and no impurity is bound to its micropores. Similarly, the PXRD patterns of the NH2TMU-53 samples activated at various temperatures (Figure S12) verify structural integrity of this material at 350 ℃. Also, the PXRD patterns of Figure S13 illustrate that immersing NH2-TMU-53 in the acetonitrile, absolute ethanol and n-hexane chemical solvents for two days does not alter its crystallinity. Since sulfur removal can be an outcome of adsorption or ODS, the involved mechanism needed to be distinguished. In this respect, first, the adsorption efficiency of NH2-TMU-53 was evaluated by varying the temperature, adsorbent dose and reaction time. The obtained results are reported in Table S4. Using the optimum adsorbent amount of 100 mg and the optimal temperature of 50 ℃, the sulfur level declined from 500 to 317 ppm within 60 min. FT-IR spectroscopy on the utilized adsorbent particles (Figure S14) confirmed the presence of adsorbed DBT molecules. The adsorption reaction should be due to the existing functional groups, π-complexation and the π-π interactions between the aromatic ring of DBT and the organic linkers of NH2-TMU-53. Similar results have been observed by other researchers.59-61 In the second step, the catalytic performance of NH2-TMU-53 in ODS of DBT was explored by optimizing the reaction time, catalyst dose, O/S molar ratio and temperature. The adopted reactor was a biphasic system containing the acetonitrile extraction solvent and the H2O2 oxidant. H2O2 was selected as the oxidant since it just generates water as a by-product, thus acting as an ecofriendly reagent.62 As Table S5 indicates, the oxidant improves sulfur removal significantly and the prepared MOF catalyzes the ODS process effectively. Since promoting ODS catalysis of compounds containing a low O/S molar ratio is challenging and most catalytic systems require high O/S molar ratios, the O/S ratio of 3 was chosen in



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this study. As no DBT conversion was observed in the absence of H2O2 (except through adsorption) the desulfurization process should involve both adsorption and catalytic oxidation. In addition, as Table S5 declares, the concentration of sulfur does not change in the absence of NH2-TMU-53 (blank) and the presence of H2O2. This means that H2O2 has a key role in the catalytic reaction. Also, Table S6 shows that increasing the catalyst dose up to 200 mg improves the ODS process by providing a greater number of active sites and remains almost constant by adding more catalyst due to the decreased surface density of adsorbed H2O2 molecules.63 Accordingly, 150 mg NH2-TMU-53 was selected as the optimal catalyst dose. Table 1 outlines the effect of reaction time on the process. Based on this table, extending the reaction increases oxidation of DBT and 34.5% of DBT converts to DBTO2 within 120 min. Sulfur removal is also affected by the reaction temperature (Table 1) and improves with the increase of temperature up to 60 ℃. After this temperature, the efficiency of the catalytic reaction declines slowly due to the fast decomposition of H2O2.64, 65 Consequently, 60 ℃ was considered as the optimal temperature. It should be noted that even at room temperature, 18.9% ODS yield was obtained within 120 min, which is a great advantage for industrialization of the catalytic process. The importance of this finding is illustrated well by comparing the activity of NH2-TMU-53 with that of the commercial P25 catalyst (Degussa P25, which consists of mixed phases between anatase and rutile), which is not able to oxidize DBT at room temperature. Table 1. Effect of time and reaction temperature on the ODS processa Entry

Time (min)

1 2 3 4 5 6 7 8 9c 10d

30 60 120 240 120 120 120 120 120 120

aReaction bSulfur

Temperature (℃) 50 50 50 50 30 40 60 70 60 60

Sulfur remained (ppm)

Sulfur adsorption (%)

316 157 104 96 273 181 103 240 407 175

36.8 (15.7b) 68.6 (31.5b) 79.2 (34.5b) 80.8 (34.75b) 45.4 (18.9b) 63.8 (26.7b) 79.4 (34.8b) 52 (21.3b) 21.7 (14.6b) 65.4 (28.3b)

conditions: 150 mg catalyst, DBT model oil (500 ppm of S), n(H2O2)/n(S) molar ratio = 3,

removal after adsorption, c[Co(TA)2(4-bpdb)4]n (TMU-53) as catalyst, and d[Zn(2-ATA)(4-

bpdb)].2DMF (NH2-TMU-17) as catalyst. 10 ACS Paragon Plus Environment

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Moreover, terephthalic acid (TA) was used as substitute of 2-ATA and the amine free isoreticular framework was constructed [Co(TA)2(4-bpdb)4]n (TMU-53), in order to investigate the effects of the amine group on the catalytic activity (Scheme 1). As shown in Table 1, significant change has been observed by changing the ligand from 2-ATA to TA, and the DBT absorption by the catalyst has decreased, which reduces the catalytic process. As it is known, the DBT absorption was equal to 7.1% when the TMU-53 catalyst was used in the ODS process, while the absorption was 44.6% when the NH2TMU-53 catalyst was used, that these two difference is obvious. Therefore, the amino group plays a very important role in absorption of the pollutant through the hydrogen bond between the DBT sulfur atom and the hydrogen atom in the amine group. When the XRD pattern for TMU-53 was recorded, the results are with the NH2-TMU-53, as shown in Figure S15. Also, zinc metal was used instead of cobalt (with completely identical ligands) to investigate the role of metal in the ODS process. This a sample previously examined by our group in a variety of applications.66 The substance of NH2-TMU-17 was studied in the ODS process and the result showed that the metal did not have a large impact like that of the ligand. As shown in Table 1, the concentration of Sulfur remained increased from 103 to 175 ppm, by changing the metal from cobalt to zinc. Therefore, the 2-ATA ligand has a greater effect than the metal.

Scheme 1. Schematic view of comparative synthesis for NH2-TMU-53 and TMU-53.



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Figure S16 shows the FT-IR spectra of NH2-TMU-53 before and after the catalytic reaction. As it can be seen, almost all vibrational bands of the two spectra are identical. However, the spectrum recorded after the reaction contains two additional peaks at 1158 and 1285 cm-1 that are related to the O=S=O double bond in the DBTO2 product. Consequently, the only oxidation product of the NH2-TMU-53catalyzed process is dibenzothiophene sulfone (DBTO2), which is produced in the oil phase and migrates into the acetonitrile phase quickly, as it is highly polar. Another important point about NH2-TMU-53 is that it presents a higher extent of sulfur removal relative to other pure MOFs since it carries NH2 on its framework. These amine groups enable the adsorption of more DBT molecules. On the other hand, πcomplexation, open metal sites, acid-base interactions and pore functionality are vital for efficient adsorption of N- and S-containing organic compounds by MOFs.55 It is the difficulty of DBT diffusion through the pores of NH2-TMU-53 which lowers its catalytic activity compared with other ODS catalysts. The time profiles of the catalysis process of DBT removal was fitted into several kinetics models to investigate kinetics of the reaction. The results are reported in Table S8, in which R0, R1 and R2 refer to the correlation coefficients of the zero-, first- and second-order models, respectively. Among these coefficients, R1 shows the best correlation. Therefore, the studied catalytic reaction can be best described as a first-order reaction. The catalytic data were also used to estimate the kinetics parameters. According to the kinetics results, therate constant of catalytic DBT removal (k) is 0.0106/min and the half-life of DBT in the catalytic system, at which [A] = [A]0/2, is also calculated by equation t1/2 = 0.693/k, (t1/2= 0.693/k) as 65.38 min, at 60 ℃. In addition, application of the Arrhenius equation at 40 ℃ (k = 0.0074) and 60 ℃ (Eqs. 1 and 2) revealed that the corresponding activation energy (Ea) is 15.57 kJ mol-1. This value is close to the activation energy of other catalytic systems and lower than the common activation energy of hydrodesulfurization, i.e. 100 to 200 kJ mol-1.67 With respect to the hydrogenation option, catalytic ODS demonstrates a higher activity. In Eqs. 1 and 2, A is the pre-exponential or frequency factor, R stands for the universal gas constant, the temperature (T) is in Kelvin, and the 1 and 2 subscripts represent the temperatures 40 and 60 ℃, respectively.


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𝑘 = 𝐴𝑒 ― 𝐸𝑎/𝑅𝑇 log

( )=―

(1)

𝑘1

𝐸𝑎

𝑘2

2.303𝑅

(2)

((𝑇2 ― 𝑇1)/𝑇1𝑇2)

Durability of NH2-TMU-53 was estimated by applying it to the catalytic ODS reaction of DBT under the optimal conditions and recycling the utilized crystals in several consecutive runs. The results are displayed in Figure S17a. As this figure shows, the activity of the recycled crystals decreases slightly within the first five cycles while no activity loss can be detected in the next runs. Performing PXRD (Figure S17b) and FT-IR spectroscopy (Figure S17c) on the recovered NH2-TMU-53 crystals revealed intactness of the catalyst structure during the catalytic runs due to the mild reaction conditions. Consequently, in addition to being low-cost and highly efficient, NH2-TMU-53 is reusable and can be considered for industrial applications. Also, to confirm the stability of the synthesized composition, a series of leaching experiments was performed to determine whether a portion of the ligand or metal was removed during the catalytic process. Leaching test was performed for ligand and metal, respectively, by using 1H NMR and ICP analysis. As shown in Figure S18 and Figure 4, the catalyst 1H NMR spectra before and after the ODS process has same peak intensity and same locations, which indicate that the framework ligands have not been decayed and destroyed, the catalytic process has progressed by keeping the ligands. Also, it can be investigate the leaching test for probably lost metal, by using ICP analysis during the catalytic process. By using ICP analysis the leaching test was done for the cobalt ions. It was specified that most of the cobalt metal center does not leach to the reaction mixture (more than 97%) and a few cobalt atoms frameworks pass into the reaction solution (less than 3%). It is proved that the base catalyst was stable in the n-hexane solvent during the reaction.



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Figure 4. 1H NMR spectra of NH2-TMU-53 after ODS process.

To gain more insight about the catalytic mechanism, excess isopropanol, or KI and 4-hydroxy-2,2,6,6tetramethylpiperidinyloxy (4-HTMP), or p-benzoquinone were added to the reactor to scavenge •OH and •O -, 2

respectively.68, 69 The applied scavenger to H2O2 molar ratios were 2, 4 and 6. Based on Figure 5,

addition of these scavengers does not alter progress of the reaction. Therefore, either it is unlikely that •OH

and •O2- are generated during the reaction, or they do not play any significant role in the mechanism.

Consequently, DBT oxidation should be a result of direct catalysis by NH2-TMU-53 and DBT sulfone formation rather than indirect oxidation and generation of oxidizing agents.


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Figure 5. Effects of various active scavengers with different concentrations on sulfur removal in the ODS process catalyzed by NH2-TMU-53 after 120 min.

According to the findings of former studies, the general oxidant-based ODS reaction of DBT should involve two steps.70, 71 In the first step, DBT oxidizes to dibenzothophene sulfoxide (DBTO) and, in the second step, the produced DBTO molecules rapidly convert into DBTO2. To investigate the mechanism of DBT desulfurization by NH2-TMU-53 and H2O2 in the established organic biphasic system, the concentrations of DBT, DBTO and DBTO2 in both the acetonitrile and n-hexane phases were monitored as a function of time. According to Figure 6a (and Figure S19a), the peak area of DBT in the n-hexane phase gradually reduces as the reaction proceeds and it becomes negligible after 120 min reaction. In this phase, also a small amount of DBTO2 is detected at 120 min since the DBTO2 molecules can easily and quickly migrate to the acetonitrile phase. On the other hand, Figure 6b (and Figure S19b) shows that DBT is present in the acetonitrile phase just at the beginning of the process since the DBT molecules extracted from the n-hexane phase rapidly convert to DBTO2.



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Figure 6. The HPLC chromatograms of the n-hexane (a) and acetonitrile (b) phases. Reaction conditions: 150 mg catalyst, DBT model oil (500 ppm S), n(H2O2)/n(S) molar ratio = 3, t = 120 min, T = 50 ℃.

GC-MS conducted on the reactor contents after a 120 min reaction identified DBT and DBTO2 at the m/z values of 184.0 and 216.3, respectively. As Figure 7 shows, DBTO2 is much more abundant than DBT after the 120 min reaction. The mechanistic results imply that the process begins by adsorption of the sulfone onto the surface of NH2-TMU-53, which is driven by the polarity of the azo and NH2 groups of the catalyst. Then, most of the adsorbed DBT molecules are oxidised to DBTO2, the only oxidation product, by the NH2-TMU-53 catalyst and the H2O2 oxidant. The catalytic role of NH2-TMU-53 could be expected since cobalt oxide and cobalt(II) salts have been reported to catalyze oxidative desulfurization reactions.72, 73 It should be noted that further investigations are required to evaluate the effect of the polar groups of the MOF on its performance in oxidant-assisted catalysis of ODS processes.


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Figure 7. Mass spectrum of the acetonitrile-phase reaction products of the ODS process catalyzed by NH2-TMU-53 after 120 min.

In addition to ODS catalysis, NH2-TMU-53 was used to fabricate a SC. A standard 3-electrode cell was employed to evaluate the electrochemical properties of NH2-TMU-53. Figure 8a exhibits the cyclic voltammograms (CVs) of the fabricated NH2-TMU-53 electrode recorded in the 6M KOH electrolyte at 50 mV s−1 scan rate. In this Figure, a pair of redox peaks can be observed, which is indicative of a pseudocapacitive activity that roots in the surface Faradic redox reactions. The cathodic and anodic peaks can be attributed to the interconversion between the Co oxidation states (Eqs. 3 and 4): Co(II)s + OH- ↔ Co(II)(OH)ad + e-

(3)

Co(II)(OH)ad ↔ Co(III)(OH)ad + e-

(4)

Figure 8b illustrates the CVs of the NH2-TMU-53 electrode at different scan rates and shows that the corresponding area and potential difference between the cathodic and anodic peaks both increase with scanning rate. The increase of the potential difference is due to the fact that the electrolyte ions get completely consumed by both outer and inner active sites at low scan rates whilst they are just consumed by the outer active sites at high scan rates. In addition to cyclic voltammetry, the electrochemical performance of NH2-TMU-53 was investigated using galvanostatic charge-discharge (GCD) 17 ACS Paragon Plus Environment


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measurements at the 5, 6, 8 and 10 A g-1 current densities (Figure 8c). Application of the following equation determined that the specific capacitance of the electrode (Csp) equals to 325, 300, 290 and 242.5 F g-1 at the 5, 6, 8 and 10 A g-1 current densities (Eq. 5), respectively (Figure 8d). C𝑠𝑝 =

𝐼 × ∆𝑡 𝑚 × ∆𝑉

(5)

Here, I (A) represents the discharge current, Δt (s) is discharge duration, ΔV (V) is the potential difference observed during the discharge process and m (g) is NH2-TMU-53 mass on the electrode. As the obtained values and Figure 8c and 8d suggest, Csp reduces with the increase of current density. The reason is that ion transfer requires a longer time and, therefore, additional charges can be stored at low current densities while the time is not sufficient for ionic transfer at higher current densities and, consequently, the specific capacitance reduces. For this electrode material, when the current density increases from 3 to 10 A g-1, the rate of the capacity retention for the NH2-TMU-53 is about 63.5% that it demonstrates good rate of capability.


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Figure 8. (a) CV curve of the NH2-TMU-53 and Ni foam at 50 mV s-1 scan rate, (b) CV curves of the NH2-TMU-53 at different scan rates, (c) GCD curves of the the NH2-TMU-53 at different current densities and (d) dependence of specific capacitance on current density.

As an electrode material, NH2-TMU-53 should exhibit cyclic stability. In this respect, 6000 continuous GCD cycles were carried out. As it can be seen in Figure 9a, 92.03% of the electrode’s specific capacitance is retained at the 6000th cycle and 5 A g-1 current density in the 6M KOH electrolyte. Therefore, the electrochemical stability of NH2-TMU-53 is noticeable. The inset of this Figure demonstrates the first 4 cycles. The time ratio of the charging and discharging processes is known as coulombic efficiency (η), in which the two processes of the current densities are equal. η can be estimated through the following equation: 𝜂=

𝑡𝐷 𝑡𝐶

× 100%

(6)



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where 𝑡𝐶 (s) and 𝑡𝐷 (s) are the duration of the charging and discharging processes, respectively. Figure 9a shows the charge and discharge cycles of the NH2-TMU-53, that the coulombic efficiency is approximately 98.5%. We conducted experiment analyses such as XRD patterns to the stability of the NH2-TMU-53 during cycling, in order to investigate the NH2-TMU-53 following the cycling measurements (Figure S20). After 6000 cycles, the key diffraction peaks of NH2-TMU-53 were reserved well, however, the crystallinity of the material is damaged that is shown in Figure S20. This figure indicates that during cycling the NH2TMU-53 structure is still preserved. Therefore, based on the XRD results, it can be concluded that during cycling the crystalline structure of NH2-TMU-53 was not altered. Electrochemical impedance spectroscopy (EIS) was conducted to measure the conductivity and charge transport properties of NH2-TMU-53 at the electrolyte/electrode interface over the frequency range of 0.1 Hz to 100 kHz. Figure 9b shows the associated Nyquist plot. From the Nyquist plot, charge transfer resistance (Rct) can be calculated as the diameter of the small semicircle that covers the high- to midfrequency zones. Equivalent series resistance (Rs) denoting the resistance of electrolyte. Also, the constant phase element (CPEQ) and the Warburg element, which is frequency dependent and refers to the diffusion of ions through the electrode (Zw) in the intermediate frequency region, can be estimated to model the double-layer capacitance. In this Figure, the diameter of the semicircle is relatively short, which indicates a low resistance against charge transfer and fast ion diffusion due to the high capacitance. Furthermore, the linear correlation observed in the low frequency region represents a considerable capacitive activity. Figure 9b inset show the measured impedance spectrum for corresponding equivalent circuit.


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Figure 9. (a) Cycling performance and coulombic efficiency of the NH2-TMU-53 electrode at 5 Ag-1 current density within 6000 cycles (inset shows first 4 cycles), and (b) Nyquist plot of the NH2-TMU-53 (inset shows the equivalent circuit used to simulate the Nyquist plot).

To evaluate the effect of the cation and concentration of the electrolyte on the charge-discharge events, CV and GCD measurements were carried on NH2-TMU-53 using NaOH and KOH solutions, which are both common alkaline electrolytes. Firstly, we investigated the influence of different concentrations of KOH. Figure 10a presents the CV results obtained in the 2, 4 and 6 M KOH solutions at 50 mV s-1. According to this Figure, the redox peak shifts to lower potentials with the increase of KOH concentration. This means that the charge/discharge potential of NH2-TMU-53 is higher at higher KOH concentrations. Figure 10b show the GCD curves of electrode at different concentrations of KOH. The GCD curves show that higher KOH concentrations provide improved capacitive behavior. Except in the curve of GCD, different concentration of KOH solutions cause the differences in GCD time of the electrode. Higher concentration of KOH cause the longer GCD time. This indicates that high alkaline concentration increase the specific capacity. So that, the 2, 4 and 6 M KOH electrolytes result in 168.7, 237.5 and 325 F g-1 specific capacitance at 5 A g-1, respectively (Figure 10c).



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Figure 10. (a) CV curves, (b) GCD curves, and (c) the specific capacitance of the NH2-TMU-53 in 2, 4 and 6 M KOH electrolytes.

To compare the NaOH and KOH electrolytes, their 2M solutions were considered. As the results suggested, the KOH electrolyte can promote redox kinetics of the electrode by declining both electronic and ionic charge-transfer resistances more noticeably than NaOH due to the higher ionic conductivity of KOH. In addition, based on Figure 11a and 11b, the KOH electrolyte presents CV enclosing a larger area and a longer discharge time. Therefore, KOH rather than NaOH can improve the capacitive activity of NH2-TMU-53. So that, the 2M KOH and 2M NaOH electrolytes result in 168.7 and 106.5 F g-1 specific capacitance at 5 A g-1, respectively (Figure 11c).


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Figure 11. (a) CV curves, (b) GCD curves, and (c) the specific capacitance of the NH2-TMU-53 in 2M KOH and 2M NaOH electrolytes.

Figure 12a show the assembly of the NH2-TMU-53 and the activated carbon (AC) into an asymmetric supercapacitor (ASC), which was assigned as NH2-TMU-53//AC ASC. This respect to revel the further potential application of electrode material of NH2-TMU-53. Figure 12b show the CV curves of threeelectrode system, which display the stable voltage window of NH2-TMU-53 from 0 to 0.4 V and AC electrodes −1.2 to 0 V. Here, for the fabricated ASC, the electrochemical active area was estimated to be 1 × 1 cm2. The mass ratio between two positive and negative electrode was balanced to obtaining the superior electrochemical performance of ASC: 74 𝑚+ 𝑚―

=

― 𝐶𝑎𝑐 × ∆𝑉 ―

(7)

𝑄+



Page 24 of 42

where, Q+ reveal the specific capacitance of the positive electrode, m+ and m− are the masses, ΔV− is the working voltage and Cac− is specific capacitance of the negative electrode. Optimal mass ratio of positive/negative electrode is about 0.47. As shown in Figure 13a and 13b, the device fabrication under various potential windows was confirmed through CV and GCD analyses. As expected, from the CV and GCD curves can be seen the stable electrochemical potential window ( up to 1.6 V), which are conducted at current density of 3 A g-1 and a constant scan rate of 50 mV s-1. Figure 13c exhibit different scan rates of the CV curves of NH2-TMU-53//AC ASC in a working voltage window of 0–1.6 V and there is no observation of increasing in scan rates with apparent distortions of the CV curves, which it is suggested that an excellent capacitive behavior is possessed by the as-assembled ASC device.75 Figure 13d show the GCD curves at different current densities (3−10 Ag−1). The specific capacitance of the ASC was calculated based on the total mass of both positive and negative electrodes. The results reveal a good performance (63.45%) in the way that the specific capacitance values are 39.1, 37.08, 28.10, 26.20, and 24.5 F g−1 at current densities of, 3, 4, 5, 7, and 10 A g−1, respectively (eq. 8).

Figure 12. (a) Schematic illustration of the assembled NH2-TMU-53//AC ASC, and (b) CV curves of the NH2-TMU-53 and AC electrodes at a scan rate of 20 mV s-1 in a three-electrode system.


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Figure 13. (a) CV curves of the NH2-TMU-53//AC ASC at different potential windows at 20 mV s-1, (b) GCD curves of the ASC at different potential windows at a fixed current density of 3 A g ―1, (c) CV curves of the ASC at different scan rates, and (d) GCD curves of the ASC at different current densities.

A pivotal factor of the long-term electrochemical stability is assessed by GCD measurements for the determination of practicability at a fixed current density. Figure 14a display a capacitance retention of nearly 90.7% after 6000 cycles for the Co-NH2-TMU-53//AC device. This devise show favorably reversible charge storage and delivery process which is due to coulombic efficiency for them that retains nearly 98% after 6000 cycles. Values of energy and power density are significant factors to evaluate the practical applications of SC devices. The estimated values of energy and power density in which based on the working area of device were calculated using eqs 9 and 10 and are displayed in the Ragone plot (Figure 14b).



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Figure 14. (a) Long-term cycling stability and coulombic efficiency of the NH2-TMU-53//AC ASC at a current density of 5 A g ―1 within 6000 cycles (inset shows first 4 cycles), and (b) Ragone plot of the ASC compared with other reported data.

𝐶𝑠 =

2𝑖𝑚 ∫𝑣𝑑𝑡

𝐸=

𝑃𝑑 =

(8)

𝑉2 𝑖𝑚 ∫𝑣𝑑𝑡

(9)

3.6

𝐸 × 3600 ∆𝑡

(10)

where 𝑃𝑑 (kW kg-1), 𝐸 (Wh kg-1), im = i/m (A g−1) are the power density, energy density and current density, respectively. I and m are the current and mass of the active material. ∫𝑣𝑑𝑡, V (V) and Cs (F g-1) are the intergral area of the discharge curve, potential and the specific capacitance, repectively.76 The maximum energy density of 50.30 Wh kg-1 at a power density of 2.31 kWkg-1 delivered for the NH2-TMU-53//AC ASC and even remaining at a power density of 8 kW kg-1 at 32 Wh kg-1, which originates from the excellent power support of AC electrode and the remarkable specific capacitance contribution of NH2-TMU-53. Moreover, as shown in Figure 14b the obtained results confirm the values of energy and power density recently reported for the asymmetric supercapacitors and it can be said these finding are even better

77-82.

To demonstrate the real application of our device, two examples are

presented in Figure 15. As shown, two devices with series connection can robustly drive a mini-rotating motor (3 V, 0.4 W), and also light up a red LED for more than 23 minutes. 26 ACS Paragon Plus Environment

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Figure 15. Two devices in series which can light up a red LED (a) and drive a mini rotating motor (b).

Using the cyclic voltammetric results and the charge-discharge tests, the charge storage mechanism for the electrode material reported is determined in this work. In cyclic voltammetric curves for battery electrode materials, the potential difference between the anode and the cathode peak is determined in the range of 0.1 to 0.2 volts. But this value is lower for pseudo-electrodes materials. Also, for battery electrode materials, charging-discharging curves show two-phase. According to reports in the literature and based on the explanations, the reported electrode material is kind of battery-like material. 83-85 MOFs have been mainly applied in fabrication of SC electrodes as composite, precursor or template materials for the synthesis of carbonaceous materials or different metal oxides. However, to reduce costs and save time and energy, NH2-TMU-53 is directly used as an electrode material in this work. Table 2 compares the electrochemical performance of NH2-TMU-53 with that of other MOFs that have been used as electrode materials and demonstrates that NH2-TMU-53 outperforms the other MOFs.



Page 28 of 42

Table 2. The performance comparative data of this work with previously reported studies. Electrode materials Nanoporous carbon derived from ZIF-67 86 ZIF-8 precursor 87 Ni-MOF 36 ZIF-8 derived carbons 88 HKUST-1/CNT derived carbon 89 Ni-MOF 90 Cu-MOF derived carbons 15 Zn-MOF precursor 91 PPF-3 MOF 92 Co-MOF (NH2-TMU-53)

Specific capacitance 272 F g-1 245 F g-1 123 mAh g-1 239 F g-1 194.8 F g-1 320 F g-1 149 F g-1 182.8 F g-1 360.1 F g-1 325 F g-1

Measurement condition 5 mV s-1 1 A g-1 1 A g-1 2 A g-1 2 A g-1 1 mA cm2 0.5 A g-1 1 A g-1 1.5 A g-1 5 A g-1

Electrolyte 6M KOH 6M KOH 3M KOH 0.5 M H2SO4 6M KOH 1M KOH 6M KOH 3M KOH 2M KOH 6M KOH

Cyclic stability

88.6% after 3000 cycle (10 Ag-1) 95% after 10000 cycle (10 Ag-1) 80% after 1000 cycle 86.8% after 2000 cycle (1 Ag-1) 98.5% after 1000 cycle (10 Ag-1) 90% after 2000 cycle (12 Ag-1) 92.03% after 6000 cycle (5 Ag-1) This work

4. CONCLUSION The crystals of [Co(2-ATA)2(4-bpdb)4]n (NH2-TMU-53) were adopted as a SC material with noticeable charge storage capacity (specific capacitance: 325 F g-1 at 5 A g-1 current density) and considerable cyclic stability with 92.03% capacitance retention after 6000 cycles. An ASC device employing NH2-TMU-53 and AC as the positive and negative electrode respectively, in which achieves a high energy density (50.30 Wh kg-1) and high power density (2.31 kWkg−1). Further, two devices connected in series light up a red LED during 23 min and drive a mini-rotating motor. These values are outstanding compared with other MOFs that have been used without pyrolysis. NH2-TMU-53 also outperformed all previously investigated MOFs with regards to specific capacitance and current density. The proposed MOF demonstrated a high efficiency for surfactant-free oxidative desulfurization of DBT in the studied biphasic organic system. Application of 150 mg catalyst, with the ratio n(H2O2)/n(S) = 3, a reaction temperature of 60 ℃ and 120 min processing, are found to be the optimum reaction conditions, leading to the sulfur content being reduced from 500 to 103 ppm. The activation energy of the associated reaction was found to be 15.57 kJ mol-1. This oxidative reaction produced DBTO2 with almost 100% selectivity. This product was so polar that all the oxidized DBT molecules moved from the oil phase to the acetonitrile phase very quickly. The reaction in the presence of NH2-TMU-53 is


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faster because of basic –NH2 group in its structure. Furthermore, performance of the catalyst decreased insignificantly after five consecutive recycles. Consequently, industrial sectors can consider NH2-TMU-53 as an effective, low-cost, reusable and ecofriendly electroactive catalyst that requires no calcination or surfactant to exhibit high catalytic activity at affordable operating conditions.

■ ASSOCIATED CONTENT Supporting Information Light microscope image, FT-IR spectra, XRD patterns, thermogravimetric profiles, N2 isotherm at 77 K, Crystal data, kinetics parameters, HPLC chromatograms, and details of optimal conditions are provided in the Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org. Accession Codes The crystallographic data was deposited with the Cambridge Crystallographic Data Centre (CCDC) as entries CCDC 1825324.

■ AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Tel: (+98) 21-82884416. Notes The authors declare no competing financial interest. E-mail: [email protected].

■ ACKNOWLEDGMENTS



Page 30 of 42

This work was supported by the Tarbiat Modares University. The authors are grateful for the financial support.

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