Abstract
Silver nanoparticles (AgNPs) are currently increasingly synthesized for their superior physicochemical and electronic properties. Good knowledge of these characteristics allows the development of applications in all sensitive and essential fields in the service of humans and the environment. This review aims to summarize the Ag NPs synthesis methods, properties, and applications in hydrogen peroxide sensors. Generally, Ag NPs can be synthesized using physical, chemical, and biological routes. Studies of Ag NPs have increased after clear and substantial support from governments to develop nanotechnology. Ag NPs are the most widely due to their various potent properties. Thus, this review discusses some different synthesis procedures and hydrogen peroxide applications of Ag NPs.
Keywords: Silver Nanoparticles; Green Synthesis; Hydrogen Peroxide; Gas Sensors
Introduction
Silver particles have been used as antibacterial agents since the 19th century, and now their uses have diversified to include many new physical, chemical and biological ones [1-4]. AgNPs are considered to be one of the most widespread NPs, with about 500 tons of annual global production [5]. More recently, AgNPs have been incorporated into industrial and surgical device coatings,dental coatings, and automotive smoke filters and textiles due to their effective properties against microbes [6]. The mechanism on this topic is currently under discussion by researchers [7]. In this review, relevant techniques of synthesis of metal nanoparticles will be discussed. After that, a detailed study of the properties and applications of AgNPs for hydrogen peroxide sensors will be presented.
Bottom-Up and Top-Down Synthesis
As a historical background for metal nanoparticles (MNPs), it
was reported that many exploited the strengthening of ceramic
matrices, including natural asbestos nanofibers, more than 4500
years ago [8]. Lead-based chemistry was pioneered in ancient
Egypt for cosmetic preparation over 4000 years ago. Here, we
look at a hair dye recipe using lead salts described in the text
since Greco-Roman times. We report direct evidence for the shape
and distribution of PbS nanocrystals that form in the hair during
darkening [9]. Likewise, “Egyptian blue” was the first synthetic
pigment prepared and used by the Egyptians using a mixture of
sintered nanometer-scale glass and quartz around the 3rd century
BC [10]. Egyptian Blue represents a complex mixture of CaCuSi4O10
and SiO2 (both glass and quartz). In the ancient geographic regions
of the Roman Empire, including Egypt, Mesopotamia, and Greece,
Egyptian blue for decorative purposes has been observed during
archaeological excavations.
Natural or synthetic ways can synthesize NPs by two basic
approaches, including various sub-preparation methods. The first
approach is called the “top to bottom” method, including breaking
down bulk solid materials into smaller pieces by applying external
energy from physical, chemical, and thermal techniques [11]. The
second approach, called “from the bottom up, “brings together and
combines atoms or molecules of gases or liquids. The top-down
approach is expensive. However, it is impossible to obtain perfect
surfaces and edges due to the cavities and roughness in NPs, while
a bottom-up approach can get excellent results of nanoparticle
synthesis. In addition, with the bottom-up approach, no waste is formed to be eliminated, and the smaller NPs can be obtained with
better control of the sizes [12-16]. However, adapting the production
of large quantities of powders on an industrial scale is not simple.
A significant advantage of treatment in solution is the possibility
of generating encapsulated NPs using surfactants as a protective
shell, which makes it possible to obtain very homogeneous and well
dispersed NPs [17].
The main bottom-up approaches are the supercritical fluid
synthesis, the use of the template, the spinning, the synthesis by
plasma or flame projection, the green synthesis, the sol-gel process,
the laser pyrolysis, the aerosol-based process, the chemical vapor
deposition, and the atomic or molecular condensation. The main
top-down approaches are the mechanical milling, the etching
(chemical), the electro-explosion (thermal/chemical), the spraying
(kinetics), and the laser ablation (thermal). The green synthesis
approach is based on biological methods (accommodating plants,
algae, the mushrooms, yeasts, actinomycetes and bacteria).
Types and Synthesis of Silver Nanoparticles
Among the various types of NPs, Ag NPs have been widely
developed to be utilized in various applications due to their
outstanding properties. Typical applications of Ag NPs include
clothing and textiles, medical devices, food storage, cosmetics,
sunscreens, laundry detergents [18], bandages [19], and sensors
[20]. Some studies have found that Ag NPs have cytotoxicity that
can induce ROS formation in cells [21]. Therefore, many products
such as detergents, toiletries, etc. In addition, their synthetic or
in-use personal care, whether industrial or household, produces a
release of NPs, which ultimately ends up in the sewer. This untreated
wastewater affects aquatic ecosystems and thus microorganisms.
Recently, Ag NPs had great concerns regarding aquatic toxicology
due to the difficulty of tracking these particles in the environment
and accessing their effects on living organisms [22]. The fate
of NPs in the aquatic environment and their interactions, the
interactions between NPs with biological and abiotic components,
and their potential for damage are not well understood, and these
uncertainties raise concerns about related risks. These molecules
impose on humans on health and the environment [23]. Based on
the Scopus database [24], the publications on Ag NPs increase with
time, where it started in 1990 (two reports) and reached 7105
reports in 2020.
Colloidal Ag NPs are molecules with an average diameter of 20-
40 nm and comprise 80% silver atoms and 20% silver ions. They
are the best-selling nanoparticles ahead of carbon nanotubes and
titanium nanoparticles and are released into the environment.
The demand for Ag NPs has increased due to their applicability
in multiple fields. Over the years, various synthesis techniques
have been developed, and procedures have been improved to
prepare small and uniform Ag NPs. Ag NPs were prepared by a
chemical reduction technique, where the silver ions are reduced by
sodium citrate [25]. As referenced, various kinds of Ag NPs have
been utilized in various applications [26]. Specifically, Ag NPs of
differing sizes and shapes have been used in a broad scope of uses
and clinical gear, such as electronic gadgets, coatings, cleansers,
swathes, etc. [27]. Explicit physical a nd optical properties of Ag
NPs are subsequently essential factors in advancing their use in
these applications. In such a manner, the accompanying subtleties
of the materials are imperative to consider in their combination:
surface property, size dissemination, clear morphology, molecule
composition, dissolution rate (i.e., reactivity in arrangement and
effectiveness of particle delivery), and kinds of diminishing and
capping specialists utilized. The blend techniques for metal NPs
are partitioned into top-down and bottom-up approaches. In these
approaches which also include chemical and green methods, the
electron transfer initiates the bioreduction through nicotinamide
adenine dinucleotide (NADH)-dependent reductase as an electron
carrier to form NAD+. The resulting electrons are obtained by Ag+
ions, which are reduced to elemental Ag NPs.
The physical technique usually utilized to prepare Ag NPs is
the evaporation-condensation method. It is commonly performed
using a tube furnace at atmospheric pressure, synthesizing
various sizes [28]. Several attempts have been made. For instance,
Tsuji, et al. [29] proposed a new method for synthesizing Ag NPs
by a laser ablation technique with focused and unfocused laser
beam irradiation carried out at 12 and 900 mJ cm−2 intensities,
respectively. The radiation wavelengths used were 355, 532, and
1064 nm. This study revealed that the surface plasmon wavelength
of Ag NPs irradiated using 355, 532, and 1064 nm is ~400 nm for
focused and unfocused beams. The famous chemical method for
Ag NPs synthesis is a reduction by natural and inorganic reducing
agents. By and large, unique reducing agents, for example, sodium
citrate, ascorbate, sodium borohydride, essential hydrogen, polyol
measure, Tollen’s reagent, N, N-dimethylformamide (DMF), and poly
(ethylene glycol)-block copolymers are utilized for the reduction
of silver particles (Ag+) in aqueous or non-aqueous arrangements.
These reducing agents decrease Ag+ and lead to metallic silver
(Ag0), trailed by agglomeration into oligomeric clusters. These
clusters ultimately arrange the metallic colloidal silver particles
[30]. It is critical to utilize defensive agents to stabilize dispersive
NPs during metal nanoparticle planning and ensure that the NPs
consumed or tied onto nanoparticle surfaces stay away from their
agglomeration [31]. Green synthesis methodologies dependent
on natural reducing agents rely on different reaction parameters
such as solvent, temperature, pressing, and pH conditions
(acidic, fundamental, or impartial). For the union of metal oxide
nanoparticles, plant biodiversity has been extensively viewed as the accessibility of successful phytochemicals in different plant
separates, particularly in leaves such as ketones and aldehydes
flavones, amides, terpenoids, carboxylic acids, phenols, and
ascorbic acids [32,33]. These parts are fit for decreasing metal
salts into MNPs [34]. The fundamental focus of such nanomaterials
has been researched for biomedical diagnostics, antimicrobials,
catalysis, atomic detecting, optical imaging, and marking of natural
frameworks.
Applications of Silver Nanoparticles
Over the last decades, the production of NPs has been increasing
rapidly for applications in electronics, chemistry, biology, and
almost all our daily life applications [35]. This is mainly due to their
properties of being very small, close to the biomacromolecules and
providing high surface area, rapid diffusion, and high reactivity
in both liquid and gas phases [36,37]. Recently, Ag NPs have
attracted attention in various applications such as biological, food,
optoelectronics, electronic devices for energy conversion, electron
field emission sources for emission displays, and surface-enhanced
Raman properties [38-41]. Accordingly, utilizing Ag NPs in sensing,
mainly for the excellent physico-chemical properties, will be
reviewed here. Developing fast, sensitive and selective gas sensors
has received great attention in environmental monitoring, national
security, and food safety applications [42]. Typically, the total
performance of gas sensors strongly depends on the specific area
surface of the materials utilized for detection gas. Thus nano-scale
sensing is predictable to display improved sensing performance
[20]. Typically, semi-conductive nano metal oxides such as ZnO and
SnO2 exhibit high sensitivity and fast responses to some gases [43].
A relatively higher temperature (150–600◦C) required for maximum
response is a big problem that restricts the practical applications
in most areas [44]. Therefore, developing suitable nanomaterials
to enhance the sensor response is highly recommended. Noble
metal nanostructures are the most promising in this field due
to LSPR. The LSPR is an optical phenomenon observed when
the electromagnetic radiation excites the surface conducting
electrons of MNPs, resulting in a coherent resonance oscillation
of the particles. The location of the extinction maximum is highly
dependent on the reflective index and dielectric properties of the
surrounding environment and the adsorption of the molecules on
the metal surface [45,46]. Therefore, the peak wavelength shift in
the extinction maximum of NPs is used to fast detect moleculeinduced
changes surrounding the NPs. Thus, UV-Vis spectroscopy
and the naked eye can observe the changes in the absorbance of the
visible and near-infrared wavelength regions.
There are many published articles on the use of LSPR sensing
applications in the liquid phase to detect organic phosphorous
pesticides [47] and ammonia [48]. Generally, SPR absorption
of noble metal NPs is strong in the visible to near-infrared (IR)
region. Moreover, SPR is particularly sensitive to its size, shape,
composition, distance, and surroundings. Therefore, it displays a
promising ability for various sensors. However, Ag NPs have higher
extinction coefficients than gold nanoparticles (Au NPs) of the
same size [49]. Due to this feature and high specific surface area,
high catalytic, high crystallinity, and their electrical and optical
properties, Ag NPs have been widely investigated as gas sensor
applications [41,50]. This section will present the recent progress
on Ag NPs as gas sensors for ammonia, methane, and hydrogen
peroxide. Despite the wide use in industry, such as fertilizers,
animal feed production, and manufacturing of paper and plastics,
ammonia is a toxic material with a harmful effect on the human
body as it can harm tissues and the immune system [51]. Ammonia
is largely produced in deteriorating food and fruitbodies by various
micro/macrofungi [52]. Thus, monitoring the concentration
of ammonia in air and liquid in the atmosphere is extremely
important. Recently, Ag NPs have been widely used to sense
organic gases such as methane and ethanol [20,53,54]. Cannilla,
et al. [55] successfully prepared Ag NPs in a poly-methacrylic acid
(PMA) matrix by a photo-induced reduction process followed by
deposition on a ceramic substrate to sense ammonia gas in resistive
base sensors. To improve the conductivity of the thin films to be
suitable for sensing, the as-prepared Ag NPs/PMA were loaded
with multi-walled carbon nanotubes (MWCNTs). The developed
sensor shows the considerable ability to work at low temperature
with a wide range of detection range and represent fast response/
recovery times. Kumar et al. prepared face-centered cubic
polyvinylpyrrolidone (PVP) capped Ag NPs at room temperature
and a chemical reduction method [41]. The prepared sample
showed an average size of ~22 nm, showing a conductive and
metallic nature. As ammonium gas sensing, the synthesized NPs
thin films showed the maximum sensitivity towards ammonia gas.
Hydrogen Peroxide Sensing
In the last decade, hydrogen peroxide (H2O2) monitoring has
gained importance due to its widely employed in many industrial,
atomic power stations, medical sectors and its application as a
disinfecting agent for water pools [56-58]. However, the high
presence of H2O2 can cause various biological damages, leading
to aging, neurodegeneration, and cancer [59,60]. Therefore,
developing a high-response, cheap method is highly recommended
for medical, pharmaceutical security, and environmental protection
[59]. Various techniques, such as spectrophotometry [60,61],
chemiluminescence [62], and electrochemistry [63], have been
utilized to detect H2O2. These methods are categorized as enzymatic
and non-enzymatic methods. In the case of enzymatic, the
peroxidase is an illustrative enzyme for H2O2 exposure; however,
both pH and temperature are limited.
As mentioned above, noble metal NPs display strong SPR
absorption with extreme sensitivity to the size, shape, composition,
and surroundings suitable for colorimetric sensors in the range
of visible to near-infrared region. For colorimetric assays, Ag NPs
have a high ability toward the decay of H2O2 [64]. This reaction can
mainly be sensed by colorimetric principles, as the colloidal Ag NPs
exhibit a characteristic color from the LSPR. The alteration in both
particle size and shape results from the incorporation of colloidal
Ag NPs with H2O2 can be identified by determining the change in
the absorption spectral at the wavelength of LSPR. For instance,
Zhang, et al. [65] investigated H2O2 via colorimetric detection using
three different morphologies of Ag NPs (triangular, spherical, and
cubic). The Ag NPs with various shapes reacted with H2O2, and the
edges of Ag NPs had been etched. The change shape transformation
induced visible color change, which was used for the quantitative
determination of H2O2. The triangular Ag NPs display the highest
sensitivity for a quite small level of H2O2 (5 mM), while the cubic Ag
NPs display lower sensitivity. Recently, Srikhao, et al. [66] prepared
Ag NPs with an average particle size of 16.9 nm by using phenolic
compound extracted from sugarcane leaves as a reducing agent. The
results showed that 90◦C and stirring for 20 min are the optimum
conditions for phenolic compound extraction. The prepared Ag
NPs were evaluated as ammonia and H2O2 solution sensing by
UV-Vis spectrophotometer and the naked eye. It observed that
the Ag NPs sensitively detect both H2O2 and ammonia even at low
concentrations.
Moreover, the prepared Ag NPs could detect these toxic agents
even after two weeks. However, measuring in spectrophotometric
methods requires some standard solutions and tools such as
standardized cuvettes, microwell plates, and spectroscopic
equipment. To overcome these limitations, Yoshikawa et al.
utilized an optical technique for detecting H2O2 in their work
Ag NPs deposited on a glass plate/Au NPs [66]. The Ag NPs chip
diffracts incident light, and the diffraction efficiency is correlated
with the amount of Ag NPs. By applying a drop of H2O2 onto the
chip, the diffraction strength debilitates due to the decay of Ag
NPs. A movable measurement technique of the diffraction intensity
changes is assembled, and the H2O2 detection in a concentration
range of 6.7–668 mmol L−1 in about 2 min by dropping the H2O2
solution onto the substrate.
The electrochemical technique is promising to detect H2O2
due to its simplicity, lower cost, ease of operation, and high
sensitivity and selectivity compared to the other techniques
[62,63]. Many electrochemical sensors based on metals and metal
oxides-based complexes have been developed to overcome the
high overpotential. Due to the high electron transfer rates, high
catalytic activity toward reducing H2O2, and significantly decreasing
overpotential at oxidizing and reducing agents, Ag NPs are widely
utilized to fabricate these sensors. Zhan, et al. [67] decorated Ag
NPs on three-dimensional graphene (3DG) via the hydrothermal
process as a sensing electrode for electrochemical detection of
H2O2 in phosphate-buffered solutions. The electrochemical results
approved that the Ag NPs-3DG based biosensor exhibits fast
amperometric sensing, low LOD, wide linear responding range,
and perfect selectivity for non-enzyme H2O2 detection. Recently,
Maduraiveer, et al. [68] utilized an electrochemical sensor for
H2O2 by using Ag NPs introduced in a silicate matrix (APS(SG). The
prepared APS(SG)-Ag NPs were deposited on glassy carbon (GC)
electrode. The electron transfer behavior of the APS(SG)-Ag NPs
was investigated by potassium ferricyanide ([FeCN)6]3−), methyl
viologen (MV2) and ruthenium hexamine ([Ru (NH3)6]3+). The
GC/APS(SG) electrode displayed a twofold increase in the peak
currents and fast electron transfer kinetics toward [Fe (CN)6]3− in
comparison with the GC electrode. The GC electrode modified with
APS(SG)-Ag NPs significantly improved electron transfer. The GC/
APS(SG)-Ag NP electrode as an electrocatalytic sensor against H2O2
offered a reduction of H2O2 at less negative potential and showed
the experimental low detection limit of 25.0 μM with the sensitivity
of 0.042 μA/μM. Additionally, an APS(SG)-Ag NP-based sensor
showed a fast response, good stability, and reproducibility.
Conclusion
This article presented the synthesis, properties, and hydrogen peroxide applications of silver nanoparticles in a brief detail. Despite the great role of Ag NPs in sensing applications for detecting gases and vapors of some organic compounds and detecting hydrogen peroxide in industry and biosystems, the function of this effect needs more study to be fully understood. Furthermore, the longterm stability and sensitivity should be more developed by adjusting the preparation conditions, utilizing eco-friendly stabilizing agents. Moreover, recycling Ag NPs from their applications wastes is an important issue from both environmental and economic points of view. This would help in developing Ag NP based nanomaterials more safe, biocompatible, and efficient for some vital applications in our life.
Conflict of Interest
No conflict of interest with any institution/organization.
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