Robust and economic reduction protocol employing immensely stable and leach-proof magnetically separable nanocomposites

Ankita Goyal and Sonal Singhal*
Department of Chemistry, Panjab University, Chandigarh, India-160014. E-mail: sonal1174@gmail.com; sonal@pu.ac.in; Fax: +91-172-2545074; Tel: +91-172-2534421 Tel: +91-9872118810

Received 7th July 2016 , Accepted 19th September 2016

First published on 19th September 2016


Abstract

Magnetically recoverable nanocomposites i.e. metal loaded over modified ferrite nanoparticles have been synthesized via a facile three step pathway. Modification of ferrite nanoparticles which serve as the core has been achieved using dopamine hydrogen chloride. Owing to this, introduction of terminal amine groups on the surface of ferrite nanoparticles takes place which provides binding sites for the stabilization of metal nanoparticles providing leach-proof nanocomposites. The synthesized nanocomposites have been characterized using various characterization techniques. Substantiation of the modification of the pristine magnetic ferrite nano particles has been done from the emergence of strong stretching vibration bands of N–H and O–H in the range of 3200–3400 cm−1, N–H stretching band in the range of 1630–1650 cm−1, C–C vibrations of the benzene ring in the range of 1480–1500 cm−1 and C–O stretching vibrations in the range of 1070–1100 cm−1. In the XRD patterns additional peaks corresponding to loaded metals (Cu and Ag) along with peaks corresponding to spinel ferrites have been observed confirming the successful formation of the composite. EDS patterns and FE-SEM elemental mapping confirmed the purity of the samples by displaying the absence of any impurity. Elemental mapping also confirmed the uniform binding of the loaded metals over the surface of modified ferrite nanoparticles. Catalytic efficiency of the synthesized nanocomposites has been explored for the reduction of nitroarenes. Both the Cu and Ag loaded samples exhibited excellent activity and efficient recyclability for the reduction of nitroarenes in the presence of NaBH4 as a reducing agent.


1. Introduction

Now-a-days catalysis has encouraged almost all kinds of organic and inorganic transformations. Out of the two basic catalytic systems, heterogeneous catalysis is preferred over homogeneous, owing to effortless management of the reaction, facile separation and regeneration of the catalyst.1 Despite these advantages heterogenized catalytic reactions are comparatively slow and usually less effective in contrast to homogenized catalytic reactions. The origin of nanocatalysis has solved the problems associated with both the catalytic systems by bridging the gap between homogeneous and heterogeneous catalysis. Nanocatalysis offers advantages associated with both the catalytic systems as nanocatalysts are endowed with a large surface area to volume ratio.2

Metal based nanocatalysts have long been fascinating the scientific community to be used as catalysts in a variety of reactions. Dispersion and stabilization of active species are two crucial factors affecting the catalytic efficiency of metal-based nanocatalysts.3 Metal nanoparticles have a strong tendency to agglomerate easily, leading to decrease in surface area and hence degradation of catalytic performance and reduction of lifetime of the catalyst. It is very hard to achieve good dispersion and stabilization in case of bare metal nanoparticles. So it is highly required and quite interesting to efficaciously protect and stabilize these nanoparticles to be effectively used as regenerable catalyst.4

To arrest the agglomeration of metal nanoparticles variety of surfactants and ligands have been used by researchers.5–9 The use of surfactants and ligands have undoubtedly solved the problem of aggregation and dispersion but, also, degraded the catalytic ability by passivating the catalytic sites. The emergence of core–shell nanostructures have provided a unique and useful way-out to protect the catalytic properties of these metal nanoparticles by proposing the idea of affixing them over some core materials.10 In this context, the use of some rigid inorganic materials having high thermal stability and chemical inertness, as a core can be of great use. Also the separation of catalyst from the product stream has always remained an issue for any catalytic process. Many research cohorts have used ferrite nanoparticles as core materials which added the advantage of facile and effective separation of the catalyst due to their inherent magnetic character.11–14

Conversely, the use of ferrite nanoparticles as a core material without modification or functionalization is not an effective idea due to lack of binding sites on the surface of ferrite nanoparticles to affix metal nanoparticles.15 So prior to metal loading over the surface of ferrite nanoparticles it is required to modify it which can be achieved by integrating the inorganic–organic moieties. Many reports have been available wherein ferrite cores have been pre-modified with various organic functionalities to incorporate effective binding sites followed by metal loading over the surface.16–19 Chang and Chen proposed the synthesis of novel magnetically recoverable Au nanocatalyst via loading of Au(III) ions on chitosan-coated iron oxide magnetic nanocarrier. The synthesized magnetically retrievable Au nanocatalyst was found to be quite stable with excellent catalytic ability even after 11 recycles.16 Chen et al. prepared Au nanoparticles loaded over polyaniline modified ferrite (Fe3O4@PANI@Au) composites exhibiting excellent magnetic and catalytic properties via a three-step procedure. The Fe3O4@PANI@Au composite catalyst showed excellent catalytic performance for various concentrations of dye wastewater for the reduction of Congo red with NaBH4.17 Well-dispersed Ag@Pd supported on magnetite nanoparticles were obtained by Jiang et al. through a simple colloidal impregnation method. The as-synthesised nanocomposite exhibited greatly enhanced catalytic reactivity and reusability towards 4-nitrophenol hydrogenation.18 Guin et al. stablized Pd nanoparticles on to the surface of amine terminated ferrite–dopamine to be used as catalyst for hydrogenation reactions.19 Out of the various organic functionalizations, the modification ferrites with dopamine have proved to be highly beneficial as minimal decrease in magnetic character has been observed to be there in contrast to others due to its lower weight. Also the presence of terminal amine groups provides efficient binding to metal nanoparticles.20

So in the present investigation Cu and Ag nanoparticles have been stabilized on the surface of dopamine modified cobalt ferrite nano particles. The catalytic activity of the synthesized magnetically retrievable nanocomposites has been evaluated for the reduction of nitroarenes. Cobalt ferrite nanoparticles have been found to be inactive catalysts for the reduction of nitroarenes as reported previously.21 Cobalt ferrite nanoparticles have been used as core material for having very good magnetic character with chemical inertness and thermal stability. So the view point of using them as core material to utilize their excellent magnetic character without any interference in the catalytic performance has been applied. Also the optimum amount of metal catalyst loaded over ferrite core to be used as catalyst has been interestingly scrutinized.

2. Experimental

2.1. Materials

Ferric nitrate nonahydrate (98%), cobaltous nitrate hexahydrate (99.5%), cupric nitrate trihydrate (99.5%) citric acid (99.57%) and were bought from Fisher Scientific. Dopamine hydrochloride was purchased from Sigma-Aldrich. Methanol (99.5%), ethyl acetate (99.5%), ethylene glycol (99%), hydrochloric acid (37%) and silver nitrate (pure) were provided by Merck. Sodium borohydride (97%), hydrazine hydrate (75%) all the nitrophenols and other nitro derivatives were contributed by Avra Synthesis. All the chemicals were used as such.

2.2. Physical characterization

The presence of dopamine shell over the ferrite nanoparticles was confirmed from the observation of the presence of various vibrational bands in the FT-IR spectrum for which iS50-FTIR (Model no. AUP1200343) instrument with the resolution of 1 cm−1 and scan range of 4000 cm−1 to 400 cm−1 was employed. The knowledge of the crystallographic data and various lattice planes present in the sample was obtained by recording the powder X-ray diffraction patterns using the Panalytical's X'Pert Pro diffractometer equipped with vertical theta–theta goniometer and x'Celerator solid-state detector. Scanning rate of 4° min−1 in the 2θ range of 10–80° was used for the measurement. Cu K-alpha-1 radiation (λ = 1.54 Å) was used whereas nickel metal acted as beta filter. The visualization of the obtained nanocomposites was done using high resolution transmission electron microscopy (HR-TEM). For the HR-TEM analysis FEI Tecnai (G2 F20) operating at 200 keV was used. Surface morphology was determined using field emission scanning electron microscopy (FE-SEM) employing Hitachi (SU-8010) operated at 15 kV. Elemental mapping associated with FE-SEM was used to establish the presence of metal ions on to the surface of ferrite–dopamine nanoparticles. To evaluate the time dependent conversion of the nitrophenols for the surface area analysis of the samples, BET surface area analyzer ((11-2370) Gemini, Micromeritics, USA) was employed. Vibrating sample magnetometer (VSM) (155, PAR) was used for the evaluation of the magnetic characteristics of the synthesized samples. UV-visible spectroscopy was employed for which Jasco double beam UV-visible spectrophotometer (Model-V-750-PC) was used. The spectrophotometer was equipped with single monochromator, deuterium and halogen lamps as light sources, photomultiplier tube detector with a wavelength range of 190–900 nm. The reduced products after the reduction of nitroarenes were analyzed using GC-MS analysis for which THERMO GC (TRACE 1300) with a Thermo TG 5MS 5% phenyl methylpolysiloxane capillary column (30 m × 0.25 mm × 0.25 mm) and a triple quadrupole Thermo MS (TSQ 8000) mass spectrometer was employed.

2.3. Fabrication of metal decorated modified magnetic nanocomposites (M@Dop@CoFe2O4)

Synthesis of M@Dop@CoFe2O4 nanocomposites was achieved in three steps. Schematic representation of the synthetic procedure is shown in Fig. 1.
image file: c6ra17387j-f1.tif
Fig. 1 Schematic representation of the synthesis of metal decorated modified magnetic ferrite nanoparticles (M@Dop@CoFe2O4).
2.3.1. Synthesis of CoFe2O4 nanoparticles. Magnetic cobalt ferrite nanoparticles were synthesized using the well-known and well explored sol–gel methodology. Sol–gel methodology has long been known to produce nanoparticles with uniform and narrow size distribution without the adoption of complex synthetic procedure and not too high temperature requirement.21 In a typical synthesis desired metal salts (Fe[thin space (1/6-em)]:[thin space (1/6-em)]Co = 2[thin space (1/6-em)]:[thin space (1/6-em)]1) i.e. cobalt nitrate, ferric nitrate and citric acid (in the ratio 1[thin space (1/6-em)]:[thin space (1/6-em)]1 to precursor metal salts) were separately dissolved in minimal distilled water to obtain clear solutions. The obtained clear metal salt solutions were then mixed together at 60 °C and stirred for 5 minutes, followed by the addition of citric acid solution. Citric acid was used as complexing agent. The stirring and heating at 60–70 °C was continued. After 10–15 minutes fixed amount of ethylene glycol was added which promoted gelation and temperature was raised to 80–90 °C. Thickening of solution took place and the obtained gels were further dried to get loose powder. The obtained powders were then annealed in a muffle furnace for two hours.
2.3.2. Modification of cobalt ferrite nanoparticles (Dop@CoFe2O4). The linkage of dopamine on the surface of magnetic nanoparticles is based on the chelation of the hydroxyl groups of dopamine with the under-coordinated surface metal atoms. To achieve such linkage, cobalt ferrite nanoparticles (1 g) were dispersed in 20 mL of distilled water by sonication for 30 min. 1 g of dopamine hydrochloride dissolved in minimum amount of distilled water was added to the ferrite nanoparticles dispersion. The obtained mixture was continuously sonicated for 2 hours while the temperature of the sonication bath was maintained at 25–30 °C. Afterwards the obtained modified Dop@CoFe2O4 nanoparticles were repeatedly washed with distilled water and acetone and were dried under vacuum for 2 hours at 60 °C.22
2.3.3. Decoration of metal nanoparticles over modified cobalt ferrite (M@Dop@CoFe2O4). Decoration of metal nanoparticles over the surface of modified cobalt ferrite nanoparticles was achieved by reduction. 1 g of the modified cobalt ferrite nanoparticles were dispersed in 30 mL of distilled water using sonication. To the obtained dispersion required amount of metal salt dissolved in 15 mL of distilled water was added and dispersion was subjected to stirring. Metal loading was varied from 2.5 wt% to 20 wt%. Hydrazine hydrate was then added dropwise to adjust the pH of the solution to 9. After the pH adjustment 0.3 g of NaBH4 was added and stirring was continued for 24 hours at room temperature. The obtained nanocomposites were then thoroughly washed with distilled water and acetone and dried under vacuum at 60 °C for 2 hours.22

2.4. Catalytic procedure for the reduction of nitrophenols

Reduction of nitrophenols was performed in aqueous medium. In a typical catalytic procedure nitrophenol solution was taken in a beaker and kept for magnetic stirring. Freshly prepared sodium borohydride solution was then added which changed the colour from pale yellow to dark yellow indicating the formation of nitro-phenolate ion. The catalytic reaction started at once with the addition of catalyst and continuous fading of dark yellow colour started to occur indicating the conversion of nitrophenol to subsequent aminophenol. The time dependent conversion was checked using UV-visible spectroscopy by taking out fixed amount of sample aliquots at different time intervals and diluting the same for absorbance measurements.

2.5. Catalytic procedure for the reduction of nitroarenes

For the reduction of other nitroarenes methanol was used as solvent due to the solubility issue of nitroarene derivatives in aqueous medium. To the solution of nitroarene fixed excess of NaBH4 was added followed by the addition of catalyst. Reaction progress was monitored by GC-MS analysis by analyzing the samples aliquots drawn at different time intervals. Prior to GC-MS analysis the organic content in the sample aliquot was extracted using ethyl acetate.

3. Results and discussion

3.1. FT-IR spectroscopy

To investigate the successful synthesis of metal loaded modified magnetic nanocomposites (M@Dop@CoFe2O4) the synthesized samples were inspected using FT-IR spectroscopy. FT-IR spectra for all the synthesized nanocomposite samples with variable metal loading are shown in Fig. 2(a) and (b). Ferrite nanoparticles which serve the core of synthesized nanocomposites confirmed their presence by exhibiting the characteristic bands in the range of 500–600 cm−1 corresponding to the M–O cluster present in the tetrahedral site of the ferrite sub-lattice.23 The corroboration of the modification of the pristine magnetic nano particles was done from the emergence of strong stretching vibration bands of N–H and O–H in the range of 3200–3400 cm−1. N–H stretching band in the range of 1630–1650 cm−1, C–C vibrations of the benzene ring in the range of 1480–1500 cm−1 and C–O stretching vibrations in the range of 1070–1100 cm−1 further confirmed the formation of modified magnetic nano particles.24,25 As the metal loading has been varied from 2.5 wt% to 20 wt%, the increase in metal loading can also be visualized from the lowering in the intensity of the characteristic bands of dopamine and ferrite with increase in metal loading for both Cu and Ag.
image file: c6ra17387j-f2.tif
Fig. 2 FT-IR spectra for synthesized nanocomposites (M@Dop@CoFe2O4) M = (a) Cu and (b) Ag with different metal loadings from 2.5 wt% to 20 wt%.

3.2. Powder X-ray diffraction studies

For the illustration of the structural characteristics of the synthesized nanocomposite samples powder X-ray diffraction technique was employed. Fig. 3(a) and (b) shows the XRD patterns of all the synthesized nanocomposites (M@Dop@CoFe2O4 (M = Cu and Ag)) for different metal loadings.
image file: c6ra17387j-f3.tif
Fig. 3 XRD patterns for synthesized nanocomposites (M@Dop@CoFe2O4) M = (a) Cu and (b) Ag with different metal loadings from 2.5 wt% to 20 wt%.

For copper decorated modified ferrite nanocomposites as can be seen from Fig. 3(a), all the peaks appearing in the XRD patterns matched well with the standard patterns corresponding to cobalt ferrite (JCPDS card no. 00-001-1121)26 and copper metal (JCPDS card no. 00-001-1242). Peaks corresponding to copper appears at 2θ (°) values of 43.47°, 50.67° and 74.67° corresponding to (1 1 1), (2 0 0) and (2 2 0) lattice planes respectively.27 As the loading of Cu was increased from 2.5 wt% to 20 wt% the peaks corresponding to copper metal were observed to grow sharper and clearer as highlighted in the figure.

Similarly, for silver decorated modified ferrite nanocomposites as is shown in Fig. 3(b), all the peaks appearing in the XRD patterns matched well with the standard patterns corresponding to cobalt ferrite and silver metal (JCPDS card no. 00-001-1167). Peaks corresponding to silver metal appears at 2θ (°) values of 38.10°, 44.41°, 64.17° and 77.55° corresponding to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) lattice planes respectively.28 The growth and sharpening of the peaks corresponding to Ag, was also observed with increase in loading from 2.5 wt% to 20 wt%.

3.3. Structural and morphological characteristics: crystallinity and elemental analysis

Structural and morphological characteristics of the synthesized nanocomposites were evaluated using HR-TEM and FE-SEM electron microscopic techniques. Fig. 4 and 5 shows the typical HR-TEM images for Cu@Dop@CoFe2O4 and Ag@Dop@CoFe2O4 nanocomposites loaded with 10 wt% of metal respectively. Fig. 4(a) and (b) and 5(a) and (b) are the low resolution TEM images of the nanocomposite samples wherein metal loaded agglomerated modified ferrite nanoparticles can be seen. It can be clearly noticed from the images that 20–25 nm sized nanoparticles of cobalt ferrites were trapped within the clouds of dopamine over which 4–7 nm sized metal nanoparticles were present. Fig. 4(c) and 5(c) represents the high resolution images wherein lattice interplanar distance is clearly noticeable. Fig. 4(d) and 5(d) represents the SAED patterns which confirmed the crystallinity of the samples owing to the presence of concentric rings corresponding to different lattice planes. EDS patterns for both the nanocomposite samples are shown in Fig. 4(e) and 5(e) respectively, which confirmed the presence of desired elements in the nanocomposite sample. It is difficult to distinguish between the ferrite and the loaded metal nanoparticles due to comparable size, so, for the verification of the uniform presence of metal nanoparticles over the surface of modified ferrite nanoparticles elemental mapping associated with FE-SEM was done. Fig. 6 and 7 display the FE-SEM elemental mapping images which confirmed the uniform presence of the loaded metal nanoparticles i.e. Cu and Ag respectively. Different elements present in the samples have been represented using different colors. Also the presence of Co, Fe, O and N were observed to be there due to the dopamine modified CoFe2O4 nanoparticles over which metal loading has been done. No extra element corresponding to any impurity was found to be there which confirmed the purity of the nanocomposite samples.
image file: c6ra17387j-f4.tif
Fig. 4 Typical transmission electron micrographs for 10 wt% Cu@Dop@CoFe2O4 (a) and (b) at low resolution (c) with visible interplanar spacing at high resolution (d) SAED pattern with corresponding electron diffraction rings and (e) EDS pattern for elemental composition.

image file: c6ra17387j-f5.tif
Fig. 5 Typical transmission electron micrographs for 10 wt% Ag@Dop@CoFe2O4 (a) and (b) at low resolution (c) with visible interplanar spacing at high resolution (d) SAED pattern with corresponding electron diffraction rings and (e) EDS pattern for elemental composition.

image file: c6ra17387j-f6.tif
Fig. 6 Typical FE-SEM elemental mapping for 10 wt% Cu@Dop@CoFe2O4 nanocomposite sample displaying elemental composition.

image file: c6ra17387j-f7.tif
Fig. 7 Typical FE-SEM elemental mapping for 10 wt% Ag@Dop@CoFe2O4 nanocomposite sample displaying elemental composition.

3.4. Magnetic characterization

Magnetic characteristics of the synthesized nanocomposites samples were established by recording room temperature hysteresis loops employing VSM. Cobalt ferrite nanoparticles which serve the core of the nanocomposite samples have previously been characterized and saturation magnetization has been found to be 50.2 emu g−1.21 Good magnetic character and high thermal and chemical stability were the major reasons behind choosing it to be used as core material.29 The room temperature hysteresis loops for all the synthesized samples (Dop@CoFe2O4 and M@Dop@CoFe2O4 (M = Cu and Ag)) for different metal loadings are shown in Fig. 8(a) and (b) respectively. The values of saturation magnetization (Ms), remanence (Mr), coercivity (Hc) and squareness ratio (S = Mr/Ms) procured from the obtained hysteresis loops for all the samples and for pristine CoFe2O4 nanoparticles are given in Table 1. With the modification of cobalt ferrite nanoparticles with dopamine hydrochloride decrease in the saturation magnetization and remanence value was observed due to coating of non-magnetic dopamine over ferrite30 while coercivity was found to increase. With the decoration of metal nanoparticles (M = Cu and Ag) over the surface of modified ferrite, further decrease in the values of saturation magnetization and remanence was observed. With increase in metal loading in case of both the metals, increase in the saturation magnetization and remanace was observed to be there. This increase in the magnetization values could be due to the interactions between CoFe2O4 and increasing amount of metal loaded over the surface of ferrite nanoparticles. Not any particular or significant increasing or decreasing trend in the values coercivity and squareness ratio was found to be there. Although, a decrease in saturation magnetization was there for nanocomposites in comparison to pristine ferrite nanoparticles but still the nanocomposites were sufficiently magnetic so that they could easily be recovered out of the reaction mixture using an external magnet.
image file: c6ra17387j-f8.tif
Fig. 8 Room temperature hysteresis loops for synthesized nanocomposites (M@Dop@CoFe2O4) M = (a) Cu and (b) Ag without any metal and with different metal loadings from 2.5 wt% to 20 wt%.
Table 1 The values of saturation magnetization (Ms), remanence (Mr), coercivity (Hc) and squareness ratio (S = Mr/Ms) for various synthesized samples
Sample Saturation magnetization (Ms) (emu g−1) Remanence (Mr) (emu g−1) Coercivity (Hc) (Oe) Squareness ratio (S = Mr/Ms) × 10−2
Pristine CoFe2O4 50.2 20.0 1116.0 39.1
Dop@CoFe 35.7 14.0 1367.5 39.2
2.5 wt% Cu 14.7 5.4 1156.0 36.7
5 wt% Cu 17.6 6.3 1218.5 35.8
7.5 wt% Cu 18.5 6.9 1165.5 37.3
10 wt% Cu 23.1 8.2 1165.0 35.5
20 wt% Cu 27.1 12.8 1723.5 47.2
2.5 wt% Ag 15.9 5.9 1567.0 37.1
5 wt% Ag 16.2 6.1 1656.0 37.7
7.5 wt% Ag 18.2 6.5 1511.0 35.7
10 wt% Ag 19.1 8.3 1874.0 43.5
20 wt% Ag 21.3 8.8 1697.0 41.3


3.5. Surface area analysis

Surface area of any heterogeneous catalyst is an important factor which contributes towards the comparative evaluation of the catalytic performance. Brunauer–Emmett–Teller (BET) theory was used as the basis for the measurement of the specific surface area of the synthesized nanocomposite samples. Using the equations given in our previous report graphs were plotted between 1/[Q{(P0/P) − 1}] vs. P/P0. P and P0 are the equilibrium and saturation pressure and Q is the quantity of the gas adsorbed on the adsorbate.31 Typically the corresponding plots for 5 wt%, 10 wt% and 20 wt% of Cu and Ag loaded over modified cobalt ferrite nanoparticles are shown in Fig. 9. From the obtained plots the values of slope (A) and intercept (I) were deduced which were further used to calculate Qm (monolayer adsorbed gas quantity) and C (BET constant) according to the following relations:
 
image file: c6ra17387j-t1.tif(1)
 
image file: c6ra17387j-t2.tif(2)

image file: c6ra17387j-f9.tif
Fig. 9 The fitting curves for the BET surface area of M@Dop@CoFe2O4 (M = Cu and Ag) for different metal loadings.

Further, the values of total surface area (Stotal) and specific surface area (SBET) were calculated according to the eqn (3) and (4).

 
image file: c6ra17387j-t3.tif(3)
 
image file: c6ra17387j-t4.tif(4)
where, N is Avogadro's number, s (0.1620 nm2) is molecular cross-sectional area, V is the molar volume of the adsorbate gas (22.4 L) and M is the mass of the adsorbent sample. The value of A, I, Qm, C, M, Stotal and SBET are given in Table 2.

Table 2 The values of slope (A), intercept (I), monolayer adsorbed gas quantity (Qm), BET constant (C), total surface area (Stotal), mass of adsorbent sample (M) and specific surface area (SBET) for various M@Dop@CoFe2O4 (M = Cu and Ag) for different metal loadings
Sample A (g cm−3) I (g cm−3) Qm (cm3 g−1) C Stotal (m2) M (g) SBET (m2 g−1)
5 wt% Cu 0.2962 0.0036 3.3354 83.8331 14.52 0.0520 279.40
10 wt% Cu 0.0574 0.0006 17.2229 89.7634 75.02 0.1838 408.17
20 wt% Cu 0.0649 0.0003 15.3274 196.0938 66.76 0.1340 496.02
5 wt% Ag 0.3704 0.0046 2.6663 80.7780 11.61 0.1373 84.590
10 wt% Ag 0.2893 0.0027 3.4241 106.8769 14.91 0.0902 165.36
20 wt% Ag 0.2503 0.0036 3.9382 71.0098 17.15 0.1095 156.67


From the values given in Table 2, both for Cu and Ag loaded nanocomposites it can be clearly noticed that specific surface area increases drastically from 5 wt% to 10 wt% and 10 wt% and 20 wt% metal loaded samples exhibited almost comparable values. Also specific surface area values for Cu loaded nanocomposites were comparatively higher in comparison to Ag loaded samples.

3.6. Catalytic studies

For the evaluation of the catalytic property of the synthesized nanocomposites, reduction of nitroarenes was carried out. Nitroarenes have been the precedence pollutants as these are common byproducts from the production of pesticides, herbicides, and synthetic dyes.32 Nitroarenes can be converted to corresponding amines via catalytic reduction in the presence of NaBH4. Aromatic amines are very useful as these can serve as reactants and intermediates in variety of organic transformations and are an important raw material for pharmaceutical industry.33 Reduction of all the nitroarenes was performed in the presence of excess of NaBH4 (50 equivalents as optimum amount) as reducing agent.
3.6.1. Reduction of nitrophenols. Reduction of nitrophenols was performed in aqueous medium and before performing the catalytic experiment with the nanocomposites, catalytic performance of bare CoFe2O4 and modified i.e. dopamine functionalized CoFe2O4 nanoparticles was checked and both were found inactive for the reduction of nitrophenols. Further reduction of all the three nitrophenols was performed in the presence of synthesized nanocomposites i.e. M@Dop@CoFe2O4 (M = Cu and Ag) where metal loading was varied from 2.5 wt% to 20 wt%. Further catalyst loading i.e. the amount of the catalyst used in the catalytic run was also varied from 5 mg to 15 mg.

The typical UV-visible spectra for the reduction of ortho-, meta- and para-nitrophenol in the presence of 10 mg of 10 wt% M@Dop@CoFe2O4 (M = Cu and Ag) are shown in Fig. 10. In the UV-visible spectra it can be clearly seen that the absorption maxima corresponding to nitrophenols gradually decreased with the passage of time. The absorbance values were noted for all the successive readings and plots were plotted between absorption maxima and time for all the catalytic experiments. The absorbance vs. time curves for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts (5 mg, 10 mg and 15 mg) of M@Dop@CoFe2O4 (M = Cu and Ag) where metal loading was varied from 2.5 wt% to 20 wt% are shown in Fig. 11 and 12 respectively. It can be closely noticed from Fig. 11 and 12, that irrespective of the nature of the metal loaded over the surface of modified cobalt ferrite nanoparticles, catalytic performance effectively got improved with increase in the metal loading from 2.5 wt% to 10 wt% while not much considerable augmentation in the catalytic performance was observed to be there when metal loading was raised above 10 wt%. With increase in the catalytic amount from 5 mg to 10 mg for all the metal loadings for both the nanocomposites noteworthy improvement was there in the catalytic performance. While, with further increase in the catalytic amount from 10 mg to 15 mg not much significant improvement in the catalytic performance was observed to be there. Also for all the cases i.e. for different metal loadings and for varying catalytic amounts, catalytic performance of Cu@Dop@CoFe2O4 nanocomposites was better than that of Ag@Dop@CoFe2O4 nanocomposites.


image file: c6ra17387j-f10.tif
Fig. 10 Typical UV-visible spectra for the reduction of ortho-, ((a) and (d)) meta- ((b) and (e)) and para-nitrophenol ((c) and (f)) in the presence of 10 mg of 10 wt% M@Dop@CoFe2O4 (M = Cu and Ag) respectively.

image file: c6ra17387j-f11.tif
Fig. 11 The absorbance vs. time curves for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts (5 mg (a–c), 10 mg (d–f) and 15 mg (g–i)) of Cu@Dop@CoFe2O4 where metal loading was varied from 2.5 wt% to 20 wt%.

image file: c6ra17387j-f12.tif
Fig. 12 The absorbance vs. time curves for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts (5 mg (a–c), 10 mg (d–f) and 15 mg (g–i)) of Ag@Dop@CoFe2O4 where metal loading was varied from 2.5 wt% to 20 wt%.
3.6.2. Kinetics of reduction. Reduction reactions were performed in the presence of large excess i.e. 50 equivalents of NaBH4 as reducing agent, so the reaction rate could considered to be solely dependent upon the concentration of the reactant nitrophenols.34 Owing to which the reduction reactions could be considered to follow pseudo-first order kinetics and follow the given rate law equation
 
image file: c6ra17387j-t5.tif(5)
wherein, Ct and C0 are the concentration of the reactant nitrophenol at any time (t) and at the start of the reaction i.e. at time (t = 0). kapp is the apparent rate constant value for pseudo-first order reduction reactions. As absorbance is directly proportional to the concentration, the kapp values were acquired from the slope of the straight lines obtained after plotting ln(At/A0) vs. time (t), where, At and A0 are the absorption maxima of the reactant nitrophenol at any time (t) and at the start of the reaction i.e. at time (t = 0). The ln(At/A0) vs. time plots for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts (5 mg, 10 mg and 15 mg) of M@Dop@CoFe2O4 (M = Cu and Ag) where metal loading was varied from 2.5 wt% to 20 wt% are shown in Fig. 13 and 14 respectively.

image file: c6ra17387j-f13.tif
Fig. 13 The ln(At/A0) vs. time curves for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts (5 mg (a–c), 10 mg (d–f) and 15 mg (g–i)) of Cu@Dop@CoFe2O4 where metal loading was varied from 2.5 wt% to 20 wt%.

image file: c6ra17387j-f14.tif
Fig. 14 The ln(At/A0) vs. time curves for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts (5 mg (a–c), 10 mg (d–f) and 15 mg (g–i)) of Cu@Dop@CoFe2O4 where metal loading was varied from 2.5 wt% to 20 wt%.

The values of completion times and apparent rate constants for the reduction of ortho-, meta- and para-nitrophenols in the presence of varying amounts of M@Dop@CoFe2O4 (M = Cu and Ag), where metal loading was varied from 2.5 wt% to 20 wt%, are given in Tables 3–5 respectively. For both the catalytic systems, significant improvement in the catalytic performance with increase in metal loading from 2.5 wt% to 10 wt% can also be confirmed from the decreasing values of completion time and increase rate constant values. Almost same completion time values and comparable rate constant values were observed for 10 wt% and 20 wt% metal loaded samples. Also lower completion times and higher rate constant values were observed for all the Cu@Dop@CoFe2O4 nanocomposites in comparison to Ag@Dop@CoFe2O4 nanocomposites.

Table 3 The values of completion times and apparent rate constants for the reduction of ortho-nitrophenola

image file: c6ra17387j-u1.tif

Nanocatalyst M@Dop@CoFe Completion time (min) (T) and rate constant (K × 10−1)
Metal loading (wt%)
2.5 wt% 5 wt% 7.5 wt% 10 wt% 20 wt%
M Catalytic amount T K T K T K T K T K
a Reaction conditions: 2-nitrophenol: 0.72 mmol, NaBH4: 50 eq., water, 25 °C, catalyst: M@Dop@CoFe2O4 (M = Cu and Ag; metal loading 2.5–20 wt%; catalyst amount: 5, 10 and 15 mg).
Cu 5 mg 8.00 3.15 4.00 9.16 2.50 10.20 1.50 17.40 1.50 17.69
10 mg 3.50 7.77 2.50 9.43 2.00 14.39 1.00 25.96 1.00 26.17
15 mg 2.50 9.03 2.00 14.26 1.75 17.37 1.00 27.74 1.00 27.76
Ag 5 mg 16.00 2.15 6.00 4.77 4.00 7.55 2.00 15.66 2.00 16.47
10 mg 5.00 6.38 4.00 6.78 3.00 10.09 1.50 18.64 1.50 19.96
15 mg 4.50 5.02 3.00 10.05 2.25 12.63 1.50 18.57 1.50 19.36


Table 4 The values of completion times and apparent rate constants for the reduction of meta-nitrophenola

image file: c6ra17387j-u2.tif

Sample M@Dop@CoFe Completion time (min) (T) and rate constant (K × 10−1)
Metal loading (wt%)
2.5 wt% 5 wt% 7.5 wt% 10 wt% 20 wt%
M Catalytic amount T K T K T K T K T K
a Reaction conditions: 3-nitrophenol: 0.72 mmol, NaBH4: 50 eq., water, 25 °C, catalyst: M@Dop@CoFe2O4 (M = Cu and Ag; metal loading 2.5–20 wt%; catalyst amount: 5, 10 and 15 mg).
Cu 5 mg 16.00 1.53 5.50 4.76 4.00 7.44 2.00 12.63 2.00 12.78
10 mg 5.00 5.46 3.00 8.51 2.50 11.06 1.50 17.87 1.50 18.89
15 mg 5.50 3.94 3.50 6.13 2.25 10.71 2.00 16.80 1.50 21.25
Ag 5 mg 40.00 0.67 7.50 3.14 6.00 4.77 3.00 9.12 2.50 9.38
10 mg 6.00 3.82 3.50 6.82 3.00 8.43 2.50 10.19 2.50 11.24
15 mg 5.50 3.00 3.50 5.13 2.25 8.07 2.00 14.11 1.50 14.94


Table 5 The values of completion times and apparent rate constants for the reduction of para-nitrophenola

image file: c6ra17387j-u3.tif

Sample M@Dop@CoFe Completion time (min) (T) and rate constant (K × 10−1)
Metal loading (wt%)
2.5 wt% 5 wt% 7.5 wt% 10 wt% 20 wt%
M Catalytic amount T K T K T K T K T K
a Reaction conditions: 4-nitrophenol: 0.72 mmol, NaBH4: 50 eq., water, 25 °C, catalyst: M@Dop@CoFe2O4 (M = Cu and Ag; metal loading 2.5–20 wt%; catalyst amount: 5, 10 and 15 mg).
Cu 5 mg 60.00 0.68 15.00 2.51 6.00 6.25 3.00 11.71 2.50 15.38
10 mg 6.00 4.78 4.00 8.06 3.00 11.21 2.00 14.21 2.00 16.96
15 mg 5.00 6.90 3.50 9.95 2.50 12.31 2.00 16.48 2.00 17.08
Ag 5 mg 80.00 0.45 40.00 0.98 20.00 1.93 3.50 8.88 3.50 10.75
10 mg 7.00 4.17 4.50 6.80 3.50 9.32 3.00 10.40 3.00 10.52
15 mg 6.00 6.14 4.00 9.11 3.00 11.89 2.50 15.02 2.50 16.84


3.6.3. Reduction of other nitroarenes. From the above given results obtained from the reduction of nitrophenols, 10 wt% cu loaded over the surface of modified cobalt ferrite nanoparticles was found to be the best catalyst. To further establish the substrate scope and versatility of the present protocol, reduction of various chloro, amino, methyl and bromo derivatives was carried out in the presence of methanol as solvent. The time dependent progress of the reduction of nitroderivatives other than nitrophenols was not associated with any colour change. So GC-MS was employed for evaluating the completion times and % conversion. 100% conversion and 100% selectivity was achieved for all the nitro derivatives as confirmed from the absence of even trace amounts of any side products in the GC-MS analysis. The details of the reduced nitro derivatives along with the completion time values are given in Table 6. All the GC-MS data for the reduction of all the nitroarenes is given in ESI file (GC-MS-1 to GC-MS-15) as mentioned in Table 6.
Table 6 The values of time taken for complete conversion, conversion% and selectivity% for all the nitroarenesa

image file: c6ra17387j-u4.tif

Serial no. Substrate Product Timeb (min) Conversion%/selectivityb% Spectra no.
a Reaction conditions: nitroarene (0.72 mmol), NaBH4 (50 eq.), methanol, 25 °C, catalyst: Cu@Dop@CoFe2O4; metal loading 10 wt%; catalyst amount: 10 mg.b Completion time, conversion% and selectivity% were obtained using GC-MS analysis.
1. image file: c6ra17387j-u5.tif image file: c6ra17387j-u6.tif 6.0 100/100 GC-MS-1
2. image file: c6ra17387j-u7.tif image file: c6ra17387j-u8.tif 20.0 100/100 GC-MS-2
3. image file: c6ra17387j-u9.tif image file: c6ra17387j-u10.tif 4.5 100/100 GC-MS-3
4. image file: c6ra17387j-u11.tif image file: c6ra17387j-u12.tif 6.0 100/100 GC-MS-4
5. image file: c6ra17387j-u13.tif image file: c6ra17387j-u14.tif 22.0 100/100 GC-MS-5
6. image file: c6ra17387j-u15.tif image file: c6ra17387j-u16.tif 6.0 100/100 GC-MS-6
7. image file: c6ra17387j-u17.tif image file: c6ra17387j-u18.tif 9.0 100/100 GC-MS-7
8. image file: c6ra17387j-u19.tif image file: c6ra17387j-u20.tif 8.0 100/100 GC-MS-8
9. image file: c6ra17387j-u21.tif image file: c6ra17387j-u22.tif 4.0 100/100 GC-MS-9
10. image file: c6ra17387j-u23.tif image file: c6ra17387j-u24.tif 3.0 100/100 GC-MS-10
11. image file: c6ra17387j-u25.tif image file: c6ra17387j-u26.tif 4.0 100/100 GC-MS-11
12. image file: c6ra17387j-u27.tif image file: c6ra17387j-u28.tif 5.0 100/100 GC-MS-12
13. image file: c6ra17387j-u29.tif image file: c6ra17387j-u30.tif 7.0 100/100 GC-MS-13
14. image file: c6ra17387j-u31.tif image file: c6ra17387j-u32.tif 0.5 100/100 GC-MS-14
15. image file: c6ra17387j-u33.tif image file: c6ra17387j-u34.tif 2.0 100/100 GC-MS-15


3.6.4. Mechanistic pathway. In polar protic solvents such as methanol and water, decomposition reaction of sodium borohydride starts at once, generating H2 gas.35 Also NaBH4 got ionized to give BH4 ions. Reaction starts with the addition of catalyst in to the nitroarene solution. Reactant nitro derivative and borohydride ions get adsorbed on the surface of the metals loaded over the modified cobalt ferrite nanoparticles to yield metal hydride complexes. Reduction reaction takes place at these metal hydride complexes where nitro moieties get converted to corresponding amines. After the completion of the reaction the products formed get desorbed from the surface and catalyst was magnetically separated out of the reaction mixture using an external magnet and washed thoroughly with distilled water and acetone and becomes free for the next reaction. The schematic representation of the reaction mechanism is shown in Fig. 15.
image file: c6ra17387j-f15.tif
Fig. 15 Schematic representation of the reaction mechanism for the reduction of nitroarenes in the presence of M@Dop@CoFe nanocatalyst.
3.6.5. Hot filtration experiment and recyclability. To discard the possibility of leaching of metal (active species) in to the reaction mixture and weakening of the catalyst over successive catalytic runs hot filtration experiment was performed. Wherein, reduction of 4-NP was performed in the presence of 10 mg of 10 wt% Cu@Dop@CoFe2O4 as catalyst and reaction was stopped after 1 minute after the start of the reaction by just filtering out the catalyst using a syringe filter. It was then observed that till one minute ∼70% conversion was achieved and after the separation of the catalyst, almost no further conversion of nitrophenol to aminophenol was observed in the supernatant solution (Fig. 16(a)). So this hot filtration experiment established the stability of the synthesized nanocomposite and also ruled out the possibility of metal leaching which is the major issue associated with the heterogeneous catalysis.
image file: c6ra17387j-f16.tif
Fig. 16 (a) Hot filtration experiment ruling out the possibility of metal leaching and (b) recyclability of the catalyst up to 5 catalytic runs.

Recyclability is the key feature of any heterogeneous catalyst. As the synthesized nanocomposite catalysts are magnetic in nature so these can be very easily recovered out of the reaction mixture after the completion of reaction using an external magnet. So after the recovery of the catalyst the catalyst was washed with acetone and distilled water repeatedly to remove any reactant or product adsorbed and was vacuum dried. So recyclability of the catalyst was checked up to 5 catalytic runs. For the recyclability experiment reduction of 4-NP was performed in the presence of 10 mg of 10 wt% Cu@Dop@CoFe2O4 nanocomposites. No significant dilapidation in the catalytic performance in terms of completion time and percent conversion was observed to be there. Recyclability experiment has been illustrated in Fig. 16(b).

4. Conclusions

A highly robust and economic reduction protocol has been procured which employs metal stabilized over modified magnetic ferrite nanoparticles (M@Dop@CoFe2O4) as catalyst. Varying amounts of both Ag and Cu metal nanoparticles were affixed over the surface of modified ferrite nanoparticles. Irrespective of the nature of the metal loaded over the surface of modified ferrite nanoparticles, catalytic performance effectively got improved with increase in the metal loading from 2.5 wt% to 10 wt% while not much considerable augmentation in the catalytic performance was observed to be there when metal loading was raised above 10 wt%. Cu@Dop@CoFe2O4 nanocomposites possessed better catalytic activity than that of Ag@Dop@CoFe2O4 nanocomposites. The synthesized nanocomposites have been established as very stable, magnetically recyclable and leach-proof competent catalyst for the reduction of nitroarenes. Substrate scope was evaluated for different nitroderivatives, so the synthesized nanocomposites have been established to be versatile catalysts that can be employed for industrial applications as well.

Acknowledgements

Financial supports from Council of Scientific and Industrial Research (CSIR) are gratefully acknowledged. The authors wish to thank Sophisticated Analytical Instrumentation Facility (SAIF), Panjab University (PU) for providing the instrumentation facility for the required characterizations. The authors are also grateful to Kunash Instruments Pvt. Ltd., Thane (W) for performing the surface area analysis of the samples.

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Footnote

Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra17387j

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