Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-018-3815-z

RESEARCH ARTICLE

Study on the influence of surface potential on the nitrate adsorption

capacity of metal modified biochar
Li Long 1 & Yingwen Xue 1 & Xiaolan Hu 1 & Ying Zhu 1

Received: 1 August 2018 / Accepted: 20 November 2018

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Carbon materials, as effective adsorbents to numerous aqueous cationic contaminants, have been hardly applied to remove anions
in wastewater. In this work, different modifying agents were used to modify corncob biochars (CC) and the surface potentials of
these modified biochars were determined. Based on the findings, modification principle was determined to reveal the relationship
between surface potentials of the biochars and their nitrate adsorption capacities. The surface potential was dominated by the
metal cations and multivalent cations led to even positive zeta potential. The formation of metal oxide not only led to the augment
in surface area but also increase the surface charge. FeCl3-modified biochar (Fe-CC) with the highest positive surface charge was
utilized to remove anions (nitrate) from aqueous solutions. Characterization results confirm that Fe2O3 structure were success-
fully formed on biochar surface. This led to the formation of iron nitrate hydrate (Fe(NO3)3·9H2O), which enabled higher nitrate
adsorption performance than that of pristine biochar. Batch experiments showed that nitrate adsorption on the Fe-CC was stable
and almost independent of experimental pH and temperature. Based on the Langmuir model results, the maximum nitrate
adsorption capacity of Fe-CC was 32.33 mg/g. Coexisting anions had negative influence on the adsorption performance.
Findings of this work suggest that the modified biochar can be used in wastewater treatment to remove anions such as nitrate.

Keywords Metal modified biochar . Surface charge . Zeta potential . Modification principle . Adsorption mechanism

Introduction been a hot subject for researchers to take an economical-

efficient and environmental friendly way to treat nitrate
With the rapid development of modern agriculture and the pollution.
acceleration of urban modernization, nitrate pollution has be- Recently, biological treatment and physical and chemical
come a serious problem. Therefore, nitrate pollution in under- removal methods have been applied to treat nitrate pollution
ground and surface water has attracted much research atten- (Du et al. 2017; Hu et al. 2018a; Villegas-Guzman et al. 2017).
tion around the world. Due to its high water solubility, nitrate Adsorption has attracted universal attention for its unique
has been found in all kinds of water bodies, which can pose a characterizations, such as considerable removal efficiency
serious threat to environment and human health. In addition to and environmental friendly process. Among numerous adsor-
eutrophication, the increase of nitrate concentration can also bents, carbon materials have been prevailing adsorbents for
cause human health problems such as (1) it can cause methe- removing contaminants. Carbon adsorbents including
moglobinemia to babies, commonly known as BBlue baby graphene (Wang et al. 2017), carbon nanotubes (Kang et al.
syndrome^; (2) it is easy to form nitrosamine compounds to 2018), activated carbon (Liu et al. 2016a), and biochar (Hu
induce cancer; and (3) it can lead to diminished intelligence et al. 2018a) are widely applied to remove aqueous
for reducing oxygen supply in body cells. Therefore, it has contaminants.
To further improve their adsorption capacities, carbon ad-
Responsible editor: Tito Roberto Cadaval Jr sorbents are often modified. To data, there have been numer-
ous modification methods for carbon materials. Hummers,
* Yingwen Xue Brodie, and Staudenmaier methods are three graphene modi-
[email protected] fication methods (Sofer et al. 2015). These synthesis ways
lead to a grapheme oxide product with varying C/O ratios
1
School of Civil Engineering, Wuhan University, Wuhan, China and oxygen functionalities on graphene basal planes and edge
 Environ Sci Pollut Res

sites. Therefore, these modification methods can make signif- capacity was 24.8 mg/g. Zhang et al. (2013) prepared Mg–
icant influences on the adsorption capacities of graphene. Al layered double hydroxides biochar and this biochar was an
Oxidation, alkali activation, and modification with other com- effective sorbent for the removal of phosphate. Wang et al.
ponents are common chemical modification methods to im- (2016) used hydrochloric acid as post modifying agent to
prove nanotubes’ properties. In these processes, various func- modify biochar to enhance nitrate removal in constructed wet-
tional groups can be generated or introduced onto nanotube land, whose adsorption capacity was 14.67 mg/g. They dis-
surfaces (at tips and sidewalls) for the removal of environmen- covered zeta potentials of the biochar increased from − 12.23
tal contaminants (Sarkar et al. 2018). In the modification of to + 5.46 mV after modification. It had been reported in some
activated carbon, thermal contraction (Qiu et al. 2017) and articles that positive zeta potential led to high anion adsorption
vapor activation (Lu et al. 2016) are aimed to increase the capacity. Zhang et al. (2016) used Fe2+/Fe3+ to modify hya-
surface area or adjust pore structure and its distribution. Due cinth biomass and then prepared modified biochar with low
to the effects of functional groups and chemical constitution positive-charged surface to remove arsenate and obtained a
on adsorption, chemical modifications are mainly used to capacity of 7.4 mg/g, which is attributed to the unique iron
change the surface acidity and basicity, introduce or remove substances formed by novel modification. Jung et al. (2017)
functional groups (Long et al. 2017). prepared a novel magnesium ferrite biochar and used it to
Biochar, an emerging carbon adsorbent, possesses a great remove phosphate. The pHpzc of the modified biochar is
adsorption capacity to many contaminants (Liu et al. 2016b; 8.52. Nevertheless, these papers have neither discussed the
Yao et al. 2011; Yu et al. 2016). The modifications of biochar possible modifying principle to increasing the surface charge,
are divided into pre- and post-modification. These make the nor determined the relationship between surface charge and
biochar physical structure and chemical component changed, adsorption capacity. Therefore, the goal of this work is aimed
which is helpful for adsorption process. To date, previous to clarify the modification principle to further increase the
articles indicated that most of the unmodified and modified positive surface charge on biochar and then use the modified
biochars possessed negative charge on the surface (Yao et al. biochar to remove anions, especially nitrate.
2011). Therefore, it has been demonstrated that biochar is a Based on the conclusions of previous researches, the spe-
wonderful adsorbent for cationic pollutants, especially metal cific objectives of this work are to (1) study the effect of
ions (Xiao et al. 2017) because of its negative charged surface. different modifying agents on biochar’s ability to remove ni-
Most modifications have been mainly aimed to increase the trate; (2) analyze the relationship between surface charge and
negative charge so that the adsorption capacities can be im- adsorption capacity and thus reveal the modification principle;
proved. Ding produced engineer biochar from hickory wood and (3) clarify the adsorption mechanism of biochar to anions.
and then further modified with NaOH (Ding et al. 2016). After
modification, the modified biochar exhibits much larger metal
adsorption capacities than the pristine biochar. Creamer used Materials and methods
metal ions to treat feedstocks to produce metal oxyhydroxide-
biochar composites and these modified biochars effectively Materials
capture CO2 (Creamer et al. 2016).
There are only few studies on anions adsorption on biochar. All the chemical reagents of analytical grades in this experi-
According to previous articles, the mechanisms of biochar to ment were acquired from Sinopharm Chemical Reagent Co.,
remove anions can be divided into three types: precipitation Ltd, and the corncob was from a local farm (Wuhan, China).
(chemical reaction occurrence), electrostatic attraction (sur- Deionized water was used to prepare chemical solutions.
face charge domination), and physical adsorption (high sur-
face area determination) (Jung et al. 2017; Wang et al. 2016; Biochar production
Yao et al. 2012; Zhang et al. 2016). The challenge of nitrate
removal is due to the high soluble ability of nitrate. For other The feedstock (corncob) was rinsed and then dried in a drying
common anions like phosphate, the immobilization could be oven at the temperature of 80 °C (Liu et al. 2016b). To prepare
easy to achieve by the chemical reactions of some metal ions. pristine biochar, the corncob sample was pyrolyzed in quartz
But for nitrate, little chemical precipitation methods could be tubes at the temperature of 600 °C with N2 flowing for 2 h.
used to immobilize nitrate. The black remainder (bulk biochar) in the quartz tube was
Previous studies have investigated the impact of surface ground and then sieved to a uniform size of 0.9~1.2 mm.
charge of biochars is sorption of anions. Wan et al. (2017) Finally, the ground biochar was rinsed by DI water, dried,
examined phosphate adsorption of bamboo biochar function- and stored for adsorption experiments (Gao et al. 2015; Hu
alized with varying amount of Mg–Al layered double hydrox- et al. 2018b). To prepare modified biochars, eight samples of
ides. Xue et al. (2016) used Mg–Fe layered double hydroxide corncob were respectively dipped in 1 mol/L modifying agent
biochar to remove nitrate and the maximum adsorption solutions (HCl, NaCl, KCl, MgCl2, ZnCl2, AlCl3, FeCl3,
Environ Sci Pollut Res

MgCl2 with HCl) for 24 h with the impregnation ratio of or HCl (0.01 mmol/L, 1 mmol/L, and 100 mmol/L) solutions
3 g:1 g. The modified feedstocks were treated the same way and measured by a pH meter (FE20, Mettler Toledo
as the pristine ones to prepare the modified biochars. Finally, (Shanghai) Co., Ltd.).
these nine biochars were labeled as CC, H-CC, Na-CC, K-CC,
Mg-CC, Al-CC, Fe-CC and H + Mg-CC, respectively.
Mathematical models
Characterization
Sorption kinetics of NO3− (50 ppm) onto the biochar were
The surface charge was obtained using a zeta potential ana- evaluated by the similar process as static test. What was dif-
lyzer (Zetasizer Nano ZS, Malvern, UK). The element analy- ferent was that the adsorption time changed to 0.5, 1, 2, 5, 10,
sis was measured by element analyzer (Vario EL III, 15, 20, 24, 48 h. The pseudo-first-order, pseudo-second-order,
Elementar, German) and the specific surface areas were mea- and Elovich models were used to simulate the sorption kinet-
sured by a surface area analyzer (TriStar II 3020, ics data and their governing equations can be written as
Micromeritics, USA). The surface morphology was obtained (Eeshwarasinghe et al. 2018):
using a scanning electron microscopy (SEM, JEM-6700F,

Hitachi Limited, Japan). Fourier transform infrared spectros- Pseudo−first−order : qt ¼ qe 1−e−k 1 t ð3Þ
copy (FTIR, NICOLET 5700, Thermo Electron Corporation,
USA) was used to determine the surface functional groups on k 2 q2e t
Pseudo−second−order : qt ¼ ð4Þ
the biochars. The crystalline minerals if the biochar samples 1 þ k 2 q2e t
were investigated by a computer controlled X-ray diffractom-
eter (XRD, PANalytical, X’Pert Pro, Netherlands). 1
Elovich : qt ¼ lnðαβt þ 1Þ ð5Þ
β
Static adsorption test
where qt and qe are the amount of sorbate removed at time t
0.1 g biochar was added into 50 ml NO3− solution (100 ppm).
and at equilibrium, respectively (mg/g); k1 and k2 are the first-
After being shaken in the mechanical shaker (120 r/min) at the
order and second-order sorption rate constants (h−1), respec-
temperature of 30 °C for 24 h, the mixture was filtered through
tively; α is the initial sorption rate (mg/g) and β is the desorp-
0.22-μm membrane filter to achieve solid-liquid separation.
tion constant (g/mg), the Elovich model is an empirical fitting
Concentrations of NO3–N were determined by the ion chro-
equation.
matograph (882 Compact IC plus; Metrohm, Herisau,
Adsorption isotherms of NO3–N onto the biochar were
Switzerland).
evaluated by a process similar to the kinetic test. The different
The adsorption amount q (mg/g) and adsorption removal
was that the initial NO3–N concentration was changed to 50,
rate R (%) of nitrate were calculated by formula (1) and for-
100, 250, 400, 600, 750, 900, 1000, and 1500 ppm. The sorp-
mula (2) based on the difference between the initial and final
tion isotherms were simulated by the Langmuir and
aqueous concentrations (Tanboonchuy et al. 2011):
Freundlich models, whose governing equations can be written
ðC 0 −C e ÞV as (Tytak et al. 2015):
q¼ ð1Þ
m KS max C e
C 0 −C e Langmuir : qe ¼ ð6Þ
R¼  100 ð2Þ 1 þ KC e
C0
Freundlich : qe ¼ K f C 1=n ð7Þ
where C0 and Ce are the initial and equilibrium concentra- e

tion of nitrate solution respectively (mg/L); m is the weight of

biochar adsorbent (g); and V is the volume of solution (ml). where K and Kf are the Langmuir bonding term correlated
with interaction energies (L/mg) and the Freundlich affinity
Effect of pH, reaction temperature, and coexisting coefficient ((mg/g) (1/mg)1/n), respectively; Smax is the
anions Langmuir maximum capacity (mg/g), Ce is the equilibrium
solution concentration (mg/L) of the sorbate, and n is the
The influence of three environmental factors on nitrate remov- Freundlich linearity constant. The Langmuir model assumes
al was studied (Table 1). The initial nitrate concentrations that monolayer adsorption onto a homogeneous surface with-
were all 100 ppm and the shaking speeds were all 120 r/min out interactions between the adsorbed molecules. The
with the reaction time of 24 h. Various pH, temperature, and Freundlich model commonly used for heterogeneous surface
coexisting anions were evaluated. pH was adjusted by NaOH as an empirical equation.
 Environ Sci Pollut Res

Table 1 Experiment of
influencing factors Influencing factors Method Value

Coexisting anions Preparing Cl−, CO32−, PO43− solutions Every solute concentration was 100 mg/L
pH Using pH meter 3, 5, 7, 9, and 11
Reaction temperature Adjusting mechanical shaker temperature 15 °C, 25 °C, 30 °C, 35 °C, and 45 °C

Results and discussion acidic, the influence of MgCl 2 agents with HCl was
assessed. There was a slight increase of zeta potentials
Comparison of biochars after acid treatment. This indicates that at acidic solution,
the modification efficient was improved to some extent.
Previous studies have demonstrated a positive correlation Furthermore, there were distinct differences of adsorption
between the adsorbent surface charge and its zeta poten- capacity among different modified biochars. The adsorp-
tial (Calero et al. n.d.; Patwardhan et al. 2012). In this tion capacities of Zn-CC, Al-CC, and Fe-CC were all
work, the surface charge of modified biochars was deter- beyond 9.5 mg/g; while those of Na-CC, K-CC, and
mined by measuring zeta potential at neutral pH. These Mg-CC were limited (below 2 mg/g). It is indicated in
modified biochars could be obviously divided into three Fig. 2 that with the increase of zeta potential, the adsorp-
groups (Fig. 1). K-CC and Na-CC were both around − tion capacity increased. Notably, there was an abrupt
50 mV, Zn-CC and Mg-CC were both around − 10 mV, jump around − 9 mV. This implies that the zeta potential
and Al-CC and Fe-CC were around + 35 mV. This obser- played a vital role in adsorption until it reached around −
vation indicates that the zeta potential of modified biochar 9 mV. As the zeta potential rose above − 9 mV, the elec-
was dominated by modifying agents. The different modi- trostatic repulsion resulted from negative surface charge
fying agents led to huge differences in zeta potential, but was not dominative in the adsorption and other factors
not all metal modification increased the zeta potential. caused the significant increase.
Compared with pristine biochar (− 23.73 mV), the higher Compared with pristine biochar, the C content of all mod-
valence of modifying metal caused more increase of zeta ified biochars decreased while H and N contents were stable
potential, even making it become positive (+ 42.67 mV of (Table 2). After modification, the relevant metal content sig-
Fe-CC and + 29.00 mV of Al-CC). This implies that the nificant increased, making the zeta potential increase in some
surface charge of modified biochars were most attributed sense. The slight difference of element contents between H +
to the metal valence rather than the metal group. Mg-CC and Mg-CC indicated that acidic condition was in
Considering some solutions of modifying agents were favor of the formation of metal substance onto modified bio-
char. Among these modified biochars, higher valence metal
elements seemed to introduce more corresponding metal ele-
ment content onto the modified biochars. This observation is
consistent with the analysis in zeta potential that the higher
valence of modifying metal led to higher Zeta potential. The
Fe content in Fe-CC reached 8.795%. This constituted a basic

12
Test data Fe
fitting line Zn
10
Al
Adsorption (mg/g)

Mg
Na 2

K
-60 -40 -20 0 20 40 60
Zeta potential
Fig. 1 The zeta potentials and nitrate adsorption capacities of different
modified biochars Fig. 2 The comparison of different modified biochar with zeta potential
Environ Sci Pollut Res

Table 2 The element

composition of different biochars Adsorbent Element content (mg/g)

C N H Na K Mg Zn Al Fe

CC 85.14 0.39 1.76 0.1975 1.0325 0.0775 0.02225 0.01175 0.135

Na-CC 83.24 0.36 1.69 2.0075
K-CC 84.34 0.38 1.90 1.985
Mg-CC 79.67 0.34 1.80 5.465
Zn-CC 73.59 0.50 1.75 5.9
Al-CC 61.37 0.36 1.22 3.335
Fe-CC 75.52 0.43 1.80 8.7975
H + Mg-CC 74.96 0.35 1.59 6.0975

foundation to the highest surface charge in the analysis of zeta metal structures (Fe2O3, MgAl2O4, MgO, ZnO) were in
potential (Yao et al. 2011), making high anion adsorption ca- favor of the increase of zeta potentials and the surface area
pacity feasible. in some extent (Long et al. 2017; Zhang et al. 2012). The
The specific surface area analysis showed that modification ZnO formed on Zn-CC and the MgO formed on Mg-CC
had huge influence on surface morphology of the biochars. just increased the zeta potentials from − 20 to − 9 mV.
Compared with CC, some modified biochars (Mg-CC, Zn-CC, MgAl2O4 is a double oxide structure and this special metal
Al-CC, Fe-CC) had higher surface area, while Na-CC and K- structure might lead to the positive surface charge of Al-
CC had lower. This difference is partly similar to the observa- CC (Cosimo et al. 1998; Wan et al. 2017). This positive
tions in surface charge analysis that Mg-CC, Zn-CC, Al-CC, surface charge (+ 29 mV) play a role in adsorption of ni-
and Fe-CC possessed higher zeta potential than that of pristine trate. Fe2O3 significantly increased the surface charge to +
CC, while those of Na-CC and K-CC were lower (Fig. 2). 43 mV and there was a peak of iron nitrate hydrate
XRD testing was applied to determine the crystallinity (Fe(NO3)3·9H2O) in Fe-CC after nitrate adsorption, which
and type of metal component in the samples. Compared might explain the highest adsorption capacity of Fe-CC.
with pristine biochar, there were some new-formed metal The FTIR spectra (Fig. 4) show that biochars pos-
dioxide structures on the modified biochars (Fig. 3). These sessed abundant functional groups. All modified biochars

Fig. 3 XRD analysis of biochars:

a CC and Fe-CC, b Al-CC, c Mg-
CC, and d Zn-CC
 Environ Sci Pollut Res

100
Fig. 4 FTIR spectrum of
before adsorption of Fe-CC
biochars: a CC and Fe-CC, b Al- after adsorption of Fe-CC
CC, c Mg-CC, and d Zn-CC 90 3440
1085

% Transmittance
80

70
3430
1380
60
(a) 1090

50
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm-1)

possessed the O–H (around 3435) stretching and the C– 2014), which is indirectly confirmed in Fig. 4d. The iron
O stretch (around 1080) (Xue et al. 2012). After adsorp- nitrate hydrate (Fe(NO3)3·9H2O) generated after the ad-
tion, the peak observed at 1380 cm−1 in Fig. 4a, b, d sorption of Fe-CC is a coordination compound. By com-
designates nitrate (Choe et al. 2010; Sembiring et al. paring the effect of these modified biochar, the best bio-
2014), indicating Fe-CC and Al-CC with positive surface char (Fe-CC) was selected as adsorbent to remove
charge were much easier to attract nitrate anions. Taking nitrate.
the similarities of Zn-CC and Mg-CC in the analyses of
zeta potential, BET and XRD into consideration, the met- Modifying principle
al Zn probably formed coordination compound (De et al.
These observations indicate that modification played a crucial
11 part in preparing modified biochars for nitrate removal. Metal-
10 modifying agents are high likely to fix metal ion on the bio-
Test data
9 chars by forming metal oxide and this makes a huge influence
8 12
Adsorption (mg/g)

7
10
6
5 8
Adsorption (mg/g)

Test data
4
6
3
4
2
1 2
0
None Cl- CO32- PO43- 0
2 4 6 8 10 12
Co-existing anions pH

Fig. 5 Effect of coexisting anions on the adsorption of Fe-CC Fig. 6 Effect of pH on the adsorption of Fe-CC
Environ Sci Pollut Res

12
Test data Table 3 Kinetic parameters of nitrate adsorption by Fe-CC
10 Kinetics Parameters

8 qe (mg/g) k (h-1) α (g/mg) β (mg/g) R2

Adsorption (mg/g)

6 Pseudo-first-order 9.027 0.516 – – 0.773

Pseudo-second-order 10.030 0.071 – – 0.902
4
Elovich – – 20.858 0.561 0.978
2

0
20 25 30 35 40 6). The increase in pH had little influence on the adsorp-
tion and the adsorption capacity of nitrate onto Fe-CC
Fig. 7 Effect of temperature on the adsorption of Fe-CC was steadily with values all beyond 9.5 mg/g. Although
pH increased, the Fe-CC possessed several properties,
on properties of modified biochars. Metal oxide structure is in such as huge surface area, high positive surface charge,
favor of the increase of specific surface area and zeta potential. and unique multilayer electrons, to maintain adsorption
Metal valence plays a vital role and higher metal valence capacity. This was vital for Fe-CC to be used to treat real
meant higher surface area and higher zeta potential. High- wastewater whose pH varies from acidity to alkalinity.
specific surface area is beneficial for surface adsorption. Changes in reaction temperature only slightly affected the
Meantime higher zeta potential means higher surface charge, adsorption of nitrate onto Fe-CC (Fig. 7). The capacity only
which is helpful for electrostatic attraction. In addition, some decreased slightly with the increase of temperature from 20 to
metal content which possessed multilayer electrons possibly 40 °C. This endurance of temperature changes made Fe-CC
formed special component such as coordination compound in suitable in real water treatment.
the adsorption process, which made corresponding modified
biochar have higher adsorption capacities. Therefore, metal
possessing multilayer electrons with higher valence was a Adsorption kinetics and isotherms
better modifying agent for the adsorption to anions.
The pseudo-first-order, pseudo-second-order, and Elovich
Effect of coexisting anions, pH, and adsorption models were applied to describe the kinetics of nitrate
temperature adsorption (Fig. 8). The model results of kinetic data are
presented in Table 3. High correlation coefficient value
It is common that nitrate is coexisting with Cl−, CO32−, and (R2 = 0.978) suggest good agreement between the experi-
PO43− in the wastewater. These three coexisting anions had mental data and fitting curve of Elovich, confirming that
different valences. All anions made negative influences on the adsorption of nitrate onto Fe-CC followed the Elovich
nitrate adsorption on the biochars (Fig. 5). With the increase model best. While the correlation coefficients of the
in negative charge of anions, the surface charge decreased and pseudo-first- and second-order were only 0.773 and
less adsorption sites were available to nitrate so the adsorption 0.902 respectively. Similar results about anions adsorption
capacity declined. This indicated that adsorption process of were obtained in the removal of trichloroacetic acid on
Fe-CC was influenced by electrostatic attraction (Wang et al. modified biochar derived from crayfish shell (Long et al.
2015). 2017).
The effect of solution pH on the removal of nitrate was 35
studied by varying the initial pH between 3 and 11 (Fig.
30
12
25
10
qe (mg/g)

20
8
qe (mg/g)

15 Test data
1st
6 order
10 Langmuir
4 2nd
order 5
2
0
0 0 300 600 900 1200 1500
0 4 8 12 16 20 24
t (h) Ce (mg/L)
Fig. 8 Kinetics of nitrate adsorption onto Fe-CC Fig. 9 Isotherm of nitrate adsorption onto Fe-CC
 Environ Sci Pollut Res

Table 4 Isotherm parameters of nitrate adsorption by Fe-CC following reaction in the adsorption, which led to the high
Isotherm Parameters adsorption capacity of Fe-CC onto nitrate.

qe (mg/g) K (L/mg) Kf (mg(1−n)Ln/g) n (mg/g) R2

Fe2 O3 þ 3H2 O→2FeðOHÞ3
Langmuir 32.33 0.005 – – 0.947
FeðOHÞ3 þ 3NO−3 þ 9H2 O→FeðNO3 Þ3  9H2 O þ 3OH−
Freundlich – – 2.332 0.354 0.932
The high surface charge indicates that Fe-CC was a
perfect adsorbent to remove anions for electrostatic attrac-
tion. The multiple electrons of Fe led to the formation of
coordination compound (Fe(NO3)3·9H2O). In addition,
To determine the maximum adsorption of Fe-CC for the considerably huge specific surface area in Table 5
nitrate, the modified biochar was contacted with varying indicates that surface adsorption played a role in the re-
initial concentrations (50–1500 ppm) of nitrate. The pat- moval process.
tern of adsorption process is shown in Fig. 9. The adsorp-
tion capacity increased with the increasing initial concen-
tration. Saturation started to establish when the equilibri- Conclusion
um concentration was about 800 ppm. Langmuir and
Freundlich models were applied to evaluate the experi- In this work, different metal modifying agents were ap-
ment data and the fitting results are showed in Table 4. plied to treat the corncob. Metal modifying agents fixed
The best fitted model was Langmuir model whose corre- metal ion on the biochars by forming metal oxide struc-
lation coefficient was 0.947, while the coefficient of tures. This increased specific surface area and surface
Freundlich model was 0.932. According to the Langmuir charge, leading to high adsorption capacity to anions.
model, maximum sorption capacity of Fe-CC to nitrate Metal possessing multilayer electrons with higher valence
was 32.33 mg/g. This result indicates that the nitrate re- was a better modifying agent. Fe-CC with the highest zeta
moval belonged to monolayer sorption (Xu et al. 2017). potential among these modified biochars showed the
highest nitrate adsorption capacity. After modification,
Fe2O3 was generated on the surface and nitrate anions
Adsorption mechanism
were absorbed on Fe-CC. As a result, Fe2O3 was trans-
formed to fix the nitrate by forming iron nitrate hydrate
Compared with pristine biochar, Fe-CC had a new crystal of
(Fe(NO3)3·9H2O). Based on results of the Langmuir mod-
Fe2O3. This was attributed to the FeCl3 modification, which
el, the maximum capacity of Fe-CC to remove nitrate was
can be probably described as:
32.33 mg/g, which is much higher than those of previous-
2FeCl3 þ 3H2 O→Δ Fe2 O3 þ 6HCl ly reported adsorbents. For future application, Fe-CC
ought to be studied to simultaneously remove nitrate, or-
The difference in the XRD and FTIR analysis before ganic pollutants, and other natural common contaminants.
and after adsorption of Fe-CC demonstrates that there Desorption and column studies will be conducted. And
was iron nitrate hydrate (Fe(NO3)3·9H2O) on the biochar these adsorbents have potential application to soil
surface after adsorption. The new substance was due to the remediation.

Table 5 The specific surface area

and pore structure of different Biochars BET surface The micropore The total pore Micropore The average
biochars area (m2/g) area (m2/g) volume (cm3/g) volume (cm3/g) pore size (nm)

CC 129.65
Na-CC 37.18
K-CC 82.90 68.98 0.05 0.04 48.96
Mg-CC 249.56 204.05 0.15 0.11 77.80
Zn-CC 230.86 184.48 0.12 0.09 32.05
Al-CC 148.37
Fe-CC 155.08
H + Mg-CC 301.81 252.94 0.18 0.13 48.54
Environ Sci Pollut Res

Acknowledgments The authors thank the anonymous reviewers for their possessed ZnO nanoparticles to remove trichloroacetic acid. J
invaluable insight and helpful suggestions. Clean Prod 166:1244–1252
Lu X, Jiang J, Sun K, Zhu G, Lin G (2016) Enhancement of Pb2+
Funding information This work was partially supported by the removal by activating carbon spheres/activated carbon composite
Fundamental Research Funds for the Central Universities (No. material with H2O vapor. Colloids Surf A Physicochem Eng Asp
2042016kf0173) and the Wuhan Water Engineering & Technology Co. 506:637–645
Ltd. Patwardhan SV, Emami FS, Berry RJ, Jones SE, Naik RR, Deschaume O,
Heinz H, Perry CC (2012) Chemistry of aqueous silica nanoparticle
surfaces and the mechanism of selective peptide adsorption. J Am
Chem Soc 134:6244
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