Journal of Saudi Chemical Society (2019) 23, 486–493

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sawww.sciencedirect.com

ORIGINAL ARTICLE

Synthesis and characterization of mesoporous zinc

layered hydroxide-isoprocarb nanocomposite

* Corresponding author at: Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900

Malim, Perak, Malaysia.

E-mail address: norhayati.hashim@fsmt.upsi.edu.my (N. Hashim).

Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

https://doi.org/10.1016/j.jscs.2018.08.0121319-6103 � 2018 King Saud University. Production and hosting by Elsevier B.V.This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Zuhailimuna Muda a, Norhayati Hashim a,b,*, Illyas Md Isa a,b,

Suriani Abu Bakar b,c, Noorshida Mohd Ali a, Mohd Zobir Hussein d,

Mazidah Mamat e, Siti Munirah Sidik a

aDepartment of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim, Perak,

MalaysiabNanotechnology Research Centre, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 TanjongMalim, Perak, MalaysiacDepartment of Physics, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim,Perak, MalaysiadMaterials Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia,43400 Serdang, Selangor, MalaysiaePusat Pengajian Sains Asas, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

Received 12 July 2018; revised 29 August 2018; accepted 30 August 2018Available online 26 September 2018

KEYWORDS

Intercalation;

Characterization;

Zinc layered hydroxide;

Isoprocarb;

Mesoporous

Abstract The ion exchange method was used to intercalate a poor water-soluble insecticide,

isoprocarb into zinc layered hydroxide (ZLH). PXRD analysis indicated the successful intercalation

with good crystallinity for the resulting nanocomposite, with a basal spacing of 33.1 A. FTIR

analyses showing the resemblance of an absorption peak of the nanocomposite with the host and

the guest anion. The thermal analysis confirmed that the nanocomposite had better thermal stability

compared to the pristine isoprocarb. The nanocomposite also characterized by elemental and

surface morphology analysis. The surface analyses of the host and nanocomposite showed

mesoporous-type material characteristics. On the whole, the intercalation process decreased the

pore size of the nanocomposite compared to the pristine host, layered zinc layered hydroxide-

sodium dodecyl sulphate (ZLH-SDS). The obtained material is believed has a great potential as

an environmentally friendly insecticide.� 2018 King Saud University. Production and hosting by Elsevier B.V. This is an open access article under

the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Tanjong

Synthesis and characterization of mesoporous zinc layered hydroxide-isoprocarb nanocomposite 487

1. Introduction

Layered metal hydroxide compounds can be classified intotwo main types, namely layered double hydroxide and lay-

ered hydroxide salt. One example is zinc layered hydroxide(ZLH) [1–3]. ZLH have a structure like brucite, but insteadof metal replacement, hydroxide ions are removed from the

structure and replaced by a water molecule, or other type ofoxoanion [1,4]. The layered hydroxide is formed when partof the hydroxyl groups from the brucite-like structure aresubstituted with water molecules. Oxoanions are then

positioned in the second coordination sphere of the metalto stabilize the electrostatic charge, or by the directsubstitution of other single charged anions [3,5]. This layered

material has potential for ion exchange, where the generalformula can be represented by M2+(OH)2�x (Am�)x/m�nH2O,in which M2+ is a metallic cation, such as Cu2+, Co2+,

Ni2+, Mn2+ or Zn2+ and A is the oxoanion with anm� charge [5].

Synthesis of mesoporous materials has attracted huge

consideration recently due to its prevalent applications suchas optical, electronic, and electrochemical devices [6]. Manyframework compositions (e.g., silica, organosilica, metal,and non-siliceous oxides) [7–9] and various morphologies

(e.g., nanoparticle, monolith, and film) [6,10] have beensynthesized under various synthetic conditions. ZLH is oneof mesoporous material that has attracted considerable

attention due to their ion exchange properties andmesoporous structures. There have been a number ofrecent reports of ZLH nanocomposites with mesoporous

properties, such as zinc layered hydroxide-salicylate [11], zinclayered hydroxide-protocatechuate [12], undoped anddoped zinc layered gallate nanohybrid with Fe3+, Co2+,

and Ni2+ [13], zinc hydroxide nitrate-3-(4-methoxyphenyl)propionate [14] and zinc layered hydroxide-para-aminosalicylilate [15].

Isoprocarb, or 2-isopropylphenyl-N-methylcarbamate, is

one of the most important carbamate insecticides, andexists as a poor water-soluble insecticide [16]. It is usedagainst various types of parasites for plants in tropical

and subtropical regions, such as fulgorids rice and cottonleafhopper [16]. A poor water-soluble insecticide is usuallydependent on an anionic surfactant that forms a

hydrophobic region in the interlayer of layered material[17].

The final properties of inorganic-organic functional hybridsare controlled by interactions between a host (inorganic lay-

ered matrix) and guest (functional organic molecule), becausethe strength and directionality of interactions affect the distri-bution, orientation and electronic properties of guest mole-

cules [18].Therefore, in this study, we have synthesized zinc lay-

ered hydroxide-sodium dodecyl sulphate-isoprocarb

nanocomposite (ZLH-SDS-ISO) by intercalating isoprocarbinto the interlayer ZLH modified with sodium dodecyl sul-phate (SDS) surfactant. The characterization of the

nanocomposite has been done using PXRD, FTIR, elemen-tal analysis, thermal study, surface morphology and surfacearea analysis.

2. Materials and methods

2.1. Materials

Sodium dodecylsulphate (SDS) and zinc nitrate (Zn(NO3)2-�6H2O) were purchased from Systerm Malaysia. Sodium

hydroxide, NaOH, was purchased from HmbG Chemicals.Whereas, isoprocarb insecticide, C11H15NO2 (ISO), was pur-chased from Nanjing Essence Fine-Chemical. All solutions

were prepared using deionized water. Each chemical utilisedin this synthesis was obtained from chemical providers andused without additional purification.

2.2. Synthesis of ZLH-SDS-ISO nanocomposite

Zinc layered hydroxide-sodium dodecyl sulphate (ZLH-SDS)was synthesized by the procedure described elsewhere [17].

Briefly, ZLH-SDS was synthesized using a co-precipitationmethod by the slow addition of 1.0 M NaOH and 40 mL of0.5 M of Zn(NO3)2�6H2O into a solution containing 40 mL

0.25 M SDS under magnetic stirring. The pH value wasadjusted to 6.5. The slurry was then centrifuged and dried inan oven at 70 �C.

Preparation of isoprocarb (ISO) intercalated into the inter-layer of ZLH-SDS (indicated as ZLH–SDS-ISO) was achievedby an ion exchange method. Various concentrations of isopro-carb solution were prepared at 0.001 M, 0.0025 M and

0.005 M. Then 0.5 g of ZLH-SDS was dissociated in an isopro-carb solution and keep under magnetic stirring for 2 ø h. Theslurry was then aged for 24 h in an oil bath shaker at 70 �C.Then the slurry was centrifuged and the final white solid wasdried in an oven for 24 h.

2.3. Characterization

There were several instruments involved in the characteriza-tion of the ZLH-SDS-ISO nanocomposites. The X-ray diffrac-tion patterns (XRD) were obtained using a Powder X-ray

Diffraction (PXRD) Bruker AXS (model D8 Advance, wave-length of 1.5406 A) with CuKa radiation at 60 kV and a cur-rent of 60 mA. The recorded region of 2h was from 2� to

60�, with a scanning rate of 2� min�1. The FTIR spectra werecollected in a Thermo Nicolet 6700 Fourier Transform Infra-red Spectrometer in the range 400–4000 cm�1. The thermal

analyses (TGA/DTG) of the sample were obtained with a Per-kin Elmer Pyris 1 TGA Thermo Balance with a heating rate of20 �C min�1 (N2 flow rate was 50 mL/min, temperatures were

25–900 �C at a rate of 10 K/min). An inductive coupled plasmaoptical emission spectrometry (ICP-OES), model Agilent, 720Axial and (CHNO-S), model Thermo Finnigan, Flash EA1112 was used to study the composition of the samples. The

surface morphology of the samples were observed by a fieldemission scanning electron microscope (FESEM) Hitachimodel SU 8020 UHR. Surface characterization of the

nanocomposites was carried out by the nitrogen gas adsorp-tion–desorption technique at 77 K using a QuantachromeAutosorb-1 and degassed in an evacuated heated chamber at

120 �C overnight.

Isoprocarb

ZLH-SDS

0.001 M

0.0025 M

0.005 M

2θ /degrees

Inte

nsity

/arb

itrar

y un

its

33.1 Å

33.1 Å

33.1 Å

33.0 Å

9.8 Å

(003

)

(009

) (0

06)

20 40 60

Fig. 1 X-ray diffraction pattern of ZLH-SDS, isoprocarb and

ZLH-SDS-ISO nanocomposite at 0.001 M, 0.0025 M, and

0.005 M concentration of isoprocarb.

488 Z. Muda et al.

3. Results and discussion

3.1. PXRD analysis

The XRD pattern of ZLH-SDS showed a basal spacing of9.8 A, corresponding to Zn5(OH)8(NO3)2�2H2O, and the peak

at 33.0 A had the same pattern with LDH-SDS that was pre-viously reported by [19]. The resulting ZLH-SDS was wellcrystallized, without impurities like ZnO, which indicated that

a complete reaction occurred during the co-precipitationbetween zinc nitrate and SDS. Upon dissolving zinc nitratehexahydrate in water, the zinc species undergoes hydrolysisreactions (Eqs. (1) and (2)) as previously reported by Moezzi

et al. [20]

Zn NO3ð Þ2 ! Zn2þ aqð Þ þ 2 NO3ð Þ� aqð Þ ð1Þ

Zn2 þ þ aqð Þ þH2O�ZnOH þ aqð Þ þHþ aqð Þ ð2ÞZinc hydroxide species can actually further transform into

ZnO nanoparticles. However, in the presence of dodecyl sul-

phate ions, these zinc hydroxide species could cause charge–assemblies to form zinc hydroxide-dodecyl sulphate layerednanosheets. The formulas below represent the main reactions

that were previously reported by Liang et al. [21].

Zn OHð Þ2�xx þ þ x=4O2 ! ZnO þ 1� 1=2xð ÞH2O ð3Þ

Zn OHð Þ2�xx þ þ xDS� ! Zn OHð Þ2 � xDSx ð4ÞThe x-ray diffraction pattern of ZLH-SDS-ISO shows a

series of basal peaks, indicated by (0 0 3), (0 0 6), (0 0 9) in

Fig. 1. A typical of intercalation peak was observed at a lowerangle, 2�, and clearly confirmed the intercalation of isoprocarbanion into the interlayer of ZLH [14]. The intercalation

occurred due an ion exchange reaction that took place betweenthe nitrate ion and isoprocarb anion. The intercalation of0.001 M, 0.0025 M and 0.005 M of isoprocarb insecticide intolayered ZLH exhibited a diffraction pattern characterization

with a sharp diffraction peak at 33.1 A and at a low 2h angle(3�) for all concentrations. Electrostatic interaction was pre-sent between the isoprocarb anion and the positively charged

layer, and those forces contained the anion insecticide insidethe interlayer of ZLH [1,22]. After the intercalation of isopro-carb into the interlayer of ZLH, the basal spacing showed a

slight increase due to adoption of different orientation angle[23]. By comparing the XRD pattern of the resulting withthe pure isoprocarb, it can be observed that the crystalline

phase of isoprocarb was not present in the ZLH-SDS-ISOnanocomposite. This was due to the successful intercalationof isoprocarb between interlayers of ZLH, with a pure phaseand well-ordered stacking layer. The sharp and intense interca-

lation peak revealed that the nanocomposite had a high crys-tallinity [24]. The intensity of the intercalation peak for theZLH-SDS-ISO nanocomposite increased as the concentration

of isoprocarb increased from 0.001 to 0.0025 M, and indicatedthat the crystallinity increased. However, the intensity of inter-calation peak decreased for 0.005 M isoprocarb due to the

presence of the large amount of isoprocarb in the interlayer,as this interfered with the crystal growth during regeneration[25]. For further characterization, a sample of 0.0025 M isop-rocarb was chosen as the phase pure well-ordered nanocom-

posite material.

3.2. FTIr

As shown in Fig. 2, the FTIR spectra of ZLH-SDS shows astrong and sharp absorption band around 3500–3700 cm�1,which corresponds to the stretching vibrations of the OH

group of the free water molecule [26]. A strong and broadabsorption band centred at 3461 cm�1 can be attributed tothe OH vibration. This band has a broad base due to the

hydrogen bonds associated with the water molecule [5].Another bending vibration at 1637 cm�1 is the HAOAH bend-ing of the water molecule in the interlayer of ZLH-SDS. Two

main doublet absorption bands appear in the 2850–2950 cm�1

region, which are due to the stretching vibration of the alipha-tic group. Another band at 1350–1480 cm�1 is due to bending

vibration of the aliphatic group. The stretching vibration at1210–1240 cm�1 was due to the presence of a sulphate groupin SDS [27]. A strong absorption band at 1364 cm�1 was dueto the presence of nitrate, as the salt used for the source of

metal ions was zinc nitrate.The FTIR spectra of ZLH-SDS-ISO resemble the ZLH-

SDS and isoprocarb spectra. A strong and broad band at

3438 cm�1 was attributed to the stretching vibration of thehydroxyl group of the water molecule. A peak at 1637 cm�1

1000200030004000

Wavenumber/cm-1

% T

rans

mitt

ance

/arb

itrar

y un

its

ZLH-SDS

ZLH-SDS-ISO

Isoprocarb

3570

3461

2913 2846

1637 1458

1364

1220 1084

3438

2913 2846

1637 1458

3314

1543

1221

1189 1056

2868 2965

1447

1360

Fig. 2 The FTIR spectra for ZLH-SDS, isoprocarb anion and

ZLH-SDS-ISO nanocomposite.

Table 1 FTIR bands for ZLH-SDS, ZLH-SDS-ISO

nanocomposite, and isoprocarb anion.

Characteristic group ZLH-

SDS

ZLH-SDS-

ISO

Isoprocarb

m (OAH), H-bonded 3461 3438 –

m (OAH) in the interlayer;

H2O

3570 – –

m (HAOAH) in the

interlayer; H2O

1637 1637 –

m (CAN) – 1360 1221

m (CAH), stretching 2846

2913

2846

2913

2868

2965

m (CAH), bending 1458 1458 1447

m (NAH), stretching – – 3314

m (NAH), bending – – 1543

m (NAO) 1364 – –

mas (S‚O) 1220 1189 –

ms (S‚O) 1084 1056 –

4.8 Å

25.1 Å

2.6 Å

2.6 Å

ZLH

Isoprocarb

SDS

Fig. 3 The proposed orientation of isoprocarb and SDS anions

intercalated within the ZLH interlayer gallery resulting in the

ZLH-SDS-ISO nanocomposite, estimated by Chemoffice

software.

Synthesis and characterization of mesoporous zinc layered hydroxide-isoprocarb nanocomposite 489

revealed that there was a free water molecule in the interlayerof the nanocomposite. Sharp doublet absorption of ZLH-

SDS-ISO nanocomposite band resembled the peak in ZLH-SDS layer at 2913 and 2846 cm�1, which was due to thestretching vibration of the C-H group that was present in the

nanocomposite. The peak at 1458 cm�1, which also resemblesthe peak in ZLH-SDS, was due to the bending vibration of thealiphatic group, CAH. The bands that appeared at 1189 and

1056 cm�1 were assigned to the asymmetric and symmetricstretching vibration of S‚O [19]. The stretching vibration ofS‚O for ZLH-SDS-ISO particles was shifted to lower fre-quencies, indicating the configuration variation of the OSO3

�

functional group [19]. Those shifts confirm the loss of S‚Obond strength, and refer to the existence of a hydrogen bondwithin the ZLH interlayer and sulphate group (S‚O

HAOAZn), as well as the electrostatic attraction [19]. Theabsence of the NAH absorption peak that should appear at3314 and 1543 cm�1 in the resulting ZLH-SDS-ISO spectra

indicated that the isoprocarb molecule was successfully loadedinto the ZLH interlayer in an ionic form. After the intercala-tion, isoprocarb may undergo an elimination mechanism in

the hydrolysis reaction [16]. The NAO peak (1364 in ZLH-SDS spectra) also disappeared in ZLH-SDS-ISO spectra,which confirmed the removal of NO3

� ion after the intercala-tion of isoprocarb into the interlayer of ZLH.

The isoprocarb spectra presented an adsorption peak at2965 and 2868 cm�1, indicating the CAH stretching vibration,while the CAH bending vibration peak appeared at 1447 cm�1.

The peak at 1221 cm�1 corresponded to the CAN stretchingvibration. Overall, the main FTIR absorption bands forZLH-SDS-ISO nanocomposite are listed in Table 1.

3.3. Spatial orientation

The proposed orientation of the ZLH-SDS-ISO nanocompos-

ite is shown in Fig. 3. Previous studies classified the arrange-ment of dodecyl sulphate into two structures: aninterdigitated monolayer arrangement with the trans-dodecyl

chain sandwich [28] and tail-to-tail bilayer arrangement ofthe dodecyl chain [29]. SDS was intercalated into ZLH as adodecyl sulphate anion [30]. Dodecyl sulphate and isoprocarbare aligned perpendicular and electrostatically attracted to

host layer surface. Hence, the dodecyl sulphate ion is shown

0

40

80

0 200 400 600 800 1000-40

-30

-20

-10

0

45

60

75

90

105

0 200 400 600 800 1000-0.0020

-0.0015

-0.0010

-0.0005

0

0.0005

99.8 % 184 °C

13.7% 239°C

74.2 % 189°C

37.0 % 198 °C

3.2 % 107 °C

Temperature/°C

Wei

ght p

erce

ntag

e/%

Der

ivat

ived

(w

/w %

)/dθ

(a)

(c)

(b)

0

20

40

60

80

100

0 200 400 600 800 1000-0.020

-0.015

-0.010

-0.005

0

0.005

9.6 % 130°C

Fig. 4 Thermogravimetric curve for (a) isoprocarb anion, (b)

ZLH-SDS-ISO nanocomposite and (c) ZLH-SDS.

490 Z. Muda et al.

to be tilted and in a monolayer arrangement, while the isopro-carb anion is in bilayer arrangement. Regarding the size of theisoprocarb molecule and interlayer space height (33.1 A) of

ZLH-SDS-ISO nanocomposite, it is reasonable to concludethat the isoprocarb molecules are intercalated into thehydrophobic region formed by dodecyl sulphate molecules in

the interlayer space of ZLH, due to the increase of the ZLH-SDS-ISO nanocomposite basal spacing, as reported elsewhere[19]. The interlayer height of ZLH-SDS-ISO nanocomposite

was estimated by the basal spacing obtained from PXRD anal-ysis, which was 33.1 A. Since the layer thickness was 4.8 A andthe Zn2+ moiety of the lattice from the basal spacing was2.6 A, the interlayer height of the nanocomposite is estimated

to be 25.1 A.

3.4. Elemental analysis

The composition analysis results for the ZLH-SDS and theZLH-SDS-ISO nanocomposite are listed in Table 2. CHNSanalysis of the ZLH-SDS indicated 2.46% of N, 24.8% of

C, 5.48% of H and 3.38% of S. ICP-OES analysis showed ahigh percentage of Zn (38.87%) for pristine ZLH-SDS usedin this work. After the intercalation process, about 61.10%

of carbon was detected. The intercalation of isoprocarb anionin the interlayer of ZLH caused the increase in percentage ofthe carbon. The percentage of S and N in the resultingnanocomposite was 0.77% and the 6.17%, respectively. The

S element represents the dodecyl sulphate ion in the interlayerof ZLH. Previously, PXRD analysis confirmed that there wasno nitrate ion after intercalation process. Therefore, the N ele-

ment detected in the resulting nanocomposite came from theamine group in the isoprocarb anion, which confirmed the suc-cessful intercalation of isoprocarb in the interlayer of ZLH.

The percentage isoprocarb anion intercalated between theinterlayer of ZLH region was 83.35%, which was calculatedfrom the percentage of N element in the nanocomposite.

ICP-OES detected 38.87% of Zn in the resultingnanocomposite.

3.5. Thermal study

The thermogravimetric analysis, TGA-DTG, obtained for iso-procarb, ZLH-SDS-ISO nanocomposite and ZLH-SDS arereported in Fig. 4. In Fig. 4(a), the thermal study shows that

the maximum temperature of pure isoprocarb was observedat 184 �C, with 99.8% of weight loss.

For ZLH-SDS-ISO, three stages of decomposition were

observed in Fig. 4(b). The first stage was due to the removalof surface-physisorbed water molecules, and dehydroxylationof the hydroxyl layer which occur at 130 �C with 9.6% of

weight loss [31]. The second stage was due to decompositionof isoprocarb, which can be observed at 189 �C with 74.2%weight loss. The final stage was due to decomposition ofSDS at 239 �C with weight loss of 13.7%.

Table 2 The composition analysis of the ZLH-SDS and ZLH-SDS

Sample N (%) C (%) H (%

ZLH-SDS 2.46 24.80 5.48

ZLH-SDS-ISO 6.17 61.10 7.14

The ZLH–SDS displayed two stages of weight loss (Fig. 4(c)). The first stage corresponded to the removal of intercalatedwater at 107 �C with 3.2% of weight loss [32]. Whereas, the

decomposition of SDS took place at 198 �C with 37.0% ofweight loss. From Fig. 4(a) and (b), the maximum temperatureof the decomposition of isoprocarb in the resulting nanocom-posite increased from 184 �C to 189 �C. Therefore, the isopro-carb that intercalated in the ZLH-SDS interlayer was provedto be thermally more stable compared to its prior form. Thisis due to the electrostatic interaction between anions and

ZLH layer [14].

-ISO nanocomposite.

) S (%) Anion (% w/w) % Zn

3.38 – 24.14

0.77 83.35 38.87

Synthesis and characterization of mesoporous zinc layered hydroxide-isoprocarb nanocomposite 491

3.6. Surface morphology

Fig. 5(a) and (b) illustrate the morphology of ZLH-SDS andZLH-SDS-ISO at 10 k magnification. The FESEM image ofZLH-SDS resembles thin flake-like nanosheets that are

expected to be layered materials [1]. The edge of ZLH-SDSsheets was quite fractured, with a cracked surface (Fig. 5(a)). After the intercalation, the crystal size decreased, withirregular thin flakes and in the micrometre range dimension

(Fig. 5(b)). The sheets were in stacked plate, sharp edges andsmooth surface. The effect of the hydrophobic interactionbetween the hydrocarbon tails was to facilitate the aggregation

of the particle, as previously reported elsewhere [19,27].

3.7. Surface area analysis

The comparison of the surface area and porosity of ZLH-SDSand ZLH-SDS-ISO nanocomposite are given in Table 3. The

(a)

Fig. 5 FESEM images of (a) ZLH-SDS, and (b) ZL

Table 3 Surface properties of ZLH-SDS and ZLH-SDS-ISO nanoc

Samples Specific BET surface area (m2/g)

ZLH-SDS 7.027

ZLH-SDS-ISO 1.196

0 0.2 0.4 0.6 0.8 1.0

Vol

ume

adso

rbed

at S

TP/ c

m3 g

-1

Relative pre

(a)

Fig. 6 Adsorption–desorption isotherms of nitroge

intercalation of the isoprocarb anion decreased the BET sur-face area from 7.027 m2 g�1 for ZLH-SDS to 1.196 m2 g�1

for the ZLH-SDS-ISO nanocomposite. As the surface area is

inversely related to particle size, this cases is attributed to theincrease in the particle size and decrease of the pore volume[33]. Particularly, specific surface area decrease with the

increase of particle size as well as pores presence, which leadto the decrease in the specific surface area [34]. This also mightbe due to a shift in the particle size distribution to a larger

mean size [35]. The decrease of surface area may take placedue to the collapse of pore structure. The collapse of the inter-connected mesoporous enlarged and changed the smallermesoporous into irregularly shaped larger mesoporous and

decreased the surface area value [36].As shown in Fig. 6, both the host and resulting nanocom-

posites possessed a relatively narrow distribution of pores,

with an average diameter of 27.83 to 25.04 nm, respectively,confirming the formation of regular mesoporous materials.This was due to the closing of the pores from insertion of

(b)

H-SDS-ISO nanocomposite at 10 k magnification.

omposite.

Average pore diameter (nm) Classification

27.83 Mesoporous

25.04 Mesoporous

0.2 0.4 0.6 0.8 1.0

ssure (P/Po)

(b)

n gas for (a) ZLH-SDS and (b) ZLH-SDS-ISO.

0

0.0001

0.0002

0.0003

0.0004

0 20 40 60 80 1000

0.00005

0.00010

0.00015

0.00020

0 20 40 60 80 100

dVp/d

r p

Pore diameter /nm

(a) (b)

Fig. 7 BJH desorption pore size distributions for ZLH-SDS (a), and ZLH-SDS-ISO (b).

492 Z. Muda et al.

the isoprocarb anion into the pores of the ZLH-SDS layer[37,38]. The presence of dodecyl sulphate and isoprocarb anionin the interlayer created a stronger bonding between the ZLH

layers and the anion, thus lowering the surface area of thenanocomposite material [22]. A The nitrogen-adsorption iso-therm for ZLH-SDS and the ZLH-SDS-ISO nanocomposites

are a type IV isotherm, with H3 hysteresis loops based onthe International Union of Pure and Applied Chemistry(IUPAC) classification [39] indicating mesoporous-type mate-

rials. The adsorption slowly increased in low relative pressurein the range of 0.0–0.6 (for ZLH-SDS) and 0.0–0.5 (for ZLH-SDS-ISO), which indicates a surface monolayer adsorptionprocess. Further increases in the relative pressure resulted in

a rapid adsorption of the adsorbent, due to the first multilayeradsorption [14]. The optimum uptake for resulting was 5 cm3/g,which indicates a low capacity for uptake of nitrogen gas com-

pared to the host, which was 32 cm3/g. This is due to the highcapacity of the isoprocarb anion intercalate in the interlayer ofZLH. A similar result was also reported elsewhere [3]. The

presence of H3 hysteresis loop in layered ZLH-SDS and theZLH-SDS-ISO nanocomposite revealed that the pores exhibitslit-shaped pores with non-uniform shape and sizes.

The Barret-Joyner-Halenda (BJH) pore size distribution for

ZLH-SDS and the ZLH-SDS-ISO nanocomposite are shownin Fig. 7. The pore size distribution of ZLH-SDS and ZLH-SDS-ISO is almost the same, with features centred at around

14 and 21 nm. In particular, the pore size distributions showthe formation of regular mesoporous in the layered ZLHnanocomposites.

4. Conclusion

In conclusion, this study showed the successful intercalation of

isoprocarb into the ZLH interlayer by an ion exchangemethod. The SDS surfactant provided a great impact in orderto intercalate the poor water-soluble insecticide, like isopro-

carb, into the interlayer of ZLH. The crystallinity of the result-ing nanocomposite is increase by increasing the amount ofisoprocarb anion. A well-crystallized nanocomposite wasobtained with basal spacing 33.1 A. The FTIR spectra of

ZLH-SDS-ISO showed a resemblance with ZLH-SDS spectraand isoprocarb spectra. The thermal stability of isoprocarbincreased after the intercalation, compared to its pure form.

The resulting nanocomposite showed a mesoporous-like char-acteristic. This study also showed that ZLH can be an excellent

host for isoprocarb. Further work in controlled release formu-lation of this nanocomposite is needed for environmentalpurposes.

Acknowledgement

The author is grateful to the support for the research providedby UPSI under GPU Grant no. 2017-0188-101-01. ZM thanksUPSI for all funding and support for this research.

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