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

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.

Available online 10 September 2021

(http://creativecommons.org/licenses/by-nc-nd/4.0/).

In-situ growth of zeolitic imidazolate frameworks into a cellulosic filter

paper for the reduction of 4-nitrophenol

Hani Nasser Abdelhamida,b,*, Aji P Mathewa,*

aDepartment of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden

bAdvanced 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

Keywords:

Whatman® filter paper

Cellulose

4-Nitrophnol

Metal-organic frameworks

Water treatment

Catalytic reduction

A B S T R A C T 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,

2019; Esquivel-Pe˜na et al., 2019; He et al., 2019; Ibrahim et al., 2019; 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: hani.abdelhamid@aun.edu.eg (H.N Abdelhamid), aji.mathew@mmk.su.se (A.P Mathew)

Contents lists available at ScienceDirect Carbohydrate Polymers journal homepage: www.elsevier.com/locate/carbpol

https://doi.org/10.1016/j.carbpol.2021.118657

Received 19 June 2021; Received in revised form 30 August 2021; Accepted 6 September 2021

irritation, inflammation, skin allergies, respiratory syndrome,

methe-moglobin or methemethe-moglobinemia, cyanosis, and unconsciousness

(Atlanta, GA: U.S Department of Health and Human Services, 1992) 4-

NP displays high biodegradation's resistance (Ayodhya &

Veerabha-dram, 2019; Esquivel-Pe˜na et al., 2019; He et al., 2019; Ibrahim et al.,

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

(Ayodhya & Veerabhadram, 2019; Esquivel-Pe˜na et al., 2019; He et al.,

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

2 Experiments

2.1 Materials and methods

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)

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 Kα 1 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)

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 Barrett- Joyner-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 4-

NP 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− A t

A0

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

3 Results and discussion

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

O O OH O H O OH O OH

O

H

O

OH

n

1) Zn 2+ for ZIF-8

Co 2+ for ZIF-67 2) NaOH

O OH

O OH O O OH O O

n

O O OH O H O OH O

OH O H O

O

n

O O OH O H O OH O

OH O H O OH

n

Zn 2+

Co 2+

Hmim

Whatman Cellulosic

Filter Paper (FP)

ZIF-8@FP ZIF-67@FP

ZIF8-TOCNF@FP

a

b

N+

OH

O

OH

H H

NaBH 4 + H 2 O NaBO 2 + 2H 2

H 2

ZIF67-TOCNF@FP

4-NP 4-NP

4-NP

ZIF67-TOCNF@FP

ZIF8-TOCNF@FP

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

3500 2800 2100 1400 700

Whatman Filter Paper (FP)

Wavenumber (Cm-1)

Zn-NaOH-TOCNF@FP

Zn-NaOH@FP

ZIF-8@FP ZIF8-TOCNF@FP ZIF-8 powder

3500 2800 2100 1400 700

Whatman Filter Paper (FP)

Wavenumber (Cm-1)

Co-NaOH-TOCNF@FP

Co-NaOH@FP

ZIF67@FP ZIF67-TOCNF@FP

ZIF67 powder

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

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

of TOCNF, e.g., C––O, O–H, and C–O (Fig 3c–d) These observations can be confirmed from the extra peaks observed in Co 2p for TOCNF-ZIF- 67@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

1000 800 600 400 200 0

Co2p3 Co2p3

O1s C1s C1s

Binding Energy (eV)

ZIF-67 O1s

N1s

N1s TOCNF@ZIF-67

Binding Energy (eV)

294 292 290 288 286 284 282 280

Binding Energy (eV)

3/2

Co 2p 1/2

Co 2p 3/2

Co 2p 1/2

ZIF-67

TOCNF@ZIF-67

Co-N

Co-N C-C

O-C-O O-C=O

C-C O-C-O

O-C=O

ZIF-67

TOCNF@ZIF-67

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

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Relative Pressure (P/P0)

Whatman Filter Paper (FP) ZIF8@FP

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

Pore Width (Å)

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

Pore Width (Å)

Whatman Filter Paper (FP) ZIF8@FP

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

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

Table 1

Specific surface area and pore volumes

Materials SBET SLang SExt VTotal VMicro VMeso

ZIF8@FP 30 37 8 0.016 0.009 0.007 ZIF8-TOCNF@FP 50 57 7 0.026 0.017 0.009

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)

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

The adsorption and reduction of 4-NP using ZIF67-based materials were recorded, as shown in Fig 5 The adsorption of 4-NP using ZIF67- based 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 4-

NP to 4-AP The reduction efficiency without catalyst or using ZIF8- based 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 ZIF67- based materials is due to the high catalytic performance of cobalt- based 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 TOCNF- ZIF67@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 4- nitrophenol (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 4-

NP (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

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)

temperature and requires inexpensive chemical reagents Furthermore,

ZIFs materials exhibited high biocompatibility compared to silver

nanoparticles (Abdelhamid, 2021a) ZIFs-based materials are also

inexpensive compared to rare elements such as ruthenium (Ru) (Barman

et al., 2021) They did not require the use of support materials such as

reduced graphene oxide (rGO) that prevent aggregation of expensive

metallic nanoparticles such as Ru (Ru@rGO) (Barman et al., 2021)

Cellulose is not only cheap but also improves the efficiency of the

cat-alysts Aerogels of bacterial cellulose (BC) aerogels and metal

nano-particles (BC-Cu-0.5) were reported as a catalyst for the reduction of 4-

NP (Song et al., 2020) Cellulose can also be used as a source for the

synthesis of nitrogen and phosphorus co-doped carbon-based metal-free

catalysts (NPC) (Xie et al., 2020) ZIF67-FP offers several advantages

including high reduction efficiency, low cost, and short reaction time

(Table 2)

4 Conclusions

A fast and straightforward wet chemical method for in-situ growth of

ZIFs crystal into cellulose filter paper with and without TOCNF was

reported The synthesis procedure involves a one-pot method and

re-quires no sophisticated conditions or expensive reagents The method

was applied for two different ZIFs; zinc and cobalt-based materials It

can be further investigated for other ZIFs or MOFs TOCNF improved the

textural properties, such as specific surface areas and pore volumes It

enhanced the catalytic activity of ZIFs materials to reduce nitroaromatic

compounds such as 4-nitrophenol as a model The catalytic performance

of the synthesized materials ensures the high potential activity of the

treatment

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

CRediT authorship contribution statement 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)

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1.0

1.2

Time (min)

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

0 20 40 60 80 100

TOCNF-ZIF

67@FP

-ZIF8

@FP

FP ZIF8@F

P ZIF67

TOCN F@ZIF6 7 TOCN F@ZIF

8

.

No Cat.

No Ca t.

No Cat ZIF-8 ZIF-67

No Cat

0 20 40 60 80

100

Cycles

TOCNF-ZIF67@FP TOCNF-ZIF67

c

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

Table 2

Summary for materials that can be used for the reduction of 4-NP using NaBH4

Catalysts Reduction conditions Efficiency

(%) Time (min) Ref

Ag NPs/FP 4-NP (10 mL, 0.1 mM),

NaBH4 (10 mL, 100 mM) 100 5 (2020Alula et al., )

Ru@rGO Cat (5 mg), 4-NP (2 mL,

1 mM), NaBH4 (1 mL,

125 mM)

et al., 2021 ) BC-Cu-0.5 4-NP (0.25 mL, 10 mM),

NaBH4 (25 mL, 0.4 mg/

mL)

100 10 ( Song et al.,

2020 ) NPC Cat (30 mg), 4-NP (30

mL, 0.015 mmol), NaBH4

(1.5 mmol)

100 20 ( Xie et al.,

2020 ) TOCNF-

ZIF67@FP Cat (100 mg), 4-NP (100 mL, 1 μg/mL), NaBH4

(100 mg)

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

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