A waste to wealth approach through utilization of nano-ceramic tile waste as an accessible and inexpensive solid support to produce a heterogeneous solid acid nanocatalyst: To kill three birds with one stone

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A waste to wealth approach through utilization of nano-Ceramic

Tile Waste as an accessible and inexpensive solid support to

produce a heterogeneous solid acid nanocatalyst: To kill three

birds with one stone

Received 00th January 20xx,

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x

Eskandar Kolvari*, Nadiya Koukabi, Somayeh Zolfagharinia, Maliheh. M. Hosseini

www.rsc.org/

Abstract

Regarding the subject of waste products/materials, recycling or reusing has had a pivotal role on account of environmental

and economic reasons. As a consequence, the essential task, nowadays, can be invention of new and practical pathways to

reuse or even recycle them. In this framework, until now, recycling of some waste products such as tile wastes have not

been taken in to consideration; so, we were prompted by the possibility of recycling tile wastes in the catalytic direction.

To this end, we use them as cost-effective, available, and nontoxic support materials for the heterogenization of sulfuric

acid catalyst, in order to prepare the novel nano-Ceramic Tile Waste supported sulfonic acid catalyst (nano-Ceramic Tile

Waste-SO₃H or n-CTW-SA). This solid acid catalyst well characterized through FT-IR, XRD, FE-SEM, EDX, TEM, TGA, BET,

BJH, pH analysis and Hammett acidity function. The as-prepared nano-Ceramic Tile Waste supported sulfonic acid catalyst

proved to be an active heterogeneous catalyst in multicomponent reactions (MRCs) for the rapid and efficient one-pot

synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles in high yields and selectivity. In comparison with

some other homogeneous and heterogeneous catalysts, nano-Ceramic Tile Waste supported sulfonic acid displayed a

greater activity. Moreover, being highly stable, inexpensive, accessible, retrievable, reusable, low toxic are some other

beneficial points of this catalyst.

Keywords: Recycling, n-Ceramic Tile Waste, Nano-Ceramic Tile Waste supported sulfonic acid, Multicomponent reaction,

Heterogeneous catalyst, Solid acid.

products can be broaden from research laboratories to the

chemical industry scopes. Till now, numbers of examples

1. Introduction

have been reported in which large scale waste

materials/products from industrial process (as by-products)

or biological resources are considered and their catalytic

applications are taken into consideration such as red mud,²

Waste products as resources, have opened an avenue to the

catalysis and, therefore, to the waste and energy

minimization. The catalytic opportunities offered by waste

materials, in the further step, can attribute to plenty of

beneficial factors connected to economy and environment.

In this regard, as reported in the literatures, waste materials

can be put to practical use either by their application directly

as catalyst, pre-catalyst, and catalyst precursors or by

aluminum dross,³fly ash,⁴raw blast furnace slag,⁵chicken

8

egg shell,⁶shrimp shell,⁷rice husk and rice husk ash

.

However, there is still a great demand that research will be

pointed toward more efficient, eco-friendly and economic

solutions so as to put other recyclable waste products in the

direction of recycling. One example of these waste products

is ceramic tile wastes whose chemical compositions, in

general, are included large amounts of clay, carbonate,

quartz, and minor amount of talc, which make the ceramic

tiles rich in the contents of SiO₂(32-67%) and Al₂O₃(8-31%).

However, a source of TiO₂, Fe₂O₃, and CaO is existed in slight

amounts in the body of the ceramic tile clay.^9-12The Fe₂O₃+

TiO₂as well as CaO must be maintained at low amount to

modifying them to produce active catalysts.¹As

a

consequence, the provided catalytic opportunities by waste

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avoid undesired colour in the ceramic product ¹³. Thanks to

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already been examined extensively.³⁰Therefore, we thought

that ceramic tile waste could offer golden opportunities to

use them as supports for immobilizing of homogeneous

catalysts (such as sulfuric acid), thereby drawing organic

transformations into the realm of green and sustainable

chemistry. Following up our research group’s attempts in

the context of investigation and application of solid acids in

chemical transformations,^31-36herein, we have designed a

novel, cost-effective, low toxic, recyclable, and reusable

nano-Ceramic Tile Wastes supported sulfonic acid, by the aid

of chlorosulfonic acid as sulfonating agent. It is worthy to

mention that supporting sulfonic acid through sulfonating

with chlorosulfonic acid, provided by the procedure first

reported by zolfigol,³⁷have garnered much attention for the

their body raw materials, ceramic tiles exhibit peculiar

characteristics such as high thermal stability, high porosity,

strong reactivity and sorption, low moisture expansion, low

cost, low toxicity, large surface areas, and ease of handling.¹¹

Therefore, the above-mentioned advantages have laid the

foundations of their applications in civil construction

architecture for covering floors or external/internal wall in

the building and for decorative or aesthetic purposes.¹⁰

While Homogeneous catalysts possess the advantages of

easy accessibility of reactants to the catalytic sites in

reaction media, high activity, and selectivity, they most of

the time render difficulties related to their separation from

products and reaction solvents; therefore, vast quantities of

homogeneous catalysts will be consumed in each reaction

sake of being a convenient, fast and efficient method for

heterogenization of sulfuric acid.^35,

run.^14-16To address this thorny issue,

a

step toward

Subsequently, we

38-44

enhancement the separation and recycling of homogeneous

catalysts has been to apply thermal or chemical recovery,

membrane processes, and multiple phase transfers.¹⁵In this

framework, soluble supporting materials for the

immobilizing catalysts have also attracted an immense focus

of attention because not only they can help the reaction

conditions in liquid-phase to maintain, but they also offer an i.

opportunity to solve problems of insoluble heterogeneous

material.^17-24Nevertheless, due to generating huge amounts ii.

of waste and, thus, being uneconomic, this approach is

impractical in chemical and pharmaceutical industry.²⁵To

studied the catalyst’s performance in the one-pot synthesis

of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted

imidazoles subsequent to the deeply investigation of the

reactivity, reusability, and stability of the as-obtained

catalyst.

Our main targets are as follow:

Recycling ceramic tile wastes in an effort to minimize cost and

land pollution as well.

Utilizing them as porous, low cost, readily available, low-toxic,

and thermally stable support materials to produce the active,

novel nano-Ceramic Tile Wastes supported sulfonic acid

catalyst.

tackle this problem, micro-sized-heterogeneous catalysts are

introduced to the industry.^26,

27

However, in comparison iii.

Applying the designed catalyst in the multicomponent (MRCs)

reaction conditions of 2,4,5-trisubstituted and 1,2,4,5-

tetrasubstituted imidazoles synthesis because of their

with homogenous systems, they suffer from lower activities

caused by steric or diffusion factors.²⁶Additionally, in such a

heterogeneous system, reactants encounter the difficulties

in terms of accessing to the catalytic sites since a high

proportion of these catalysts are deep within the supporting

matrix.²⁶Nano-scale supporting materials or catalysts have

set a milestone effect on the improvement of the activity

and selectivity of catalysts through their increased ratio of

surface areas to volumes. Consequently, the support

materials can be evenly dispersed in solution, generating a

homogenous emulsion.^{26, 28}Moreover, in the system where

nanocatalysts are presented the problems regarding the

porosity and transport of reactants and/ or products to and

from the catalytic sites can be approached.

applications in biological, therapeutic and agricultural sectors.

45-53

2. Experimental section

2.1. Instrumentation, analysis, and starting materials

All chemicals were purchased from Merck and Aldrich

companies and used without any further purification.

Ceramic tiles Waste was prepared from Semnan Tile (Iran).

According to manufacturing formula of the Semnan Tile

factory, ceramic tile is produced from clay, sand, feldspar,

quartz, and water. Ceramic tile powder was prepared by

two-cup planetary ball mill of Iran. All yields refer to the

isolated products after purification. Products were

characterized by their physical constants and comparison

with authentic samples. The purity of products was checked

by thin layer chromatography (TLC) on glass plates coated

with silica gel 60 F254 using n-hexane/ethyl acetate mixture

as mobile phase. Melting points were determined in open

capillaries using an Electrothermal 9100 without further

corrections. Fourier transform infrared spectroscopy (FTIR)

was recorded on a Shimadzu 8400s spectrometer using KBr

pressed powder discs. The NMR spectra were measured

with a Bruker Avance 300 spectrometer (¹H NMR 300 MHz

Based on our knowledge, there were no reports on recycling

ceramic tile wastes; we were, thus, inspired by the feasibility

of recycling waste ceramic tiles through their utilization as

support materials for the heterogenization of sulfuric acid

catalysts. As mentioned before, quartz and clay are found in

ceramic tiles. Clay structures composed of sheets of

tetrahedral silicon dioxide (SiO₂) and octahedral aluminium

oxide (Al₂O₃) linked through bridging oxygen atoms. Some of

the oxygens on the surface of the ‘sheets’ and within the

clay structure are in the form of OH groups.²⁹Besides, clay

minerals exhibit interesting catalytic properties that have

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and ¹³C NMR 75 MHz) in pure deuterated chloroform with

tetramethylsilane (TMS) as the internal standard. Field

emission scanning electron microscope (FE-SEM) images

were acquired using Zeiss field emission scanning electron

microscope (Sigma, Germany) instrument operating at 15

kV, equipped with an Oxford X-ray detector (EDX; Oxford

Instruments, Oxford, UK). TEM images were also obtained

through transmission electron microscope (TEM; Philips –

CM300 - 150 KV). The average particle size distribution was

determined by using Image software. Thermogravimetric

analyses (TGA) were carried out on a Du Pont 2000 thermal

analysis apparatus at a heating rate of 5 °C min^-1under air

completed. The progress of the reaction was followed by thin

layer chromatography (TLC) [7: 3 hexane: ethyl acetate]. After

completion of the reaction (checked by TLC), hot ethanol (5 mL)

was added and centrifuged. Then the resulted solution was

filtered in order to separation of the catalyst from the mixture.

The filtrate was concentrated under rotary vacuum evaporation

and the crude product recrystallized from ethanol to afford

pure imidazole derivatives. The products were confirmed by

1

comparisons with authentic samples, IR, H NMR spectra and

melting points.

2.4.2. General procedure for the synthesis of 1,2,4,5-

tetrasubstituted

atmosphere. BET surface area was measured using

a

BELSORP-mini apparatus (BEL Japan, Inc.). X-ray diffraction

(XRD) was detected by Philips using Cu-Ka radiation of

wavelength 1.54 Å. Presented UV-vis spectra were obtained

as carbon tetrachlorid solutions (10^-4M) on a Shimadzu UV-

1650PC spectrophotometer.

A mixture of benzil (1 mmol), ammonium acetate (1 mmol),

aldehyde (1 mmol), primary aromatic amine (1 mmol) in the

presence of n-CTW-SA (0.003g, 10 mol%) as catalyst was stirred

with a glass bar at 120 °C under solvent free condition for the

appropriate time. After the reaction was completed, monitored

by TLC, the reaction mixture was dissolved in ethanol (5 mL)

and the catalyst was separated by filtration after being

2.2. Preparation of neat ceramic tile powder

Initially, ceramic tile wastes were crushed with ball mill to get a

soft and tiny powder. Then, 20g of the as-obtained powder was

carefully washed with 200 ml methanol and ethanol, three

times, to take all organic compounds away from the powder.

After washing with excess amount of distilled water, the

precipitated ceramic tile wastes powder was sent through a

filter and, then was dried at 120 °C.

centrifuged. The filtrate was concentrated on

a rotary

evaporator under reduced pressure and the solid crude product

obtained was washed with water and recrystallized from

ethanol to afford pure imidazole derivatives. The remaining

reactions were performed following this general procedure and

the physical data (Mp, IR, and NMR) of all known compounds

were identical with those reported in the literature.

2.3. Preparation of n-CTW-SA

3. Results and discussion

To a suction flask equipped with a constant-pressure dropping

funnel, containing chlorosulfonic acid (0.3856 g, 0.0033 mol),

and a gas inlet tube for conducting HCl gas into water as an

adsorbing solution, 1.0 g of ceramic tile waste powder in dry

CH₂Cl₂(20 ml) was added. Then, neat chlorosulfonic acid added

dropwise over a period of 15 min at room temperature. During

stirring the mixture, HCl gas immediately evolved from the

reaction vessel. After addition, the mixture continued stirring

for 1 h at room temperature while the residual HCl was seized

by suction.³⁷Subsequently, the solid powder was washed with

water (10 mL) and dried at 80 ˚C. Finally, the as-obtained solid

acid catalyst n-Ceramic Tile Waste supported sulfonic acid in

1.44 g is ready to use in organic transformation.

In the present study, our prime target is to demonstrate the

synthesis of n-Ceramic Tile Waste-sulfonic acid and elucidate its

performance as solid acid catalyst. Aiming at recycling

ceramic tile wastes, we use these wealthy waste materials as

resources for catalytic applications in the form of surface

decorated with sulfonic groups. Through this study, we found

that ceramic tile wastes can provide a cheap, available,

recoverable, and reusable platform to heterogenize sulfuric

acid. The preparation of this catalyst is showed in the schematic

route 1. In the procedure, ceramic tile waste powder nicely

reacted with chlorosulfonic acid during which HCl gas evolved

from the reaction vessel very soon. Therefore, any further

work-up is needed which can serve as an easy and clean

procedure. Other beneficial traits of the present work, that can

be mentioned, are simple catalyst preparation by using

inexpensive and easily accessible waste materials that helped

creating the heterogeneous, stable solid acid catalyst. The

“inorganic solid acid catalysts” were fully characterized by X-ray

diffraction (XRD), thermogravimetric analysis (TGA), Fourier

transform infrared spectroscopy (FT-IR), energy dispersive X-

ray spectroscopy (EDX), scanning electron microscopy (SEM),

transmission electron microscopy (TEM), BET, BJH and

Hammett acidity function method. Additionally, in order to find

the relationship between the effect of different size of catalysts

2.4. Application of n-CTW-SA catalyst for multicomponent

one-pot synthesis of heterocyclic compounds

2.4.1. General procedure for the synthesis of 2,4,5-

trisubstituted imidazoles

To a test tube equipped with a stir bar, a mixture of aromatic

aldehyde (1.0 mmol), benzil (1.0 mmol), ammonium acetate (2

mmol) and n-CTW-SA (0.006g, 20 mol%) as catalyst was added.

The mixture was reacted under solvent free condition at 100 °C

(in an oil bath) for the appropriate time until the reaction was

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on the reaction efficiency, a set of two samples of CTW with

two mesh sizes of 250 and 500 μm were functionalized with

3.1.2

Surface acidity of the catalyst

The acid strength of n-CTW-SA was determined through the

Hammett indicator function (H₀).⁵⁴It can be calculated using the

following equation:

SO₃H function and tested in the reaction condition. The loading

of SO₃H per g was calculated by pH analysis, and it is found to

be 2.88, 1, 0.5 mmol g⁻¹of n-CTW-SA, CTW-SA₂and CTW-SA₁,

respectively. Related data was summarized in the table 1.

Subsequent to the initial characterization of the catalyst, its

catalytic activity was examined in the multicomponent reaction

for the one-pot synthesis of some heterocyclic compounds such

as of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted

imidazoles as showed in the brief route in scheme 2 and 3.

H₀= pK(I)aq + log ( [I]s / [IH⁺]

In the equation, ‘I’ is the indicator base (mainly substituted

nitroanilines) and [I]s and [IH⁺]s are the molar concentrations of

the un-protonated and protonated forms of the indicator,

respectively. The pK(I)aq values, which are known (for instance the

pK(I)aq value of 4-nitroaniline is 0.99), can be obtained from many

references. According to the Lambert–Beer law, the value of

[I]s/[IH⁺]s can be determined and calculated using the UV-visible

spectrum. In our experiment, 4-nitroaniline and CCl₄were selected

as the basic indicator and the aprotic solvent, respectively. The

maximal absorbance of the un-protonated form of 4-nitroaniline

was observed at 330 nm in CCl₄. When n-CTW-SA catalyst was

added to the indicator solution, the absorbance of the un-

protonated form of the indicator weakened, indicating that the

indicator was partially in the form of [IH⁺]. The obtained results are

listed in Table 2, showing the acidity strength of n-CTW-SA (Table

2). According to the results of the Hammett acidity function (H₀), it

is confirmed that the new catalyst was synthesized with a good

density of acid groups (–SO₃H groups) on its surface (Table 2).

Table 1. Acid capacity measurement of catalysts with different particle sizes.

Equivalent

Sieve

Acid capacity^[a]

particle

diameter

(μm)

Entry

Sample

mesh

size

Catalyst

(mmolH⁺g^-1)

1

2

3

n-CTW

CTW₁

CTW₂

<35

35

60

0.02-0.03

500

250

n-CTW-SA

^bCTW-SA₁

^cCTW-SA₂

2.88

0.5

1

[a] Determined by PH analysis

[b] CTW (500 μm mesh size) functionalized with SO₃H groups

[c] CTW (250 μm mesh size) functionalized with SO₃H groups

OSO₃H

M

Table 2. Hammett acidity function (H₀) data for n-CTW-SA.

ClSO₃H

C

OH

+ HCl

OSO₃H

A

HO₃SO

CH₂Cl₂

r. t.

Entr

Catalyst

-

[I]_s(%)

100

[HI⁺]_s(%)

0

H₀

-

Q

A_max

2.74

1.49

y

C=calcite

Q=quartz

A=albiite

M=mullite

HO₃SO

1

1.3

2

n-CTW-SA

54.27

45.73

Condition for UV-visible spectrum measurement: solvent, CCl₄; indicator, 4-

nitroaniline (pK(I)aq= 0.99), 1.44*10^-4mol/L; catalyst, n-CTW-SA (20 mg), 25 °C.

Scheme 1. Preparation of nano-Ceramic Tile Waste supported sulfonic acid.

3.1. Characterization of n-CTW-SA

3.1.1.

PH analysis of catalyst

The acid capacities of n-CTW-SA were determined by acid–base

potentiometric titration in which the aqueous suspension of the

weighed amount of the catalyst was titrated with standard NaOH

solution. Before titration, 100 mg n-CTW-SA was dispersed in 20

ml H₂O by ultrasonic bath for 60 min. By addition of standard

NaOH solution (0.08 N), the amount of the acid was neutralized,

till the equivalence point of titration that required 3.5 ml of

NaOH. The optimum concentration of H⁺sites was ascertained to

be 2.8mmol/gram of catalyst (values calculated by the weight of

n-CTW-SA) at 25°C. Through consecutive experiments to measure

the concentrations of the residual H⁺on the recovered catalyst, it

was found that the loss of H⁺was very small or marginal, which

was a sign that the SO₃H groups were tightly anchored to ceramic

tile waste base, probably through a covalent linkage.

Fig. 1. Absorption spectra of (a) 4-nitroaniline (indicator), (b) nano-

Ceramic Tile Waste-SO₃H (catalyst) in CCl₄.

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3.1.2. FT-IR spectral analysis of the catalyst

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The infrared spectra of n-CTW and n-CTW-SA are presented in Fig.

2. In the case of n-CTW, The peaks at ca. 3419 and 1632 cm⁻¹

correspond to the -OH stretching vibration of the adsorbed water

and the bands at 1074 and 796, and 777 cm⁻¹can be collectively

attributed to Si-O stretching vibrations.⁵⁵The peaks appeared at

464 and 532cm^-1are assigned to the Si-O-Si and Si-O-Al stretching

56

vibration. The spectrum of sulfonated n-CTW displays almost the

same pattern as that of pristine n-CTW, but the n-CTW-SA

spectrum shows a relatively broad band around 2700 to 3600 cm^-1

that is due to OH stretching absorption of the SO₃H group.⁵⁷The

broad band around 1100 cm^-1is assigned to stretching modes of Si-

O and S-O bands which are overlapped together.

Fig 3. The TGA curve of n-CTW and n-CTW-SA

3.1.5.

Field emission scanning electron microscopy

The samples of n-CTW, n-CTW-SA, CTW-SA₁and CTW-SA₂were

analyzed by field emission scanning electron microscopy (FE-SEM),

as represented in Fig. 4(a-e). From picture a, it was found that the

material is composed of macro porous structure. Besides, it is clear

that there are some particles on the surface of the material. The

particles sizes are about 30 nm to 500 nm. However, with

modifying the material with SO₃H function, as shown in figures 4b-

c, the morphology was changed to the multilayer structures in nano

to micrometer size range. The thickness size of the layers is about

30 nm to 250 nm. Besides, there are some spherical particles on

the surface of the material. Their diameter sizes are about 20 – 50

nm. As can be seen from figures 4d and e, the CTW-SA₁and CTW-

SA₂samples have the multilayer structures morphology. The

material used to produce CTW-SA₁and CTW-SA₂catalysts had

mesh sizes of 500 and 250 μm. However, functionalization with

chlorosulfonic acid caused the sizes of CTW-SA₁and CTW-SA₂

catalysts to be smaller than the bear ones.

Fig 2. The FT-IR spectra of n-CTW and n-CTW-SA.

3.1.4.

Thermogravimetric analysis

Thermogravimetric analysis (TGA) of n-CTW-SA in comparison with

n-CTW is displayed in Fig. 3. The TGA curve of n-CTW (Fig. 3a)

showed a weight loss (5 wt. %) below 100 °C which corresponds to

the loss of the physically adsorbed water. For the n-CTW-SA, the

thermogravimetric curve seems to indicate three-stage

decomposition. The first weight loss found bellows 130°C (12 wt. %)

to be due to the loss of physically adsorbed solvent or trapped

water from the catalyst. The mass loss occurred between 120°C

and 310°C (about 15 wt. %), is related to the slow mass loss of SO₃H

groups and the last loss of weight (about 20 wt. %) started from

310°C to 740°C, was attributed to the sudden mass loss of

covalently bounded SO₃H groups. ^{57, 58}Additionally, it is understood

from the TGA measurement that n-CTW-SA has a great thermal

stability (until 220 °C) and can be safely applied in organic reactions

at temperatures up to 220°C.

Fig 4. The FE-SEM images of n-CTW (a), n-CTW-SA (b and c), CTW-SA₂and CTW-

SA₁(d and e).

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3.1.6.

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Transmission electron microscopy (TEM)

b

Figure 5a-d shows the TEM images as well as the particle size

distribution profile. As could be seen from the figures, the materials

are consisted of nearly homogeneous narrow size distributed

spherical particles. It also indicates that the maximum particle size

distributions were in the range of 20 - 30 nm.

Fig 6. The EDX spectra of n-CTW (a), and n-CTW-SA (b).

3.1.8.

XRD (X-ray diffraction) spectral analysis

Figures 7 a and b show the XRD patterns of the n-Ceramic Tile

waste and n-CTW-SA, respectively. The phases identification of the

XRD spectral was carried out according to previous reports ^{59, 60}. It

is clear that with modifying the tile material, the crystalline count

for the material was reduced. It may be due to the addition of a

non-crystalline phase (SO₃H) to the tile material. Besides, there is

another confirmation for the presence of the non-crystalline phase

in the material. It is the broadening of the XRD pattern showed in

figure 7b in the 2θ range of about 20 - 30˚ compared to the XRD

pattern showed in figure 6a.

Fig 5.The TEM images of n-CTW-SA (a-c), particle size distribution profile (d).

3.1.7.

Energy-dispersive X-ray spectroscopy (EDX)

The elemental composition of the n-CTW from EDX analysis was

exhibited in Fig. 6a that represents the presence of O, Si, Al, Ca, Fe,

and Ti elements. The EDX spectrum of n-CTW-SA was also showed

in fig. 6b which showed the appearance of the sulfur peak and

clearly confirms the presence of -SO₃H groups from chlorosulfonic

acid (Fig. 6b). However, the acid treatment could cause the

elimination of mineral impurities and exchangeable metal cations

from the clay material in the tile body.⁵⁶Therefore, Ca, Ti and Fe

are partially washed out from the n-CTW structure through

modification with chlorosulfonic acid as can be seen from the EDX

spectrum of n-CTW-SA.

Fig 7. The XRD patterns of n-CTW (a), and n-CTW-SA (b).

a

3.1.9.

BET and BJH texture analysis of the catalyst

The n-CTW-SA, CTW-SA₁and CTW-SA₂catalysts and the n-CTW

were characterized for their surface area, pore volume and pore

size by using the Brunauer-Emmett-Teller (BET) and Barrett–

Joyner–Halenda (BJH) equations. BET surface area was evaluated

using a BELSORP-mini apparatus (BEL Japan, Inc.). Prior to N₂-

physical adsorption measurement, the samples were degassed at

150 ˚C for 120 min in the nitrogen atmosphere. The specific

surface area (SBET) of the as-prepared catalyst was determined

with adsorption-desorption isotherms of N₂at 77 K. The obtained

results related to the textural properties of the sample (in terms of

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BET surface area, total pore volumes, BJH pore size) are listed in

table 3. The investigated results in the table suggested that the n-

CTW-SA has larger surface area and total pore volume than that of

n-CTW. However, the BJH pore size diameter of n-CTW-SA is

smaller than that of n-CTW. Moreover, The BET surface area of

CTW-SA₂is larger than that of CTW-SA₁.

was the effect of solvent on the model reaction. In order that,

different classical solvents such as EtOH, MeOH, CH₃CN, CH₂Cl₂, and

H₂O were tested in the reaction condition. As obvious in the table 4

(entries 10-14), using these solvents gave products in lower yields

and longer reaction times. These results proved that solvent-free

reaction condition is the best condition in which no volatile

solvents are used, therefore this condition kept pace with the

green chemistry protocols. As a result, the reaction parameters

which we optimized were: 100 °C, 20 mol% of the n-CTW-SA

catalyst, and solvent-free conditions (Table 4, entry 5). In an

attempt to investigate how catalyst particle size can affect the

reaction outcome, CTW-SA₁and CTW-SA₂were put in the

optimized reaction condition (i.e. 100 °C, 20 mol% of the catalyst,

and solvent-free conditions). Comparison of the results showed

that the reaction operated in the presence of n-CTW-SA rendered

higher yields of product in 10 minutes (Table 5). It was suggested

that the higher BET surface area and acid capacity, smaller particle

sizes and total pore sizes were the effective parameters which

caused n-CTW-SA to give the satisfactory results. Moreover, with

the presence of higher weighed amount of CTW-SA₁and CTW-SA₂,

the pathways for attacking substrates to each other are presumably

obstructed, thereby lowering the reaction efficiencies. Besides, the

larger particle sizes of these catalysts may hinder reactants to react

with each other in the reaction vessel (Table 5, entries 2-3). In the

final step, the scope of the reaction was further investigated under

the established optimal reaction conditions. As shown in table 6, a

wide range of aromatic aldehydes including electron-rich

(deactivated) and electron-deficient (activated) were subjected to

the cyclization with benzil and ammonium acetate which prepared

the corresponding 2,4,5-trisubstitutedimidazoles in good yields

(Table 6). It should be noticed that aldehydes bearing either

electron-withdrawing or electron-donating groups perform equally

well in the reaction. The nature of the substituents on the aromatic

aldehyde has not significant effect on yield of reaction (Table 6).

Table 3. BET and BJH data showing the textural properties of n-CTW, n-CTW-SA,

and CTW-SA

Entry

Samples

S_BET^[a][m²g^-1] V_p^[b][cm³g^-1] Pore size^[c][nm]

1

2

3

4

n-CTW

n-CTW-SA

CTW-SA₂

CTW-SA₁

1.16

3.93

0.94

0.03

0.009

0.015

0.006

0.005

6.96

1.21

18.94

25.55

[a] BET surface area. [b] Total pore volume. [c] BJH pore size diameter.

3.2.

Application of n-Ceramic Tile waste-supported sulfonic

acid as heterogeneous solid acid catalyst in the synthesis of

multisubstituted imidazoles

When the initial characterization of the n-Ceramic Tile Waste

supported sulfonic acid catalyst was performed, we were inspired

by the investigation of its catalytic performance, in

multicomponent reactions, not only for the preparation of 2,4,5-

trisubstituted imidazoles from aromatic aldehydes, benzil and

NH₄OAc but also for the production of 1,2,4,5-tetrasubstituted

imidazoles from aromatic aldehydes and amines, benzil, and

NH₄OAc in solvent free conditions (Scheme 3 and 5).

3.2.1.

Optimization of the reaction parameters for one-pot

synthesis of 2,4,5-trisubstituted imidazoles

At the onset of this study, we examined the above-mentioned

reaction of benzaldehyde, benzil, NH₄OAc for the synthesis of

2,4,5-trisustituted imidazole at 100 °C in the absence of the catalyst

under solvent-free condition, that low yielding reaction in the long

reaction time was observed (Table 4, entry 1). In the next step, with

the view to optimizing the reaction conditions, we investigated the

reaction in the presence of different amounts of n-CTW-SA as

catalysts (ranging from 5-20 mol %) under solvent-free condition at

100 °C. It was observed that the optimal amount of catalyst was

20mol% with the product yielding of 99% in 10 min (Table 4, entries

2-5). Additionally, these results were compared with the reactions

performed in the presence of unfunctionalized ceramic tile waste

powder (without the SO₃H groups appended), confirming the fact

that the n-CTW-SA catalyst is a more suitable option. The greater

catalytic activity of n-CTW-SA was most likely attributed to the

catalyst surface decoration with SO₃H groups, which could offer

efficient acidic sites. When optimized the catalyst loading, we

decided to probe the model reaction by adding 20 mol% of the n-

CTW-SA as catalyst under solvent free condition in the different

temperatures (70, 80, 90, and 100 °C), because temperature is a

key factor for the synthesis of imidazole compounds (Table 4,

entries 5-9). According to the obtained data, within 10min, the

most efficient reaction temperature was 100 °C at which 99%

product yield was provided (Table 4, entry 5). The further study

Table 4. Optimization of the reaction condition for the synthesis of 2,4,5-

trisubstituted imidazoles^a

Catalyst

[mmol]

Time

[h[min]]

Yield

[%]

Entry

Solvent

Condition

1

2

3

4

5

6

7

8

9

10

11

12

13

14

Solvent-free

H₂O

100

90

80 ͦC

70 ͦC

60 ͦC

Reflux

C

-

2

70

92

94

96

99

90

83

76

72

70

75

67

85

80

0.05

0.1

0.15

0.2

[10]

1[20]

[10]

CH₃CN

CH₂Cl₂

EtOH

MeOH

^aReaction condition: benzil (1mmol), benzaldehyde (1mmol), and NH₄OAc (2

mmol)

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10), it was revealed that n-CTW-SA is superior to most of the others

regarding reaction conditions, time and product yield. Therefore, it

can be seen that n-CTW-SA is a very useful and efficient catalyst in

the synthesis of multisubstituted imidazoles.

Table 5. Catalysts particle size effect on the the synthesis of 2,4,5-trisubstituted

imidazoles reaction condition^a

Entry

Catalyst

Catalyst amount [g]^b

Yield [%]

Plausible mechanism for the synthesis of 2,4,5-trisubstituted and

1,2,4,5-tetrasubstituted imidazoles catalyzed by n-CTW-SA

The probable mechanism for the formation of trisubstituted

imidazole using n-CTW-SA is represented in Scheme 4. The reaction

can be started through increasing the electrophilicity of the

carbonyl group of the aldehyde by the help of n-CTW-SA and then

1

2

3

n-CTW-SA

CTW-SA₁

CTW-SA₂

0.06

0.4

0.2

99

73

80

^aReaction condition: benzil (1mmol), benzaldehyde (1mmol), and NH₄OAc (2

mmol), solvent-free, 100 °C.

^bCatalyst amount is equal to 0.2 mmol H⁺

condensing to form diamine intermediate

1

afterwards,

3.2.2.

Optimization of the reaction parameters for one-pot

synthesis of 1,2,4,5-tetrasubstituted imidazoles

intermediate 1 condenses with benzil to form intermediate 2,

which in turn rearranges to the trisubstituted imidazole. Similarly,

the possible mechanism for the synthesis of tetrasubstituted

imidazoles initiates with the formation of intermediate 3 by the

reaction of an aldehyde, phenyl amine and ammonium acetate in

the presence of catalyst. Intermediate 3 condenses with benzil to

form intermediate 4, and then tautomerizes to the tetrasubstituted

imidazole (Scheme 5).

For the optimization of the reaction condition for the one-pot

synthesis of 1,2,4,5-tetrasubstituted compound, initially, a mixture

of benzil, ammonium acetate, benzaldehyde, and aniline was

reacted without adding the catalyst at 120 °C under solvent free

condition. However, the desired product, obtained in this reaction,

was in low yields (Table 7, entry 1). Disappointed with the obtained

results about the model reaction performed in the presence of bare

ceramic tile waste support, we examined the above-mentioned

reaction in the presence of different amounts of the n-CTW-SA as

catalysts (ranging from 5-20 mol %) under solvent-free condition at

120 °C and 10mol% was proved to be superior in reaction efficiency

and time (Table 7, entries 2-5). In further step, reaction

temperature was optimized in view of the fact that temperature

can affect the synthesis of highly substituted imidazols. In order

that, the model reaction was conducted under solvent-free

conditions at 90°C, 100°C, 110°C, and 120°C (Table 7, entries 3, 6-

9). According to the table 7, by increasing the reaction temperature

up to 120°C, the efficiency of the reaction was improved; therefore,

the most effective temperature was 120°C (Table 7, entry 3).

Eventually, the model reaction was conducted under solvent

conditions, in order to investigate the effect of different classical

solvents such as EtOH, MeOH, CH₃CN, CH₂Cl₂and H₂O (Table 7,

entries 10-14). The results showed that the reaction performed in

the presence of these solvents rendered desired products in good

yields in 60 min, but solvent-free reaction condition offered the

product in significantly higher yields and lower reaction times. As a

consequent, solvent-free reaction condition was chosen as the key

factor to design a sustainable protocol. Further substrate scope

investigations, to prepare 1,2,4,5-tetrasubstituted imidazoles,

were all carried out under solvent-free conditions using 10 mol% n-

CTW-SA as catalysts, at 120 °C (Table 7, entry 3). According to the

obtained data about the reactions in which the several substituted

aromatic aldehydes and amines were participated under optimal

reaction conditions, aldehydes with either electron-withdrawing or

electron-donating substituents perform equally well in the

reactions (Table 8). The nature of the substituents on the aromatic

aldehyde has not significant effect on the reaction efficiencies.

As compared n-CTW-SA performance with other catalysts reported

in the literature for the one-pot synthesis of 2,4,5-trisubstituted

imidazoles (Table 9) and 1,2,4,5-tetrasubstituted imidazoles (Table

3.3. Reusability of the catalyst

From the view point of green chemistry, catalysts with good

recovery and reusability are highly preferable. Therefore, in this

work, we studied the level of reusability of the n-CTW-SA in the

model reaction for the synthesis of multisubstituted imidazoles

under the optimum conditions.

After each run, the catalyst is simply recovered from the reaction

mixture by filtration. The recovered catalyst was first washed with

ethanol and water, and then dried at 110 °C. The recovered catalyst

was added to reaction mixture of fresh reactants under same

conditions for seven runs with no remarkable drop in yield and its

catalytic activity (Fig. 8). For determination of the percent leaching

of the acid,⁶¹the model reaction, for the synthesis of tetra

substituted imidazole, was performed in the presence of n-CTW-SA

for 20 min and at that point the catalyst was removed by filtration.

The residual solution was then allowed to react, but no significant

progress was observed after 2 h. Therefore, this experiment

signified that SO₃H moiety was tightly anchored to the support,

which is a further testimony to the heterogeneous nature of the

catalytic system.

Fig 8. Recyclability of n-CTW-SA

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Scheme 2. Synthesis of 2,4,5-trisubstituted imidazoles in the optimum condition.

Table 6. n-CTW-SA-catalyzed one-pot synthesis of 2,4,5-trisubstituted imidazoles^a

Entry

Aldehyde

T [min]

Yield [%]^b

Mp[

ͦ

Lit. Mp [ ͦC]ref.

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

benzaldehyde

4-chlorobenzaldehyde

2-chlorobenzaldehyde

2,4-dichlorobenzaldehyde

4-fluorobenzaldehyde

3-bromobenzaldehyde

3-nitrobenzaldehyde

4-nitrobenzaldehyde

10

20

15

10

20

45

35

45

25

35

20

15

20

50

20

35

40

99

95

88

95

96

90

83

87

80

89

90

92

94

93

94

82

271-273

261-262

200-201

175-177

261-262

306-309

265-266

237-239

230-232

209-211

210-212

258

256-257

227-228

265-267

221-223

252-255

256-257

272-273 ⁶²

262-263 ⁶²

199-201 ⁶³

174-175 ⁶⁴

260-262 ⁶⁵

>300 ⁶⁶

265-267 ⁶²

239-242 ⁶⁷

230-233 ⁶⁸

210 ⁶⁹

2-nitrobenzaldehyde

2-methoxybenzaldehyde

2-hydroxybenzaldehyde

3-hydroxybenzaldehyde

4-hydroxybenzaldehyde

4-methylbenzaldehyde

3-ethoxy-4-hydroxybenzaldehyde

3,4-dimethoxybenzaldehyde

4-isopropylbenzaldehyde

4-N,N-dimethylbenzaldehyde

209-211 ⁷⁰

258 ⁶⁸

256-257 ⁶²

226-227 ⁶²

268-269 ⁶⁶

222-224 ⁷¹

252-255 ⁷²

255-256 ⁷³

^aReaction condition: benzil (1 mmol), aromatic aldehyde (1mmol), NH₄OAc (2 mmol)and n-CTW-SA (0.2 mmol), solvent-free, 100 °C.

^bYields refer to isolated products.

Table 7. Optimization of the reaction condition for the synthesis of 1,2,4,5-tetrasubstituted imidazoles^a

Entry

Solvent

Condition

Catalyst [mmol]

Time [h[min]]

Yield [%]

1

2

3

4

5

6

7

8

9

10

11

12

13

14

Solvent-free

H₂O

120

110

100

90

C

-

4

Trace

85

94

90

87

90

85

80

75

60

67

50

79

70

0.05

0.1

0.15

0.2

0.1

1[30]

[40]

1[20]

1[40]

1[20]

2

2[35]

3[15]

[60]

ͦ

60 ͦC

Reflux

CH₃CN

CH₂Cl₂

EtOH

MeOH

a

Reaction condition: benzil (1mmol), benzaldehyde (1mmol), and NH₄OAc (1 mmol), aniline (1mmol)

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Scheme 3. Synthesis of 1,2,4,5-tetrasubstituted imidazoles in the optimum condition

Table 8. n-CTW-SA-catalyzed one-pot synthesis of 1,2,4,5-tetrasubstituted imidazolese^a

Entry

Aldehyde

T [h [min] ]

Yield [%]^b

Mp[

ͦ

Lit. Mp [ ͦC]ref.

Amine

74

1

2

3

4

5

6

7

8

9

benzaldehyde

Aniline

[40]

1

94

91

87

93

82

97

87

80

90

85

95

92

218-219

161-163

185-187

182-184

281-282

191-193

165-167

188-190

220-222

148-150

187-190

277-290

218

4-chlorobenzaldehyde

4-nitrobenzaldehyde

4-methoxybenzaldehyde

4-hydroxybenzaldehyde

4-methylbenzaldehyde

4-chlorobenzaldehyde

4-nitrobenzaldehyde

3-nitrobenzaldehyde

4-methylbenzaldehyde

4-hydroxybenzaldehyde

160-163 ⁷⁵

184-186 ⁷⁶

180-182 ⁷⁶

280-281 ⁷⁷

1[20]

1[35]

[45]

1[10]

2

2[10]

1

1[15]

1[35]

1[45]

74

Aniline

189

4-chloroaniline

4-methylaniline

166-168 ⁷⁶

187-189 ⁷⁸

219-220 ⁷⁹

149-151 ⁷⁹

187-190 ⁷⁶

>275 ⁷⁸

10

11

12

a

Reaction condition: benzil (1 mmol), aromatic aldehyde (1mmol), NH₄OAc (1 mmol), aromatic amine (1 mmol) and n-CTW-SA (0.1 mmol), solvent-free, 120 °C.

^bYields refer to isolated products.

Table 9. Comparison of the efficiency of n-CTW-SA with different catalysts in the synthesis of 2,4,5-trisubstituted imidazoles

Yield

[%]

Entry

Catalyst

Condition

Time [h[min]]

Ref

69

80

81

82

83

80

84

64

1

2

3

4

5

6

7

8

9

Nano-SPA^a

Nano-crystalline SZ^b

KH₂PO₄

Yb(OPf)₃

NiCl₂.6H₂O/Al₂O₃

Zeolite

Solvent-free/140

Reflux in EtOH

C

3

90

87

93

80

89

80

75

73

90

99

[45]

[40]

6

1[30]

1

1[30]

12

2[30]

[10]

C₁₀F₁₈/80 ͦC

Reflux in EtOH

MeOH/r.t

Reflux in EtOH

Solvent-free/100

Montmorilonite K10

InCl₃.3H₂O

Zr(acac)₄

n-CTW-SA

10

Present work

^aNano silica phosphoric acid

^bSulfated zirconia

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Table 10. Comparison of the efficiency of n-CTW-SA with different catalysts in the synthesis of 1,2,4,5-tetrasubstituted imidazoles

Entry

Catalyst

Condition

Time [h[min]]

Yield [%]

Ref

85

86

77

85

87

76

87

1

2

3

4

5

6

7

8

Bf₃/SiO₂

NaHSO₄/SiO₂

SbCl₅/SiO₂

MgCl₂

Solvent-free/140

Solvent-free/80

Solvent-free/140

Reflux in EtOH

C

2

[45]

2

92

90

60

53

85

88

94

ͦ

AlCl₃

WD^a/SiO₂

H₃PMo₁₂O₄₀

n-CTW-SA

[15]

[40]

Solvent-free/120

Present work

^aWells–Dawson heteropolyacid supported on silica

4. Conclusion

n-CTW-SA was synthesized, not only to develop the current

important areas of heterogenization of sulfonic acid, but also to

utilize waste products. The n-CTW-SA heterogeneous solid acid

catalyst displayed great activities in the multi component reactions

for the simple, efficient, and rapid one-pot synthesis of heterocyclic

compounds such as 2,4,5-trisubstituted as well as 1,2,4,5-

tetrasubstituted imidazoles. The proposed reaction conditions

which are used the recyclable catalyst, can be considered as a green

process due to be kept pace with the green chemistry principles

such as high Yields, low-cost, short reaction times, low-toxicity,

solvent-free conditions and so on. Additionally, being

heterogeneous, non-toxic, low-cost, easily accessible, simple

preparation, recoverable and reusable are significant beneficial

properties of this catalyst.

Scheme 4. Proposed mechanism for the synthesis of 2,4,5-trisubstituted

imidazole.

Acknowledgements

We gratefully acknowledge the Faculty of chemistry of Semnan

University for supporting this work.

Note and references

Department of Chemistry, Semnan University, Semnan, Iran. E-mail:

kolvari@semnan.ac.ir; Fax: +98-23-336-54110; Tel: +98-23-336-

54058

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A waste to wealth approach through utilization of nano-ceramic tile waste as an accessible and inexpensive solid support to produce a heterogeneous solid acid nanocatalyst: To kill three birds with one stone

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