International Journal of Environmental Studies

ISSN: 0020-7233 (Print) 1029-0400 (Online) Journal homepage: https://www.tandfonline.com/loi/genv20

Investigating metal-organic framework based on

nickel (II) and benzene 1,3,5-tri carboxylic acid
(H3BTC) as a new photocatalyst for degradation of
4-nitrophenol

Abdelaziz Arroussi, Hafida Gaffour, Malika Mokhtari & Leila Boukli-Hacene

To cite this article: Abdelaziz Arroussi, Hafida Gaffour, Malika Mokhtari & Leila Boukli-Hacene
(2019): Investigating metal-organic framework based on nickel (II) and benzene 1,3,5-tri carboxylic
acid (H3BTC) as a new photocatalyst for degradation of 4-nitrophenol, International Journal of
Environmental Studies, DOI: 10.1080/00207233.2019.1584479

To link to this article: https://doi.org/10.1080/00207233.2019.1584479

Published online: 08 Mar 2019.

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 INTERNATIONAL JOURNAL OF ENVIRONMENTAL STUDIES
https://doi.org/10.1080/00207233.2019.1584479

ARTICLE

Investigating metal-organic framework based on nickel (II)

and benzene 1,3,5-tri carboxylic acid (H3BTC) as a new
photocatalyst for degradation of 4-nitrophenol
Abdelaziz Arroussia, Hafida Gaffoura,b, Malika Mokhtaria and Leila Boukli-Hacenea
a
Laboratory of Inorganic Chemistry and Environment, Faculty of Sciences, University of Tlemcen, Tlemcen,
Algeria; bDepartement of Chemistry, University of Adrar, Adrar, Algeria

ABSTRACT KEYWORDS
Metal-organic framework nickel (II) benzene tricarboxylate Ni3(BTC)2 MOF-Ni; photocatalyst;
·12H2O (MOF-Ni) has been synthesised under solvothermal condi- organic pollutant;
tions and characterised by single crystal X-ray diffraction, Fourier 4-Nitrophenol (4-NP);
degradation
transform infrared spectroscopy (FT-IR) and thermogravimetric ana-
lysis (TGA). The photocatalytic degradation of 4-nitrophenol (4-NP)
using MOF-Ni under UV light irradiation was investigated and
showed satisfactory results. A catalytic mechanism is proposed in
terms of the HOMO-LUMO (highest occupied molecular orbital-
lowest unoccupied molecular orbital) gap and the associated light-
induced transition. The results showed that the studied MOF-based
photocatalyst can be reused three to five times in the photocata-
lysis process and can degrade and mineralise 74% and 48% of 4-NP,
respectively.

Introduction
In the last two decades, metal-organic frameworks (MOFs) have been extensively
studied in various fields including gas storage [1,2], catalysis [3,4], drug delivery [5],
adsorption [6–9], separation [10,11], polymerisation [12], electrode materials [13,14]
and luminescence [15]. Similarly, in wastewater treatment, they have attracted equal
attention owing to their high porosity, large surface area and tunable pore size [6,16–
19]. Furthermore, their high absorption capacity, ability to encapsulate photosensitisers,
and charge transporting behaviour make them highly efficient catalysts for photode-
gradation and purification of environmental wastewaters [20,21]. Indeed, when a MOF
structure is exposed to the light irradiation, electrons freely migrate and allow the
production of reactive radical species. This semiconductor-like behaviour makes MOFs
efficient photocatalysts.
Since the first application of MOFs as photocatalyst in 2006 [22], many photocata-
lysis studies have been carried out [23–27]. In 2015, Xu and co-workers reported
photocatalytic hydrogen evolution experiments performed by irradiating the solution
in the presence of the Fe-MOF using a white-light LED [28]. Recently, Li and co-
workers investigated MIL-125-derived mixed phase of TiO2 and its application in

CONTACT Leila Boukli-Hacene [email protected]

© 2019 Informa UK Limited, trading as Taylor & Francis Group

Published online 08 Mar 2019

2 A. ARROUSSI ET AL.

nitrobenzene degradation [29]. It was found that the new material has better photo-
catalytic performance than anatase or rutile phase TiO2 because the constructed
structure of energy levels leads to the reduction of electron-hole pairs combination.
Benzene tri-carboxylic acid (H3BTC) has been used as organic linker in various
MOFs [30]. Besides being inexpensive and readily available, BTC anion presents multi-
dimensional coordination modes with various metal centres owing to the presence of
three carboxylate groups. Here, we report a modified synthesis of [Ni3(BTC)2,12H2O],
single X-ray diffraction analysis and the investigation of this coordination polymer as
a new photocatalyst for the degradation of 4 nitrophenol (4-NP).

Experimental
Materials
1,3,5-Benzenetricarboxylic acid (H3BTC, 98% purity), nickel (II) nitrate hexahydrate
(Ni(NO3)2.6H2O, 79%), ethanol (C2H5OH, 96%), sulphuric acid (H2SO4, 99%) and
dimethylformamide (DMF, 99%) were obtained from Sigma-Aldrich Co. 4-NP (99.5%)
and sodium hydroxide (NaOH, 95–97%) were obtained from Fluka Co. All compounds
were used as received.

Preparation of MOF-Ni
The compound was synthesised with a slight modification of the method reported by
Britt et al. [31]. A solid mixture of Ni(NO3)2.6H2O (1.81 mmol) and 1,3,5-benzene-
tricarboxylic acid (1.12 mmol) was dissolved in a mixture of DMF (5 mL), ethanol
(5 mL) and water (3 mL). The solution was stirred for 15 min and placed in a stainless-
steel vessel, which was heated at 100°C in an oven for 24 h, then cooled to room
temperature. The product was filtrated, washed several times with water and ethanol,
and then dried to give 0.36 g of the compound.

Characterisation
The structure and crystallinity of the as-synthesised MOFs were characterised by single
crystal diffraction. Crystal data were collected on an Xcalibur diffractometer at room
temperature with graphite monochromatic Mo Kα radiation (λ = 0.71073 Å). IR
spectrum was recorded in the range of 4000–400 cm−1 on a Perkin Elmer FT-IR
spectrophotometer using a KBr pellet. Thermo-gravimetric analyses were recorded
with SDT Q600 V20.9 build 20 (DSC-TGA) operating at 10°C/min.

Analytical procedures
The pH value of solutions was determined using a pH metre (HANNA, pH 301).
Chemical oxygen demand (COD) was measured using Loviband MD200 COD VARIO
photometer and COD WTW CR 2200 V1.04 heating block. Hydrogen peroxide was
monitored by measuring the absorbance at λ = 350 nm using Lambda 25 Perkin Elmer
UV-Vis spectrometer.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL STUDIES 3

Table 1. Crystallographic parametres and summary of data collection of Ni3(BTC)2·12H2O.

Chemical formula C18H30O24Ni3
Crystal system, space group Monoclinic, I2(C2)
Temperature (K) 293 K
a, b, c (Å) 6.5279 (1), 12.8600(2), 16.1068 (2)
α, β, γ (°) 90°, 90.522 (1), 90°
V (Å3) 1352.09 (3) Å3
Z 4
µ (mm−1) 0.76
No. of measured, independent and observed [I > 2σ(I)] reflections 4219, 2451, 2449
Rint 0.018
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.116, 1.25
ρmax, ρmin (e° A−3) 0.70, −1.78

X-ray analysis
The structure was solved by direct methods using the SHELXT program [32], and then
refined with full-matrix least-square methods based on F2 [32] with the aid of the
WINGX program [33]. All non-hydrogen atoms were refined with anisotropic atomic
displacement parametres. H atoms were finally included in their calculated positions.
Table 1 shows parts of crystallographic data and structure refinement. Further
crystallographic parametres have been deposited with the Cambridge Crystallographic
Data Centre (No. CCDC 1845514).

Application of MOF-Ni as photocatalyst for degradation of 4-NP

The photocatalytic activity of MOF-Ni catalyst was evaluated by photodegradation of
4-NP, as a model pollutant, in aqueous solution under UV irradiation (25 W, 18 mA).
All photocatalytic experiments were carried out in a 500 mL photoreactor with constant
stirring at room temperature. For degradation of 4-NP, a weighed quantum of catalyst
(MOF-Ni) was suspended in 300 mL of 4-NP aqueous solution. Before illumination, the
suspension was sufficiently stirred in the dark for 15 min to disperse the catalyst. At
regular times of UV irradiation, 3 mL of 4-NP solution was taken and centrifuged to
remove the catalysts. Photodegradation of 4-NP was monitored by measuring the
maximum absorption peak at 317 nm using a Lambda 25 UV-Vis spectrometer.

Statistical analysis
All the experiments were conducted in triplicate and the statistical mean was calculated
by Microsoft Excel 2013.

Results and discussion

Crystal structure
A single crystal analysis was undertaken on the prepared Ni-based MOF, and the
crystallographic details analysis revealed that the compound is isostructural with
a previously reported Ni-based MOF [34] with a space group transformation from I2
4 A. ARROUSSI ET AL.

Figure 1. A view of the molecular structure of Ni3(BTC)2·12H2O, with atoms labelling.

to C2. The structure analysis shows a structure composed of 1D zigzag chains built
from two different nickel (II) units and BTC ligands (see Figure 1). Each metal ion is
differently coordinated to carboxylate units: Ni1 is coordinated to two carboxylate ions
in axial positions in a nearly perfect octahedral geometry; Ni2 coordinate the second
carboxylate unit in a bidentate mode (equatorial positions) in a distorted octahedral
geometry. Both Ni1 and Ni2 coordinations are completed by four water molecules. All
water molecules are involved in hydrogen bonds to either a carboxylate or water oxygen
establishing a huge 3D framework. Table 2 shows selected bond lengths and angles. The
bond length and angle values show no significant deviation from those observed for
other similar compounds [34].

Table 2. Selected bond lengths (Å) and bond angles (°) for the titled
compound.
O1—Ni1 2.062 (3) O2—Ni1 2.025 (3)
O3—Ni1 2.096 (3) O4—Ni1 2.023 (3)
O5—Ni1 2.091 (3) O6—Ni1 2.077 (3)
O10—Ni2 2.101 (3) O11—Ni2 1.984 (4)
O12—Ni2 2.088 (3) C14—Ni2 2.441 (5)
O4—Ni1—O2 175.05 (12) O1—Ni1—O6 176.13 (13)
O4—Ni1—O1 86.32 (11) O4—Ni1—O6 93.71 (12)
O2—Ni1—O1 91.16 (11) O2—Ni1—O6 89.09 (11)
O11—Ni2—O10 100.0 (2) O11—Ni2—C14 130.51 (18)
O12—Ni2—O10 87.85 (13) O12—Ni2—C14 91.87 (9)
O4—Ni1—O2 175.05 (12) O1—Ni1—O6 176.13 (13)
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL STUDIES 5

Figure 2. FT-IR spectral analysis of H3BTC and MOF-Ni.

FT-IR characterisation
FT-IR spectra of MOF-Ni exhibited a significant difference when compared to that of
H3BTC (Figure 2). Peaks at 1636 and 1449 cm−1 are attributed to the stretching
vibration of C=O aromatic and C=C aromatic, respectively with a significant shift of
the absorption peak of CO group indicating the deprotonation of the carboxylate
moieties of the ligand. A wide and intense peak at 3416 cm−1 is related to absorption
of water molecules. The band located at 634 cm−1 corresponds to out-of-plane vibration
of C-H aromatic bond [35,36].

TGA analysis
The thermogravimetric analysis (TGA) of MOF-Ni (Figure 3) shows two major weight
losses. The elimination of water molecules occurs at 100°C. A weight loss of 62% was
noted at temperature up to 400°C. Above 400°C, a second weight loss is observed which
can be assigned to the decomposition of the organic ligand [37]. At 600°C, the residue
weight was about 26%.

Photocatalytic degradation of 4-NP

Effect of initial pH
The pH value must be studied and monitored in the photocatalytic oxidation processes
because it affects the production of hydroxyl radical, a powerful oxidising agent,
dissociation of compounds in the solution, and the charge of the catalyst surface. In
this approach, the effect of solution pH on the efficiency of the photodegradation
6 A. ARROUSSI ET AL.

Figure 3. TGA analysis of the MOF-Ni.

Figure 4. Effect of the pH on degradation of 4-NP ([4-NP] = 20 mg/L, [MOF-Ni] = 0.025g/L,

V = 300 mL).

process was investigated in the pH range of 3–10, maintaining the other parametres
constant. Best photodegradation of 4-NP (64%) was obtained at pH 10, using 0.025 g/L
of MOF-Ni as first suggested weight (Figure 4).
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL STUDIES 7

In aqueous solution at alkaline medium, the adsorption of anions (phenolate ions) is

favoured, and the interaction of 4-NP molecules and the catalyst surface is optimum,
resulting in the best degradation efficiency [38,39].
At pH lower than 10, the decrease in the degradation efficiency may be caused by the
repulsion between the surface of MOF-Ni and anions of 4-NP. These results are slightly
different from those in the literature [40,41].

Effect of MOF-Ni concentration

The influence of the catalyst amount on the photodegradation of 4-NP was investigated
over the concentration range of 0.025–0.5g/L (see Figure 5). Maximum photodegrada-
tion of pollutant was observed at 0.1g/L, which can be caused by:

- The insufficiency of the photocatalyst concentration (<0.1g/L) to destruct 20 mg/L

of 4-NP.
- The agglomeration of MOF-Ni particles at their high concentration (>0.1 g/L),
decreasing the accessible surface-active sites and OH radicals generated during the
illumination of particles by UV irradiation [42–45]. These entities reacted on the
4-NP molecules to produce 4-nitrocatechol, catechol, hydroquinone, benzoquinone
and organic acids.

Effect of 4-NP concentration

Any treatment process was affected by the concentration of studied pollutant. The effect
of this parametre was carried out over the concentration range of 10–40 mg/L. The

Figure 5. Effect of MOF-Ni on the degradation of 4-nitrophenol (pH = 10, [4-NP] = 20 mg/L,
V = 300 mL).
8 A. ARROUSSI ET AL.

Figure6. Effect of [4-NP] on degradation of 4-NP (pH = 10. [MOF-Ni] = 0.1 g/L, V = 300 mL).

photodegradation of 4-NP was important at 10 and 20 mg/L of 4-NP (74%), decreasing

thereafter (Figure 6). These results can be explained by the important rate of transfer
phenomena between catalyst surface and dissolved particles of 4-NP at low concentra-
tions of these organic molecules. But, when the concentration of 4-NP was more than
20 mg/L, the active sites of photocatalyst can be saturated and they reached the
reduction of HO. Further, the irradiation of catalyst was difficult with 4-NP molecules
(absorbed UV and covered catalyst) [46].

Determination of COD; peroxide, nitrates and nitrites concentrations

The aim of the photocatalytic process is to mineralise the organic matter. The photo-
degradation of 4-NP in the presence of MOF-Ni catalyst was accompanied with the
COD measure (Figure 7).
The mineralisation of 4-NP (20 mg/L), using 0.1 g/L of MOF-Ni, indicated the
COD value of 48% at 120 min of irradiation. It remained constant for 60 min,
decreasing thereafter. This variation of 4-NP photodegradation was accompanied
with an increase in H2O2 concentration to reach a limit value of 0.11 mmol/L after
180 min of reaction. This value remained constant until 240 min. Hence, the destruc-
tion of 4-NP was carried out with the performance of generated HO and H2O2 in the
reaction medium [47].
The concentrations of nitrites and nitrates generated during this elimination process,
increased from 0 to 4.241 and 4.099 mg/L, respectively. But, after 180 min, these values
decreased. This could be explained by the successive oxidation and cleavage of 4-NP
and/or by-products; mainly, with hydroxyl radicals [46].
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL STUDIES 9

Figure 7. Monitoring of COD, nitrates, nitrites and H2O2 ([4-NP] = 20 mg/L. [MOF-Ni] = 0.1 g/L,
pH = 10, V = 300 mL).

Photocatalytic mechanism approach

Figure 8 shows a suggested mechanism of 4-NP photodegradation. It can be seen
that the illumination of MOF-Ni particles involved the excitation of electrons from
the valence band (VB) to conduction band (CB) and positive holes (h+) in VB.

Figure 8. Schematic diagram of MOF-Ni photoexcitation and photocatalytic mechanism of 4-NP

under UV irradiation [48,50].
10 A. ARROUSSI ET AL.

These h+ were responsible for the oxidation of water molecules to hydroxyl radicals.
Meanwhile, the migrated electrons reduced O2 to the superoxide radical (O2) and
the Ni2+ ions in the centre of MOF-Ni into Ni+ and/or Ni metal. Therefore, the
degradation of 4-NP was achieved by OH action [48–51].
The reusability of MOF-Ni was investigated after washing the used particles by
ionised water and drying at room temperature. The results showed that this used
photocatalyst could be reused three to five times in the photocatalysis process.

Proposed pilot study

Without effective global action on climate change and global warming, there will be
serious effects on natural ecosystems, and on the resilience, security and well-being of
the population. The effects of climate change on resources and access to water are
already visible and are multiple. On the one hand, droughts are increasing in many
parts of the world. They will expose more than a third of the world population to
periods of water stress. One consequence is the reduction of deep-water resources.
Concerned populations must use surface water that is unhealthy. On the other hand,
high rainfall events and melting snow and ice are a factor in soil erosion and faster
dispersion of pollutants in groundwater.
Nitrophenols (NPs) are nitroaromatic products widely used in the environment as
intermediates in the preparation of carbonaceous chemicals, petrochemicals, dyes,
explosives, pesticides and by-products of chemical degradation and pharmaceutical
products. These compounds were classified among 114 toxic and dangerous pollu-
tants, owing to their carcinogenicity, irritation (skin, eyes, soft tissue). There is an
urgent need to reduce the use of NPs by using alternative products with the same
effect and low toxicity. At least contaminated wastewater in all factories must be
handled with care.
Compared to classic methods of pollutant treatment (adsorption, extraction, etc.),
AOPs represent a potential alternative approach able to destroy and to reduce the
aqueous recalcitrant pollutant ratio with the action of hydroxyl radicals, produced
during the treatment. OAPs methods also allow the mineralisation, in an aqueous
medium, of organic pollutants which are toxic for human beings and the environment.
Degradation of organic pollutants by photodissociation type processes could be sig-
nificantly accelerated in the presence of a heterogeneous catalyst. Many advanced
oxidation processes have been studied at the laboratory scale (reaction mechanisms,
kinetic study, etc.) [52–56] or at the pilot scale (feasibility study, technical-economic
evaluation, etc.) [57].
To develop our work, we present here a proposal of a pilot scheme for the photo-
degradation of 6000 cm3 of 4-NP in the presence of MOF-Ni in the semi-pilot scale.
Experiments are carried out in a 10,000 cm3 Pyrex glass photoreactor recovered with
highly polished aluminium film. This reactor consists of a quartz tube (699 mm length,
135-mm-wide inner diametre) surrounded internally by 20 low-pressure UV lamps
with maximum emission at 254 nm (18 mA, 25 W). The homogenisation of reaction
mixture is reached using recirculation loops as seen in Figure 9.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL STUDIES 11

Figure 9. Sketch of the experimental set-up.

The 4-NP aqueous solution (under optimum conditions) stored in tank is pumped to
the photoreactor and mixed with appropriate quantum of MOF-Ni (0.6 g) before being
exposed to UV irradiations.

Conclusion
MOF-Ni as a novel heterogeneous photocatalyst has been synthesised, characterised by
single X-ray diffraction, FT-IR and TGA analysis. The photodegradation investigation
of an organic pollutant 4-NP under UV light irradiation showed that the titled MOF
can degrade 74% of 4-NP under operator conditions of pH = 10, [4-NP] = 20 mg/L,
[MOF-Ni] = 0.1 g/L, V = 300 mL. The COD measurement revealed a mineralisation of
48% after 120 min. A catalytic mechanism is proposed in terms of the HOMO-LUMO
gap and the associated light-induced transition. The photocatalytic results indicate that
the non-modified MOF exhibits good photocatalytic activity for the degradation of
4-NP and could be a promising heterogeneous photocatalyst.

Acknowledgements
The authors are grateful for the support provided by the Algerian Ministry for Education and
Research.

Disclosure statement
No potential conflict of interest was reported by the authors.

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