Nano adsorbants

Introduction :
The application of magnetic nanoparticles (MNPs) as adsorbent materials in solving
environmental problems has recently received great attention due to their unique
physical and chemical properties, which make them superior to traditional adsorbents.
The ability of functionalization by anchoring specific functional groups on their
surface makes possible the synthesis of different types of engineered MNPs for the
removal of a large number of both organic and inorganic contaminants. However, the
successful implementation of the MNPs-based adsorption technology needs of the
evaluation and optimization of the magnetic recovery stages, the regeneration process
and the management of both the spent regeneration solution and the exhausted
adsorbent. This work presents a comprehensive review on the use of MNPs in the
treatment of polluted wastewaters with toxic metals and dyes. In addition, the
magnetic recovery options and the possible strategies that can be employed for the
nanomaterials regeneration and reuse are analyzed.
In recent years, magnetic nanomaterials have attracted considerable attention because
of their unique properties that make them very useful in different fields. Magnetic
nanomaterials have at least one dimension smaller than 1 lm and are possible to be
manipulated under the influence of an external magnetic field [1]. In addition, below
certain critical dimensions, that vary with the material parameters, magnetic materials
become superparamagnetic [2,3] thus the nanomaterials exhibit no magnetic
properties upon removal of the external field and therefore have no attraction for each
other, offering the advantage of reducing risk of particle aggregation, and more
importantly, they provide a strong response to an external magnetic field [3–5].
Advances in the synthesis methods over the past decade have led to availability of
superparamagnetic nanoparticles with different shell and surface modifications [6–
11].
Magnetic nanoparticles (MNPs) are generally composed of magnetic elements, such
as iron, cobalt, nickel, or their oxides like magnetite (Fe3O4), maghemite (c-Fe2O3),
nickel ferrite (NiFe2O4), cobalt ferrite (CoFe2O4), etc. [4]. Usually MNPs are coated
with organic layers (e.g., surfactants or polymers such as dextran and polyethylene
glycol) or inorganic components, such as metallic elements (e.g., gold or platinum),
metal oxides (aluminum oxide, cobalt oxide), activated carbon, silica, etc. [2,7–9] in
order to make them stable against oxidation, corrosion and spontaneous aggregation,
to increase their physicochemical stability and to provide a functionalizable surface
[2]. Despite the significant advantages offered by MNPs, it was not until the last half
of the 20th century when scientists began to study their characteristic behavior [3].
MNPs exhibit great potential for their applications as catalytic materials, pigments,
coatings, gas sensors, magnetic recording devices, magnetic data storage devices,
magnetic resonance imaging, drug delivery, magnetic hyperthermia, bioseparation,
etc. [1,4,5,7–14]. On the other hand, the application of MNPs in solving
environmental problems has recently received great attention [12,15–18] due to
several reasons first, the higher economical and environmental efficacy of those
processes based on the enhanced physical and chemical properties of MNPs (i.e. high
surface area, ease of functionalization, chemical stability, etc.) [18] and second, the
advantages that the superparamagnetic behavior of MNPs provide to the design of
separation and recovery steps in complex multiphase systems [19]. The integrated
design of an adsorption process based on the use of MNPs must take into account
different stages: (i) adsorption separation, (ii) magnetic recovery of the adsorbent for
further reuse, (iii) adsorbent regeneration, and (iv) management of both the spent
regeneration solution and the saturated adsorbent. Although the technical feasibility of
MNPs as adsorbent materials for water treatment processes has been widely reported
in the literature, the adsorbent regeneration stage and material reusability have
received much less attention in spite of their great importance for the process
economy. Moreover, the design of suitable magnetic separation devices, which allow
the magnetic recovery of the adsorbents should be considered as a crucial stage since
it is required for the further re-use of MNPs.
Finally, the management of both the solid and liquid wastes generated in the process
by either material recovery or by final disposal is an issue of concern which has not
been previously reviewed in the literature. Hence, this work aims at the analysis of the
different individual stages taking part in the design of MNPs-based adsorption process
with the purpose of detecting their level of development and bottlenecks thus,
providing useful guidelines to conceive novel integrated separation processes based
on the use of nanoadsorbents and able to mitigate environmental problems of concern.
In particular the integration of MNPs in the design of novel adsorption processes in
either wastewater treatment or water remediation is analyzed in this work through two
different applications focused on the removal of two groups of inorganic and organic
model pollutants namely, heavy metals and dyes. 2. Adsorption of heavy metals and
dyes by MNPs Water pollution by heavy metals and dyes has become a serious
problem because of their adverse effects on ecological systems and human health
[19,20].
Heavy metals like copper, chromium, cadmium, lead, zinc, mercury, nickel or arsenic,
are released into the environment as consequence of different natural or human
induced activities such as mining, metal finishing, painting and printing processes,
pesticides and fertilizers manufacture, etc. [21–23]. The major concern about heavy
metals is that most of them are highly toxic, carcinogenic and mutagenic at even
relatively low concentrations [23–25]. Also, heavy metals are nonbiodegradable and
thus they tend to accumulate in living organisms [19]. Their deleterious effects
depend on the specific metal characteristics. Arsenic for example is commonly known
as a deadly poison since ancient times due to its lethality, but others like lead,
cadmium, chromium and mercury have also serious toxic effects [15]. On the other
hand, dyes can be toxic to the aquatic life in receiving waters, being some of them
mutagenic and carcinogenic. There are more than 100,000 types of dyes which are
used in different industries including paper, plastic, leather, pharmaceutical, food,
cosmetic and textile [26–29]. In particular, textile industries produce large amounts of
colored effluents which are directly discharged into surface water [30] without any
treatment due to technological and economical limitations [31]. In addition, the
degradation by-products of some organic dyes such as synthetic azo-dyes represent a
potential environmental hazard since they contain aromatic amine compounds that are
toxic to many organisms [32]. Although some dyes are banned in many countries
because of health concerns [32], in other regions they are still used, generating
hazardous effluents that are hardly remediated using conventional biological
treatments owing to their stability to light, heat and oxidizing agents thus being
difficult to be mineralized in conventional water treatment plants [32,33]. As
consequence of the environmental hazards and health effects, drinking water and
wastewater regulations have been toughened thus promoting the development of
efficient processes able to accomplish with the concentration values imposed. Various
technologies have been developed for the removal of heavy metals and dyes from
industrial wastewater, such as coagulation/precipitation [34], ion exchange [35],
solvent extraction [36], electrodeposition [34], membrane filtration [34],
electrodialysis [37], advanced oxidation processes [29], etc.
However, the application at large scale must face and solve many drawbacks shown
by most of those methods such as their cost, complexity, efficiency, or sludge
generation [33,38]. Adsorption is considered as one of the most promising
technologies owing to its simplicity of design, ease of operation, low cost, potential
for regeneration, sludge free operation and high retention efficacy when applied with
the proper adsorbent [18,33]. MNPs have been studied as nanoadsorbent materials for
heavy metals and dyes removal and their superior characteristics in comparison with
traditional adsorbents (i.e. large surface area, high number of active surface sites, low
intraparticle diffusion rate and high adsorption capacities), make their use very
promising for the treatment of polluted waters, reducing costs and producing less
contamination [39,40]. Moreover, the recent advances in the synthesis methods allow
the easy anchorage of different functional groups on the surface of the nanoadsorbents
which take part in the
adsorption process as specific binding sites, increasing the adsorption capacity and
improving the selectivity of the process for each specific pollution problem.
Furthermore, their recovery can be easily performed with magnetic separators,
overcoming the pressure drop developed in traditional fixed bed adsorption columns.
Carbon Nanoadsorbents for Removal of Organic Contaminants from Water
The removal of organic contaminants is of great concern in water treatment. This
chapter elucidates the adsorption wastewater treatment processes using carbon
nanoadsorbents with adsorbents. It is discussed the characteristics that make such
nanostructures extremely interesting for adsorption process. In addition, a discussion
of the main kinetics and isotherms models used to obtain information on the
mechanisms and dynamics of the process is carried, as well as how these models are
used and interpreted. Additionally, this chapter compiles relevant current knowledge
about the experimental and theoretical adsorption activities of carbon nanotubes and
graphene family as nanoadsorbents for removal of organic environmental pollutants.
The accumulated data indicate that carbon nanomaterials can be successfully used for
treating organic pollutants wastewater.
Kinetic, equilibrium, and thermodynamic studies on the adsorption of
ciprofloxacin by activated carbon produced from Jerivá (Syagrus
romanzoffiana)
High specific surface area activated carbon prepared from endocarp of Jerivá
(Syagrus romanzoffiana) (ACJ) was used for ciprofloxacin (CIP) antibiotic removal
from aqueous effluents. The activated carbon (AC) was characterized via scanning
electron microscope, Fourier transform infrared spectroscopy, N2
adsorption/desorption, and pH value at the zero-charge point. Avrami kinetic model
was the one that best fit the experimental results in comparison to the pseudo-first-
order and pseudo-second-order kinetic models. The equilibrium data obeyed the Liu
isotherm equation, showing a maximum adsorption capacity of 335.8 mg g⁻¹ at 40 °C.
The calculated thermodynamic parameters indicate that the adsorption of CIP was
spontaneous and endothermic at all studied temperatures. Also, the free enthalpy
changes (∆H° = 3.34 kJ mol⁻¹) suggested physical adsorption between CIP and ACJ.
Simulated effluents were utilized to check the potential of the ACJ for wastewater
purification. The highly efficient features enable the activated carbon prepared from
endocarp of Jerivá, an attractive carbon adsorbent, to remove ciprofloxacin from
wastewaters.

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