Chemical Engineering Journal 358 (2019) 283–290

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Chemical Engineering Journal

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Removal of radioactive palladium based on novel 2D titanium carbides T

⁎
Wanjun Mu, Shenzhen Du, Xingliang Li, Qianghong Yu, Hongyuan Wei, Yuchuan Yang ,
⁎
Shuming Peng
Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, 64# Mianshan Road, Mianyang, Sichuan Province 621900, PR China

H I GH L IG H T S

• HF exfoliation temperatures have an important influence on the morphology and structure of MXene materials.
• The excellent MXene adsorbent was obtained at higher exfoliation temperature.
• It exhibited the higher adsorption capacity and remarkably selectivity for removal of Pd from HNO medium.
2+
3

A R T I C LE I N FO A B S T R A C T

Keywords: A series of MXene materials with high specific surface areas was obtained by HF treatment of MAX materials at
MXene 25 °C, 35 °C and 45 °C, named MXene-25, MXene-35 and MXene-45, respectively. These materials exhibited
Layer spacing excellent ability to remove Pd2+ from HNO3 aqueous solution due to their large specific surface area and wide
Palladium layer spacing, especially for the materials prepared at higher temperature. Adsorption experiments indicated
Adsorption
that these adsorption behavior better fitted the Langmuir model, with the maximum adsorption capacity of Pd2+
Nuclear wastewater
being 184.56 mg g−1, 163.82 mg g−1, and 118.86 mg g−1 for MXene-45, MXene-35 and MXene-25, respectively;
this is higher than for most other inorganic adsorbents, and is attributed to the wide layer d-spacing and large
surface area. Moreover, these materials can retain high selectivity for Pd2+ in simulated nuclear wastewater, and
thermodynamic analysis revealed that low temperatures benefit adsorption of Pd2+. Remarkably, MXene-45
exhibits excellent regeneration performance and reusability, with no obvious loss after five cycles of adsorption.
The present results suggest that 2D MXene materials are promising adsorbents for removing radioactive palla-
dium from radioactive wastewater.

1. Introduction
Palladium, possessed versatile physical and chemical properties, has
been extensively applied in many fields such as electrical and electronic
devices, catalysis, medicine, dentistry and jewelry. Recently, the
amount of palladium increased quickly due to the fast development of
electronic devices [1–3]. Palladium is mainly obtained from mineral
ores and waste electrical devices, but the amount of palladium is lower
and farther to content the industrial needs [4,5]. Thus, it is urgent to
recover more palladium from other resources for both environmental
protection and resource conservation.
There are some palladium isotopes such as 107Pd, 105Pd present in
spent nuclear wastewater produced by fission of uranium, and mostly
they are non-radioactive or only very weakly radioactive [6]. For ex-
ample, the radioactive intensity of 107Pd (a β-emitter at 35 keV) is weak
and can be tolerated for industrial production, and is also lower than for
other platinum metal elements (Rh and Ru). In addition, spent nuclear
wastewater is stored by a process of vitrification to reduce its threat to
environment, and the liquid wastewater turns into a glass-forming
matrix. However, the presence of palladium species could influence the
stability and homogeneity of this vitreous product because palladium
easily forms a separate phase, so it is important to removal of palladium
from nuclear wastewater for safe and efficient storage of nuclear was-
tewater [7]. In view of the recovery of palladium and disposal of nu-
clear wastewater indicated that capturing palladium from nuclear
wastewater has attracted more and more interest.
Many methods have been used to effective recovery of precious
metals form aqueous solutions, for example, precipitation [8,9], ex-
traction [10], filtration [11], and adsorption [12–16]. Among these,
adsorption technology seem to be the most promising for the recovery
of precious metals from environmental wastewater, due to its low cost,
simplicity, little or no use of organic solvents, and high efficiency. Until

⁎
Corresponding authors.
E-mail addresses: muwj1012@163.com (Y. Yang), pengshuming@caep.cn (S. Peng).

https://doi.org/10.1016/j.cej.2018.10.010
Received 17 August 2018; Received in revised form 29 September 2018; Accepted 1 October 2018
Available online 03 October 2018
1385-8947/ © 2018 Published by Elsevier B.V.
W. Mu et al.
now, there are various inorganic adsorbents, such as lignin [17], acti-
vated carbon [18], cellulose [19] and chitosan [20], have been used to
capture palladium from aqueous solution. However, the relatively low
sorption capacities of most adsorbents, and high cost, limit their wide-
scale implementation. In addition, most previous reports have mainly
focused on the recovery of Pd (II) from hydrochloric acid media, and
anion exchange resins are commonly used to for palladium separation
in industrial recovery of palladium. In these adsorption systems, pal-
ladium exists in the form of PdCl42− for ion-exchange purposes, while
fission nuclear wastewater is a strong HNO3 medium, and chloride ions
must be strictly excluded because of their limited miscibility with the
molten glass used in the vitrification process [21,22]. Recently, re-
covery of palladium from nitrate media has been carried out by resin
ion-exchange with great progress in theory and technology, but the
high cost of resins limits their extensive application [23,24]. Therefore,
it is very desirable to develop new types of materials which can removal
of cationic Pd (II) species from nitric acid solution.
Due to their unique physical and chemical properties, and excellent
stability, carbon based materials are considered promising adsorbents
for removal of metal ions form aqueous solution. Some active ad-
sorbents such as activated carbon, carbon nanotubes, chitosan, and
graphene derivatives have been studied for capturing of radionuclides
[25–28]. Recently, new two-dimensional materials, transition metal
(M) carbides and cabonitrides (MXenes) were discovered by removing
the A layer (A = Al, etc) from MAX phase materials using a chemical
etching method. Based on their unique 2D structures, MXene materials
have diverse potential applications in areas such as electrochemical
energy storage, electromagnetic shielding, and polymer nanocomposi-
tion [29–31]. Moreover, due to their ready availability and hydrophilic
behavior, and the tunable chemistry, their application in water pur-
ification and environmental pollution has been concerned, for example,
some of MXene materials have been used as an adsorbent for removal of
Pd2+ [32], Ba2+ [33], Cu2+ [34] and Cr3+ [35] from wastewater,
further broadening the environmental uses of MXene materials. Re-
cently, VxC2Tx and Ti3C2Tx materials have been used for removal of
actinide (U) from nuclear wastewater by surface adsorption [36,37],
and exhibited excellent properties. These results demonstrated that
MXene materials had the ability to resist strong radiation and acid, and
made them as ideal candidates for removing radionuclides from nuclear
wastewater. However, some disadvantages of Mxene materials, such as
a narrow layered space, could be influence their adsorption capacities
and limit their further application in environment, although previous
researches have demonstrated that a narrow layered space in MXene
materials promote their applications in energy and catalysis. The
narrow layer d-spacing could prevent adsorbate movement and reduce
the contact chance between adsorbates and adsorbents. Some work has
been carried out to improve their adsorption capacity for metal ions by
increasing their layer distance. For example, the single-layer or few-
layer-thick structure of Ti3C2Tx nanosheets were obtained by ultra-
sonication, and they exhibited excellent properties for capturing Cu2+
from aqueous solution due to its larger surface area and abundant ad-
sorption sites [34]. Besides, the interlayer space of Ti3C2Tx can be ra-
tionally controlled via a hydrated intercalation strategy, allowing
highly efficient removal of uranium [36]. However, present methods
for modifying MXene materials are complicated and difficult to be
performed in actual application, as well as being costly. Moreover, most
MXene materials have been used in medium or weakly acidic solution,
but their properties in nitric acid medium are unclear, which is a key
issue for their further application in nuclear wastewater disposal.
In this work, we consider how to simply improve the adsorption
ability of MXene materials. Such materials were prepared at various
exfoliating temperatures, and their properties were characterized in
various ways. Palladium adsorption onto MXene materials was carried
out in a nitric acid medium, and adsorption thermodynamics, kinetics,
and isotherm modeling studies were performed for the better under-
standing of the palladium adsorption process and the changes of
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properties of MXene materials. In addition, the recovery and reuse of
MXene materials were also studied in detail. The results indicated that
MXene material obtained at 45 °C with the larger layer d-spacing ex-
hibited excellent performance in adsorption of palladium from a nitric
acid medium.
2. Materials and methods
2.1. Synthesis of Ti3C2Tx and Alk-Ti3C2Tx
Ti3AlC2 powder (> 98 wt% purity, 400 mesh, Beijing Forsman
Scientific Co., Ltd) was slowly added to 40 wt% hydrofluoric acid (HF)
in a ratio of 1 g Ti3AlC2:10 mL etching solution. The reaction mixture
was stirred for 24 h at 25 °C, 35 °C, 45 °C, respectively. After HF treat-
ment, the Ti3C2Tx powders were collected after drying in air at room
temperature for 48 h.
2.2. Characterization
The morphologies and sizes of as-prepared samples were observed
by using field emission scanning electron microscope (FE-SEM Philips
XL30 FEG, Eindhoven, Netherlands). The crystalline structure of sam-
ples was characterized by X-ray diffraction (PXRD, X’Pert PRO,
PANalytical, Almelo, Netherlands) with Cu-Ka radiation
(λ = 0.15406 nm at 40 kV and 45 mA); The composition and chemical
state were determined by X-Ray photoelectron spectroscopy (XPS)
using an RBD-upgraded PHI-5000C ESCA system (Perkin-Elmer) with
Mg-monochromatic X-rays at a power of 25 W, an X-ray-beam diameter
of 10 mm, and a pass energy of 29.35 eV. The binding energy was ca-
librated using the C1s hydrocarbon peak at 284.8 eV. Nitrogen ad-
sorption and desorption isotherms were measured at 77 K with a
Beckman Coulter SA 3100 surface area analyzer. The
Brunauer–Emmett–Teller (BET) method was used to determine the
surface area. Zeta potential of Ti3C2Tx samples was measured by Zeta
Meter (ZetaPals, BLK, USA); Fourier transform infrared (FT-IR) spectra
of the samples were obtained on a Perkin-Elmer 1730 infrared spec-
trometer in the range 400–4000 cm−1.
2.3. Adsorption experiments
A batch of adsorption experiments for removal of palladium from
HNO3 media onto various Ti3C2Tx samples was performed, and the
effect of HNO3 concentration, contact time, initial concentration, and
competing ions on Pd2+ adsorption was investigated. In a typical ex-
periment, 50 mg of adsorbent was added to a 100 mL vial with different
concentrations of Pd2+ solutions. After shaking the vial for sufficient
time to achieve adsorption equilibrium, the aqueous solution was re-
moved and passed through a syringe type filter. The initial and residual
Pd2+ concentrations were analyzed using an inductively coupled
plasma-optical emission spectrometer (ICP-OES). The sorption amount
qe (mg g−1) of adsorbed metal ions was calculated using:
(C0−Ce) × V
qe =
m
where C0 (mg L−1) is the initial concentration of metal ions, Ce
(mg L−1) is the equilibrium concentration, V (L) is the volume of the
test solution and m (g) is the sorbent dose.
3. Results and discussion
3.1. Material characterization
The morphologies of MXene materials prepared under the different
exfoliating conditions were assessed by SEM. As shown in Fig. 1, typical
layered morphologies of Ti3C2Tx were obtained by exfoliation of
Ti3AlC2 powder using 40% HF for 24 h at 25 °C, 35 °C, 45 °C,
W. Mu et al.
Fig. 1. SEM images of (a) TiAlC3, (b) MXene-25, (c) MXene-35 and (d) MXene-
45.
respectively, and perfect book-like morphology was obtained at 45 °C.
However, this perfect book-like morphology disappeared when the
exfoliating temperature reached to 55 °C (Fig. S1), indicating that high
temperature is unfavorable to obtain the book-like Mxene material,
which is possible attributed to the high temperature could decrease the
amount of HF during the exfoliating reaction process.
These MXene materials were further measured by TEM, and the
perfect book-like morphology was further confirmed (Fig. S2). In ad-
dition, the layer d-spacing of MXene materials along the c-axis were
shown in HRTEM images (Fig. 2). The layer d-spacing of these materials
are about 0.216 nm, 0.278 nm and 0.313 nm for MXene-25, MXene-35
and MXene-45, respectively, suggesting that the exfoliating tempera-
ture had a strong influence on the inter-structure of MXene materials,
and, demonstrating that the layer d-spacing increased with increasing
HF exfoliating reaction temperature. Additionally, the corresponding
SAED pattern (Fig. S3) exhibits highly uniform and ordered diffraction
spots, revealing the poly-crystal nature of MXene materials.
The morphologies of inorganic materials have a direct relationship
with their specific surface area. As shown in Fig. 3a, the specific surface
areas of MXene materials were measured by a surface area analyzer,
based on the adsorption-desorption of liquid of N2 at 77 K. The specific
surface areas are 19.78 m2 g−1, 65.42 m2 g−1 and 76.42 m2 g−1 for
MXene-25, MXene-35 and MXene-45, respectively, further confirming
that exfoliating temperature influences the specific surface area of
MXene materials. Moreover, for capturing metal ions, adsorbents with
Fig. 2. HRTEM images of (a) MXene-25, (b) MXene-35 and (d) MXene-45.
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Chemical Engineering Journal 358 (2019) 283–290
larger surface area could provide many more adsorption sites, and
further improve their adsorption capabilities.
The inter-structures of MXene materials were further detected by
XRD. As shown in Fig. 3b, the elimination of the (1 0 4) peak containing
Al (39°) indicates the loss of Al after immersion in HF solution, showing
that the Ti3AlC2 was successfully exfoliated by HF [20,38]. Remarkably,
the exfoliating temperature has an obvious effect on the structure of the
final samples. It can be found that the diffraction peak at (0 0 2) shifts to
a lower angle with increases exfoliating temperature, indicating the
inter-layer d-spacings of MXene material become wider. However, the
intensity of the (0 0 2) diffraction peaks of MXene materials become
weaker and shift to a higher angle when the reaction temperature in-
creases from45 °C to 55 °C, indicating that crystallision of these samples
may be decreased, and its layer-structure destroyed (Fig. S4). The result
is consistent with the morphological analysis of sample prepared at
55 °C: HF is a key factor for exfoliating and removing Al from the MAX
material and forming the book-like morphology, but most HF could
have escaped at the higher reaction temperature, in turn influencing the
layer-structure and layer morphology of the final sample. In previous
research, most MXene materials were obtained at low temperature
(under 40 °C), and their inter-layer d-spacings were adjusted by costly
and complicated chemical or physical method, while in our work, by
systemically studying the effect of reaction temperature of HF on the
layered structure of MXene material, we can adjust the layer d-spacing
of MXene material via the simple control of exfoliating temperature,
providing a new approach to adsorbents design and preparation. Be-
sides, we note that TiO2 peaks were not found in our MXene materials
due to the amount of TiO2 on the surface of Ti3C2Tx is lower, and below
the detection limit, although previous studies have shown that MXenes
are unstable in air, and with a surface easily oxidized to form TiO2
particles [33,34].
3.2. Material stability
Most fission wastewater is acidic or weak acidity due to use of
strong HNO3 for dissolving the uranium targets, so a promising ad-
sorbent should remain stable under such conditions. Thus, the stability
of MXene-45 was investigated as follows: the prepared sample was
immersed in 0.1 mol L−1 HNO3 solution. After shaking for 12 h and
centrifugation, the collected sample was assessed by XRD (Fig. S5) and
SEM (Fig. S6). The results showed the crystal phase and morphology of
MXene-45 had no obvious change after acid treatment, demonstrating
that this material possessed excellent stability under acidic condition.
Previous studies have demonstrated that few other conventional in-
organic adsorbents can tolerate such high acidity without decomposing,
so MXene materials could be considered as promising adsorbents used
in actual nuclear wastewater disposal. In addition, excellent resistance
to radiation is also a key factor for adsorbents used in nuclear waste-
water, a property we hope to systemically study in future work.
W. Mu et al.
Fig. 3. (a) N2 adsorption-desorption isotherm and (b) XRD pattern of samples with different exfoliating temperatures.
3.3. Adsorption experiments
3.3.1. Effect of HNO3 concentration
Palladium isotopes are fission products, and exist in nuclear was-
tewater having a high concentration of HNO3 used to dissolve the ur-
anium targets. Concentration of HNO3 in the adsorption system is a key
factor influencing metal binding to the adsorbent. Previous research has
indicated that the dominant species of palladium is [PdCl4]2− in HCl
media, while the main palladium species is Pd2+ in HNO3 media [21].
Moreover, studies have demonstrated that PPF resin has higher affinity
for cationic Pd2+ than anionic [PdCl4]2−, showing that cationic pal-
ladium is readily adsorbed [39]. In this work, the effect of the con-
centration of HNO3 on Pd2+ adsorption onto MXene materials was
studied. See Fig. 4: the Pd2+ adsorption capacities on MXene materials
decreased with increasing concentration of HNO3.This is probably at-
tributable to competitive adsorption of H+ ions and the formation of
nonionic complex Pd(NO3)2 at higher nitric acid concentrations. We
suggest that the acidity of HNO3 in actual applications could be ad-
justed to be under 0.1 mol L−1 to obtain a higher recovery rate. Ad-
ditionally, the adsorption capacity of Pd2+ on MXene materials is close
to their Zeta potential value detected in the same adsorption environ-
ment. As shown in Fig. 4b, the negative value of Zeta potential indicates
a large amount of negative charge covers the surface of the MXene
materials in lower concentration HNO3 media, favoring the adsorption
of Pd2+, while the Pd2+ adsorption capacity obviously decreases in
higher concentration HNO3 media due to the increase in surface Zeta
potential. It can be seen that the surface Zeta potential for MXene be-
comes positive and loads positive charges, which is bad for capturing
metal ions. The maximum adsorption capacity of Pd2+ was found in a
0.1 mol L−1HNO3 medium. Thus, to better simulate the actual nuclear
Fig. 4. (a) Effect of HNO3 concentration on Pd2+ adsorption onto MXene materials, (b) Zeta potential of MXene materials diffusing in HNO3 solutions with different
concentrations.
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Chemical Engineering Journal 358 (2019) 283–290
wastewater environment, an HNO3 medium with concentration of
0.1 mol L−1 was selected as the appropriate adsorption system for the
following adsorption experiments. The MXene-25, MXene-35, and
MXene-45 samples exhibited excellent ability to remove Pd2+ from
media with different concentrations of HNO3, due to their larger surface
area and wide layer distance.
3.3.2. Effect of initial concentration
The effect of initial concentration of Pd2+ adsorption on MXene-45,
MXene-35 and MXene-25 was investigated in a 0.1 mol L−1 HNO3
medium. See Fig. 5a: the Pd2+ adsorption capacity increased with in-
itial concentration increase. Moreover, MXene-45 exhibited better
ability for removal of Pd2+ than MXene-35 and MXene-25 due to its
larger surface area which provided many more adsorption sites for
metal ions.
To investigate the Pd2+ distribution between liquid and adsorbent
phases, and determine maximum adsorption uptake, experimental data
were further analyzed using Langmuir and Freundlich adsorption iso-
therm models (Table S1). A higher correlation coefficient for the
Langmuir adsorption isotherm model indicates that Pd2+ adsorption on
MXene materials is a monolayer (Fig. 5b), and the maximum adsorption
capacities of Pd2+ for MXene-45, MXene-35 and MXene-25 are
184.56 mg g−1 163.82 mg g−1 and 118.86 mg g−1, respectively, sur-
passing other inorganic adsorbents in acidic solution (Table1).
Most inorganic adsorbents lose their adsorption ability in acidic
solution, so preparation of adsorbents which is capable of removal of
metal ions from fission nuclear wastewater is a significant achievement.
Although previous researches has proved that MXene materials have
good ability to remove metal ions such as Pb2+, Cu2+ from aqueous
solution, our work has further studied the adsorption properties of
W. Mu et al. Chemical Engineering Journal 358 (2019) 283–290

Fig. 5. (a) Effect of pH on Pd2+ adsorption on MXene materials, (b) the Langmuir isotherm model (0.1 mol L−1, T = 293 K).

MXene materials in HNO3 media, and demonstrated that MXene ma-
terials could be used as adsorbents for capturing metal ions from fission
nuclear wastewater, which greatly broadens the application of these
materials.
3.3.3. Effect of contact time
To reduce the potential for radioactive harm to human beings,
treatment of nuclear wastewater should be fast and efficient. Thus, it is
necessary to investigate the adsorption kinetics of Pd2+adsorption.
Fig. 6 shows data for adsorption of Pd2+ by MXene-45, MXene-35 and
MXene-25 at different time intervals. Pd2+adsorption on MXene ma-
terials is fast. Adsorption at about 61.23%, 54.98% and 51.3% occurred
within the first 90 min for MXene-45, MXene-35 and MXene-25, re-
spectively, and gradually reached equilibrium in approximately
600 min. At the initial stage, the Pd2+ adsorption is fast due to the
abundant adsorption sites on the surface of MXene materials, and outer-
surface adsorption occurs. However, Pd2+ adsorption becomes slower
and slower with increasing contact time, and inter-surface adsorption
occurs. With the obvious decrease in outer-surface adsorption sites,
Pd2+starts to slowly enter into the inter-layer structure of MXene ma-
terials, and is adsorbed on the inter-surfaces. Due to the larger surface
area of MXene-45, it can capture many more Pd2+ ions than MXene-35
and MXene-25.
To further investigate the adsorption of Pd2+ on MXene materials,
kinetic data was analyzed using pseudo-first-order and pseudo-second-
order models (Table S2). Compared to the pseudo-first-order kinetic
model, the pseudo-second-order model has better correlation
(R2 = 0.9978, Fig. 6b) and more appropriately describes the kinetics of
the adsorption process, indicating chemical adsorption to be the main
rate limiting factor during adsorption.
3.3.4. Effect of temperature
The effect of temperature on Pd2+ adsorption by MXene materials
was measured at 293 K, 303 K and 313 K. The adsorption capacity of
Pd2+ decreases with increasing temperature, indicating low
temperatures benefit removal of Pd2+ (Fig. 7a). To investigate the
mechanism involved in adsorption, the thermodynamic behavior of
Pd2+ adsorption onto MXene materials was evaluated using the fol-
lowing equations:
ΔS∘ ΔH ∘
ln K d = −
R RT
ΔG∘ = ΔH ∘−T ΔS ∘
where Kd (mL g−1) is the distribution coefficient, R
−1 −1
(8.314 J mol K ) is the gas constant, and T (K) is the absolute
temperature of the aqueous solution. ΔH° and ΔS° were respectively
calculated from the slope and intercept of the linear variation between
lnKd and (1/T) (see Fig. 7b). Thermodynamic parameters are given in
Table S3. The positive value of ΔH° confirms the overall endothermic
nature of the adsorption process, and the positive value of ΔS° suggests
increasing randomness at the solid/solution interface during adsorp-
tion. Negative ΔG° indicates that the adsorption process is spontaneous
and irreversible at all studied temperatures.
3.3.5. Effect of co-existing ions
Fission nuclear wastewater is a very complicated system, containing
many metal ions such as K+, Na+, Sr2+, Pd2+, etc. Selectively for Pd2+
is thus also an important issue in the evaluation of adsorbents. We
considered various main metal elements present in nuclear wastewater,
and investigated their effects on the efficiency of removal of Pd2+ by
MXene materials in simulated nuclear wastewater. Fig. 8 shows that the
presence of other ions has no obvious influence on Pd2+ adsorption
onto MXene-45. On the one hand, the large surface area of MXene-45 is
a key factor, as it can provide many more sites, both inter-layer and on
the outer layer. On the other hand, compared to other metal ions, Pd2+
possesses lower hydration energy, and easily collocates with the active
groups on the surface of MXene materials. Previous research has in-
dicated that divalent cations are adsorbed in the presence of abundant
–OH groups on the surface of inorganic materials.

Table 1
Comparison of the maximum adsorption capacities of Pd2+ by various materials.
Adsorbents pH Adsorption capacity References
(mg g−1)

ASUiO-66 HNO3 45.4 [39]

Aquatic moss (Racomitrium lanuginosum) pH 5.0 37.2 [40]
Ethylenediamine immobilized lignophenol gel 0.5 mol L−1 25.3 [16]
Bayberry tannin immobilized collagen fiber pH 4.0 22.7 [41]
Glycine modified cross-linked chitosan resin pH 2 120.4 [42]
Chitosan (rubeanic acid derivative) 0.1 mol L−1 HCl 352 [20]
MXene-45 0.1 mol L−1 HNO3 184.56 This work

287
W. Mu et al.
Fig. 6. (a) Effect of contact time on Pd2+ adsorption, (b) pseudo-second-order model (initial concentration 100 mg L−1, 0.1 mol L−1 HNO3, T = 293 K).
Fig. 7. (a) Effect of temperature on Pd2+ adsorption, (b) Plot of LnKd vs.1000/T for adsorption of Pd2+ onto MXene materials.
Fig. 8. Removal efficiency of co-existing elements in simulated nuclear was-
tewater (initial concentration of elements is 100 mg L−1, 0.1 mol L−1 HNO3,
T = 293 K).
3.4. Adsorption mechanism
In our previous studies, we have found that Alk-Ti3C2Tx (MXene
treated with NaOH) has a good ability for removal of Ba2+ from aqu-
eous solution, and ion-exchange is a main interaction between the Alk-
MXene and Ba2+. Thus, in order to further study the intercalation be-
tween the Pd2+ and MXene material, the MXene-45 sample was further
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Chemical Engineering Journal 358 (2019) 283–290
treated with KOH and NaOH following our previous researches, to
produce MXene-45-K and MXene-45-Na, respectively. Then MXene-45-
K and MXene-45-Na were used as adsorbents for removal of Pd2+ from
aqueous solution. After adsorption and solid-liquid separation, the
concentrations of K+ and Na+ ions in liquid solution were measured by
ICP-AES. K+ and Na+ were not detectable, indicating that Pd2+ is not
exchanged by the K+ and Na+ ions existing in the inter-structure of
MXene. This results demonstrated that ion-exchange is not the main
interaction between the adsorbent and Pd2+. In addition, the Pd2+
adsorption capacity on MXene-45, MXene-45-K and MXene-45-Na is
almost the same (Fig. S7), demonstrating that metal ions intercalated in
MXene materials have no obvious effect on Pd2+ adsorption onto
MXene materials.
Based on the analysis of the properties of MXene materials, we see
that there are many more functional groups (–OH, –F) on the surface of
MXene materials, which can act as available sites for capturing cationic
metal ions. To further confirm the actual adsorption mechanism, XPS
spectra were taken to analyze adsorbents before and after Pd2+ loading.
The presence of elemental Pd after adsorption indicated that Pd2+ had
successfully been adsorbed by MXene materials (Fig. 9a), and Pd2+ ions
had been loaded onto the MXene-45. The binding energies for Pd 3d
peaks centered at 337.71 eV and 343.08 eV for Pd 3d5/2 and Pd3d3/2
(Fig. S8), respectively [16], corresponding to XPS peaks of divalent
state palladium. The above result suggested that the chemical state of
palladium was not changed during its adsorption. In addition, the
structures of MXene-45 before and after Pd2+ adsorption were analysed
by XRD (Fig. 9b). The results showed that the diffraction peak at (0 0 2)
shifted to a lower angle, indicating increasing d-spacing after Pd2+ ion
adsorption. This result not only indicated that Pd2+ ions successfully
W. Mu et al.
Fig. 9. (a) XPS spectra and (b) XRD pattern of before and after adsorption of Pd2+.
loaded onto the layered MXene-45 but also proved that a strong in-
teraction existed between palladium and MXene-45. This is consistent
with previous studies that correlated the behavior of Pb2+ adsorption
on MXene material. Thus, a surface chemical adsorption is the main
form of interaction between MXene materials and Pd2+.
3.5. Desorption and reuse
Recycling and regeneration properties of an adsorbent are key fac-
tors for reducing the cost of radioactive waste disposal. We have de-
termined that MXene material can be reused for multiple cycles of Pd2+
removal. Compared to other elute agents such as HCl, HNO3, etc.
Thiourea was shown to be an efficient agent for stripping the Pd2+
species off the MXene material solid matrix. It can be seen from
Fig. 10a, 0.5 mol L−1 thiourea exhibited the highest desorption effi-
ciency for Pd2+from adsorbent, with an efficiency of 99.3%. After five
time successive adsorption-desorption processes (Fig. 10b), the ad-
sorption capacity of Pd2+ slightly decreased from 185.63 mg g−1 to
167.2 mg g−1. This demonstrates that MXene-45 exhibited excellent
adsorption capability and reusability, meaning that it is a promising
adsorbent for removal of palladium isotopes from fission nuclear was-
tewater.
Fig. 10. (a) Desorption efficiency of Pd2+–immobilized adsorbents using various eluent, (b) performance of MXene-45 during the adsorption-desorption process.
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4. Conclusion
In this work, MXene materials with high specific surface area were
obtained by controlling the temperature of HF exfoliation, and their
morphologies and structures were determined systematically. The ex-
foliation temperature has an obvious influence on the morphology and
inter-structure of MXene materials, and the high temperature is favor-
able to prepare the ideal MXene materials with larger specific surface
area and wide layer d-spacing. Adsorption experiments demonstrate
that these materials work well for removal of radioactive Pd2+ from
HNO3 media, and the maximum adsorption capacity of Pd2+ fitting
with the Langmuir model is 184.56 mg g−1, 163.82 mg g−1 and
118.86 mg g−1 for MXene-45, MXene-35 and MXene-25, respectively.
This is higher than that of most inorganic adsorbents used for palladium
removal. The higher adsorption capacity of Pd2+ on MXene-45 is at-
tributed to its wider layer d-spacing and larger surface area. Kinetics
studies indicated that Pd2+ adsorption on MXene material is fast, and
they can retain high selectively for Pd2+ in simulated nuclear waste-
water. Most importantly, MXene-45 exhibited excellent regeneration
performance and reusability, with Pd2+adsorption capacity having no
obvious loss after five cycles. The present results suggest that MXene
material is a promising adsorbent for removing Pd2+ from radioactive
wastewater. However, nuclear wastewater is complicated, and ad-
sorbents must not only possess good resistance to acid but must remain
stable in a strongly radioactive environment. This will be assessed in a
W. Mu et al.
further study to determine the applicability of MXene materials to nu-
clear wastewater disposal.
Acknowledgments
We wish to acknowledge financial support from the Foundation of
the Chinese Academy of Engineering Physics and the National Natural
Science Foundation of China (no: 21501159)
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2018.10.010.
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