Separation and Purification Technology 305 (2023) 122435

Contents lists available at ScienceDirect

Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

A comprehensive guide for characterization of adsorbent materials

Leandro Pellenz a, *, Carlos Rafael Silva de Oliveira b, Afonso Henrique da Silva Júnior a,
Layrton José Souza da Silva c, Luciano da Silva d, Antônio Augusto Ulson de Souza a,
Selene Maria de Arruda Guelli Ulson de Souza a, Fernando Henrique Borba e,
Adriano da Silva a, **
a
Federal University of Santa Catarina, Chemical Engineering Department, Laboratory of Mass Transfer and Numerical Simulation of Chemical Systems, Zip Code 88040-
900 Florianópolis, SC, Brazil
b
Federal University of Santa Catarina, Textile Engineering Department, Zip Code 89036-004 Blumenau, SC, Brazil
c
Department for Nanostructured Materials, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
d
Centro de Investigación en Química Aplicada (CIQA), Saltillo, Coahuila, Mexico
e
Federal University of Fronteira Sul, Postgraduate Program of Environment and Sustainable Technologies, Zip Code 97900-00 Cerro Largo, RS, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Given the great relevance that adsorption processes have for many applications, especially for the water and
Microscopy wastewater treatment, the development and improvement adsorbent materials is a key research topic. When a
Spectroscopy new adsorbent is proposed, a good characterization of the material is fundamental to in order to know its
Physicochemical characterization
properties, support its application and understand its performance in the desired process. There is a variety of
Surface analysis
Adsorption
physical and chemical information that can obtained by different techniques, whose choice depends on the type
of material to be studied and on the available instrumentation. The available techniques include UV–vis, FTIR,
Raman, XPS, EDX, zeta potential, XRD, SEM/FESEM, TEM, AFM, surface area and porosimetry, VSM, DLS,
thermoanalytical analysis (TG, DTA, DSC and DTG), among several others. These techniques enable the iden­
tification, location and quantification of chemical constituents, like elements, functional groups and molecules,
as well as the study of the structure, topography, morphology, magnetic properties, and size, among other
physical properties of materials. This information can provide great support for the assessment of the synthesis/
functionalization of adsorbent materials as well as in the study of the adsorption process by the interactions
between adsorbent and adsorbate. In the face of that, this review intends to be a comprehensive and concise
guide for researchers that study adsorbent materials to consult the available characterization techniques and
choose the most suitable ones for their specific needs.

1. Introduction characteristics of the adsorbate, properties of the media, operation

The adsorption phenomenon has been known for more than a cen­
tury and since its discovery, it has served in many applications,
including air purification [1], recovery of nutrients [2], detection of
chemicals [3], humidity removal [4], purification of fuels [5,6], solar
energy conversion [7], wastewater treatment [8] and water purification
[9] among others. Adsorption is a mass transfer process whose driving
force is the difference of concentration between adsorbate in the fluid
(liquid or gas) and solid (adsorbent surface) phases [10]. Yet several
other distinct factors affect the adsorption mechanisms such as the
conditions, and especially the physical and chemical characteristics of
the adsorbent material [9,11]. The relevance of the adsorption processes
is highlighted by the increasing scientific interest on the topic. Searching
the Science Direct database with the keyword “adsorbent”, we 122,099
publications have been found since 2000, with significant growth over
the years (Fig. 1).
Over the decades, the advancement in adsorption has led to the
discovery and/or synthesis of many adsorbent materials, that can be
classified in many ways. They can be classified as organic, inorganic, and
hybrid adsorbents, with different particle sizes (nano and micro) as well

* Corresponding author.
** Corresponding author.
E-mail addresses: leandro.pellenz@posgrad.ufsc.br (L. Pellenz), adriano.silva@ufsc.br (A. da Silva).

https://doi.org/10.1016/j.seppur.2022.122435
Received 10 August 2022; Received in revised form 21 September 2022; Accepted 18 October 2022
Available online 22 October 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

directly related to the adsorption mechanisms, such as include hydrogen

bonding, complexation, coordination/chelation, electrostatic, hydro­
phobic and π − π stacking interactions. The chemical characterization
techniques most frequently applied in adsorbent material are ultra­
violet–visible spectroscopy (UV–vis), Fourier transform infrared spec­
troscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy
(XPS), X-ray energy dispersive spectroscopy (EDX), and Zeta potential.

2.1. UV–vis

UV–vis Spectroscopy (or Spectrophotometry) is a quantitative tech­

nique applied to measure how much a chemical substance absorbs light.
This is done by measuring the intensity of light that passes through a
sample compared to the intensity of light through a reference sample or
blank (Fig. 2a). The UV spectrum arises from electronic excitation (σ/σ*,
n / σ*, n / π* and π / π*) of the molecule by the irradiating light. The
energy for the σ/σ* and n / σ* transitions is relatively high (absorption
in the UV region), whereas the energy for the π / π* electronic transitions
Fig. 1. Number of publications per year, from 2000 to 2021, displayed in the
it is lower (absorption in the near UV–vis region). An important conse­
Science Direct database performing a search using the keyword “adsorbent”.
quence is that the spectra in the UV region are diagnostic of unsaturation
in the absorbing molecule. This is because, with few exceptions, only
as membranes. The source of adsorbents can also vary from natural to molecules with multiple bonds have sufficiently stable excited states to
synthesized materials, which can be raw, physically, and/or chemically
modified, frameworks and composite materials. Some of the materials
frequently applied are activated carbon, zeolites, siliceous materials,
clay materials (kaolinite, bentonite), biomass/biochar, metal–organic
frameworks (MOFs), carbon nanomaterials (graphene, carbon nano­
tubes), polymers (biopolymers, synthetic fibers, geopolymers, hydro­
gels, aerogels) and others [12–19]. Furthermore, due to its efficiency,
low cost, and operation simplicity, the adsorption process is one of the
most important routes of pollutant removal from water and wastewater,
being extensively applied worldwide to remove a great variety of
organic and inorganic water contaminants. Therefore, considering the
increasing demand for clean water and environmental quality, the study
of adsorbent materials and their applications on aqueous media has been
a topic of great interest among the scientific community [8,9,20–22].
For these applications, studies involving the characterization of the
adsorbent material are essential to provide information on the material’s
structure, morphology, topography, stability, composition, and size,
among other important properties for the adsorption processes. This
information supports planning new adsorbents, comparing and selecting
adsorbents, and implementing adsorption systems/plants in real-scale
[10,23].
A variety of materials characterization methods are covered by
literature, usually in papers or books presenting detailed information
regarding one specific technique and its general applications, with no
particular focus on adsorbents. However, there is still a lack of literature
objectively compiling and discussing the characterization techniques
applicable to adsorbent materials. This, along with growing interest in
the development and application of adsorbents, made us feel the need to
complement the literature with a concise guide for adsorbent charac­
terization. Therefore, this paper presents a compilation of the most
relevant materials characterization techniques with an objective
approach to their application in assessing adsorbent materials,
comprising the fundamentals of each technique, a schematic represen­
tation of the apparatus, and a discussion of its expected results.

2. Chemical characterization

There is a variety of techniques available for chemical character­

ization of adsorbent materials, that provide relevant information on
their chemical constituents, like identification, location and quantifi­
cation. This type of characterization, beyond providing information
about the composition of adsorbents, can also provide insights into the
functional groups present on the surface of the material, which are
Fig. 2. UV–vis analysis. (a) - Schematic illustration of the UV–vis technique
working principle; (b) – UV–vis light absorbance profile as a function of the
wavelength of graphene oxide (GO) and GO subjected to sonication with a
probe sonicator (PS) (sonication times 5, 15, 60 and 120 min), with a con­
– C and
centration of 50 mg/L, in which it is possible to identify signals of C–
C–O bonds [Copyright 2019, Elsevier, [27]; reproduced with permission].

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L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

give rise to absorption in the near-UV region. Thus, saturated hydro­

carbons, alcohols, and ethers are transparent in this region, while
monofunctional olephines, acetylenes, carboxylic acids, amides, and
oximes have maximum absorption just outside the UV region, near 200
nm, and in general display only an end absorption peak in the spectra
[24]. Since it is a very fast and simple technique, UV–vis often used to
determine the presence and concentration of some compounds or
functional groups in the sample. The absorption is a consequence of the
transition of an electron in the chemical structure of the sample from the
ground energy state to the excited state. The numerical value obtained in
UV–vis spectroscopy is called absorbance and is based on the Beer-
Lambert Law. Furthermore, the technique allows using a range of
wavelengths or selecting specific wavelengths for analysis. In this case,
monochromators such as interference filters, absorption filters, cutoff
filters and bandpass filters are used in order to narrow the selected light
wavelengths for more accurate measurements and improve the signal-
to-noise ratio [25–27].
UV–vis is widely applied as an agile technique to quantify the con­
centration of compounds dissolved in liquid samples. Still, it can also be
employed to characterize nano-size adsorbent suspension [28]. Gra­
phene derivatives are often characterized by UV–vis, and present an
adsorption peak at 230–240 nm and a shoulder at 270–335 nm, related
to the π–π* transition of the aromatic (C– – C) bonds and to the and n–π*
transition of the carbonyl/carboxyl (C– – O) bonds, respectively, and
these signals can dislocate depending on the modifications made on the
material (Fig. 2b) [26,29–31]. The example presented in Fig. 2b in­
dicates that the sonication process promotes exfoliation and fragmen­
tation of the GO, with no chemical alterations, which increases its
UV–vis signals but does not dislocate them. Yet, the normalized spectra
of the same study indicates a decrease in the C–– O proportion, which can
be associated with decarboxylation [27]. Furthermore, the reduction of
GO causes the disappearance of the signal related to the n–π* of tran­
sition of the carbonyl/carboxyl C– – O bonds and the increase in the π–π*
transition of the aromatic C– – C, which confirms the elimination of
oxygenated functional groups [31,32]. On the other hand, the func­
tionalization of graphene typically weakens/shifts the C– – C signal
indicating the insertion of new groups in the aromatic structure [26].
The presence of metal oxides in materials such as perovskites and other
nanocomposites results in broad UV–vis adsorption peaks in the regions
between 200 and 650 nm, which result from the overlapping of several
different electronic transition energies [33–35]. Since UV–vis spectros­
copy is a very simple and accessible technique, it is not often applied in
the study of saturated adsorbents, and could be more used for this
purpose, supporting in the discussion of the adsorption performance and
mechanisms.

2.2. FTIR
Infrared spectroscopy (IR) is a technique based on the vibrations of
atoms in organic or inorganic materials. The IR spectrum of a material is
sensitive to its chemical composition, isomorphic substitution, layer
stacking order, or structural modifications. This makes FTIR the most
informative technique, not only for determining functional groups, but
also for determining different interactions between materials. The
principle of this technique is the excitation of a molecule by IR radiation,
which results in vibrations of its molecular bonds at different fre­
quencies in the IR region [36]. The currently used FTIR spectrometers
are typically equipped with a Michelson interferometer. A source emits a
beam of infrared radiation into the interferometer, where it hits a
beamsplitter that splits the beam into two. The two beams are then
redirected to the beamsplitter, recombined with interference and
directed to the sample, that precedes a detector (Fig. 3a). The raw signal
provided by the detector is then mathematically converted by Fourier
transform into a plot of intensity (transmittance or absorbance) versus
wavenumber, based on the movable mirror position. The division of the
sample spectrum by the reference spectrum (no sample) results in the
Fig. 3. FTIR analysis. (a) - Schematic illustration of the FTIR technique working
principle; (b) - FTIR spectra showing absorption peaks related to several
chemical bonds of Cymbopogon flexuosus biomass immobilized on sodium
alginate beads before (black line) and after adsorption of Cr(III) (red line)
[Copyright 2021, Elsevier, [38]; reproduced with permission]. (For interpre­
tation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
FTIR transmission spectrum. Some radiation is reflected, some passes
through, and some is absorbed by the sample by causing stretching and
bending vibrations in the molecular bonds. The absorption peaks at
given wavenumber ranges are fingerprints of specific functional groups
[36,37].
The functional groups present on the surface of an adsorbent play an
important role in the adsorption process, providing interaction sites for
the fixation of the target adsorbates. Thus, FTIR can be used in the
characterization of materials by identifying the functional groups pre­
sent in the adsorbent material. Likewise, the presence of adsorbate in the
adsorbent can be confirmed and investigated by determining the sites of

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L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

interaction as well as the adsorption mechanisms of organic and inor­

ganic compounds [39,40]. The FTIR absorption peaks related to bending
and stretching of a specific bond occur in different wavenumbers and
different shapes (strong/weak; broad/sharp) depending on the func­
tional group and structure of the compound in which it is present.
Several references in the literature report information on FTIR wave­
numbers related to specific bonds. The most frequent are O–H
stretching (2500–3750 cm− 1), O–H bending (1160–1440 cm− 1), C–H
stretching (2600–3000 cm− 1), C–H bending (1280–1465; 1650–2000
cm− 1), C–
– O stretching (1560–1815 cm− 1), C–O stretching (900–1400
cm ), N–H stretching (2800–3500 cm− 1), N–H bending (1400–1660
− 1

cm− 1), S–H stretching (2550–2600 cm− 1) (Fig. 3b) [40–45]. In acti­
vated carbon, a widely used adsorbent, researchers have identified via
FTIR the presence of carboxylic acids, quinones, phenolic groups, lac­
tones, ketones, ethers, pyridine-like groups, amides, and amines, among
others [40]. Furthermore, the functionalization of adsorbents in order to
increase their adsorption sites is often performed with oxygen, nitrogen
and sulfur-containing groups. The insertion of these new groups can be
verified and relatively quantified with FTIR analysis [46,47]. FTIR is a
qualitative technique, but the comparison between signal strengths of
different groups can be used to quantify the formation of certain func­
tional groups. Yet, it is important to note that some are formed by the
sum of signals of more than one bond [40]. Additionally, when the FTIR
analysis is carried out in a loaded adsorbent, slight shifts in the peaks
and changes in intensity indicate that the respective functional groups
are involved in the adsorption process [48–50].

2.3. Raman

This spectroscopic analysis provides chemical and structural infor­

mation about a material, including identifying its lattice structure and
assessing compounds present in the sample through the unique Raman
fingerprint of its molecular bonds. This technique consists of a mono­
chromatic light near the visible region that is emitted by a laser towards
a sample. Typically, a part of this light is scattered, most of it at the same
frequency as the incident light (Rayleigh scattering). A small amount of
the scattering, called Raman scattering, occurs in different wavelengths,
depending on the chemical structure of the analyte. This inelastic scat­
tering is identified by a detector that converts it into a Raman spectra
chart displaying peaks of different intensities and wavelengths (Fig. 4a).
Each peak corresponds to the vibration of a specific molecular bond of
the sample. This technique’s most common laser wavelengths are 532
nm, 785 nm, 830 nm, and 1064 nm. Smaller lasers wavelength has
greater Raman scattering between cross-sections, so the resulting signal
is larger [51,52]. Several types of bonds can be detected by Raman
spectroscopy in various materials, such as C–H, C–C, C– – C, and N–O,
as well as groups of bonds such as aromatic rings, lattice nodes, and
polymer chains [52].
Carbonaceous adsorbents, such as activated carbon, graphene,
graphite and carbon nanotubes (CNT), are often characterized by Raman
spectroscopy. These materials present two characteristic bands in the
Raman spectra. A D band (1316–1368 cm− 1), related to the sp3 hy­
bridized atoms in disordered hexagonal structures, and a G band
(1580–1611 cm− 1), ascribed to the bi-dimensional stretching vibration
of sp2 hybridized carbon atoms in ordered hexagonal lattices, which is
characteristic, but not exclusive, of graphite/graphene [53,54]. The
disorder degree of carbonaceous materials is often estimated by the
relative intensity of these two peaks, namely I(D)/I(G), where a higher
index indicates higher disorder [55,56]. Usually, modifications on
carbonaceous adsorbents tend to increase the level of disorder in the
material and/or slightly shift the bands in the spectra, so Raman spec­
troscopy is another technique that can be used to verify and evaluate the
modification [56–58]. In the example presented in Fig. 4b this can be
verified by the increase of the I(D)/I(G) of GO from 1.54 to 1.83 in the
GO-ethylene diamine aerogel, indicating that the amino groups added
promoted a disruption in the stacking order of graphene and/or
Fig. 4. Raman analysis. (a) – Schematic illustration of the Raman technique
working principle; (b) – Raman spectra of GO and GO-ethylene diamine aerogel
samples using a 633 nm excitation wavelength in which the adsorption peak in
the D and G bands are displayed along with the I(D)/I(G) index of each material
[Copyright 2021, Elsevier, [44]; reproduced with permission].
insertion of sp3 defects, which tends to provide a higher surface area
with more available functional groups and consequently, more adsorp­
tion sites [44]. Similar behavior has been observed in other modifica­
tions in graphitic materials, such as exfoliation [56], addition of ZnO
[53], functionalization with L-Tryptophan [58], oxidation of CNT [59],
and oxidation/thermal treatment of activated carbon [57,59]. Further­
more, some materials such as graphene and CNT present a second order
band (two phonons), called G’ or 2D between 2650 and 2750 cm− 1
[59,60]. In addition, the surface-enhanced Raman scattering (SERS)
technique can also be used to study adsorbents and adsorption pro­
cesses. The method consists of using precious metals, usually silver, as
substrates to enhance the intensity of the Raman spectrum in materials
with weak or no response, such as functional groups or the target
adsorbate present on the adsorbent [61,62].
2.4. XPS
This surface-sensitive method assists in the identification of atoms
and functional groups present on the surface of a solid sample. The XPS
equipment has a photon source that emits X-rays toward the sample with
energies high enough to remove electrons from atoms present on the
surface of the analyte. These electrons are captured by a hemispherical
analyzer, which measures the number of electrons (intensity), and ki­
netic energy (velocity) of these electrons (Fig. 5a). The kinetic energy is
related to the binding energy of the electron and provides information
about the chemical composition of the surface, and the intensity is
proportional to the amount of a specific atom/functional group present
on the analyzed material [63,64].

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L. Pellenz et al.
Fig. 5. XPS analysis. (a) - Schematic illustration of the XPS technique working
principle; (b) – XPS spectra of several GO-amine-based composites with a zoom
in the N 1 s binding energy range (395 – 404 eV) of polypyrrole-GO-amine
aerogel displaying peaks corresponding to –NH–, pyrrolic N, –C– – O and
NH2/NH3+ [Copyright 2018, Elsevier, [65]; reproduced with permission].
In adsorbent materials, XPS can be used to characterize the chemical
composition of the surface of materials, assisting evaluation of different
synthesis and functionalization processes, as well as the characterization of
an adsorbent saturated with the adsorbate [65–71]. Researches have re­
ported binding energies of 283.8–289.0 eV for C 1 s (C–OH/C– – O/
O–C– – O/C–C/C– – N/=C–NH) [56,65,67,71,72]; 531.1–533.8 eV for O
1 s (C–O–C/C– – O/C–O–H) [56,72–74]; 397.9–401.6 eV for N 1 s
(–NH–/=N–/–NH+-/–NH3+/C–N/amine/amide/pyrrolic N/graphit
ic N) [56,71,72]; 709.8–711.4 eV for Fe 2p3/2, 724.3–725.2 eV for Fe 2p1/2
[68,70,73,75], among several others (Fig. 5b). XPS can be complementary
to FTIR analysis in the chemical characterization of adsorbents. In the
example presented in Fig. 5b, researchers have obtained the full XPS spectra
for different materials, namely GO, GO-tetraethylenetetramine, GO-poly­
pyrrole, and GO-tetraethylenetetramine- polypyrrole aerogels, presenting
peaks regarding the C 1 s, N 1 s and O 1 s binding energies, which allowed to
observe higher or lower amounts of these elements in the different com­
posites [65]. Additionally, by zooming in on these peaks, it is possible to
break them down and identify the different peaks, each regarding these
atoms present in specific structures [65,67]. The same analysis has been
carried out to analyze adsorption processes. The reduction of certain XPS
peaks in the loaded adsorbent indicates these atoms are involved in
complexation reaction [71], and the increase in the binding energy
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Separation and Purification Technology 305 (2023) 122435
(positive dislocation of peaks) suggests that its respective elements/func­
tional groups were involved in irreversible adsorption [75]. Furthermore,
the rise of new signal can be ascribed to the presence of a new element
(adsorbate), like Cr(VI) (577.6 and 586.4 eV), Cr(III) (576.3 and 583.8 eV),
Cd(II) (405.0 and 411.8 eV) [74], As(V) (40.0–47.0 eV) [73], U(VI) (381.9
and 392.7 eV) [75] and Hg (II) (100.5 eV and 104.6 eV) [56].
2.5. EDX
This technique, also abbreviated as EDS, EDXS or XEDS, is widely
applied for elemental identification and compositional mapping of a
solid sample [76,77]. The technique consists of the excitation of the
sample by focused X-rays generated by an electron gun. Some of the
accelerated electrons from the beam collide with electrons present in
lower energy levels of the atoms and remove them. Consequently, an
electron from a higher energy level fills the spot of the removed electron
and releases energy through of X-rays. The released energy can be
measured by a detector providing information about this specific atom
(Fig. 6a). Different elements emit unique signals when excited (X-ray in
characteristic wavelengths), allowing their identification, as well as
their quantification by the intensity of the signal [76]. EDX is often
coupled to SEM/FESEM microscopes, so both analyses can be carried out
in a complementary way [77].
In adsorbent materials, EDX is commonly performed along with
SEM/FESEM analysis to identify the percentage of each element on the
surface of the sample. In can be used to characterize the adsorbent
material, confirm successful chemical modifications, verify the presence
of the adsorbate on its surface, and evaluate changes after adsorption/
desorption cycles [56,79–83]. Many adsorbents are carbon-based ma­
terials, thus presenting a predominance of C, followed by O, in its
composition evaluation via EDX [56,79,83–85]. Inorganic adsorbents
can be composed of a variety of elements such as O, N, S, Si, Fe, Mg, Al,
Ti, Ca, among others, depending on the precursors used in their syn­
thesis [81,86,87]. When adsorbents are dopped (synthesis) or saturated
(adsorption process) EDX analysis presents clear signals of these ele­
ments [79–83,85,86], thus, beyond characterizing the material, EDX
could also be applied after adsorption/desorption cycles could be used
to evaluate the efficiency of these cycles as well as the stability of the
adsorbent. EDX coupled to SEM can also perform an elemental mapping
of the adsorbent, showing the distribution of its constituent elements
along its surface (Fig. 6b) [71,88,89]. The elemental mapping can give
information on how well the elements/functional groups are distributed
on the surface of the adsorbent, as well as how the adsorbate is
distributed after adsorption, providing insight on possible interactions
with the functional groups of the adsorbent [78,88].
2.6. Zeta potential
Fundamental in colloidal systems, the Zeta potential is also used in
adsorption processes to investigate the surface charge of adsorbents and
their possible interactions with the adsorbates. Solid particles dispersed
in liquids have an electric double layer on their surface formed by ions
strongly attached to the particle surface (stationary layer), and more
externally, ions with variable distribution (slipping plane). The electric
potential at the slipping plane of the particle is known as Zeta potential
and its value varies depending on the surface of the particle, pH and
ionic strength of the medium. [90,91]. The Zeta potential is experi­
mentally measured through the electrophoretic mobility of the particles.
The method consists of applying an electric field in the suspension,
which induces movement of the particles at a velocity proportional to
their surface charge. Simultaneously, a laser beam is emitted through
the sample and is scattered proportionally to the movement speed of the
particles. A detector reads the electrophoretic scattering and provides
the Zeta potential compared with a reference laser (Fig. 7a). Using the
same mechanism, the Zeta potential can also be measured by changes in
the laser beam frequency after crossing the sample (Doppler shift) [91].
L. Pellenz et al.
Fig. 6. EDX analysis. (a) - Schematic illustration of the EDX technique working principle; (b) EDX results obtained in a SEM-EDX equipment showing the C, N, O, Al,
and Co percentage in a zeolitic imidazolate framework-molecularly imprinted composite and the mapping of C, N, O and Co along the surface of a region of the
material [Copyright 2013, Elsevier, [78]; reproduced with permission].
Increasing the pH of a solution causes deprotonation of the adsor­
bents and reduces their zeta potential. A simple and frequently applied
measurement in adsorbent material is the isoelectric point, commonly
known as point of zero charge (PzC), which identifies the pH value under
which the zeta potential is zero. The method consists in adding the
adsorbent to solutions within a range of pH values in order to verify the
point (pH value) at which there is no change in the solution pH caused
by the material (Fig. 7b) [16,93]. The presence of functional groups on
the adsorbent that can be protonated and deprotonated, like carboxyl
and amine, enhances the variation of the zeta potential with the change
of the solution pH [92,94]. The charge of the adsorbent is especially
relevant in the adsorption of charged molecules, such as metals and ionic
forms of organic compounds, since it can be favored or hindered by
electrostatic interactions and complexation reactions between adsorbent
and adsorbate [95,96]. Thus, considering the electrostatic interactions
mechanism, negatively charged adsorbents have more affinity for
positively charged adsorbates, and vice versa [83]. This becomes more
relevant when adsorbents are designed for real applications where the
pH cannot be adjusted for adsorption. In these cases, adsorbents with a
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Separation and Purification Technology 305 (2023) 122435
suitable zeta potential value tend to perform better in separating ionic
adsorbates [83,94]. It has been reported that functionalization and
chemical modifications of the surface of materials typically change their
Zeta potential, making it a parameter worth investigating in adsorbent
synthesis processes [92,94,95,97].
3. Physical characterization
The structure, topography, morphology, magnetic properties and
size are some of the most important physical features to consider in
evaluating an adsorbent material. These studies can be carried out by X-
ray diffraction analysis (XRD), scanning electron microscopy (SEM),
field emission scanning electron microscopy (FESEM), transmission
electron microscopy (TEM), atomic force microscopy (AFM), surface
area and porosimetry analysis, vibrating sample magnetometry (VSM),
and dynamic light scattering (DLS), among other techniques.
L. Pellenz et al.
Fig. 7. Zeta potential analysis. (a) - Schematic illustration of the Zeta potential technique working principle; (b) – Zeta potential profiles of GO and Fe3O4-SiO2-NH2,
Fe3O4-SiO2-GO and Fe3O4-SiO2-GO-2-phenylethyl amine in suspensions of 300 mg/L in the pH range from 2 to 12 [Copyright 2018, Elsevier, [92]; reproduced
with permission].
3.1. XRD
XRD is widely used to study the crystal properties of materials,
assessing the atomic arrangement, crystal size, lattice parameters, and
imperfections. Therefore, a laser beam of X-rays is emitted at a certain
angle toward a sample placed on a solid surface. At certain angles of
incidence of the beam, the atoms present on the material diffract it with
constructive interference (amplification). A detector, that moves at the
same angle as the laser on the opposite side, captures these diffraction
peaks identifying the angle on which they occurred (Fig. 8a). Based on
the diffraction angle, it is possible to determine spacing between ordered
atoms of a sample using Bragg’s law [98].
Crystalline adsorbent materials have distinctive diffraction peaks at
specific angles, and some of these appear with more intensity, such as 2θ
of 26.0–27.0◦ for pristine graphene/graphite, ~10.0◦ for GO [56,72],
12.0◦ and 25.0◦ for kaolinite [99], 10.4◦ and 20.0–21.0◦ for chitosan
[81,100], 22.0◦ for SiO2 and 26.0◦ for TiO2 [81]. Furthermore, XRD
broad peaks indicate amorphous structure, while sharp peaks evidence
crystalline arrangement. Chemical modifications often change the ma­
terial structure, which can be observed by the change in intensity,
breadth, and angle shift of the peaks, as well emergence of new XRD
peaks [56,71,100–103]. XRD has been applied to assess the synthesis of
some adsorbents which can be verified, for example, with the combi­
nation of the XRD peaks in the formation of a binary or multicomponent
material (Fig. 8b) [71,81,100,103]. Another application has been in
evaluation of GO, an increasingly studied adsorbent in recent years that
is often synthesized from the oxidative exfoliation of graphite. While,
according to the literature, graphite presents a sharp peak with inter­
planar distance of 0.33–0.34 nm, graphene shows a broader peak with
an interplanar distance between 0.77 and 0.95 nm, which indicates the
insertion of oxygen functional groups and a potential improvement as
adsorbent [16,56].
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Separation and Purification Technology 305 (2023) 122435
3.2. SEM/FESEM
SEM is a widely applied technique for microstructural analysis of
adsorbent materials. It provides information about morphology, topo­
graphic features, crystal structure and orientation, variation of the
composition, phase distribution, and the location of electrical defects in
the material [104]. The technique consists of the excitation of the
sample by an electron beam that is generated by an electron gun and
crosses a set of electromagnetic lenses inside a vacuum chamber. The
beam hits the sample releasing secondary electrons that are captured by
detectors, which convert this information into a scanning image
(Fig. 9a). Nonconductive samples are coated with an ultrathin film of a
conductive metal, frequently gold, in order to enhance the signal.
[104,105]. As an enhanced version of SEM, FESEM produces a narrower
electron beam and generates images with improved spatial resolution,
sub-nanometer in some cases. SEM/FESEM can also be equipped with an
EDS detector, which is performs an elemental analysis on the surface of
the material [105].
SEM/FESEM is one of the most applied characterization techniques,
whether just to present an image of a particular adsorbent material and
observe its features or to visualize modifications of its structure by
physical/chemical treatments or functionalization/decoration of its
surface [82,84,107–109]. Furthermore, some researchers have also
applied SEM/FESEM to observe the saturation of the surface and pores
of adsorbents with the target adsorbate [110–112]. The analysis can be
carried out in relatively low magnification (<1000 times) to visualize
the shape and porous structure of micro size adsorbents, such as acti­
vated carbon [113,114], mineral [115,116] biomass [82,107,117,118]
and synthetic-based [119] materials (Fig. 9b), or in higher magnifica­
tions (>30,000 times) to observe nano size adsorbents, like the forma­
tion of aggregates in metal organic frameworks (MOF) [108], dispersion
of metals in supporting materials [109,113], or the arrangement/shape
of nanocomposites such as graphene and CNT-based adsorbents
[120–122]. Also, SEM/FESEM analysis could be used strategically to
evaluate the adsorbent after the process, as well as after adsorption/
L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

Fig. 8. XRD analysis. (a) - Schematic illustration of the XRD technique working
principle; (b) – XRD spectra of MnFe2O4/Bi2MoO6/PPy and MnFe2O4/Bi2MoO6
composites and of single Bi2MoO6 and MnFe2O4, presenting 2θ peaks at 23.6◦ ,
28.3◦ , 32.7◦ , 33.2◦ , 36.1◦ , 47.2◦ , 55.7◦ , 56.3◦ and 58.5◦ for Bi2MoO6; at 30.1◦ ,
35.4◦ , 43.1◦ , 56.8◦ and 62.4◦ for MnFe2O4 and 10.9◦ ; and the combination of
these set of peaks in the composites with the two components [Copyright 2022,
Elsevier, [71]; reproduced with permission]. Fig. 9. SEM/FESEM analysis. (a) - Schematic illustration of the SEM/FESEM
technique working principle; (b) – SEM images of peach stone activated carbon
impregnated with H3PO4 and modified with HNO3 showing the morphology of
desorption cycles to verify the stability of the material. Activated car­
the material obtained with a magnification of 600 times with an accelerating
bons typically have porous structures that make them good adsorbents voltage of 20 kV [Copyright 2020, Elsevier, [106]; reproduced
in general, like the SEM image presented in Fig. 7b, where mesopores with permission].
(2–50 nm) can be visualized with micropores (<2 mm) inside them
[106]. Thermal and chemical activation of materials to produce adsor­
the emission of an electron beam with uniform current density towards
bents can also be clearly visualized using SEM, with changes like the
an ultrathin sample. The beam crosses a set of lenses that allow the
destruction of its original structure and the formation of pores [119].
variation in the illuminated area of the sample. The irradiated sample
Other modifications in adsorbents may cause morphological changes
suffers different types of scattering according to the material, and the
that are visible in SEM images, such as a rough and edgy sand that be­
scattered electrons behind the sample are imaged through a lens system
comes smoother and covered with iron-oxide spherical particles [109],
(Fig. 10a) [124].
or the filling some activated carbon pores with metal nano-particles
Unlike SEM, in the TEM analysis, the electron beam has to cross the
[111,113], or even the filling of pores with adsorbate [112]. In some
sample; therefore, it is commonly applied to characterize very small-size
cases, high-resolution FESEM can also show textural changes in the
adsorbents, often nanocomposites. In graphene-based adsorbents TEM is
adsorbent surface when saturated with the adsorbate [110,112].
used to observe defects, thickness, arrangement, agglomeration of the
nanosheets and size of particles, before and after functionalization/
3.3. TEM modification processes [16,72]. Polymeric adsorbents have also been
characterized by TEM to determine particle size, stacking and arrange­
TEM is applied to analyze the chemical and electronic structures of ment of fibers [71,126,127]. Mineral and metal-based nano adsorbents
materials and identify defects, such as vacancy and dislocations, but it and carbonaceous materials decorated with metals are also often
can also provide information about the shape, thickness and approxi­ analyzed by TEM to observe the crystal and particle size, shape and
mate sizes of particles [123]. Conventional TEM apparatus consists of

8
L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

3.4. AFM

This advanced microscopy method is used to assess the topography

of a material, yielding 3-dimensional images with atomic resolution (<1
nm). AFM is classified as a single molecule force spectroscopy (SMFS)
technique and consists of a probe made of a sharp tip that is moved very
close to the sample and then away in a constant tapping mode, making a
scan. When the probe gets close to the sample the tip-sample forces,
namely van der Waals, electrostatic and meniscus, act on it. A cantilever
that holds the probe and makes the taping movement also deflects a laser
projected on it, thus enabling a detector to read changes in the oscilla­
tion frequency, caused by the variation in the topography along the
sample (Fig. 11a) [134,135].
The evaluation of the topography of adsorbent materials is essential
since it directly influences the adsorption process. The high-quality 3-
dimensional images yielded by AFM have also been used to observe
the surface roughness of a different adsorbent materials before and after
modification or adsorption processes, such as alginate/amine [136],
hydrogels [137], and fly ash/bentonite [138]. Furthermore, AFM can be

Fig. 10. TEM analysis. (a) - Schematic illustration of the TEM technique
working principle; (b) – TEM image of commercial kaolinite (Saca-B®) showing
its pseudo-hexagonal shape in the basal plane, overlapping of layers, and
approximate size [Copyright 2021, Elsevier, [125]; reproduced
with permission].

agglomeration of particles [28,128,129], as well as the distribution of

metals on the surface of a substrate and the formation of composite
materials [111,130]. The information on particle size and agglomera­
tion provide support to understand the behavior of adsorbents in solu­
tions and to propose strategies for its separation. In adsorbent materials
that are arranged in layers, such as kaolinite (Fig. 10b) [125] and GO
[72], TEM images can provide insights into the thickness/number of
layers, which is directly related to the surface area of the material and its Fig. 11. AFM analysis. (a) - Schematic illustration of the AFM technique
adsorption capacity. Furthermore, high-resolution transmission electron working principle; (b) – AFM image (4 × 4 µm) showing the surface topography
of an amine-functionalized sodium alginate membrane loaded with Cr(III) ions
microscopy (HRTEM) can also be applied to obtain enhanced TEM im­
after the adsorption process, where the light color areas represent the elevated
ages of a material’s lattice structure and obtain information like the
points and the dark color ones represent depressions points on the surface of the
interplanar distance [131–133]. membrane, which presented a roughness average (height fluctuation) of 27.6
nm. [Copyright 2013, Elsevier, [136]; reproduced with permission].

9
L. Pellenz et al.
used to estimate the particle size of nano adsorbents such as MgO and
ZnO and the lateral dimension of graphene nanosheets [139–141]. Re­
searchers often apply AFM to determine sheet thickness and height
fluctuation of sheet-like and membrane adsorbents. Usually, the func­
tionalization or the saturation of an adsorbent with an adsorbate in­
creases its sheet thickness and the roughness of its surface. It has been
measured via AFM that a specific pure GO sheet has a thickness of ~0.8
nm and a height fluctuation of ~0.1 nm, and after adsorption of MB the
thickness increases to ~ 0.9 and the height fluctuation to ~ 0.4 nm
[142], and functionalized GO sheet can present increased sheet thick­
ness, up to 2.5 nm [16,141]. An amine-functionalized sodium alginate
membrane described in the literature presented a roughness average of
8.2 nm before adsorption, and 27.6 nm after the adsorption of Cr(III)
(Fig. 11b) [136]. The differences in the surface roughness upon
adsorption/functionalization can also often be visually observed in the
3-dimensional AFM images [136,137,141,142].
3.5. Surface area and porosimetry
BET is one of the most widely applied surface area analyses in porous
materials, including many adsorbents. The analysis starts with the
sample being degassed and placed under a vacuum. Then it is exposed to
an inert gas, typically nitrogen, at constant temperature (77 K for ni­
trogen) and increasing relative pressure, from 0 to 1. The gas molecules
are adsorbed by the material and cover first the micropores, then mes­
opores and macropores, and ultimately, form a monolayer of molecules
over the whole area of the sample. Furthermore, more layers of mole­
cules can be formed, as the gas pressure increases. The amount of gas
adsorbed as a function of the pressure, as well as the reverse process
(desorption), can be measured (Fig. 12a) [143]. With this data, the BET
model, as well as other derived models such as Barrett-Joyner-Halenda
(BJH) and Dollimore-Heal (DH) models are able to estimate the specific
surface area, pore volume, and area, as well as the pore size distribution
of the material [144]. Additionally, based on the gas adsorption and
desorption isotherms, the International Union of Pure and Applied
Chemistry (IUPAC) classifies materials into six groups: Isotherm types I –
mostly micropores (< ~2.5 nm); Isotherm type II – absence of micro­
pores; Isotherm type III – weak adsorbent-adsorbate interactions;
Isotherm type IV – mesopores (2 – 50 nm)/capillary condensation;
Isotherm type V – weak adsorbent-adsorbate interactions/capillary
Fig. 12. BET analysis. (a) - Schematic illustration of the BET technique working
principle; (b) – BET curve chart where it is possible to visualize nitrogen
adsorption and desorption profile as a function of the relative pressure in a
sample of kaolin-based geopolymer, which presented a specific surface area of
26.60 m2/g and a total pore volume of 0.24 cm3/g [Copyright 2022, Elsevier,
[146]; reproduced with permission].
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Separation and Purification Technology 305 (2023) 122435
condensation; Isotherm type VI – formation of layers on an uniform and
nonporous surface (Fig. 12b) [145].
The specific surface area is directly related to fundamental physical
properties of particle size, porosity, surface energy, and uniformity of
the material. Since the surface area and porosity greatly influence in the
adsorption capacity, porous adsorbents, like carbonaceous materials,
porous minerals and polymers, are often characterized by BET analysis
[6,147–151]. Their properties may vary significantly depending on the
raw material and the physical/chemical processes applied to their pro­
duction. Researchers have reported activated carbons with BET surface
areas up to 2630 m2/g and pore volume up to 1.91 m3/g with varied
sizes of pores (micro, meso, and macropores (>50 nm)) [147–149,152].
As for zeolites, authors have observed surface areas up to 2300 m2/g
with predominance of micropores [150,151,153]. Graphene and CNT-
based materials have gained importance as adsorbents due to its possi­
bilities of modification/functionalization and relatively high surface
area with reported values up to 1000 m2/g, depending on the synthesis
method, and varied pore sizes, depending on the composite
[16,46,72,154,155]. Polymeric adsorbents usually present a smaller
surface area when compared with the above and a varied porosity,
depending on the polymerization conditions [71,146,156]. Although
the pore size is inversely proportional to the surface area, it also matters
in assessing an adsorbent since the pores can allow more or less diffusion
of the adsorbate inside the adsorbent. Large molecules of organic com­
pounds are normally trapped inside macropores, while small inorganic
species can enter in micropores [157]. Macropores (>50 nm) allow a
wide range of adsorbates to diffuse rapidly inside adsorbents, besides
facilitating adsorbent recycling by allowing eluting agents to diffuse
through the material [46,157].
3.6. VSM
VSM is a technique that provides information about the magnetiza­
tion of a material. In adsorbents it can be applied to evaluate magnetic
composites to evaluate their suitability for magnetic separation when
dispersed in a liquid media [158]. The VSM apparatus consists of a
magnetic field that first magnetizes the sample and then is removed. The
magnetized sample then generates its own magnetic field and is vibrated
by the equipment, generating an electric field proportional to the
magnetic field applied to the sample, which is captured by a set of coils
and provides data about the magnetization of the material (magnetiza­
tion curve and magnetic saturation) (Fig. 13a) [159].
In magnetic adsorbent characterization, VSM analysis is normally
carried out with the application of a magnetic field range from − 20 to
20 kOe and the results are expressed in terms of saturation magnetiza­
tion (emu/g) in curves (Fig. 13b) [71,128,158]. The necessary magne­
tization for separating a dispersed adsorbent material from a solution
may vary depending on several factors, like its morphology, size and
shape, as well as the external magnetic field strength and the layout of
the system [161]. Authors have reported that saturation magnetization
values of ~ 15.0 emu/g for MnFe2O4/Bi2MoO6/Polypyrrole [71], 23.6
emu/g for L-cystine/Sodium alginate/Fe3O4 [162], 35.0 emu/g for MOF-
Fe3O4/potassium nickel hexacyanoferrate [163], 29.3 emu/g for amine/
Fe/GO [75], 22.2 emu/g for Fe3O4/cyclodextrin/chitosan/GO [158],
16.9 emu/g for Reduced GO/Fe3O4/polydopamine [85], and 33.0 emu/
g for Fe3O4/SiO2/GO/2-phenylethyl amine [92] were sufficient for easy
magnetic separation of the composite from aqueous media in batch
systems. Currently, magnetic separation is more often applied to cata­
lysts, but it could be an alternative for separating of powder-like ad­
sorbents that are being increasingly developed and studied, like carbon
nanomaterials, metal oxides and nanocomposites [161,164].
3.7. DLS
DLS, also called Photon Correlation Spectroscopy (PCS), is widely
applied to evaluate the dimensions of suspended particles [165]. When
L. Pellenz et al.
Fig. 13. VSM analysis. (a) - Schematic illustration of the VSM technique
working principle; (b) – VSM magnetization curves of iron oxide particles and
polyaniline-iron oxide polymer nanocomposites performed at room tempera­
ture with magnetic field amplitude of ± 30 kOe [Copyright 2021, Elsevier,
[160]; reproduced with permission].
the sample is illuminated by a light source (laser), it scatters light in all
directions with fluctuations caused by its motion. DLS analyzes the
scattered light intensity fluctuations at a certain angle (Fig. 14a). For
monodisperse and diluted samples in Brownian motion (random) it is
possible to extract the translational diffusion coefficient of the particle.
For Brownian motion situations, the particle size estimate is correlated
with the motion, with small particles moving faster and large particles
moving slower [166]. If the particles are assumed to be spherically
symmetrical and not permeable to the solvent, the Stokes-Einstein
equation is used to calculate their hydrodynamic diameter [167].
In the characterization of adsorbents, DLS is applied mostly to
determine the size distribution of nanomaterials, providing information
about the synthesis, aggregation of particles, homogeneity, and enabling
to assess alternatives of separation of the material from the media
(Fig. 14b) [168–171]. A wider size distribution, like goethite presented
in Fig. 14b, indicates that the material forms aggregates with varied
sizes. In contrast, a narrower size range suggests that the particles are
11
Separation and Purification Technology 305 (2023) 122435
more uniform and single [168]. Furthermore, adsorbents made of milled
materials, like some activated carbons, normally have a wide size dis­
tribution [172,173]. Also, the increase and decrease in the average
particle size of adsorbents after modifications indicate aggregation and
disaggregation of the particles, respectively [169]. Although other
characterization techniques, such as SEM/FESEM, TEM, and AFM, can
also be used to determine the size of particles, they only analyze one or a
small number of particles whereas DLS yields more accurate size dis­
tribution information [174].
4. Thermal characterization
Thermal analysis can be carried out through several techniques in
which the physical properties of a material and/or reaction products are
evaluated as a function of temperature [175]. The evaluated materials
are subjected to a controlled temperature program and under a specified
atmosphere. These analytical methods are based assessment of a phys­
ical property as a function of temperature, and include thermogravim­
etry (TG), differential thermal analysis (DTA) and differential scanning
calorimetry (DSC), Temperature Programmed Reduction/Oxidation
(TPR/TPO), among others [176]. TG evaluates the mass as a function of
temperature and its first derivative, the DTG, corresponds to the first
derivative of the mass variation with respect to time. In DTA, the tem­
perature difference between the studied material and a thermally inert
reference material is measured while both are subjected to the same
controlled temperature program [177]. DSC analysis evaluates the
enthalpy of a sample as a function of temperature. The thermal events
that generate changes in the DSC curves can be first and second-order
transitions. The first-order transitions present enthalpy variations
(endothermic and/or exothermic), and the second-order transitions are
characterized by the variation of the specific heat at constant pressure
but without enthalpy variations [178]. Most thermal analysis in­
struments have similar configurations with a few differences. The main
difference among these instruments is the type of transducer, which
converts the evaluated physical properties into electrical signals [179].
The instrument consists of an oven in which the sample is heated or
cooled at a controlled rate, under a previously established atmosphere.
Changes in sample properties are monitored by a selective transducer
based on (i) thermocouples, (ii) scale, (iii) colorimetric sensor, among
others. The transducer generates an electrical signal that is amplified
and transferred to the controller unit, maintaining permanent commu­
nication with the measurement cell. Finally, the controller unit is con­
nected to a digital device that controls the operation, data acquisition
and analysis and the recording of the generated thermoanalytical curves
(Fig. 15a) [178]. Temperature Programmed Reduction (TPR) has some
differences from the thermal analysis methods discussed above. It is
mainly applied in the assessment of catalysts and evaluates a material’s
reducibility as a function of temperature. During the analysis, a gas flow
(H2 or CO) goes through the sample while its temperature varies in a
certain range, often between 0 and 1000 ◦ C. In essence, the equipment
measures the variation of gas consumption as a function of temperature,
which occurs due to the reduction of the sample, providing information
about the temperature of reduction of the material [180,181].
In adsorbents, the thermoanalytical studies are important to inves­
tigate the thermal stability of a material, providing information about its
contents such as enthalpy, reducibility, and temperature under which
each of them changes its physical state. Knowing the thermal behavior
and stability of a material can provide support for the synthesis/acti­
vation of adsorbents via thermal processes, and for defining the ideal
operating conditions of an adsorption processes. For adsorbent materials
the temperature range used in these analyses depends on the material
but normally lies between 0 and 1000 ◦ C [81,86,183]. TGA/DTA are
thermoanalytical analysis most frequently applied in adsorbents,
including carbonaceous materials [59,171,183], minerals-based mate­
rials [184,185] and synthetic polymers [100,186] and nanocomposites
[86], in which researchers identify peaks of weight loss at certain
L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

Fig. 14. DLS analysis. (a) - Schematic illustration of the DLS technique working principle; (b) DLS result presenting the particle size distribution of lepidocrocite and
goethite nanoparticles in a sample containing 5 % W/V (nanoparticle/water), with an average particle size of 268.8 nm for lepidocrocite and 145.6 for goethite
[Copyright 2015, Elsevier, [168]; reproduced with permission].

Fig. 15. Thermal analysis. (a) - Schematic illustration

of the thermoanalytical analysis technique working
principle; (b) The graphs represent TGA (left) and DSC
(right) analysis of modified collagen fibers, unloaded
(green line) and loaded with dyes (red, blue and black
lines), with the equipment operating in N2 atmo­
sphere, flow rate of 20 cm3 min− 1 and scanning rate of
10 ◦ C, within 30 and 700 ◦ C [Copyright 2018, Elsev­
ier, [182]; reproduced with permission]. (For inter­
pretation of the references to color in this figure
legend, the reader is referred to the web version of
this article.)

12
L. Pellenz et al.
temperatures and ascribe them to the loss of specific constituents of the
material. The first degradation peak normally occurs at 100 ◦ C, in which
the adsorbents lose their moisture, since water molecules are adsorbed
physically by weak hydrogen bonds. This can be clearly observed in
Fig. 15b by a mass loss in the TGA analysis and an endothermic peak in
the DSC chart, both around 100 ◦ C [81,182]. Other degradation peaks
can be related to the elimination of volatile organic compounds
(250–480 ◦ C) and amines (250–350 ◦ C) [100,182]. Functionalized ad­
sorbents normally have less thermal stability in comparison with non-
functionalized material. This occurs because the functional groups on
the surface are degraded at lower temperature than the material itself.
However, the thermal removal of functional groups normally starts at
temperatures higher than 200 ◦ C, and most adsorbent applications occur
at mild conditions, often at ambient temperature [59,100]. No signifi­
cant mass losses are observed beyond a certain temperature, 550 –
900 ◦ C, depending on the material, and the remaining mas is related to
the inorganic contents of the adsorbent [81,100,182].
5. Additional techniques
Here we present briefly a few physical and chemical characterization
techniques that are not frequently used in the characterization of ad­
sorbents but could be alternatives for researchers to obtain more infor­
mation about these materials.
X-ray absorption fine structure (XAFS) techniques, which include X-
ray absorption near-edge structure (XANES) and extended X-ray ab­
sorption fine structure (EXAFS), can be applied to study the adsorption
mechanism of metals into nano adsorbents since they can provide in­
formation on the oxidation state and coordination geometry of a metal
in on the adsorbent, coordination number and distance of a metal atom
with neighbors atoms, coordination type and bond length [187,188].
In the analysis of biomass-based, such as activated carbons, rapid
analysis of carbon, hydrogen, nitrogen, and sulfur (CHNS) contents can
be carried out in automated analyzers. These analyzers perform com­
bustion of the sample, converting carbon into carbon dioxide, hydrogen
into water, nitrogen into nitrogen gas/ oxides and sulfur into sulfur di­
oxide, which can be further separated and quantified via thermal con­
ductivity [86,189,190].
Chemical titration is another alternative method that can be applied
to quantify acidic (lactonic, carboxylic, phenolic and carbonyl) as well
as alkaline (pyrone, chromene) functional groups present on the surface
of an adsorbent based on selective neutralization of these groups and
measurement of the amount of acid/base necessary to neutralize them
[191–193].
Solid-state nuclear magnetic resonance (ss NMR) is another available
chemical characterization technique that can be applied to study the
atomic level structure of an adsorbent material and to investigate the
molecular level interaction between the adsorbate with the adsorbent
[194,195]. In this technique, the sample is subjected to an external
magnetic field, which makes the atom nuclear spins, that are random in
natural conditions, to align with the magnetic field. A coil sends radio­
frequency pulses into the sample and perturbation of the aligned spins,
that further return to the original state producing a signal that is
detected and recorded. This data is processed as resonance frequencies
of a specific atom, compared to a reference, that varies depending on the
electronic environment in which it is located [196].
Scanning transmission electron microscopy (STEM) is a variation of
TEM in which the electrons beam is focused towards de sample at an
angle and allows observing with higher contrast individual atoms, like
metals, inside the adsorbent framework, as well as analyzing particle
size, defects, and crustal morphology. Furthermore, STEM microscopes
can be equipped with an electron energy loss spectroscopy (EELS) de­
tector that performs an elemental identification similar to EDX
[197,198]. In adsorbents, some researchers have used STEM to visualize
the distribution of high-density elements on the surface of the material
[199–201].
13
Separation and Purification Technology 305 (2023) 122435
Another characterization method that can be applied in adsorbents
available is temperature programmed desorption (TPD). This technique
can be applied to study the kinetics and thermodynamics of the
desorption process, as well as the surface chemistry of the adsorbent
material [100,202]. TPD consists of heating the adsorbent-adsorbate
with a linear temperature increase and simultaneously measuring the
amount of adsorbate that is transferred to the gas phase, typically by gas
chromatography or mass spectrometry, obtaining a desorption profile as
a function of temperature [202].
Depending on the conditions of applications, some adsorbents like
membranes can be also subjected to mechanical characterization,
including tension, compression, shear, bending and indentation tests to
measure deformation as a function of the force under different condi­
tions (temperature, pressure, humidity, etc.) [203].
6. Conclusion and future outlook
There is a great variety of characterization techniques that can be
applied to study adsorbent materials and enable researchers to assess
several physical, chemical, and thermal features of a sample in various
ways and levels of detail. Normally, researchers apply at least one
chemical characterization technique and one physical to provide basic
information about the material. However, the future perspectives lie in
the improvement of the quality of these techniques and especially in
their effective use. Much of the literature on new adsorbent materials, in
our opinion, does not present enough characterizations or presents
incomplete analyses. Characterization can be carried out in (i) raw
materials or precursors, (ii) synthesized/composite or functionalized/
modified adsorbents, (iii) adsorbents loaded with the adsorbate, and (iv)
adsorbent after adsorption/desorption cycles, in order to study the
material, to identify/confirm modifications, to identify/confirm
adsorption, and to study stability and reusability of the material,
respectively. The choice of the techniques to be employed depends
primarily on the type of material, type of adsorbate, media to be applied,
and inevitably, on the available resources. It is expected that with
technological development these techniques will become, in general,
more affordable and with results of ever-increasing quality and accu­
racy. This improvement is extremely positive for the research on ad­
sorbents, and can help to address a well-known challenge in laboratory
studies of new materials, which is the scale-up from controlled bench
conditions to real applications. An extensively studied and well-
characterized new material provides to the scientific community and
industry quality information, potentializing future improvements and
application steps.
Declaration of Competing Interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Leandro Pellenz reports financial support was provided by National
Council for Scientific and Technological Development.
Data availability
No data was used for the research described in the article.
Acknowledgments
The authors wish to thank Conselho Nacional de Desenvolvimento
Científico e Tecnológico – CNPq for the financial support.
The authors are grateful to the Laboratory of Mass Transfer (LAB­
MASSA-UFSC) for the available infrastructure.
L. Pellenz et al. Separation and Purification Technology 305 (2023) 122435

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