Accepted Manuscript

A novel MnFe2O4/ Graphitic carbon nitride (g-C3N4) nanocomposites as effi-

cient magnetically retrievable catalyst in crossed aldol condensation

Bishal Bhuyan, Dibya Jyoti Koiri, Meghali Devi, Siddhartha Sankar Dhar

PII: S0167-577X(18)30185-X
DOI: https://doi.org/10.1016/j.matlet.2018.01.168
Reference: MLBLUE 23816

To appear in: Materials Letters

Received Date: 18 October 2017

Revised Date: 23 January 2018
Accepted Date: 30 January 2018

Please cite this article as: B. Bhuyan, D. Jyoti Koiri, M. Devi, S. Sankar Dhar, A novel MnFe2O4/ Graphitic carbon
nitride (g-C3N4) nanocomposites as efficient magnetically retrievable catalyst in crossed aldol condensation,
Materials Letters (2018), doi: https://doi.org/10.1016/j.matlet.2018.01.168

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A novel MnFe2O4/ Graphitic carbon nitride (g-C3N4) nanocomposites as efficient magnetically

retrievable catalyst in crossed aldol condensation

Bishal Bhuyan, Dibya Jyoti Koiri, Meghali Devi, Siddhartha Sankar Dhar*

Department of Chemistry, National Institute of Technology, Silchar, Silchar-788010, Assam, India

*Corresponding authors. Tel: +91-03842-242915; fax: +91-03842-224797

Email: ssd_iitg@hotmail.com (S.S. Dhar)

Abstract:

Novel MnFe2O4/g-C3N4 composites were successfully synthesized via a facile hydrothermal route in

combination with ultrasonication and calcination techniques. XRD patterns of the as-synthesized

composite furnished evidence for presence of both MnFe2O4 and g-C3N4 components. SEM and TEM

micrographs also confirmed the successful formation of the MnFe2O4/g-C3N4 composite. The catalytic

efficiency of the synthesized composite was investigated in crossed aldol condensation of acetone with

benzaldehyde. The results demonstrated that the condensation reaction produced dibenzylideneacetone

(DBA) in excellent yields under reasonably mild conditions. Owing to the presence of g-C3N4 nanosheets,

MnFe2O4/g-C3N4 composite exhibited a larger specific surface area and also an inherent basic

characteristic. The other key feature of the composite is its easy magnetic recovery.

Keywords:

Nanocomposites; magnetic materials; crossed-aldol condensation; MnFe2O4; g-C3N4

Introduction:

Improvement of existing catalytic protocols for synthetically important organic reactions may be

considered as an important goal for all fundamental research. Literature survey confirms that such

improvements have always been at the forefront of research activity for many generations from time to

time [1-2]. Aldol and crossed-aldol condensation is a powerful tool for formation of carbon-carbon bond

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in many kinds of carbonyl compounds [3]. There have been large number of reports wherein self and

crossed-aldol condensations of ketones and aldehydes have been carried over solid base catalysts [4,5].

Homogeneous bases like NaOH, Ca(OH)2, KOH etc. were largely used previously for carrying

out base catalyzed reactions [6]. These bases were needed in excess and were quite difficult to remove

from the reaction mixtures after completion. Several additional steps such as base neutralization, tedious

product separation and purification, management of corrosion and waste were needed to be handled to

accomplish the reactions [7]. Such drawbacks of homogeneous catalytic systems motivated researchers to

develop heterogeneous catalytic procedures for self and crossed-aldol condensation reactions.

Nanocatalysts fall into a domain which practically acts as a bridge between homogeneous and

heterogeneous character of catalysts. Among these, magnetic nanocatalysts have attracted an enormous

attention due to their unique physico-chemical properties as evidenced in their wide applicability in

magnetic storage devices, catalysis, microwave absorption, drug delivery, etc. [8]. Magnetic spinel

ferrites (M(2+)Fe2(3+)O4), particularly MnFe2O4 are a special class of spinel structured nanoparticles. There

are numerous reports on use of MnFe2O4 as magnetically retrievable efficient nanocatalyst in recent times

[9]. In addition, graphitic carbon nitride (g-C3N4) is a carbon based material which is emerging as a highly

efficient and promising metal free heterogeneous catalyst. g-C3N4 have some uncondensed amino groups

in the forms of –NH2 and –NH– groups at the edges of the graphitic sheets, which can be used in several

base catalyzed reactions [10]. As a part of our ongoing endeavour on synthesis and application of

nanocatalysts [11-14], we contemplated to fabricate a novel nanocomposite MnFe2O4/g-C3N4 and study its

efficacy as magnetically retrievable catalyst for the condensation reaction between benzaldehyde and

acetone to produce DBA. It is reasonable to believe that g-C3N4 provides a basic characteristic to our

magnetically recoverable MnFe2O4/g-C3N4 nanocatalyst which meets the requirement of our objective.

2. Experimental:

2.1 Synthesis of graphitic carbon nitrite (g-C3N4)

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For the preparation of g-C3N4, 5.0 g of urea was placed in a crucible with a lid and was heated to 550° C

in a muffle furnace for 3 h in air atmosphere. The resulting final pale yellow coloured powder was

allowed to cool to room temperature and stored until further use.

2.2 Synthesis of MnFe2O4/g-C3N4 NCs

MnFe2O4 NPs was prepared by reported method (see ESI) [15]. An amount of 0.5 g of MnFe2O4 and 20 wt

% of g-C3N4 were taken and ultrasonicated for 30 min in 20 mL of ethanol. It was then followed by

continuous stirring for 12 h to get a homogeneous suspension. The resultant mixture was then centrifuged

at 7500 rpm for 10 min and dried in an oven to get the desired product.

2.3 Crossed aldol condensation of acetone with benzaldehyde

Acetone (5.0 mmol) was mixed with benzaldehyde (10.0 mmol) in a 50 mL RB flask connected with a

condenser. The catalyst, MnFe2O4/g-C3N4 was then added to the mixture (10 mol %). The mixture was

then heated in an oil bath at 70° C for 2 h to get the desired product. After completion, the mixture was

allowed to cool at room temperature. The catalyst was then separated by using an external magnet. The

filtrate was kept undisturbed at room temperature for approximately 12 h to afford yellow crystalline

product. Product was filtered and recrystallized from acetonitrile. The characterization of the product was

made by melting point determination, 1H NMR and 13C NMR spectroscopy.

The yield of dibenzylideneacetone (DBA) was calculated as follows:

Yield of DBA (%) = 100 x (Grams of DBA obtained / Grams of DBA obtained theoretically)

3. Results and discussions:

3.1 Characterization of the as-synthesized catalyst:

The crystalline phase and purity of MnFe2O4, g-C3N4 and MnFe2O4/g-C3N4 samples were characterized by

X-ray powder diffraction (XRD) analysis. In Fig. 1(a), the diffraction peaks matches well with the

reported data of MnFe2O4 NPs (JCPDS File no. 89-2807). The system is cubic. Likewise, in Fig. 1(b), the

pure g-C3N4 shows strong diffraction peak at 25.39°, 26.5° and 46.19° which corresponds to (101) (002)

(201) plane due to interlayer stacking of conjugated aromatic system (JCPDS file no. 87-1526, system-

hexagonal, lattice- primitive). Fig.1(c) suggests coexistence of both MnFe2O4 and g-C3N4 in MnFe2O4/g-

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C3N4 NCs. Besides, no other impurity phases were detected which indicate high purity of the MnFe2O4/g-

C3N4 nanocomposite.

Figure 1: XRD patterns of synthesized (a) MnFe2O4 NPs, (b) g-C3N4, (c) MnFe2O4/g-C3N4, TEM images

of (d) MnFe2O4/g-C3N4, (e) magnified view of MnFe2O4/g-C3N4, (f) SAED patterns of MnFe2O4/g-C3N4.

TEM micrographs are consistent with the XRD findings. Fig. 1(d) shows MnFe2O4 /g- C3N4 NCs

where the existence of two components is quite obvious. Fig. 1(f) shows polycrystalline nature of the

composite, perhaps due to the uniform distribution of polycrystalline MnFe2O4 NPs in g-C3N4 sheets. It is

obvious, from the micrographs that two types of materials can be seen in these images which correspond

to MnFe2O4 (dark colour) and g-C3N4 sheets (grey colour). Similar observations were correspondingly

noted from the SEM micrographs (see section S3 in ESI). EDAX mapping of as-synthesized MnFe2O4 /g-

C3N4 NCs are displayed in Fig. 2. The mapping depicts the various elements present in the composite in

different colours. This further ascertains the successful fabrication of the composite. VSM analysis was

also measured for the composite (Fig. S.3.1(d) in ESI). Herein, magnetization changes were recorded with

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the applied magnetic field sweeping of ±15000 G. The magnetic hysteresis loops show a super-

paramagnetic behaviour. The saturated magnetization (Ms) was recorded to be 2.9043 emu g-1.

Figure 2: EDAX mapping analysis of synthesized MnFe2O4/g-C3N4 NCs

3.2 Catalytic efficiency of MnFe2O4/g-C3N4 NCs for crossed aldol condensation of acetone with

benzaldehyde

After investigating the successful formation of MnFe2O4/g-C3N4 NCs, the efficiency of the as-prepared

NCs as heterogeneous catalysts for crossed aldol condensation reaction was explored in the condensation

reaction between benzaldehyde and acetone. Various parameters such as catalyst amount, reaction time

(hours) and reaction temperature (°C) have been optimized to obtain best possible results.

In order to optimize the catalyst amount, the reaction was carried out with 5 mol % to 15 mol % of the

catalyst with respect to substrate (Fig. 3(a)). It was observed that there was an increase in yield percentage

of DBA from 5 mol % to 10 mol % of the catalyst, however beyond 10 mol %, no such increase in yield

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of DBA was observed. Thus, 10 mol % was the optimized amount of the catalyst to perform the reaction.

Next, we optimized the reaction temperature. The reaction was allowed to attain various temperatures

ranging from 50o C to 80o C. There was an incremental increase in yield percentage of DBA with different

temperatures, giving maximum yield at 70o C (Fig. 3 (b)). Reaction time also plays a crucial role in

organic transformations. To evaluate the effective time for completion of reaction, the reaction was

performed at 70o C for reaction times ranging from 1 h to 3 h. Interestingly, it took 2 h to provide

maximum yield (DBA, 92%) (fig. 3 (c)). Similar performance of the catalyst was evaluated upon

repetition of the process with MnFe2O4 indivitually. Due to the absence of g-C3N4 components, it showed

no such catalytic performance in DBA synthesis. The synergistic effect between g-C3N4 and

MnFe2O4 is assumed to play a vital role in the catalytic performance. In the present study, the

inherent basic nature of g-C3N4 is certainly responsible for efficient condensation of acetone and

benzaldehyde to DBA.

Figure 3: Effect of various reaction parameters on crossed aldol condensation of acetone with

benzaldehyde: (a) catalyst amount, (b) Reaction temperature, (c) Reaction time, (d) Recyclability test of

the catalyst.

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 Though the exact mechanism cannot be comprehended at the present moment, it is believed that

the inherent basic character of g-C3N4 provides some degree of basicity to MnFe2O4/g-C3N4 NCs. This

basicity of the composite perhaps helps in abstracting a proton from acetone, which then transforms into a

nucleophile. The nucleophilic centre then attacks electron deficient C-atom of benzaldehyde to form the

desired product of DBA [16].

3.3 Recyclability of catalyst:

To check the efficiency of the reused catalyst, after each catalytic run, the catalyst was magnetically

recovered, washed thoroughly with ethanol, acetone and reused for multiple times. The same catalytic

reaction under identical conditions was carried out with the recovered catalyst. Interestingly, the activity

of the catalyst after 4 consecutive run did not lead to any obvious turn down in terms of yield (Fig 3(d)).

Conclusions:

In conclusion, a facile preparation method of a novel MnFe2O4/g-C3N4 NCs was developed. The method

involves hydrothermal treatment followed by ultrasonication technique. Thorough characterization

suggests the uniform distribution of MnFe2O4 over g-C3N4 nanosheets. Previously, composites based on g-

C3N4 have not been used in crossed aldol condensation. The reported MnFe2O4/g-C3N4 NCs was found to

be highly efficient catalyst for synthetically important crossed aldol condensation between acetone and

benzaldehyde. Salient features of this catalytic protocol are its magnetically retrievable nature and

reusability.

Acknowledgements:

The authors thank STIC Cochin, SAIF, IIT Bombay and SAIF, Gauhati University for analysis. BB

acknowledges Director, NIT Silchar for providing institutional fellowship.

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Graphical abstract

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Highlights

• Novel MnFe2O4/g-C3N4 nanocomposites were synthesized by a hydrothermal route.

• XRD patterns furnished evidence for presence of both MnFe2O4 and g-C3N4 components.

• TEM and SEM findings were indicative of formation of the nanocomposite.

• Composite showed high catalytic efficacy in crossed aldol condensation reaction.

• Crossed aldol condensation was carried out between acetone and benzaldehyde.

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