You are on page 1of 7

Results in Physics 12 (2019) 405–411

Contents lists available at ScienceDirect

Results in Physics
journal homepage:

Adsorption of heavy metal sewage on nano-materials such as titanate/TiO2 T

added lignin

Yuan Fua,b, , Xin Liua, Guanyi Chenb
China Coal Research Institute Co., Ltd., Beijing 100013, China
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China


Keywords: Biomolecules (lignin) were used as additives for the synthesis of titanate/TiO2 nanomaterials, and their ad-
Titanate sorption properties and photocatalytic properties were studied. They were based on corn stalks, cotton stalks,
Lignin poplar twigs and willow shavings, respectively. Lignin was extracted from it to aid in the synthesis of titanate
Adsorption nanotube material. The products were characterized by XRD (X-Ray Diffraction), FESEM (Field emission scan-
Heavy metal
ning electron microscopy), TEM, FTIR (Fourier Transform Infrared Spectroscopy) and BET, and their adsorption
properties were studied. The study found that by comparing the maximum adsorption capacity of heavy metal
ions (Pb2+, Cu2+, Cd2+) with four different lignin-containing titanate nanotube materials, the adsorption
performance of the lignin-assisted synthesis of titanate nanotubes (WL-TNTs) was optimal. WL-TNTs material
had good adsorption effect on Pb2+, Cu2+ and Cd2+, especially Pb2+ had a good adsorption effect over a wide
pH range (pH of 2–7). At pH = 6 (lead ion was 5.5) and at 25 °C, the maximum adsorption capacity of WL-TNTs
for Pb2+, Cu2+ and Cd2+ reached 677.6 mg/g, 258.2 mg/g and 308.5 mg/g, respectively, and the adsorption
rate was fast. The lead ions can be adsorbed almost completely in 5 min and the best dosage of adsorbent was
only 0.2 g/L. At the same time, the material had excellent adsorption and analytical regeneration performance. It
was a good and economical adsorbent and had broad application prospects.

Introduction and glycine were used as external additives for the synthesis of titanate/
TiO2 nano-materials, which improved the adsorption performance of
Because of its large surface area and strong ion exchange capacity, heavy metal waste water.
titanate nanomaterials have a wide range of applications in many fields
such as adsorption, photovoltaics and so on. However, studies at home Analysis methods and materials
and abroad in recent years have shown that the prepared nano-titanates
are easily agglomerated [1], which results in unsatisfactory adsorption Lignin is a natural polymer compound containing aromatic rings
performance. It is necessary to add additives to improve the structure and multiple hydroxyl groups. As a natural polymer compound, it is
and adsorption performance during the synthesis process. abundant in nature and exists in almost all plants. Together with cel-
Lignin (including sodium lignin sulfonate) has a large amount of lulose and hemicellulose, it forms the skeleton of the plant. More than
output and low price, and it is the main pollutant of paper-making 90% of the wood components belong to the above three types of
waste-water discharge. The utilization rate of industrial lignin produced compounds [4,5].
every year worldwide is extremely low, resulting in a great waste of
resources, which is bound to bring about serious environmental pro- Structure and classification of lignin
blems and economic problems. Therefore, no matter from the per-
spective of resource utilization or environmental protection, the de- As a natural polymer compound, lignin has a very complex struc-
velopment of new methods for the utilization of lignin and the ture. The reason is that the repeating units in the molecular structure
improvement of the utilization of lignin can not only reduce environ- have no regularity and are not as ordered as the cellulose and protein
mental pollution, but also alleviate resource crisis and maintain sus- molecular structure. It was found that phenylpropanyl is the structural
tainable development [2,3]. unit of lignin. According to the different structural units of lignin, we
In this paper, lignin (including sodium lignin sulfonate), chitosan can classify lignin into the following three categories [6]:

Corresponding author at: China Coal Research Institute Co., Ltd., Beijing 100013, China.
Received 30 October 2018; Received in revised form 20 November 2018; Accepted 23 November 2018
Available online 27 November 2018
2211-3797/ © 2018 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
Y. Fu et al. Results in Physics 12 (2019) 405–411

Guaiac wood lignin: polymerized from guaiacyl propane structural structure is formed by winding a single-layer film under hydrothermal
units. conditions [10].
Lilac-based lignin: Polymerized from syringyl propane structural
units. Preparation of titanate nanotubes
P-hydroxyphenyl lignin: Polymerized from p-hydroxyphenyl pro-
pane structural units. There are many methods to prepare titanate nanotubes, including
hydrothermal method, anodization method and template synthesis
Physicochemical properties of lignin method. The hydrothermal method has been widely used by researchers
because of its simple operation and easy control of the reaction process.
The physical properties of lignin vary greatly depending on the The hydrothermal method refers to fixing a certain temperature under
method of extraction and separation, the site and species of the plant. strong alkaline conditions, putting TiO2 nanoparticles into a closed
Color Natural lignin is generally light in color, most of which are reaction vessel, and after a certain time of reaction process, then, after
white or colorless. The molecule contains a benzene ring, a carbonyl pickling, washing to prepare titanate nanotubes. Titanate nanotubes
group, and a vinyl group, which can form a large conjugation system. prepared by hydrothermal method have advantages of opening at both
The п electrons in the system can absorb light with a longer wavelength ends, thin tube diameter, high aspect ratio, and high specific surface
and cause a transition, thereby causing the substance to produce a area. Through high-power transmission electron microscopy, it can be
color. In addition, the presence of color-evolving genes such as eOH, seen that the wall of the titanate nanotubes is a multi-layered structure
eCOOH, eOR, eNR, eX, etc. will also make the substance display with a number of layers ranging from 1 to 10, with a layer spacing of
color. In addition, the phenolic hydroxyl groups in the lignin molecules 0.78 nm [11].
are easily oxidized to quinones to deepen the lignin color [7].
The soluble lignin is a natural polymer compound containing many Properties of titanate nanotubes and their application in adsorption
organic groups and has characteristics such as high molecular weight
and poor lyophilicity. Therefore, natural lignin is generally insoluble in Titanate nanotubes have large specific surface area and strong ion
water and organic solvents, but the isolated lignin has a certain solu- exchange capacity, so they can quickly adsorb inorganic and organic
bility. For example, lignosulfonates exist as soluble salts and so it dis- nanoparticles, thereby forming one-dimensional nanomaterials. These
solves in water; alkali lignin is insoluble in acidic solutions but soluble properties are derived from its morphology, such as porous and hollow
in alkaline solutions [8]. structures. These characteristics improve its superiority in adsorption.
Heat-stabilized lignin molecules contain aromatic rings and inter- Studies have shown that the pore structure of titanate nanotubes has a
molecular hydrogen bonds, so they have good thermal stability. From certain degree of stability. When the inorganic organic particles pass
the thermogravimetry curves of alkali lignin and acidolysis lignin under through the tube wall, the interlayer spacing of titanate nanotubes does
nitrogen atmosphere, it is found that the static pyrolysis characteristics not change. This advantage allows the material to not block the pipe
are basically the same. When the temperature is higher than 200 °C, the during the ion exchange process because the solid particles are too
decomposition rate of lignin increases suddenly and the thermal de- large, thereby increasing the ion exchange capacity of the titanate na-
composition rate is maximum at 359.7 °C and 288.9 °C respectively. notubes. Due to the above characteristics of the structure, titanate na-
When the temperature continues to increase to 760 °C, there is a small notube materials become a highly efficient adsorbent in removing
deviation in the content of non-volatile components in the two lignin heavy metal ions [12].
The relative molecular weight of lignin as a natural polymer com- Application of assisted synthetic nanotubes
pound, lignin not only has a large molecular weight but also has an
aromatic character, so its carbon content is higher than that of common Nanotube-assisted synthesis additives mainly include surfactants
glycans such as cellulose and hemicellulose hydrolysates. Although the and biomolecules. Surfactants mainly include cationic, anionic, and
relative molecular weight of natural lignin is in the hundreds of thou- non-ionic surfactants. The surfactants of shorter fatty chains include
sands, the relative molecular weight of lignin extracted by high-tem- sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide
perature cooking is only between several thousands and tens of thou- (CTAB). Surfactants have a certain degree of dispersion. Therefore, the
sands. For example, after straw-like alkali lignin is cooked at high use of surfactant-assisted synthesis of nanotube materials can reduce
temperature, the molecular weight of lignin is reduced from particle agglomeration and improve the performance of nanotubes to
20,000–50,000 to 1000–20,000. The main reason is that lignin is af- varying degrees.
fected by a series of chemical reaction conditions such as condensation, The use of biomolecules as additives to assist in the synthesis of
degradation, and denaturation in the process of extraction and se- nanotube materials has the characteristics of hydrophilicity, bio-com-
paration, resulting in a decrease in the relative molecular weight. patibility, and no pollution to the environment, and is increasingly
welcomed by the majority of scholars. Experiments have shown that the
Titanate nanotube structure optimal concentration of solvent DMSO is 10–20% aqueous solution. At
this concentration, the loose spiral of amylose is discontinuous, which
So far, many researchers believe that the nanotubes are titanic acid proves that the primary condition for the synthesis of single-walled
or sodium titanate, but different scholars believe that titanic acid or carbon nanotubes is not the spiral state of the amylose. Cyclodextrins
sodium titanate has a different crystal structure. The crystal form of the are adsorbed by van der Waals forces and hydrophobic interactions on
titanic acid nanotubes HxTi2-x/4□x/4O4 belongs to the lamellar he- the surface of carbon nanotubes and can be uniformly dispersed in
matite type. The positions of the diffraction angle 2θ are 9.5°, 24.5°, water. Functionalized carbon nanotubes have certain special functions
28°, 48°, and 62° respectively, and correspond to the (0 2 0), (1 1 0), in the construction of electrochemical and composite electrodes.
(1 3 0), (2 0 0), (0 0 2) planes of the fibrinite-type titanate material. Carbon nanotubes and proteins are mainly fixed by physical action, and
Through XRD, HRTEM and SAED analysis of titanate nanotubes, it was the resulting carbon nanotubes have obvious advantages in the field of
found that the cross-section of the material was a coiled thread-shaped heterogeneous electron transfer [13].
structure, and the distance between the layers was 0.78 nm. Alkali
metal titanates also have a layered structure. Each layer is a single- Methods
layered structure in which the titanium oxygen octahedron forms a
zigzag shape via a common edge and a common corner top. The tubular Lignin is a natural polymer compound containing aromatic rings

Y. Fu et al. Results in Physics 12 (2019) 405–411

Table 1 centrifugation. The filtrate was heated at 50 °C in a water bath, heated

Drugs and reagents. while stirring, while dropwise adding 10% hydrochloric acid to the
Reagent Specification filtrate pH was about 3, so that the lignin was completely precipitated,
and the precipitate was taken out after 45 min. After aging for 60 min,
Hydrochloric acid Analytical purity the precipitate was separated by centrifugation, washed repeatedly
Sodium hydroxide Analytical purity
with distilled water to a pH of 6, and finally dried overnight at 102 °C.
Sodium Lignosulfonate Analytical purity
Nitric acid Analytical purity
Lead nitrate Analytical purity Natural lignin assisted synthesis
Copper nitrate Analytical purity
Cadmium nitrate Analytical purity Titanate nanotubes accurately weighed 1 g anatase TiO2 and 0.10 g
Acetone Analytical purity
of each lignin powder were added to 50 mL 10 mol in the L-1 NaOH
Anhydrous ethanol Analytical purity
solution, the mixture was stirred magnetically for 45 min at room
temperature to make the mixture homogeneous. Then, the suspension
and has a complex structure. Its distribution in plants has a certain rule was transferred to a 100-mL reaction vessel lined with tetra-
to follow. Generally speaking, lignin content is 14–24% in herbaceous fluoroethylene and reacted at 150 °C for 24 h. The reactor was removed,
plants. The content of woody plants is 20–33%. Extracting lignin from and after cooling to room temperature, filtered by suction and washed
waste plants has the advantages of being non-toxic, easily available, with distilled water until the pH is approximately 7, and finally dried
and cheap, and it can reduce the cost of experiments by making rational overnight at 80 °C. The lignin-assisted titanate nanotube material ex-
use of lignin resources. At the same time, it can also contribute to en- tracted from corn stalks was recorded as CL-TNTs, and the lignin-as-
ergy conservation and emission reduction. No application has been sisted titanate nanotube material extracted from cotton stalks was de-
reported on the application of lignin to assisted synthesis of titanate signated as CNL-TNTs. Lignin-assisted synthetic titanate nanotube
nanomaterials. material extracted by wood chips as raw material is referred to as WL-
In this chapter, alkali lignin was extracted from plant stalks by al- TNTs, and lignin-assisted synthesized titanate nanotube material ex-
kaline method to obtain alkali lignin. Then, lignin was separated and tracted from poplar wood chips is referred to as PL-TNTs.
purified by acid precipitation. Titanate nanotubes were then prepared
as additives. Through a series of characterization and adsorption per- Adsorption performance test
formance tests such as XRD, SEM/TEM, FT-IR, BET, etc., the properties
of this material for the adsorption of heavy metal ions were in- All groups were tested in a 50-mL plastic centrifuge tube. 30 mL of
vestigated. the appropriate initial concentration of metal ions was accurately re-
moved. The pH of the solution was adjusted with dilute sodium hy-
Experimental section droxide or dilute nitric acid to 6 (lead ion is 5.5), and then added the
prepared adsorbent to a concentration of 0.1 g/L and then these cen-
Instruments and reagents trifuge tubes were placed in a shaking incubator to maintain the tem-
See Tables 1 and 2. perature of 25 °C and the rotation speed was 240 r/min for 4 h (where
the heavy metal lead ions were 2 h). Finally, the heavy metal ion so-
lution was filtered and the concentration of heavy metal ions was
Extraction of lignin
measured by an atomic absorption spectrophotometer. The amount of
adsorption calculation see formula (1)
Raw material
The required raw materials include corn stalks, cotton stalks, willow (Cn − Cep) V
sap, and poplar stalks and so on. m (1)
The raw materials were washed several times with tap water and
Among it; Cn – initial concentration, mg/L; Cep – concentration at
distilled water in order to remove impurities such as sediments on the
equilibrium, mg/L; V – volume of solution, mL; m – mass of adsorbent,
surface. Then put them in the oven and dry them overnight at 60 °C.
mg; q – adsorption, mg/g.
After removing them, pulverize them with a universal grinder and pass
Change the adsorption time, the pH of the solution, and the amount
them through a 20-mesh sieve.
of dosing to study the adsorption properties of the material, and then
make the removal rate and influencing factor curve.
Preparation The calculation of the removal rate is shown in formula (2)
Weigh 7 g of the above four powders into four beakers containing
50 mL of 16% NaOH and magnetically stir for 1 h at room temperature C0 − Ceq
Removal rate(\% ) = *100%
to disperse them into a uniform suspension. Then transfer to 100 mL C0 (2)
stainless steel high pressure reaction vessel lined with teflon. The au- Among it: Ceq – equilibrium concentration, mg/L; C0 – initial con-
toclave was placed in an oven at 130 °C for 2 h. After the reactor was centration, mg/L.
cooled to room temperature, the filter residue was filtered off by
Desorption test
Table 2
Instruments and Equipment.
20 mL/L heavy metal ion solution (30 mL) was added to a plastic
Instrument centrifuge tube (50 mL). The pH was adjusted and the adsorbent was
added. The temperature was maintained at 25 °C in a constant-tem-
Ultrasonic cleaner KH-100B
Magnetic heating stirrer HJ-4 perature shaker and the rotation was 240 r/min for 4 h (adsorption of
Electronic analytical balance AUY120 heavy metal lead ions for 2 h), the pH was constantly adjusted during
Desktop electric thermostatic drying oven WHL-25A the adsorption process and remained constant. After the shaking was
Low-speed large-capacity centrifuge DL-5 completed, the adsorbent was filtered, dried, and then 0.1 mol/L hy-
Machine HZQ-F160
drochloric acid was added and placed on a thermostatic shaker at a
Incubator T6 New Century
Atomic Absorption Spectrophotometer XL-600B temperature of 25 °C and a speed of 240 r/min. After shaking for 6 h,
desorbed the solution and measured its concentration.

Y. Fu et al. Results in Physics 12 (2019) 405–411

Material characterization peak is stronger. The bending vibration peak of HeOeH in water is
around 1630 cm−1. The stretching vibration peaks of TieO and
X-ray powder diffractometer (XRD): manufactured by BRUKER TieOeTi are near 900 cm−1 and 480 cm−1 respectively. It is clear that
GmbH, Germany, using Cu target Kα radiation source, λ is 0.15406 Â, the wave numbers and intensities of these four materials in the center of
scanning speed is 0.02°2θ s−1, scanning range is 5–75°, and S-4800 type the above four peaks are basically similar.
field emission Scanning Electron Microscopy (FESEM): Accelerating
voltage of 3 kV, manufactured by Hitachi, Japan; H-7500 Transmission BET analysis
Electron Microscope (TEM): accelerating voltage of 80 kV produced by
Hitachi, Japan; VERTEX 70 Fourier Transform Infrared-Raman-Infrared Fig. 4 shows the N2 sorption-desorption isotherms of the four
Microscope Coupled Spectrometer (FTIR): produced by Brooke, samples. The N2 adsorption-desorption isotherms of all the prepared
Germany, with a few samples and 200 mg KBr sheet, frequency range samples conformed to type IV and had a hysteresis loop of type H3,
4000–400 cm−1, resolution 2 cm−1, potassium bromide as a reference; demonstrating the presence of mesopores in these four samples (aper-
Quantachrome NOVA4000e series specific surface tester (BET): ture range 2–50 nm). At the same time, we can also calculate the spe-
Quantachrome is produced by Conta USA. TGA-7 type thermogravi- cific surface area (BET) of nanotubes, in which the specific surface area
metric analyzer: manufactured by P-E, USA, with a heating rate of of CNL-TNTs is the largest, about 236.4 m2/g; the specific surface area
0.1–200 °C/min. of PL-TNTs is second, about 175.4 m2/g; the specific surface areas of
WL-TNTs and CL-TNTs were 166.3 m2/g and 141.3 m2/g, respectively.
Results and discussion That is, the order of specific surface areas of the four samples is:
XRD analysis
Adsorption properties of heavy metal ions on materials
The XRD pattern of the lignin-assisted synthetic titanate material
extracted from four different raw materials (see Fig. 1). As can be seen Effect of solution pH on adsorption of heavy metals
from the figure, these four materials are all weaker diffraction lines, In the heavy metal adsorption test, the influence of pH is the main
which proves that the four materials have lower crystallinity. Their influencing factor of adsorbate and adsorbent acting force. The ad-
diffraction angle 2θ is about 10.5°, 24.5°, 28° and 48°. The formula can sorption rate-pH curve of Pb2+, Cu2+ and Cd2+ on the material is
be expressed as Na2Ti3O7, and the characteristic peak at 10.5° corre- shown in Fig. 5. In the figure, all four curves move in the direction of
sponds to the (0 0 1) crystal plane of Na2Ti3O7. 2θ ≈ 24.5° and 48° low pH. From the figure, it can also be seen that the removal rate of
indicate that the material contains sodium titanate and titanic acid, Pb2+ in WL-TNTs material reaches more than 65% at pH = 2, and the
while the broad peak at 2θ ≈ 10.5° corresponds to the interlayer spa- removal rate of Pb2+ is almost 100% when pH = 5. The removal rate of
cing of the layered titanate. PL-TNTs material at pH = 2 was only 28%, and the removal rate at
pH = 6 was 96%; the removal rate of Cu2 + on WL-TNTs material in-
TEM analysis creased rapidly at pH = 2–5, the removal rate was almost completely
removed at pH 6, and the removal rate of PL-TNTs materials increased
Fig. 2(a) and (b) are transmission photographs of CL-TNTs and CNL- slowly with increasing pH, and the removal rate was only 60% at
TNTs. The diameter of CL-TNTs is between 80 and 150 nm, and there pH = 6. The difference in the removal rate of Cd2+ between WL-TNTs
are many non-crimp nanosheets; while most of CNL-TNTs are fiber- and PL-TNTs materials with pH changes is not too great. The experi-
tubular with a diameter of about 10 nm and nanotube lengths of mental results show that for the adsorption of Pb2+, Cu2+ and Cd2+,
150–500 nm. (c) and (d) are transmission pictures of PL-TNTs and WL- the removal rate of the four materials increases sharply with the in-
TNTs. PL-TNTs and WL-TNTs are tubular, but the tubes of PL-TNTs are crease of pH, and ultimately reaches the same level; in which the WL-
short and agglomerated. WL-TNTs are well dispersed. The length of TNTs material has a wider pH value when adsorbing lead ions. The
nanotubes also increases from 150–300 nm to 300–700 nm. range (pH 4–7) has higher adsorption performance.

IR analysis Adsorption isotherms of materials

An important indicator to measure the performance of adsorbent
Fig. 3 shows the infrared spectra of the four materials prepared. The materials is the maximum adsorption capacity. The adsorption capacity
stretching vibration absorption band of OeH in the titanate is in the of WL-TNTs for Pb2+, Cu2+ and Cd2+ is much higher than that of PL-
range of 3400–3200 cm−1, and the absorption band is wider and the TNTs. The adsorption isotherms of the materials can well conform to
the Langmuir adsorption model. The maximum adsorption of WL-TNTs
to Pb2+, Cu2+ and Cd2+ was calculated to be 677.6 mg/g, 258.2 mg/g,
and 308.5 mg/g, respectively. On the other hand, PL-TNTs materials
have the worst performance in adsorbing heavy metal ions. The max-
imum adsorption capacity of PL-TNTs for Pb2+, Cu2+ and Cd2+ were
546.8 mg/g, 169.3 mg/g and 245.4 mg/g, respectively. The results
showed that the maximum adsorption capacity of heavy metals ad-
sorbed by willow lignin-assisted titanate nanotubes was significant. The
use of this adsorbent to remove heavy metals in water has broad ap-
plication prospects.

WL-TNTs adsorption properties

Kinetic curve
According to the experimental study in the previous section, WL-
TNTs are the best adsorbents among these four materials, so we will
further study their adsorption performance in this section. Fig. 6 shows
Fig. 1. XRD spectra (a) CL-TNTs (b) CNL-TNTs (c) PL-TNTs (d) WL-TNTs. the kinetics curve of Pb2+, Cu2+ and Cd2+ adsorption for WL-TNTs.

Y. Fu et al. Results in Physics 12 (2019) 405–411

Fig. 2. TEM image of the sample (a) CL-TNTs (b) CNL-TNTs (c) PL-TNTs (d) WL-TNTs.

Fig. 3. IR map of the sample (a) CL-TNTs (b) CNL-TNTs (c) PL-TNTs (d) WL-
Fig. 4. Nitrogen adsorption and desorption curve of the sample.

Adsorption from adsorption to adsorption for 5 min, the removal rate of

heavy metal ions rose very fast, basically a linear trend. The removal Dosage study
rate of Pb2+, Cu2+, Cd2+ by WL-TNTs reaches 87%, 71%, and 73%, Fig. 7 shows the effect of WL-TNTs material dosage on the removal
respectively, when the adsorption time reaches 5 min. After 5 min of rate. With the increase of dosage, the removal rate of Pb2+ in WL-TNTs
adsorption time, the rising trend of the kinetic curve became slower, materials increased gradually. When the dosage of materials was 0.2 g/
and after 120 min, the removal rate basically did not increase, ie the L, the removal rate of Pb2+ was the largest, and with the increase of
adsorption reached equilibrium. When the adsorption reached equili- dosage, the removal rate of Pb2+ was basically the same. Therefore, we
brium, the removal rates of Pb2+, Cu2+, and Cd2+ were 99.9%, 99.7%, believe that the best dosage of the adsorbent is 0.2 g/L. Under this
and 99.7%, respectively. Therefore, it can be seen that WL-TNTs ma- condition, the removal rate of Cu2+ is more than 90%. With the in-
terials can completely remove heavy metal ions in a short time. crease of dosage, the removal rate of Cu2+ changes very little. Simi-
larly, the removal rate of WL-TNTs material above 0.2 g/L does not

Y. Fu et al. Results in Physics 12 (2019) 405–411

solution was 0.1 mol/LHC, adsorbent 0.1 g/L, temperature 25 °C, re-
volution 240r/min, resolution time 6 h, four cycles of desorption, the
desorption rate of three ions was slightly reduced, and it can also
maintain a desorption rate of more than 90%. From the results of the
WL-TNTs material rejuvenation test, the material was an excellent ad-
sorbent, and its application in practical water treatment was bound to
save costs. Corn stalks, cotton stalks, poplar swarf, and willow swarf
were used as raw materials to extract lignin and assist in the synthesis
of titanate nanotubes. The product was characterized by XRD, SEM and
TEM, FTIR and BET, and its adsorption performance was studied. The
following conclusions were drawn: The maximum adsorption capacity
of heavy metal ions (Pb2+, Cu2+, Cd2+) was compared by the four
modified materials. It was found that the adsorption performance of the
lignin-assisted synthesis of titanate nanotubes (WL-TNTs) is optimal.
Fig. 5. Adsorption rate of Pb2+, Cu2+ and Cd2 + on the material-pH curve (a) Moreover, from the Pb2+, Cu2+ and Cd2+ adsorption rate-pH curves of
Pb2+ (b) Cu2+ (c) Cd2+. WL-TNTs materials, Pb2+ has a good adsorption effect over a wide pH
range (pH of 2–7), at pH = 6 (lead ions are under the condition of 5.5)
and 25 °C, the maximum adsorption capacity of WL-TNTs materials for
Pb2+, Cu2+ and Cd2+ reaches 677.6 mg/g, 258.2 mg/g and 308.5 mg/
g, respectively. From the kinetic curve, the material absorbs heavy
metals. The adsorption rate is fast, in which the lead ion can be almost
completely adsorbed in 5 min; the optimum dosage of the adsorbent is
only 0.2 g/L. At the same time, the material has excellent adsorption
and desorption regeneration performance, and it is a good and eco-
nomical adsorbent with a wide application prospect.


By comparing the maximum adsorption capacity of heavy metal

ions (Pb2+, Cu2+, Cd2+) with four different lignin-containing titanate
nanotube materials, the adsorption of WL-TNTs assisted by willow
lignin was optimum. WL-TNTs material had good adsorption effect on
Pb2+, Cu2+ and Cd2+, especially Pb2+ had a good adsorption effect
over a wide pH range (pH of 2–7), at pH = 6 (lead ion is 5.5) and at
25 °C, the maximum adsorption capacity of WL-TNTs for Pb2+, Cu2+,
Fig. 6. Kinetics of Adsorption of Heavy Metals on WL-TNTs. Cd2+ reached 677.6 mg/g, 258.2 mg/g, 308.5 mg/g, respectively, and
the adsorption rate was fast, and lead ions can be almost completely
adsorbed in 5 min. The best dosage of adsorbent was only 0.2 g/L. At
the same time, this material had excellent adsorption and analytical
regeneration performance. It is a good and economical adsorbent with
broad application prospects.


[1] Xie A, Dai J, Cui J, et al. Novel graphene oxide-confined nanospace directed
synthesis of glucose-based porous carbon nanosheets with enhanced adsorption
performance. ACS Sustainable Chem Eng 2017;5(12):11566–76.
[2] Cui W, Li J, Dong F, et al. Highly efficient performance and conversion pathway of
photocatalytic NO oxidation on SrO-clusters@ amorphous carbon nitride. Environ
Sci Technol 2017;51(18):10682–90.
[3] Dhandole LK, Kim SG, Seo YS, et al. Enhanced photocatalytic degradation of organic
pollutants and inactivation of listeria monocytogenes by visible light active Rh–Sb
Codoped TiO2 nanorods. ACS Sustainable Chem Eng 2018;6(3):4302–15.
Fig. 7. Effects of different dosages on adsorption of Pb2+, Cu2+ and Cd2+ [4] Cui R, Lin Y, Qian J, et al. Two-Dimensional porous SiO2 nanostructures derived
from renewable petal cells with enhanced adsorption efficiency for removal of ha-
(temperature 25 °C, revolution 240 r/min, heavy metal ion concentration
zardous dye. ACS Sustainable Chem Eng 2017;5(4):3478–87.
20 ppm, pH 6 (lead ion concentration 40 ppm, pH 5.5)). [5] Klementová M, Motlochová M, Boháček J, et al. Metatitanic acid pseudomorphs
after titanyl sulfates nanostructured sorbents and precursors for crystalline titania
with desired particle size and shape. Cryst Growth Des 2017;17(12):6762–9.
change much. From an economic point of view, the optimal dosage [6] Ren CE, Hatzell KB, Alhabeb M, et al. Charge-and size-selective ion sieving through
should be 0.2 g/L. Ti3C2T x MXene membranes. J Phys Chem Lett 2015;6(20):4026–31.
[7] Hu Z, Kurien U, Murwira K, et al. Development of a green technology for mercury
recycling from spent compact fluorescent lamps using iron oxides nanoparticles and
electrochemistry. ACS Sustainable Chem Eng 2016;4(4):2150–7.
Regeneration performance research [8] Yang Y, Hoffmann MR. Synthesis and stabilization of blue-black TiO2 nanotube
arrays for electrochemical oxidant generation and wastewater treatment. Environ
Regeneration performance is an important criterion for the quality Sci Technol 2016;50(21):11888–94.
[9] Dominguez-Ramos A, Chavan K, García V, et al. Arsenic removal from natural
of adsorbents. WL-TNTs adsorbed on Pb2+, Cu2+ and Cd2+, and the waters by adsorption or ion exchange an environmental sustainability assessment.
removal rate of the three ions was slightly reduced after four cycles of Ind Eng Chem Res 2014;53(49):18920–7.
adsorption, but the removal rate was still more than 90%. The deso- [10] Li L, Luo J, Liu Y, et al. Self-propagated flaming synthesis of highly active layered
CuO-δ-MnO2 hybrid composites for catalytic total oxidation of toluene pollutant.
rption cycles of Pb2+, Cu2+ and Cd2+ for WL-TNTs were: desorption

Y. Fu et al. Results in Physics 12 (2019) 405–411

ACS Appl Mater Interfaces 2017;9(26):21798–808. nanorods for efficient solar-driven photocatalytic performance. ACS Appl Mater
[11] Zhan S, Zhu D, Ren G, et al. Coaxial-electrospun magnetic core-shell Fe@ TiSi Interfaces 2016;8(40):26851–9.
nanofibers for the rapid purification of typical dye wastewater. ACS Appl Mater [13] Stenlid JH, Johansson AJ, Brinck T. Local lewis acidity of (TiO2) n (n= 7–10)
Interfaces 2014;6(19):16841–50. nanoparticles characterized by DFT-Based descriptors tools for catalyst design. J
[12] Zhang Y, Xing Z, Liu X, et al. Ti3+ self-doped blue TiO2 (B) single-crystalline Phys Chem C 2017;121(49):27483–92.