Low Cost Well Designed Heterogeneous Catalyst derived from Eggshell

Waste and its Application in Heterogeneous Catalysis

Manashjyoti Konwar

Research Scholar

Due to the greater toxicity problem and expenditure of the volatile organic chemicals

(VOCs) it is very necessary to reuse and recycle the all the chemicals and catalysts as much as

possible for the superior and greener future of the environment. Keeping these points on our

mind, we have to plan all our research work in a green manner so that there should be less

harmful effect on the environment. Again, ‘Sustainable Chemistry’ focuses on design of products

and processes that diminishes the use and generation of harmful chemical substances. Therefore,

use of green catalytic systems and protocols could be able to develop more resource proficient

and necessarily safer design of molecules, products and processes which will be useful in near

future.

There are two types of catalyst, homogeneous (in which reactants and catalyst are in

same phase) and heterogeneous type (in which reactants and catalyst are in different phases).
Although, homogeneous catalyzed reactions are well acknowledged in synthetic organic

chemistry with some disadvantages like hard to separate from the reaction mixture, non

recyclable nature etc. After the reaction, this kind of catalyst might be breakdown and eventually

losses its activity. On the other hand, heterogeneous catalysts are simple and easy to recover

from the reaction mixture. In recent years, the improvement of green heterogeneous catalytic

systems attributed great implication to the field of synthetic organic and material science

chemistry which may cause benign environment consequences with high selectivity of the

required molecules, great yield and along with fewer amounts of side products.

Calcium carbonate is the most commonly used carbonate compound used in the daily life

of agriculture for neutralizing acidic soil making, medicinal purpose as the dietary calcium

supplement etc. It is a substance found in the form of calcite and aragonite (most commonly as

limestone) as the minerals and is the main component of the egg shell and pearls. Therefore, egg

shell is an important natural feedstock of calcium carbonate along with little percentage of

calcium phosphate. Literature reveals that egg shell contains approximately 95% CaCO3, 2%

Ca3(PO4)2, 2% magnesium MgCO3 and 1% of organic substances mostly of albuminous

character.1 Due to the basic nature of Egg Shell Powder (ESP), we thought it could be widely

used in synthetic organic processes as a base alternative and/or as a solid support for

heterogeneous catalysis.

To explore the catalytic activities of the ESP, several organic transformation were carried

out in presence of it as a base alternative and/or as a solid support.2 Recently, we explored its

basic activities by using it as a base alternative in the peptide coupling and Click reactions at

room temperature.3-4 Similarly, Suzuki-Miyaura reactions were also carried out in presence of

ESP with a dual role of acting as a base alternative and as a solid support where in situ
generation of palladium nanoparticles were formed at room temperature.5 In here, in situ

generated palladium nanoparticles were impregnated in the ESP surface which was characterized

by using Scanning Electron microscope (SEM), Transition Electron Microscope (TEM), Powder

X-ray Diffraction (XRD) and Energy-dispersive X-ray Analysis.

Click reaction

ESP R N N N
R N3 + R'
CuSO4. 5H2O, Water, RT
R'

Aromatic Aromatic
Azide Alkyne 1,4-disubstituted-1H-1,2,3-triazole

Peptide coupling
O R1
O R1 R2 H
N COOMe
+ ESP Ph N
Ph N COOH H2N COOMe. HCl H O
H R2
EDC.HCl, RT
water
L-amino acid methyl
Bz-L-amino acid Bz-L-AA1-L-AA2 methyl ester
ester hydrochloride

Suzuki-Miyaura reaction through insitu generated palladium nanoparticles

Br B(OH)2 R2
ESP
+

R1 R2 Pd (OAc)2 ,
R1
Water, RT
Substituted biaryls
Aryl boronic
Aryl bromide acid

Figure: Synthetic organic transformation carried in presence of ESP

TEM image of in situ generated Pd

SEM image of ESP nanoparticles in ESP as a solid support
 TEM-EDX of Pd-ESP complex

The heterogeneous nature and recyclability power of ESP make it very extensive and

inexpansive catalyst for robust synthesis many other desired chemicals. The full scope of this

catalyst is still unexplored due to its broad probable applications and researches were going on to

explore its further scopes and applications that could be applicable for further synthetic organic

transformations in near future.

References

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Brun, M. Lupo, D. A. Delorenzi, V. E. Di Loreto, A. Rigalli, Int. J. Food Sci. Nutr.,

2013, 64, 740–743. (c) S. E. Scheideler, J. Appl. Poult. Res., 1998, 7, 69–74. (d) T. R.

Rao, Chem. Eng. Technol., 1996, 19, 373–377; d) I. Halikia, L. Zoumpoulakis, E.

Christodoulou, D. Prattis, Eur. J. Miner. Process Environ. Prot., 2001, 1, 89–102.

2. (a) S. Patil, S. D. Jadhav, S. K. Shinde, CES as an Efficient Natural Catalyst for

Synthesis of Schiff Bases under Solvent-Free Conditions: An Innovative Green

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3. M. Konwar, A. A. Ali, D. Sarma, A green protocol for peptide bond formation in

WEB, Tetrahedron Lett., 2016, 57, 2283–2285.

4. M. Konwar, A. A. Ali, M. Chetia, P. J. Saikia, N. D. Khupse, D. Sarma, ESP

Promoted “On Water” Click Reaction: A Highly Economic and Sustainable Protocol

for 1,4-Disubstituted-1H-1,2,3-Triazole Synthesis at Room Temperature,

ChemistrySelect, 2016, 1, 6016 – 6019.

5. M. Konwar, P. R. Boruah, P. J. Saikia, N. D. Khupse, D. Sarma, ESP-Promoted

Suzuki-Miyaura Cross-Coupling and Peptide Bond Formation Reactions in Water at

Room Temperature, ChemistrySelect, 2017, 2, 4983 – 4987.