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Chemical Engineering Journal 251 (2014) 35–42

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Adsorptive denitrogenation of model fuel with CuCl-loaded
metal–organic frameworks (MOFs)
Imteaz Ahmed, Sung Hwa Jhung ⇑
Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701, Republic of Korea

h i g h l i g h t s

g r a p h i c a l a b s t r a c t 

Cu(I) was introduced on a metal–

organic framework at ambient
Introduced Cu(I) improved the
performances of adsorptive
Supported Cu(I) increased adsorption
capacity even though decreased
Supported Cu(II) decreased both
porosity and adsorption capacity.

a r t i c l e

i n f o

Article history:
Received 7 March 2014
Received in revised form 8 April 2014
Accepted 10 April 2014
Available online 24 April 2014
Adsorptive denitrogenation
Cuprous ion
Metal–organic framework

a b s t r a c t
CuCl impregnated MIL-100(Cr) was prepared with a facile method and then utilized for the adsorptive
denitrogenation of model fossil fuels. CuCl was produced from CuCl2 solution at ambient temperature
and pressure by reduction of CuCl2 using sodium sulfite as a mild reducing agent. Although the porosity of the adsorbent was reduced after impregnation, the adsorption of nitrogen-containing compounds (NCCs) increased. However, the adsorption of NCCs over CuCl2/MIL-100(Cr), which was
produced in a similar manner but in the absence of Na2SO3, was decreased as a result of the reduced
porosity. The maximum adsorption capacities of CuCl/MIL-100(Cr) as compared to pristine MIL100(Cr) for quinoline (QUI) and indole (IND) were improved by 9% and 15%, respectively, which
may be attributed to the p-complexation effect of the Cu+ sites of CuCl.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction
With the continuous increase in the worldwide population and
consumption of energy, the optimized utilization of energy and
stable environmental parameters are the primary concerns of the
human race in this century. Because of the scarcity of regular
sources, new and unusual sources of fossil fuels need to be
exploited in the upcoming decades for the high amount of energy
required by society. Therefore, fossil fuels containing high amounts
of contaminants, particularly sulfur- and nitrogen-containing
compounds (SCCs and NCCs), need to be utilized [1–4]. Acid rain
⇑ Corresponding author. Fax: +82 53 950 6330.
E-mail address: (S.H. Jhung).
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.

produced from SCCs and NCCs is also a serious environmental
concern and many governments across the globe are becoming
stricter regarding the emission of these compounds. Therefore,
the removal of SCCs and NCCs from fossil fuel is an important topic
of research within the scientific community.
The removal of SCCs from fossil fuel has been extensively
studied over the past several decades and these compounds are
typically removed by the hydrodesulfurization (HDS) process.
NCCs [5,6] are one of the contaminants that should be removed
before the removal of SCCs because NCCs have an adverse effect
on both catalysts and conventional HDS processes [5–7]. NCCs
are typically removed by hydrodenitrogenation (HDN) in the
presence of expensive hydrogen at high temperatures and pressures; thus, HDN is an energy-intensive and costly process.

5. However. As the field of materials chemistry continues to grow. 1.18] including Ti-HMSs [19]. Ahmed. because of their low thermal and chemical stability [64]. catalysis. Characterization The X-ray powder diffraction patterns were obtained using a diffractometer D2 Phaser (Bruker.0 mL) of a 0. HDN. p-complexation adsorbents have typically been prepared through the high temperature calcination of metal-ion-exchanged materials which requires excessive energy and subsequently causes the process to be quite expensive [59].2 M CuCl2 aqueous solution and stirred magnetically for 30 min at room temperature.14].5. the MOF was filtered. polymerization. A wide variety of adsorbents have been used for ADN thus far including activated carbons [5. it was successfully utilized for the selective removal of NCCs such as quinoline (QUI) and indole (IND) by adsorption from a model fuel containing NCCs. Interest in MOF materials is a result of the relatively simple tunability of their pore size and shape from the microporous to the mesoporous scale upon altering the connectivity of the inorganic moieties and the nature of the organic linkers.9–13]. Furthermore.2. Ni-based adsorbents [12]. microporous carbons [20]. activated aluminas [12]. The nitrogen adsorption experiments of the adsorbents were carried out at 196 °C with a surface area and porosity analyzer (Micromeritics. quinoline (QUI). For example.25 mM Na2SO3 and 3. HCl-loaded silica–aluminas [15]. Metallic chromium. physicochemical properties. The synthesis kinetics. with Cu Ka radiation). 2. MOFs are promising materials for adsorption-related applications because their pore surfaces can be easily modified which leads to the selective adsorption of specific guest molecules containing particular functional groups. MOFs need to be exploited by mild. separation. compared with HDS.8]. An equal amount (0. indole (IND). Several studies have been also carried out using MOFs impregnated with suitable functional materials and a large portion of them were capable of the adsorptive removal of certain contaminants [53–56]. . high temperatures or high pressures and is therefore more cost effective than other processes.67:265. luminescence. this process would be more feasible if the materials can be prepared or impregnated under ambient temperature and pressure. loading specific metal salts onto porous support materials through re-crystallization could be an effective method to incorporate p-complexing metal ions. XPS analyses were carried out using a Quantera SXM X-ray photoelectron spectrometer (ULVAC-PHI) equipped with a dual beam charge neutralizer. trimesic acid (H3BTC) and metallic chromium (Cr) were obtained from Sigma–Aldrich Co. an alternative method to remove NCCs from fuels is very important. and most importantly. and adsorptive-denitrogenation (ADN) is one of the choices that can be used to remove NCCs because this procedure does not require expensive hydrogen. An exact amount (0. S. the wet solids were transferred to a vacuum oven (to avoid air contact) and dried overnight at 100 °C. Ag+. a high amount of hydrogen is consumed during the HDN process and this process. drug delivery. Hydrochloric acid (HCl. easy availability and low cost. and potential applications of MOFs can be vastly improved by modifying the MOFs with suitable materials [48–52]. ion exchange resins [16]. NCCs can be easily removed compared to SCCs due to the selectivity of the adsorption of NCCs over SCCs [39. Experimental 2. Tristar II 3020) after evacuation at 150 °C for 12 h. is an inefficient process because the nitrogen in NCCs can only be removed after the heterocyclic-rings have been hydrogenated.1 g) of MIL-100(Cr) was transferred to glass vials containing 0.H. Detailed synthetic procedures for MIL-100(Cr) are listed below. washed. many functional materials are rapidly emerging and porous materials such as metal–organic frameworks (MOFs) are one of the fastest growing fields of research [22–31]. or 2.41–43]. electrode materials. MIL-100(Cr) is one of the highly porous MOFs having composition of Cr3F(H2O)3O[C6H3-(CO2)3]2nH2O (n 28) [66] with various applications. and purified by stirring at first with water then with ethanol and finally dried in a drying oven at 100 °C. and NiMoS [21]. easy and cost effective way suitable for them. The mixture was then transferred to a Teflon-lined autoclave and heated in a microwave oven (Mars-5. [41] confirmed that MOFs could be used in ADN and/or ADS processes if they are selected and reduced appropriately. After the preparation. For example. compared with HDS.31.6.57–63]. The mixture was then filtered and washed with sulfurous acid solution. magnetism.0 mL of 0. Jhung / Chemical Engineering Journal 251 (2014) 35–42 Additionally. SCCs and aromatics. After synthesis. 1. Pd2+ or Pt2+ have shown that they can effectively remove SCCs and NCCs from commercial fuels through p-complexation which is a special bond between specific metal ions and the p-orbital of olefins and aromatics [34. Although MOFs alone exhibit many promising physical and chemical properties in various aspects.14]. All the chemicals in this study were used without further purification.42. MIL-100(Cr) through the room temperature reduction of CuCl2 in the presence of sodium sulfite (Na2SO3) as the mild reducing agent. cannot be used as support materials for these types of active metal components through high temperature calcination [30. their properties can be further improved by modifying or specifying its structure or chemical nature in various ways. porous materials such as MOFs. imaging [44–47]. meso-silicas [17. Chemicals and synthesis of adsorbents p-Xylene and n-octane were purchased from Junsei chemical company. 2. The loading procedure was very simple to apply and did not require much energy.0 mL of 0.36 I. H3BTC and H2O were mixed at a molar ratio of 1:2:0.0%) were obtained from OCI Company Ltd. 35%) and hydrofluoric acid (HF. Finally. Additionally. In particular. The sulfurous acid solution was prepared by mixing 25.2 M HCl. is a kinetically slow process [5. Maes et al. adsorptive removal of SCCs is quite common with these materials but there have been very few reports on their use in ADN [7. CEM) for 2 h at 220 °C.35. MOFs can be used for a plethora applications which contain gas adsorption/storage such as adsorptive desulfurization (ADS) [32–38] and ADN [39–43].0 mL of a 0. Benzothiophene (BT). The resulting mixture was allowed to stir for 30 min and then 1 mL of a sulfurous acid (H2SO3) solution was added. carriers for nanomaterials.1. Porous adsorbents containing transition metal ions such as Cu+. The syntheses were carried out solvothermally under microwave irradiation [67]. 48. we demonstrated for the first time the loading of CuCl onto a porous MOF. In this report. The adsorbents were named CuCl (x)/MIL-100(Cr) where x corresponds to the volume of the CuCl2 (or Na2SO3) solution used in the preparation. In order to utilize their promising adsorptive properties.6. Although. porous materials with low thermal and chemical stabilities cannot be used as a support material for the loading of active metal components because of the requirement of high temperature calcination or harsh chemical treatment.1 M Na2SO3 aqueous solution was then added dropwise while stirring to the CuCl2 solution containing MIL-100(Cr). MOFs grafted or impregnated with acidic and basic materials can affect the adsorption behavior of SSCs and NCCs due to acid–base interactions [39. morphology. materials containing Cu+ have been widely investigated and applied because of their promising p-complexing properties.52]. Cu(I)-Y zeolites [7.0 or 2.0. Therefore. Therefore. HF.65]. Therefore.

000 ppm) of the model fuel were prepared separately for the three adsorbates (BT. Therefore.5 lm) and analyzed with a GC (DS Science. hydrophobic. the adsorbents were dried in a vacuum oven at 150 °C for 12 h and stored in a desiccator. A solution containing a fixed concentration of NCCs and SCCs (400 ppm QUI.4 0. Pure CuCl and CuCl2 are also included in both figures for reference. and IND) by dissolving them in a mixture of 75 vol% n-octane and 25 vol% p-xylene. Ahmed. Ci the initial concentration of the adsorbate (mg/ml). The adsorption isotherms under various conditions have been plotted to follow the Langmuir equation [68.0 15 30 45 Pore Diameter (Å) Fig. a solution of QUI and IND was prepared separately at varying concentrations (300–1200 ppm) in the same solvent mixture. S. qe the amount adsorbed at equilibrium (measured similarly as qt. QUI.0)/MIl-100 (Cr) 4 2 150 0 0 0. After adsorption. mg/g) and b is the Langmuir constant (L/mg).u) 2. V the volume of the solution subjected to a single adsorption (ml) and m is the mass of the adsorbent taken during a single adsorption (g). (a) N2 adsorption isotherms and (b) pore size distributions of MIL-100(Cr) and CuCl (1. To calculate the adsorption capacities of the individual adsorbates. General procedures for the adsorption experiments 45 960 2 theta (deg) 940 BE (eV) Fig.0)/MIL-100(Cr). Prior to adsorption. which exhibited a similar structure of the virgin and impregnated (b) CuCl (1.0)/MIL-100(Cr). 60 . an exact amount of the adsorbents (5. 400 ppm IND.2 0.69]: Ce Ce 1 ¼ þ qe Q o Q o b where Ce is the equilibrium concentration of the adsorbate (mg/L). Jhung / Chemical Engineering Journal 251 (2014) 35–42 Stock solutions (each at a concentration of 10. mg/g). and 800 ppm BT) was used to determine the adsorption capacity at various adsorption times.0)/MIL-100 (Cr) CuCl + CuCl2 Cu + Cu + Cu Intensity (a. IGC 7200) equipped with an FID.3.H.1. 2.37 I. 1. Qo the Langmuir constant (maximum adsorption capacity. 1(a) displays the XRD patterns of MIL-100(Cr) and CuCl (1. Results and discussion 3.u. 0. the maximum adsorption capacity Qo can be obtained from the reciprocal of the slope of a plot of Ce/qe against Ce.0 mg) was added to the model fuel solution (5. the solution was separated from the solid using a syringe filter (PTFE. For each adsorption experiment. along with the XRD patterns of CuCl and CuCl2.) MIL-100 (Cr) CuCl (1. 3.8 Relative pressure (P/Po) 1. 8 600 (b) 6 450 300 MIL-100 (Cr) CuCl (1. Combined solutions of varying concentrations were prepared by successive dilution and mixing of the three solutions. All the adsorption capacities (mg/g) were calculated from the difference between final concentration and initial concentration of an adsorbate by using following equation: ðC i  C f ÞV qt ¼ m (a) Intensity (a.0)/MIl-100 (Cr) dV/dlog (D) Quantity adsorbed (cm3/g) (a) MIL-100 (Cr) CuCl (1.0)/MIl-100 (Cr) CuCl CuCl2 15 30 where qt is the adsorbed amount in time t (mg/g). (a) XRD patterns and (b) nitrogen XPS spectra of MIL-100(Cr) and CuCl/MIL-100(Cr). Cf the final concentration after adsorption (mg/ml).0 mL) and stirred magnetically for a predetermined amount of time (2–120 min) while the adsorption temperature was maintained at 25 °C. The maximum adsorption capacity (Qo) was calculated with the Langmuir adsorption isotherm.6 0. Textural properties and characteristics of CuCl/MIL-100(Cr) Fig.0 0.

materials. Ahmed.22  103 30 250 (a) (b) MIL-100 (Cr) CuCl (0. Therefore.06  103 3.2. 3. see below) indicated that a uniform. 2 show that the surface area and the pore volume of CuCl (1.2°. Fig. The nitrogen adsorption analyses also supported the XRD data because there was small effect of impregnation procedure on the surface area or pore volume of the MOF.0)/MIL-100(Cr) and Langmuir parameters of QUI and IND adsorption over the two adsorbents.5)/MIl-100 (Cr) CuCl (1.0)/MIl-100 (Cr) CuCl (2.985 0. The impregnated salt was in the Cu+ state which was confirmed by the XPS analysis (Fig.14  103 1. commercial fuels usually contain approximately 25% aromatics. Adsorption of (a) BT.38 I. 1(b)). p-xylene was used as an aromatic compound to mimic the composition of the commercial fuels.399 QUI IND QUI IND 420 149 457 171 7. 3. The usual preference for the adsorption of fossil fuel components is NCCs > SCCs > aromatic hydrocarbons.03  102 3. The XPS patterns of impregnated adsorbent was compared to those of standard CuCl and CuCl2 [70] and only the peaks corresponding to CuCl were found in the impregnated adsorbent. The absence of CuCl diffraction patterns (the presence of CuCl was confirmed by XPS. Table 1 and Fig. 26. Therefore.2°.0)/MIl-100 (Cr) qt (mg/g) qt (mg/g) 20 200 150 100 10 50 0 0 0 1 2 4 3 5 6 0 1 2 3 4 5 6 Time (hr) Time (hr) 60 (c) qt (mg/g) 45 30 15 0 0 1 2 3 4 5 6 Time (hr) Fig. therefore.3° and 43. No diffraction patterns for CuCl2 were observed because of the reduction of CuCl2 into CuCl or well-dispersed CuCl2.3°. as shown in Fig. 3 shows the adsorption results of different adsorbates over the various adsorbents. Moreover. well-dispersed.1° while CuCl2 shows peaks mainly at 16°. Jhung / Chemical Engineering Journal 251 (2014) 35–42 Table 1 Textural properties of MIL-100(Cr) and CuCl (1.0)/MIL-100(Cr) were slightly smaller than those of the virgin MIL-100(Cr).402 CuCl (1. 38. and small amount of CuCl was present within the pores of MIL-100(Cr).635 0. (b) QUI and (c) IND with time over MIL-100(Cr) and CuCl/MIL-100(Cr)s. The selective adsorption of NCCs over SCCs could be explained by much more .0)/MIL-100(Cr) 1310 0. CuCl shows peaks at angles 24. It was observed that both QUI and IND were selectively adsorbed by both the virgin and impregnated MIL-100(Cr) to a much greater extent than BT in the combined system despite the BT concentration being much higher than QUI or IND. the loading procedure affected the pore structure of the MOF a bit because the pore volume (particularly the large pore) decreased for the loaded MIL-100(Cr). a solution containing high concentration of BT as an SCC was prepared (along with QUI and IND) because SCCs are usually present at a high concentration in fuels relative to NCCs. Adsorption results As mentioned earlier. NCCs should be removed prior to the removal of SCCs.5° and 49. 31. Additionally. in order to investigate the selectivity of the adsorption.H. 2. Adsorbent BET surface area (m2/g) Total pore volume (cm3/g) Micropore volume (cm3/g) Adsorbate Qo (mg/g) b-Value (L/mg) MIL-100(Cr) 1510 0. The adsorption experiments were carried out at 25 °C over a period of 6 h. it was very difficult to observe any trend of BT adsorption. S.

6.5 h 2h 4h 6h 50 20 0 0 0. Adsorption isotherms for (a) QUI and (b) IND over MIL-100(Cr) and CuCl (1. 4 displays the relationship between the adsorbed amount of NCCs and the CuCl2 content (used in impregnation). Correlation factors (R2) are shown alongside the respective plots. 5.995 1. The adsorbed amounts of both .5 2.5 nm. Adsorbed amounts of (a) QUI and (b) IND over CuCl/MIL-100(Cr)s having different amount of CuCl in various adsorption times.0)/MIl-100 (Cr) 150 50 0 0 0 300 600 900 1200 0 300 600 Ce (ppm) 900 1200 Ce (ppm) Fig.0 3 0.0 1. Acid–base interaction also favors the adsorption of NCCs over SCCs [39.0)/MIl-100 (Cr) 0.0 1.5 1.995 1. negative adsorption enthalpies of NCCs compared with SCCs according to a previous report [7].5 1.997 6 2 R = 0. S. Fig.5 MIL-100 (Cr) CuCl (1. 450 150 (a) (b) 300 qe (mg/g) qe (mg/g) 100 MIL-100 (Cr) CuCl (1. Langmuir plots obtained from adsorption isotherms for (a) QUI and (b) IND over MIL-100(Cr) and CuCl (1.0 0.0)/MIL-100(Cr). the overall kinetics of the adsorption was remarkably fast which confirms the favorable adsorption of NCCs over the adsorbents.0 0 0 400 800 1200 Ce (ppm) 0 400 800 1200 Ce (ppm) Fig.984 2 R = 0. 3. it can be concluded that the selectivity of NCCs for the adsorbents was much higher compared to the SCCs.0)/MIL-100(Cr).5 2 R = 0. which was adopted from Fig.0 2 R = 0.H.0 CuCl2 Loading amount (ml) Fig. 2) of the adsorbents. The kinetics between different adsorbents did not vary much due to the relatively large pore sizes (1. as shown in Fig. Therefore. However.0 (b) (a) 9 2.41. Jhung / Chemical Engineering Journal 251 (2014) 35–42 250 60 (a) (b) 200 qt (mg/g) qt (mg/g) 40 150 100 0.0 0. Ahmed.0 CuCl2 Loading amount (ml) 0.39 I.5 2. 3. 4.42].5 ce/qe ce/qe 2.

71]. The adsorption of QUI and IND in this . adsorbents using p-complexation have been extensively investigated for adsorptive desulfurization processes since they allow higher selectivities and capacities for organosulfur compounds compared to normal physisorption processes [57–63. Ahmed. Although the porosity of the loaded MOF slightly decreased (Table 1). respectively. over CuCl (1. which is a very mild. For CuCl (1. QUI and IND generally increased as the loading of CuCl2 increased up to a certain point. the b-value for QUI adsorption over CuCl (1.0)/MIL-100(Cr) > virgin MIL-100(Cr) > and CuCl2 (1. QUI.H. The b-values of the corresponding Langmuir isotherms also show favorable adsorptions over CuCl (1.0)/MIL-100(Cr) in the case of IND.0)/MIL-100(Cr). S. In this case a combined solution of BT.40 I. Jhung / Chemical Engineering Journal 251 (2014) 35–42 300 75 (a) (b) 1 hr 6 hr 225 qt (mg/g) qt (mg/g) 50 150 25 75 0 0 MIL-100 (Cr) CuCl/MIL-100 (Cr) CuCl2 /MIL-100 (Cr) MIL-100 (Cr) Adsorbent CuCl/MIL-100 (Cr) CuCl2 /MIL-100 (Cr) Adsorbent Fig. The maximum adsorption capacities (Qo) were calculated using the Langmuir plots shown in Fig. It was found that the adsorbed amounts of QUI and IND followed the trend of CuCl (1.0)/ MIL-100(Cr). In the case of short adsorption time of 0. the Qo value of QUI increased from 420 mg/g to 457 mg/g and that of IND increased from 149 mg/g to 171 mg/g relative to the virgin MIL-100(Cr).43.0)/MIL100(Cr) and virgin MIL-100(Cr) were used for further experiments. the adsorbed amount of QUI decreased with increasing the CuCl2 content probably caused by partial blocking of the pores with the impregnated CuCl species. The impregnated material showed an improved adsorption capacity of QUI and IND relative to the virgin MIL-100(Cr) as a result of p-complexation. CuCl (1. an adsorption experiment was also carried out using the CuCl2 loaded onto MIL-100(Cr) without reducing the CuCl2 with Na2SO3. the adsorption capacities were enhanced.60]. and thus CuCl (1. Therefore. 7 shows the adsorption results of QUI and IND over the virgin MIL-100(Cr). 4. and IND was used under the same conditions as the previous experiments.60].2 M CuCl2 solution (0. solutions of varying concentrations of the adsorbates QUI and IND were prepared separately and the adsorption amount was measured. To obtain the maximum adsorption capacities of MIL-100(Cr) and CuCl (1. the optimized loading amount was determined to be 1.0)/MIL100(Cr) was around 1. The minimal adsorption of QUI and IND over CuCl2 (1. The isotherms which are shown in Fig.0)/MIL-100(Cr) and CuCl2 (1.1 g of MOF. In order to confirm the effects of p-complexation in the adsorption procedure.5 h. As shown in Table 1. In this report we were able to show the ADN process by using p-complexing materials in a new way which was carried out under mild operation conditions.0)/MIL-100(Cr) was likely a result of the reduced porosity and the lack of interactions between CuCl2 and the adsorbates. In this study. However. Fig. Comparison of adsorptions of (a) QUI and (b) IND over MIL-100(Cr).57. and CuCl2 (1.0)/MIL-100(Cr).0)/MIL-100(Cr).0 mL of the 0. These improvements could be attributed to the selective interaction between the NCCs and the loaded CuCl materials through p-complexation. CuCl2 is known to not exhibit p-complexion which makes CuCl2 loaded MIL-100(Cr) less capable of adsorption compared to CuCl loaded MIL-100(Cr) or the virgin MIL-100(Cr). using p-complexing materials (obtained through impregnation) for the removal of NCCs is not commonly practiced and previous studies typically utilized modified zeolites by ion exchange (with precursors for p-complexing metal sites) [7.0)/MIL-100(Cr). Recently. the CuCl particles were produced through the facile reduction of the loaded CuCl2 in the presence of sodium sulfite under ambient conditions in which the sodium sulfite was used as a mild reducing agent for the redox process shown below. CuCl (1. 6.5 times of that of pristine MIL-100(Cr). the increase in the adsorption of QUI and IND was approximately 9% and 15%.027 g of CuCl2) per 0. The p-complexation occurred as a result of the interaction between the p-electrons of NCCs and Cu+ ions with d-electrons and empty s-orbital [7]. and then decreased as the amount of CuCl2 further increased. compared to the virgin MIL-100(Cr). The maximum adsorption capacities along with the physicochemical properties were summarized in Table 1. the thermal reduction of loaded CuCl2 to CuCl [72] or a mild reducing procedure (from CuCl2 to CuCl) with Na2SO3 [33]. Therefore.14].0)/MIL-100(Cr). 5 were obtained by plotting the adsorbed amount against the equilibrium concentration of the adsorbates. It has been well reported that Cu+ sites impregnated into suitable materials can significantly improve the adsorption of SCCs as well as NCCs [35. Each adsorption was carried out for 6 h which was considered to be a sufficient amount of time to reach the adsorption equilibrium. There have been previous reports detailing the preparation of p-complexing materials by impregnating CuCl with the help of strong mineral acids [57. Conclusion The impregnation of the Cu+ sites onto a MOF (MIL-100(Cr)) was carried out for the first time by reducing CuCl2 salt with sodium sulfite. facile and energy efficient procedure.0)/MIL-100(Cr). and the value was slightly increased for CuCl (1. 2CuCl2 ðaqÞ þ Na2 SO3 ðaqÞ þ H2 O ! 2CuCl ðsÞ þ Na2 SO4 ðaqÞ þ 2HCl ðaqÞ þ 2 þ or 2Cu2þ þ SO2 3 þ H2 O ! 2Cu þ SO4 þ 2H The +1 oxidation state of the loaded copper species was the active component for ADN which was demonstrated for the favorable interaction between Cu+ and SCCs [33] or NCCs [43] through p-complex formation. 7.0)/MIL100(Cr).

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