In-situ growth of zeolitic imidazolate frameworks into a cellulosic filter paper for the reduction of 4-nitrophenol

Carbohydrate Polymers 274 (2021) 118657

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

In-situ growth of zeolitic imidazolate frameworks into a cellulosic filter
paper for the reduction of 4-nitrophenol
Hani Nasser Abdelhamid a, b, *, Aji P. Mathew a, *
a
b

Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden
Advanced Multifunctional Materials Laboratory, Department of Chemistry, Faculty of Science, Assiut University, Assiut 71515, Egypt

A R T I C L E I N F O

A B S T R A C T

Keywords:
Whatman® filter paper
Cellulose
4-Nitrophnol
Metal-organic frameworks
Water treatment
Catalytic reduction

Whatman® cellulosic filter paper was used as a substrate for the synthesis of two zeolitic imidazolate frameworks
(ZIFs); ZIF-8 and ZIF-67 with and without 2,2,6,6-tetramethyl-1-piperidine oxoammonium salt (TEMPO)oxidized cellulose nanofibril (TOCNF). All synthesis procedures take place at room temperature via a one-pot
procedure. The synthesis steps were followed using X-ray diffraction (XRD), scanning electron microscopy

(SEM), and Fourier transforms infrared (FT-IR). Data indicated the formation of metal oxide that converted to a
pure phase of ZIFs after the addition of the organic linker i.e. 2-methyl imidazole (Hmim). The materials were
characterized using XRD, FT-IR, SEM, energy dispersive X-ray (EDX), nitrogen adsorption-desorption isotherms,
and X-ray photoelectron microscope (XPS). Data analysis confirms the synthesis of ZIFs into Whatman® filter
paper. The materials were used for the reduction of pollutants such as 4-nitrophenol (4-NP) compound to 4-ami­
nophenol (4-AP). The materials exhibit high potential for water treatment and may open new exploration for
hybrid materials consisting of cellulose and ZIFs.

1. Introduction
Cellulose has advanced several industrial applications including
paper making, textiles, and food-related applications as well as filtration
(Haldar & Purkait, 2020; Huang et al., 2020; Lizundia et al., 2020; Teo &
Wahab, 2020; Georgouvelas et al., 2021). Cellulosic filter paper has used
a substrate to measure the hydrolytic efficiency for cellulase enzyme
(Mboowa et al., 2020), a substrate for surface-enhanced Raman spec­
troscopy (SERS) (Siebe et al., 2021), metal adsorption (El-Shahawi et al.,
2020), immobilize enzyme for biosensing (Ma et al., 2020), monitor
salmon spoilage via the detection of amine vapor (Jiang et al., 2020),
platform in point-of-care (POC) devices for rapid detection of DNA (Song
& Gyarmati, 2020), “lab on paper” and molecularly imprinted polymers
(MIPs) (Akbulut & Zengin, 2020). The cellulosic structure of filter paper
can be modified with metallic nanoparticles (Siebe et al., 2021), en­
zymes (Ma et al., 2020), chromophoric organic molecules (Jiang et al.,
2020), and dendrimers (Song & Gyarmati, 2020). The cellulosic filter
paper is a good substrate for materials immobilization (Park & Oh,
2017).
Metal-organic frameworks (MOFs), including zeolitic imidazolate
frameworks (ZIFs), are hybrid porous materials with high surface area,

high porosity, several active metal sites, and simple synthesis procedures

(Furukawa et al., 2013; Wang et al., 2014; Zhou et al., 2020). Most of the
synthesis procedures produce powder materials or require undesirable
or environmentally unfriendly chemicals as template molecules
(Abdelhamid et al., 2017; Abdelhamid et al., 2019). Biopolymers such as
cellulose are attractive template molecules with environmentally
friendly properties (Kim et al., 2019; Zheng et al., 2021). Cellulose-ZIFs
materials where MOFs are supported by cellulose are attractive for
several advantages, including their easy processibility (Richardson
et al., 2019; Sultan et al., 2018). The cellulose-based paper was reported
for a smartphone-assisted biomimetic MOFs paper device for POC
detection (Kou et al., 2020). Thus, it could be a useful substrate for the
synthesis of ZIFs materials (Abdelhamid & Mathew, 2021).
The contamination of drinking water due to industrial release is
increasing over time. Among several organic pollutants, nitroaromatic
compounds such as para-nitrophenol (4-NP or 4-hydroxy nitrobenzene)
were considered as hazardous pollutant compounds according to the US
Environmental Protection Agency (EPA) (Ayodhya & Veerabhadram,
˜ a et al., 2019; He et al., 2019; Ibrahim et al., 2019;
2019; Esquivel-Pen
Liu et al., 2019; Lv et al., 2019; Nimita Jebaranjitham et al., 2019; Xu
et al., 2020). 4-NP shows a significant potential threat to humans such as

* Corresponding authors at: Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden.
E-mail addresses: (H.N. Abdelhamid), (A.P. Mathew).
/>Received 19 June 2021; Received in revised form 30 August 2021; Accepted 6 September 2021
Available online 10 September 2021
0144-8617/© 2021 The Authors.
Published by Elsevier Ltd.
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H.N. Abdelhamid and A.P. Mathew

Carbohydrate Polymers 274 (2021) 118657

irritation, inflammation, skin allergies, respiratory syndrome, methe­
moglobin or methemoglobinemia, cyanosis, and unconsciousness
(Atlanta, GA: U.S. Department of Health and Human Services, 1992). 4NP displays high biodegradation's resistance (Ayodhya & Veerabha­
˜ a et al., 2019; He et al., 2019; Ibrahim et al.,
dram, 2019; Esquivel-Pen
2019; Liu et al., 2019; Lv et al., 2019; Nimita Jebaranjitham et al., 2019;
Xu et al., 2020). The reduction of 4-NP (with a lethal dose 50 (LD50) of
282 mg⋅kg− 1 and 202 mg⋅kg− 1 in mice and rats, respectively) to 4-ami­
nophenol (4-AP, LD50 of 375 mg⋅kg− 1 and 10,000 mg⋅kg− 1 for rat and
rabbit, respectively) mitigates the cytotoxicity. Furthermore, 4-AP is an
essential source for the synthesis of pharmaceuticals, analgesics, and

antipyretic drugs. The reduction process requires usually a catalyst
˜ a et al., 2019; He et al.,
(Ayodhya & Veerabhadram, 2019; Esquivel-Pen
2019; Ibrahim et al., 2019; Kassem et al., 2021; Liu et al., 2019; Lv et al.,
2019; Nimita Jebaranjitham et al., 2019; Xu et al., 2020). Some of these
catalysts are expensive, suffer from aggregation, and lack a high
reduction rate.
Herein, Whatman® cellulosic filter paper was used as a substrate for
the in-situ growth of ZIFs (ZIF-8 and ZIF-67). TEMPO (2,2,6,6-tetra­
methylpiperidine-1-oxyl radical)-mediated oxidized cellulose nano­
fibers (TOCNF) was used as a modulator during the growth of ZIFs
crystals. The synthesis procedure is a one-pot procedure that involves
the successful addition of metal salts (Zn for ZIF-8 and Co for ZIF-67)
followed by the addition of TOCNF and 2-methyl imidazole (Hmim).
The materials were characterized using X-ray diffraction (XRD), scan­
ning electron microscopy (SEM), Fourier transforms infrared (FT-IR),
energy dispersive X-ray (EDX), nitrogen (N2) adsorption-desorption
isotherms, and X-ray photoelectron microscope (XPS). They were used
as catalysts for the reduction of 4-NP using sodium borohydride (NaBH4)
as a reducing agent. The materials exhibit high catalytic performance.

degassed at 100 ◦ C for 5 h. Specific surface areas were evaluated using
Brunauer-Emmett-Teller (BET, SBET) and Langmuir method (SLan). The
external surface area (SExt) was evaluated using the t-plot method. The
pore size distribution of the membranes was evaluated using BarrettJoyner-Halenda (BJH) and density functional theory (DFT) methods.
X-ray photoelectron spectroscopy (XPS) spectra were recorded using a
Thermo Fisher (K-alpha, Al Kα radiation). Thermogravimetric analysis
(TGA) curves were carried using a thermogravimetric analyzer (Perki­
nElmer TGA 7).
2.4. Adsorption and catalytic reduction of 4-NP

A stock solution of 4-NP was prepared via dissolving one gram of 4NP into H2O (100 mL). One milliliter of the stock solution was added to a
beaker and completed to 100 mL. NaBH4 (100 mg) was added in the
presence of filter paper-loaded ZIFs materials or powder of ZIFs mate­
rials (100 mg) as catalysts. The reaction was followed with time via
measuring UV–Vis spectroscopy (Cary Eclipse, Agilent) using 0.5 mL of
the solution that was completed to 4 mL before measurements. The
reduction efficiency as a percentage was calculated using Eq. (1) as
follows:
Efficiency (%) =

A0 − At
× 100%
A0

(1)

2. Experiments

where Ao is the absorbance of the initial concentration of 4-NP and At is
the absorbance at the termination stage.
The recyclability was performed following the same procedure. After
the reaction was completed, the beaker was recharged with 1 mL of 4-NP
and NaBH4. The reaction was monitored using a UV–Vis spectropho­
tometer after the yellow color of the solution turned brown as previously
described.

2.1. Materials and methods

3. Results and discussion

TEMPO-oxidized cellulose nanofibers (TOCNF, 0.3 wt%) were pre­
pared following a previously reported method (Isogai et al., 2011).
Whatman® cellulosic filter paper (φ 25 mm), sodium borohydride
(NaBH4), Zn(NO3)2⋅6H2O, Co(NO3)2⋅6H2O, sodium hydroxide (NaOH),
2-methyl imidazole (Hmim) were purchased from Sigma Aldrich (USA).

3.1. Materials characterization
The synthesis procedure for ZIF-8 and ZIF-67 is schematically rep­
resented as shown in Fig. 1a. The procedure is a one-pot method that
involves the additions of the reactants, metals (Zn for ZIF-8 and Co for
ZIF-67), and Hmim as a linker. The synthesis was performed with and
without TOCNF. All the additions take place on Whatman® cellulose
filter papers, consists of high-quality cotton liners with a content of 98%.
The materials were characterized using XRD (Figs. S1–S3, Electronic
Supplementary File), FT-IR (Fig. 2), SEM images and EDX mapping
(Figs. S4–S5), XPS (Fig. 3), and nitrogen adsorption-desorption iso­
therms (Fig. 4). The phases formed during the chemical's additions were
monitored using XRD (Fig. S2) and FT-IR (Fig. 2).
XRD patterns for Whatman® filter paper (FP) before and after in-situ
growth of ZIF-8 and ZIF-67 with and without TOCNF during static and
stirring conditions are reported (Fig. S1). XRD pattern for Whatman®
filter paper (FP) displays diffraction peaks at Bragg's angle 14.8◦ , 16.5◦ ,
22.7◦ , and 34.2◦ corresponding to Miller indexes 1¯ı0, 110, 200, and 004,
respectively of cellulose I. The extra peaks observed for ZIF-8@FP and
ZIF-67@FP are related to ZIFs crystals formed into the cellulose of FP.
The powder crystals formed during the synthesis were also separated
and characterized using XRD (Fig. S3). XRD pattern confirms the suc­
cessful synthesis of a pure phase of ZIF-8 onto FP (Fig. S3). XRD data
reveals that both stirring and static conditions produce pure phases of
ZIF-8 and ZIF-67.

The chemical bonding and interactions within the materials were
confirmed using FT-IR (Fig. 2). FT-IR spectrum of Whatman® filter
paper shows peaks at 3300 cm− 1 and 1033 cm− 1 corresponding to O–H
and C–O stretching, respectively (Fig. 2). The in-situ growth of ZIF-8
and ZIF-67 was confirmed from the peak at 421 cm− 1 corresponding
to Zn–N (Hmim) and Co–N (Hmim), respectively.

2.2. Synthesis procedure for ZIFs-filter paper
The synthesis procedure of ZIFs-filter paper was performed at room
temperature. A filter paper was replaced in a plastic dish. The metal
solutions (Zn for ZIF-8 and Co for ZIF-67, 0.8 mL) were added to filter
paper with and without stirring. A sodium hydroxide solution (0.1 mL, 1
mM) was added followed by TOCNF solutions (1 mL, 0.3 wt%) and
finally, Hmim solution (8.0 mL, 0.84 M). The solution was left for 30
min. The powder materials were separated using centrifugation (13,500
rpm, 30 min). The filter was removed from the dish. Powder samples and
filter papers were washed several times with water (2 × 3 mL) and
ethanol (2 × 3 mL). The materials were dried in an oven at 85 ◦ C
overnight.
2.3. Characterization
X-ray diffraction (XRD) was recorded using a PANalytical X'PertPRO
X-ray system (Cu Kα1 radiation, at current 40 mA, and tension 45 kV).
Fourier transfer infrared spectroscopy (FT-IR) spectra were recorded
using a Perkin Elmer Spectrum 2000 FT-IR spectrometer. The surface
morphology and elemental analysis of the filter papers were imaged
with a scanning electron microscope (SEM, TEM-3000, Hitachi, Japan)
and energy-dispersive X-ray spectroscopy (EDX). Nitrogen (N2)
adsorption-desorption isotherms were measured at 77 K using a
Micromeritics ASAP 2020 instrument (UK). The filter papers were
2

H.N. Abdelhamid and A.P. Mathew

ZIF-8@FP

Carbohydrate Polymers 274 (2021) 118657

O

O

O
HO

OH

OH

O
n

ZIF-8@FP

1) Zn2+ for ZIF-8
Co2+ for ZIF-67

2) NaOH
Whatman Cellulosic
Filter Paper (FP)

OH
O

O

OH

HO
O
HO

O

Co2+

O
OH

O

O
OH

O

O

HO

HO

OH
O

OH
O
OH

OH
O

O
HO

Zn2+

O

O
HO

OH
OH
O
OH

ZIF67-TOCNF@FP

O

HO

ZIF-67@FP

OH

OH

ZIF8-TOCNF@FP

a

O
n

O
n

Hmim

ZIF8-TOCNF@FP

O

OH

b

NaBH4 + H2O

ZIF67-TOCNF@FP

NaBO2 + 2H2

4-NP

4-NP
O

–

+

N

H2

O

N

ZIF-8@FP

H

4-NP

4-NP

4-NP

ZIF8-TOCNF@FP ZIF-67@FP ZIF67-TOCNF@FP

4-AP

4-NP
OH

H

ZIF-67@FP

n

Yellow

Brown OH

Fig. 1. a) Chemical modification of cellulose filter paper with and without TOCNF for in-situ growth of ZIFs (ZIF-8 and ZIF-67), the image also contains a photograph
image for the synthesized filter papers for both materials as well as EDX mapping for Co and Zn elements, and b) Chemical reduction of 4-NP using NaBH4, a source
for hydrogen, as a reducing agent.

a ZIF-8 powder

b

ZIF67-TOCNF@FP

Transmittance (a.u.)

ZIF8-TOCNF@FP

Transmittance (a.u.)

ZIF67 powder

ZIF-8@FP

Zn-NaOH-TOCNF@FP

Zn-NaOH@FP

ZIF67@FP

Co-NaOH-TOCNF@FP

Co-NaOH@FP

Whatman Filter Paper (FP)

Whatman Filter Paper (FP)

3500 2800 2100 1400 700
Wavenumber (Cm-1)

3500 2800 2100 1400 700
Wavenumber (Cm-1)

Fig. 2. FT-IR spectra for a) ZIF-8 and b) ZIF-67 synthesized onto a Whatman filter paper (FP).

3


H.N. Abdelhamid and A.P. Mathew

Carbohydrate Polymers 274 (2021) 118657

O1s

C-C

C1s

N1s

e Co 2p

ZIF-67

Counts (s)

Co2p3

Co 2p3/2
ZIF-67

Co 2p1/2
Co-N

O-C-O

O-C=O

d

C1s ZIF-67
O1s N1s

f

TOCNF@ZIF-67
C-C

Co2p3

TOCNF@ZIF-67
Co 2p3/2

Counts (s)

b

Counts (s)

Counts (s)

c

TOCNF@ZIF-67
C1s

Counts (s)

a

O-C-O

Co 2p1/2
Co-N

O-C=O

1000 800 600 400 200
Binding Energy (eV)

0

294 292 290 288 286 284 282 280 810
Binding Energy (eV)

800
790
780
Binding Energy (eV)

770

1.2
1.0

Whatman Filter Paper (FP)

ZIF8@FP
ZIF8-TOCNF@FP
ZIF67@FP
ZIF67-TOCNF@FP

b

0.8
0.6
0.4
0.2
0.0
0.0

0.2
0.4
0.6
0.8
Relative Pressure (P/P0)

1.0

c

Whatman Filter Paper (FP)
ZIF8@FP
ZIF8-TOCNF@FP
ZIF67@FP
ZIF67-TOCNF@FP

0

200

400
600
Pore Width (Å)

dV/dW Pore Volume (m²/g·Å)

1.4

dV/dlog(w) Pore Volume (cm³/g)

a

Adsorbed N2 Amount (mmol/g)

Fig. 3. XPS analysis for ZIF-67@Filter paper and TOCNF-ZIF-67@Filter paper, a) survey, b) C 1s, and c) Co 2p.

800

Whatman Filter Paper (FP)
ZIF8@FP
ZIF8-TOCNF@FP
ZIF67@FP
ZIF67-TOCNF@FP

0

200

400
600
Pore Width (Å)

800

Fig. 4. a) Nitrogen adsorption (closed symbols)-desorption (open symbols) isotherm, and pore size distribution using b) BJH and c) DFT method.

The synthesis mechanism of the materials was explored using XRD
(Fig. S2), SEM images and EDX mapping/analysis (Fig. S4), and FT-IR
(Fig. 2). The Joint Committee on Powder Diffraction Standards
(JCPDS) database was investigated to characterize the observed crystal
during the in-situ crystals of ZIF-8 and ZIF-67. XRD analysis reveals the
presence of a mixture of zinc hydroxide nitrate (Zn5(OH)8(NO3)2⋅2H2O,
JCPDS card 24-1460) and Zn(OH)(NO3)⋅H2O (JCPDS card 84-1907)),
and zinc oxide (JCPD card 36–1451) for ZIF-8 and Co(NO3)2⋅6H2O
and Co3O4 (JCPDS card No.42-1467), cobalt hydroxide (Co(OH)2,
JCPDS card No.49-1125) for ZIF-67 (Fig. S2). These phases covered the
cellulosic fibers of filter paper (Fig. S4). The distribution of the observed
phased is homogenously over the used filter paper (Fig. S4). The
chemical bonds and interactions within the materials were investigated
using FT-IR (Fig. 2). Besides the vibrational bands of Whatman® filter
paper, the spectra show new vibrational bands at 1651 cm− 1 and 1314
cm− 1 corresponding to bending of H-O-H and stretching vibration of
NO3− ions intercalated in the interlayer, respectively (Fig. 2).
XPS spectra for ZIF-67 and TOCNF@ZIF-67 onto filter paper were
reported (Fig. 3). XPS survey for the materials confirms Co, N, O, and C
elements (Fig. 3a–b). XPS analysis of C 1s for ZIF-67@FP shows peaks at

binding energies of 285.0 eV, 286.6 eV, and 288.2 eV corresponding to
C-C/C-N, C-O-C, and O-C=O, respectively (Fig. 3c–d). XPS analysis of C
1s for TOCNF-ZIF-67@FP shows peaks at binding energies of 284.0 eV,
285.1 eV, 286.5 eV, and 288.2 eV (Fig. 3c–d). The extra peaks are due to
the interaction between Co of ZIF-67 and the oxygen functional groups

– O, O–H, and C–O (Fig. 3c–d). These observations
of TOCNF, e.g., C–
can be confirmed from the extra peaks observed in Co 2p for TOCNF-ZIF67@FP (Fig. 3e–f). The interaction between Co (ZIF-67) and oxygen
functional groups of TOCNF can be confirmed from the new bond Co–O
(TOCNF) at binding energy 790.5 eV (Fig. 3e–f).
The porosity of the materials and their textural properties were
evaluated using nitrogen adsorption-desorption isotherms (Fig. 4a). The
specific surface areas using BET (SBET), Langmuir method (SLan), and
external surface area (SExt) are tabulated in Table 1. The materials
synthesized using TOCNF exhibit higher surface areas (Table 1). The
addition of TOCNF during the in-situ growth of ZIF crystals into filter
paper also improves the pore volume of the synthesized materials
(Table 1). The pore size distribution using the BJH method (Fig. 4b) and
DFT method (Fig. 4c) reveals the formation of the hierarchical porous
structure containing both mesopore and macropore regimes. TOCNF
Table 1
Specific surface area and pore volumes.
Materials

SBET

SLang

SExt

m2/g
FP
ZIF8@FP
ZIF8-TOCNF@FP
ZIF67@FP
ZIF67-TOCNF@FP

4

2
30
50
54
65

VTotal

VMicro

VMeso

0.0001
0.009
0.017
0.020
0.020

0.0049
0.007

0.009
0.010
0.016

m3/g
2
37
57
70
82

2
8
7
8
9

0.005
0.016
0.026
0.030
0.036


H.N. Abdelhamid and A.P. Mathew

Carbohydrate Polymers 274 (2021) 118657

enhances the pore volume of ZIF-8 and ZIF-67 (Fig. 4b–c). This obser­
vation could be due to the use of TOCNF as a template to grow the crystal

surround TOCNF molecules and between the cellulose fibers of filter
paper.
The morphology, ZIFs distribution, and their contents on FP were
determined using SEM images, EDX analysis, and mapping (Fig. S5).
Data analysis reveals the homogenous distribution of ZIF-8 and ZIF-67
into filter paper. EDX analysis reveals the content of 18.0%, 14.6%,
7.6%, and 7.2% for ZIFs in ZIF-8@FP, TOCNF-ZIF8@FP, ZIF-67@FP,
and TOCNF-ZIF67@FP, respectively. The thermal stability of the ma­
terials was evaluated using TGA (Fig. S6). The filter paper containing
ZIFs exhibits thermal stability up to 325 ◦ C (Fig. S6).

The adsorption and reduction of 4-NP using ZIF67-based materials
were recorded, as shown in Fig. 5. The adsorption of 4-NP using ZIF67based materials as adsorbent shows the only transformation of 4-NP to
4-NP− (Fig. 5). After the addition of NaBH4 as a reducing agent, the
absorbance of 4-NP− is significantly decreased over time (Fig. 5). A new
absorption peak was observed at 300 nm referring to the reducing
product, i.e., 4-aminophenol (4-AP).
The change in the absorbance of 4-NP− over time using ZIF67-based
materials as a catalyst is shown in Fig. 6a. The absorbance is signifi­
cantly decreased within 5 min, indicating the complete reduction of 4NP to 4-AP. The reduction efficiency without catalyst or using ZIF8based materials shows efficiencies of 30% and 35%, respectively
(Fig. 6b). On the other side, ZIF67-based materials exhibit an efficiency
of 92–94% (Fig. 6b). These observations reveal the high performance of
ZIF67-based materials as catalysts. The high performance of ZIF67based materials is due to the high catalytic performance of cobaltbased materials for the hydrolysis of NaBH4 and producing hydrogen
with a high hydrogen generation rate (HGR) (Abdelhamid, 2021b; Xing
et al., 2020). This observation can be confirmed from the bubble for­
mation using ZIF-8/FP (left-hand beaker) and ZIF-67/FP (right-hand
beaker) (Movie 1, ESI). The chemical reduction of 4-NP to 4-AP using
ZIF-67/FP can be confirmed from the color change from yellow to brown
color of 4-AP (Fig. 1b). Both materials; TOCNF-ZIF67 and TOCNFZIF67@FP can be recyclable several times without significant loss of
the material's performance (Fig. 6c).

Several materials were reported as a catalyst for the reduction of 4nitrophenol (Abdelhamid, 2021c; Kassem et al., 2021). A summary of
our materials and other reported materials is tabulated in Table 2. Silver
nanoparticles (Ag NPs) were immobilized into a filter paper to reduce 4NP (Alula et al., 2020). The synthesis procedures involve the soaking of a
filter paper in Tollen's reagent (Ag(NH3)2OH). The silver ions were
reduced to silver nanoparticles using glucose as a reducing agent in a
water bath at a temperature of 55 ◦ C (Alula et al., 2020). Ag NPs/Filter
paper exhibits a complete reduction of 4-NP within a short reaction
time. The synthesis procedure of our materials takes place at room

3.2. Adsorption and reduction of 4-nitrophenol (4-NP)
The applications of the synthesized materials were investigated for
the adsorption and chemical reduction of 4-nitrophenol (4-NP, Fig. 1b)
as a model for organic pollutants (Figs. 5–6, S7). The aqueous solution of
4-NP exhibits a strong absorbance peak at 417 nm and a weak absor­
bance at 405 nm (ε = 0.2 mM− 1⋅cm− 1) (Bowers et al., 1980). The
alkaline solution of 4-NP shows a strong absorbance peak at 400 nm
corresponding to phenolate species (4-nitrophenoxide, 4-NP− ).
The catalytic performance of ZIFs materials as a powder or a filter
paper was recorded for ZIF-67 (Fig. 5–6) and ZIF-8 (Fig. S7). ZIF-8 based
materials show a small change in the absorbance peak of 4-NP with the
observation for a new peak at 410 nm (Fig. S7). The changes in the
absorbance wavelength are due to the conversion of 4-NP to 4-NP−
species (Fig. S7). The conversion is due to the alkalinity of the aqueous
solution caused due to the dissociation of water molecules into the
external surface of ZIF-8 crystals (Abdel-Magied et al., 2019; Chizallet
et al., 2010). The transformation shows an isosbestic point for 4-nitro­
phenol/4-nitrophenoxide at 348 nm (ε = 5.4 mM− 1⋅cm− 1, Fig. S7).
The changes in the water's alkalinity in TOCNF-ZIF-8 are significant due
to the alkalinity of TOCNF. The adsorption or reduction of 4-NP using
ZIF8-based materials is low compared to ZIF67-based materials.

Fig. 5. UV–Vis spectra for the adsorption and reduction of 4-NP using ZIF-67 based materials; a) ZIF-67, b) TOCNF@ZIF-67, c) ZIF-67@FP, and TOCNF-ZIF67@FP.
The highlighted region represents 4-amino phenol (4-AP).
5


H.N. Abdelhamid and A.P. Mathew

ZIF-67
ZIF-67@FP

0.8
0.6
0.4
0.2
0.0

b100
Efficiency (%)

Absorbance (a.u.)

1.0

TOCNF@ZIF-67
TOCNF-ZIF67@FP

5

10 15 20

Time (min)

25

30

ZIF-8

ZIF-67

80
60
40

No

c 100

TOCNF-ZIF67@FP

TOCNF-ZIF67

80
60
40
20

20
0

0

No Cat.

Efficiency (%)

a 1.2

Carbohydrate Polymers 274 (2021) 118657

t.
.
.
.
Ca IF8 F67 Cat IF8 F67 Cat FP FP Cat FP FP
Z ZI No @Z ZI No 8@ 7@ No 8@ 67@
F F6
F IF
F
I
@
I
Z ZI
Z
CN NF
F- F-Z
TO TOC
CN CN
TO TO

0

1

2

Cycles

3

4

Fig. 6. a) The change in the absorbance of 4-NP− peak over time, b) reduction adsorption of 4-NP using ZIF67-based materials, and c) recyclability.

treatment.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.carbpol.2021.118657.

Table 2
Summary for materials that can be used for the reduction of 4-NP using NaBH4.
Catalysts

Reduction conditions

Efficiency
(%)

Ag NPs/FP

4-NP (10 mL, 0.1 mM),

NaBH4 (10 mL, 100 mM)
Cat (5 mg), 4-NP (2 mL,
1 mM), NaBH4 (1 mL,
125 mM)
4-NP (0.25 mL, 10 mM),
NaBH4 (25 mL, 0.4 mg/
mL)
Cat (30 mg), 4-NP (30
mL, 0.015 mmol), NaBH4
(1.5 mmol)
Cat (100 mg), 4-NP (100
mL, 1 μg/mL), NaBH4
(100 mg)

100

5

100

9

100

10

(Song et al.,
2020)

100

20

(Xie et al.,
2020)

95

5

This study

Ru@rGO
BC-Cu-0.5
NPC
TOCNFZIF67@FP

Time
(min)

Ref.

CRediT authorship contribution statement

(Alula et al.,
2020)
(Barman
et al., 2021)

Hani Nasser Abdelhamid: Conceptualization, Methodology,

Writing – review & editing, Data curation, Writing – original draft,
Investigation. Aji P. Mathew: Funding acquisition, Visualization, Su­
pervision, Validation, Resources, Writing – review & editing.
Acknowledgments
This project is funded by The Swedish Foundation for Strategic
Environmental Research (Mistra), project name MISTRA TerraClean
(project no. 2015/31).

Note: FP, filter paper; rGO, reduced graphene oxide; Silver nanoparticles, Ag
NPs.

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A fast and straightforward wet chemical method for in-situ growth of
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reported. The synthesis procedure involves a one-pot method and re­
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