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Sensors and Actuators B: Chemical
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Fabrication of PdAg nanoparticle infused metal-organic framework for
electrochemical and solution-chemical reduction and detection of toxic 4-
nitrophenol
Shamim Ahmed Hira, Muthuchamy Nallal, Kang Hyun Park
⁎
Department of Chemistry, Pusan National University, Busan, 46241, South Korea
ARTICLE INFO
Keywords:
Metal organic framework
4-Nitrophenol
Sensor
Electrochemical detection
Reduction
ABSTRACT
In this study, we utilized functionalized metal organic frameworks (MOFs) as a host matrix to embed silver and
palladium (AgPd) bimetallic nanoparticles. The physicochemical properties of the as-synthesized materials were
characterized Via UV, FT-IR, XRD, SEM, TEM, XPS, BET and TGA analysis. The as-synthesized materials pre-
sented excellent activities toward the electrochemical detection of 4-nitrophenol and its reduction by NaBH
4
under ambient conditions. The constructed sensor displayed selective and sensitive determination of 4-NP in the
linear concentration range 100–370 μM with a limit of detection of Σ32 nM. Moreover, because of its high
specific surface area, high conductivity, and fast charge transfer ability, the sensor displayed good electro-
catalytic activity. Moreover, it exhibited excellent selectivity toward 4-NP in the presence of common interfering
species. The synthesized catalyst exhibited good catalytic activity for the reduction of 4-NP. It was reusable for
five consecutive cycles without a significant loss in its catalytic activity. The applicability of the constructed
sensor was explored via the detection of 4-NP in tap water samples at a recovery of ∼100.97%.
1. Introduction
Day-by-day water pollution is increasing because of hazardous
waste and toxic organic contaminants. The amount of waste released
into water is a critical problem in the modern era [1]. Nitroaromatic
compounds are steady organic pollutants commonly found in different
industrial effluents and are released from pesticides, plasticizers, dyes,
and the pharmaceutical industries [2]. Among the various nitroaro-
matic compounds, nitrophenols are listed as one of the top 114 organic
pollutants by the Unites States Environmental Protection Agency
(USEPA). 4-Nitrophenol (4-NP) is one of the obnoxious phenolic pol-
lutants found in chemical industrial wastewaters [3]. Because of its
high polarity, it is easily soluble in water and also displays high bioa-
vailability. Therefore, the sensitive determination of 4-NP and its re-
duction into non-toxic molecules has become a current research hotspot
[4,5].
Traditionally, the quantitative determination of 4-NP has been
achieved by different analytical techniques such as gas chromato-
graphy-mass spectrometry [6], high-performance liquid chromato-
graphy [7,8], capillary zone electrophoresis [9], fluorescence detection
[10] and Ultraviolet-visible (UV–vis) spectrophotometry [11]. How-
ever, these techniques have limitations including sample pre-treatment,
expensive instrumentation, high cost, and limited selectivity. Mean-
while, the electrochemical method has been gaining significant interest
because of its quick response, low cost, high sensitivity, and good se-
lectivity. Additionally, several other techniques, including adsorption,
microwave-assisted catalytic oxidation, electrochemical oxidation, and
membrane separation, are also available for the removal of 4-NP and its
forms [12–15]. Nevertheless, conventional treatment approaches major
shortcomings such as high costs and long reaction times. In a broad
sense, the conventional clean up method can be classified in two ways:
(i) permanent dismissal of the expected pollutants and (ii) conversion of
the target pollutants into less or non-toxic forms. Contrary to 4-NP,
4–aminophenol (4-AP) is less toxic and is an important intermediate
that can be applied in many industrial fields [16]. Hence, the sensitive
detection and reduction of 4-NP is an important and urgent environ-
mental issue.
Numerous nanostructured materials have been utilized as electro-
catalysts to construct electrodes for the electrochemical determination
of 4-NP and other analytes including novel metal (Ag, Au, and Pd)
nanoparticles [17–19], carbon-based materials (carbon nanotubes, or-
dered mesoporous carbon, and graphene) [20–22], metal oxides (ZnO
2
,
Fe
2
O
3
, and MnO
2
), [23–25] and conducting polymers (polyaniline,
polypyrrole, and conjugated polymers) [26–28]. Due to the high cost of
https://doi.org/10.1016/j.snb.2019.126861
Received 5 April 2019; Received in revised form 21 July 2019; Accepted 22 July 2019
⁎
Corresponding author.
E-mail address: chemistry@pusan.ac.kr (K.H. Park).
Sensors & Actuators: B. Chemical 298 (2019) 126861
Available online 23 July 2019
0925-4005/ © 2019 Elsevier B.V. All rights reserved.
T