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Manuscript_23f4db3609bdb72dc08f3e08c9e2d303

1 Removal of 2,4,6-trichlorophenol from water by Eupatorium adenophorum

2 biochar-loaded nano-iron/nickel
3 Guo Liua,b,c*1，Haoran Tanga,b,c,1，Jiajun Fana,b,c，Zhihao Xiea,b,c， Tianyu Hea,b,c，Rui Shia,b,c，Bing

4 Liaoa,b,c
5 a. State Key Laboratory of Geohazard Prevention and Geoenvironment Protection，
6 Chengdu,610059,.China
7 b. State Environmental Protection Key Laboratory of Synergetic Control and Joint Remediation for
8 Soil&Water Pollution SEKL-SW，Chengdu,610059,China
9 c. Chengdu University of Technology, College of Environment and Ecology, Chengdu,610059,China
10 Abstract: From the perspective of waste utilization, the invasive species, Eupatorium
11 adenophorum was used to prepare biochar, which was then loaded with iron/nickel
12 bimetals. Compared with pure biochar, the biochar-loaded nano-iron/nickel bimetals
13 have a significant effect on the removal of 2,4,6-trichlorophenol (2,4,6-TCP) from water,
14 and their degradation rate can be increased by 39.7%-71.6% under different conditions.
15 Several factors can influence the removal of 2,4,6-TCP, including the load ratio, pH of
16 the solution, concentration of 2,4,6-TCP, and coexisting ions in water (HCO3-, SO42-,
17 NO3-). Based on the density functional model (DET), Ni can activate H2 (produced in
18 the reaction between nano-Fe and H2O) to convert to H*, which can then substitute Cl.
19 The activation energy is 109.5 kJ/mol, indicating the reaction is easy to take place.
20 Keyword: Eupatorium adenophorum, biochar, nano-iron/nickel, 2,4,6-trichlorophe

*Corresponding author at: Chengdu University of Technology, Sichuan 610059, Tel.:13308000115 ,

E-mail：liuguo@cdut.edu.cn
1 These authors contributed to the work equally and should be regarded as co-first authors..
© 2019 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
 1 1.Introduction
2 Biochar is a porous carbonaceous material produced through thermal cracking of
3 organic matter under anoxic conditions (Ahmad et al., 2012; Van et al., 2017). As the
4 most commonly used and effective adsorbent, biochar has been widely studied (Lee et
5 al., 2018; Zhang et al., 2018; Mohan et al., 2014). Biochar has high adsorption capacity
6 due to its large surface area and available functional groups (Hammes et al., 2019). The
7 biomass becomes stable after pyrolysis. There is less carbon returned in the atmosphere
8 through the biochar production than the natural degradation of biomass. In addition,
9 biochar is a good way of storing carbon dioxide and other types of greenhouse gas (Sohi
10 et al., 2010). The biochars produced by woody and herbaceous biomass contain more
11 carbon than those produced by sludge and livestock manure (Kameyama et al., 2016). In
12 China, Eupatorium adenophorum is in the first rank of invasive alien species (Yan et al.,
13 2012), which causes serious ecological damage. As one of the herbaceous biomass,
14 Eupatorium adenophorum can be utilized to prepare biochar as an absorbent. Therefore,
15 the biological value of Eupatorium adenophorum can be achieved as well as ecosystem
16 protection and comprehensive utilization of waste.
17 Biochar is particularly effective for the adsorption of immobilized organic
18 compounds, such as pesticides (Liu et al., 2018), oxyfluorfen (Wu et al., 2019),
19 glyphosate (Hall et al., 2017), and antibiotics (Jiang Et al., 2018). Along with the
20 pyrolysis temperature increases, the content of carbon in the biochar increases while the
21 contents of hydrogen and oxygen decrease, which results in the decreased polarity of the
22 biochar (Godlewska et al., 2017). The lower the oxygen content on the surface of
23 biochar is, the stronger the π-π effect on the aromatic organic matter is, which enhances
24 the adsorption of organic matter. While the oxygen content on the surface of biochar is
25 high, the proton in water and the oxygen functional group in biochar are bonded through
26 hydrogen bonding, which occupies the adsorption site on the surface of the biochar and
27 competes for the adsorption with the organic substance. As a result, the adsorption of
28 organic matter by the biochar is inhibited (Zhu et al., 2005). Chlorophenols (CPs) are
29 organic compounds formed by replacing all of the expected hydrogen atoms in the
30 hydroxyl groups with chlorine atoms. They are highly toxic, persistent and
31 bioaccumulative (Barik & Gogate, 2018). 2,4,6-trichlorophenol (2,4,6-TCP) is one of
32 the chlorophenolic organic compounds, which tends to contaminate groundwater by
33 leaching after transferred to the soil (Danis & Albanis, 1996). Biochar has a strong
34 adsorption capacity for chlorophenols (Lang et al., 2014). However, the application of
35 the traditional biochar is just limited to the pollutant adsorption. If the surface of the
36 biochar is modified, more excellent performances can be obtained.
37 Nanoscale zero-valent iron can efficiently reduce and degrade chlorinated alkanes
38 (Arnold & Roberts, 2000), chlorinated olefins (Clark et al., 2003), organochlorine
39 pesticides (Sayles & You, 1997), chlorinated aromatic compounds (Kim & Carraway,
40 2000), and other organic matters. Through the high-efficiency reduction by the
41 nanoscale zero-valent iron, organic pollutants are converted to small molecules or
42 biodegradable organic substances, and the toxicity of pollutants to microorganisms is
 1 highly reduced. Compared to the traditional restoration techniques, this technique is
2 more efficient for the in situ remediations of groundwater and soil (Song et al., 2008). In
3 addition, another metal (Pd, Ni, Ag, Co, etc.) is often doped on the surface of nanoscale
4 zero-valent iron (Ghauch et al., 2010; Yan et al., 2013) to promote the electron transfer
5 between Fe0 and the target contaminants through a galvanic mechanism, which results
6 in higher reactivity and more completed degradation. However, through the aggregation
7 of the bimetallic particles induced by the high surface energy and the intrinsic magnetic
8 action, the nanoparticles with chain structures are produced, which cause a significant
9 decrease in catalytic reactivity.
10 Various nanoscale iron-supported materials, including montmorillonite, bentonite,
11 vermiculite, silica, etc., have been used as fixed nanoparticles to remove contaminants
12 from aqueous solutions (Gao, 2017; Wan, 2014; Wang, 2013; Mishra et al., 2017).
13 Using the fixed nanoparticles can effectively prevent the agglomeration of nanoscale
14 zero-valent iron, while the contact area between materials and pollutants can increase.
15 In this study, Eupatorium adenophorum was used as a raw material for biochar. The
16 biochar was loaded with the bimetallic nanoparticles to alleviate the agglomeration
17 between nanoparticles. In addition, compared with pure biochar that can only adsorb
18 2,4,6-TCP (Mubarik S., et al., 2016) or metals that can only degrade 2,4,6-TCP
19 (Christoforidis K C., et al., 2011), the biochar-loaded bimetallic nanoparticles can
20 achieve a better effect on 2,4,6-TCP removal through adsorption as well as reduction
21 and degradation. In the process of ecological environmental restoration and control, the
22 waste that Eupatorium adenophorum was used as a raw material of biochar. This
23 realizes the waste utilization and has massive economic and environmental benefits.
24 2 Methods
25 2.1 Preparation of biochar from Eupatorium adenophorum
26 Eupatorium adenophorum was used as the raw material to prepare biochar (EaB).
27 First, Eupatorium adenophorum was placed in a wide-mouth bottle and rinsed with
28 water to remove the sundries. The dried Eupatorium adenophorum was pulverized, then
29 the Eupatorium adenophorum powder was put into the ceramic crucible and compressed.
30 After that, the ceramic crucible was covered with a lid and placed in a muffle furnace.
31 The inner chamber of the muffle furnace was purged with N2 for 10 minutes. Then the
32 muffle furnace was heated to the endpoint temperature for the thermal cracking, 600 °C
33 (the highest pyrolysis temperature under the temperature limit of thermal cracking), at
34 the rate of 5 °C/min. The endpoint temperature was maintained for 2 h. After a natural
35 cooling process, the biochar was taken out from the muffle furnace and then washed
36 with 1 mol/L hydrochloric acid (GR) for 6 h. Then the biochar was washed with
37 ultrapure water to a chlorine-free ion, dried in an oven at 60 °C, and sieved (60 mesh).
38 2.2 Preparation of biochar-loaded nano-iron/nickel
39 The biochar-loaded nano-Fe/Ni materials (EaB-Fe/Ni) were prepared by
40 liquid-phase synthesis (Shi, 2011) by using the biochar from Eupatorium adenophorum.
 1 First, N2 was introduced into a three-necked flask to ensure that the preparation
2 environment was an oxygen-deficient environment. Then 1 g of FeSO4·7H2O (AR) was
3 dissolved in 90 mL of the hydroalcoholic system (ultra-pure water and absolute ethanol
4 (AR) at the volume ratio of 6:3). The solution was placed in the treated three-necked
5 flask and stirred at 500 rpm/min with an electric agitator. After the FeSO4·7H2O was
6 dissolved, 0.1 g, 0.2 g, 0.4 g, and 0.8 g of EaB particles were continuously stirred to
7 prepare the materials with various loading ratios of 2: 1, 1:1, 1:2, 1:4 (mass ratio of
8 Fe/Ni to biomass). Then 0.36 g of NaBH4 (AR) was dissolved in 10 mL of ultrapure
9 water and added into the three-necked flask by a peristaltic pump (AB08) at a rate of 2
10 mL/min to reduce Fe2+ to Fe0. After 10 minutes, 1 ml of 9.29 g/L NiCl2 solution was
11 added dropwise to ensure the molar ratio of Ni:Fe to be 2%. Through displacement
12 reaction, Ni was produced from Ni2+ on the surface of nano-zero-valent iron. During the
13 experiment, N2 was continuously passed to the three-necked flask to ensure anoxic
14 environment and the stirring lasted for 30 minutes until the end of the reaction. The
15 obtained EaB-Fe/Ni was first washed with absolute ethanol once and then washed with
16 ultrapure water repeatedly until there was no Cl-. The EaB-Fe/Ni was then collected
17 with a magnet and dried in a vacuum drying device. The ultrapure water used in the
18 reaction was exposed to N2 for deoxidation treatment. Using this method, Eupatorium
19 adenophorum biochar-loaded nano Fe/Ni materials with the load ratios of 2:1, 1:1, 1:2,
20 1:4 were prepared.
21 2.3 Characterization of materials
22 The gold spraying treatment was applied to the materials of EaB-Fe/Ni with the
23 various load ratios, nano-Fe/Ni, and EaB to enhance their conductivity. These materials
24 were observed by a scanning electron microscope (S-4800, HITACHI) with 5 kV of the
25 voltage. Before and after the reaction between EaB-Fe/Ni (load ratio of 1:2) with
26 2,4,6-TCP, the element type and valence state in the reaction system were qualitatively
27 analyzed by using X-ray photoelectron spectroscopy (esca lab 250Xi, Thermo). The
28 crystal morphology, chemical composition, and existing form of EaB-Fe/Ni (load ratio
29 of 1:2) were analyzed by using X-ray diffractometer (X`Pert Pro, PANalytical B.V.).
30 2.4 Adsorption experiment
31 2.4.1 Impact of load ratio
32 In the experiment, 1 g/L (calculated with the mass of iron) pure nano-Fe/Ni, four
33 types of EaB-Fe/Ni with different load ratios of 2:1, 1:1, 1:2, 1:4, and EaB were used to
34 remove 2,4,6-TCP (20 mg/L). 2,4,6-TCP in solution was detected by high-performance
35 liquid chromatography (1260, Agilent Technologies Inc.) and Cl- in the solution were
36 detected by ion chromatography (861-Adwanced Compact IC, Metrohm). Cl- was
37 measured at 120 minutes of the reaction.
38 2.4.2 Effect of 2,4,6-trichlorophenol concentration
39 In the experiment, 2 g/L (calculated with the mass of iron) of EaB-Fe/Ni (load ratio
 1 of 1:2, nickel doping ratio of 2%) was used to remove the 2,4,6-TCP. The initial pH of
2 the solution was 6 and the ambient temperature was 20 °C. The initial concentrations of
3 2,4,6-TCP were 10, 20, 50, 100, 200 mg/L.
4 2.4.3 Effect of pH of the solution
5 In the experiment, 2 g/L (calculated with the mass of iron) of EaB-Fe/Ni (load ratio
6 of 1:2, nickel doping ratio of 2%) was used in the experiment to remove 20 mg/L of
7 2,4,6-TCP. The pH values of the solutions were set to 3, 5, 7, 9, and 11, respectively.
8 The ambient temperature was 20 °C.
9 2.4.4 Effect of coexisting ions
10 In the real water environment, there are multiple ions to interfere with the reaction.
11 Previous studies have found that SO42-, HCO3- and NO3- can inhibit the reduction
12 performance of Fe0. In this experiment, SO42-, HCO3- and NO3- were selected as the
13 coexisting ions to investigate the effect of coexisting ions on the removal of 2,4,6-TCP
14 by EaB-Fe/Ni. The initial concentration of 2,4,6-TCP was controlled to be 20 mg/L, the
15 reaction temperature was 20 °C, the pH was 6, and the dosage of EaB-Fe/Ni was 2 g/L.
16 The concentrations of ions were set as follows: 100 mg/L of SO42-, 100 mg/L of HCO3-,
17 and 50 mg/L of NO3-.
18 2.5 Adsorption kinetics
19 The solid-liquid chemical reaction taking place on the solid surface was fitted by
20 the Langmuir-Hinshelwood kinetic model (Alvarez-Ramirez et al., 2015), which can be
21 expressed as the follow equation:
1 1 1 1
22
r0
=k ×C +k (1)
1 k2 0 1

23 where r0 is the average reaction rate in the first 90 minutes in the unit of
24 mg(Lmin)-1, C0 is the initial concentration of 2,4,6-TCP in the unit of mg/L, k1 is the
25 reaction rate constant in the unit of mg(Lmin)-1, k2 is the Langmuir adsorption constant
26 in the unit of L/mg. In addition, 1/C0 and 1/r0 were plotted and linearly fitted.
27 2.6. Reaction pathway
28 Since biochar itself has strong adsorption capacity for chlorophenols, the presence
29 of biochar caused that the intermediates could not be detected. Thus 1 g/L of nano-Fe/Ni
30 was added to the solution of 100 μmol/L of 2,4,6-TCP and the reaction products were
31 analyzed.
32 2.7 Calculation of density functional model
33 Considering 2,4,6-TCP as the target pollutant, the B3LYP method was used in the
34 Gaussian09 program. According to the literature, the Ni atom was selected from the
35 lanl2dz basis group (Hay & Wadt, 1985), the other four atoms, C, H, O, and Cl, were
36 selected from the 6-311++g(d,p) basis set. The obtained geometry was optimized to
37 calculate the total energy of each stagnation point on the potential energy surface.
 1 3 Experimental results and analysis
2 3.1 Material characterization
3 Nano-Fe /Ni particles distribute in a chain-like manner. Due to the effect of the
4 magnetic force, the agglomeration between the materials is obvious that may lead to the
5 reduction of catalytic reaction performance (Zhang et al., 2002). The low specific
6 pressure zone has a high starting point (p/p0<0.1) and contains a large number of
7 microporous structures. This curve is a typical type IV adsorption-desorption curve with
8 obvious hysteresis loops and a certain amount of mesoporous structure. The specific
9 pressure (p/p0) between 0.1 and 0.9 is not obvious and the relative pressure (p/p0) 0.9~1
10 shows a slight upward trend, which indicates that the material contained a small amount
11 of macroporous structure. The nano-iron/nickel particles were successfully loaded on
12 the surface of the biochar, causing the surface of the biochar to be rough. The
13 agglomeration between iron/nickel particles was weakened and the nano-iron/nickel on
14 the biochar was spherical with a diameter less than 150 nm.
15 The composition and valence of the elements on the EaB-Fe/Ni surface . Before
16 the reaction, there were mainly C, O, and Fe elements on the surface of EaB-Fe/Ni, and
17 the corresponding characteristic peaks of the binding energy were 284.0 eV, 530.0 eV,
18 711.0 eV, respectively. In addition, a small amount of Ni element was detected
19 corresponding to the characteristic peak of the electronic binding energy of 854.5 eV.
20 The element C was derived from Eupatorium adenophorum biochar. Elements Fe and
21 Ni were derived from nano-iron/nickel, indicating that Ni had been successfully loaded
22 on the composite material. The element O was derived from oxygen in the air and
23 nano-iron oxides in biochar. After the reaction, in addition to the C, O, and Fe elements,
24 Cl was also detected on the surface of EaB-Fe/Ni. The electron binding energy had the
25 peak of Cl- at 199.2 eV, which indicated that the bound state of Cl in 2,4,6-TCP was
26 reduced to the ionic state of Cl. It demonstrated that 2,4,6-TCP was degraded
27 successfully by EaB-Fe/Ni.
28 The change of Fe element in the EaB-Fe/Ni before and after the reaction with
29 2,4,6-TCP was also analyzed. The peak of the binding energy at 706.9 eV corresponded
30 to Fe0. For Fe2p3/2, the peaks of the binding energy were obtained at 710.6 eV and
31 713.0 eV, corresponding to Fe2+ and Fe3+, respectively (Dong et al., 2017). For Fe2p1/2,
32 the peaks of the binding energy were obtained at 724.5 eV and 726.4 eV, corresponding
33 to Fe2+ and Fe3+, respectively (Zhou, 2016). After the reaction between EaB-Fe/Ni and
34 2,4,6-TCP, the relative content of Fe0 decreased while the relative contents of Fe2+ and
35 Fe3+ increased, indicating that Fe0 was converted to Fe2+ and Fe3+. In addition, during
36 the reaction between EaB-Fe/Ni and 2,4,6-TCP, Fe0 was corroded by water and
37 converted to Fe2+. Therefore, there were two production sources of Fe2+ and Fe3+. One
38 was the reaction between EaB-Fe/Ni and 2,4,6-TCP, the other was the reaction between
39 EaB-Fe/Ni and water.
40 The composition and atomic structures of both the nano-Fe0 material and the
41 EaB-Fe/Ni material before and after the reaction were characterized by XRD after the
42 vacuum drying process. The broad peak in the diffraction angle at 20~30° is the
 1 amorphous C peak of biochar (Xu, 2015). The characteristic peaks of both the nano-Fe0
2 material and the EaB-Fe/Ni material before and after the reaction appeared at the
3 diffraction angle of 44.6°. Among them, the diffraction peak of pure nano-Fe0 had a
4 sharper shape and higher intensity. In contrast, the EaB-Fe/Ni particles before and after
5 the reaction had wider diffraction peaks with lower response intensity. This
6 phenomenon might be caused by the presence of fine Ni particles that were dispersed on
7 the surface of the zero-valent iron particles in an amorphous form. As a result, the
8 response intensity of the Fe0 diffraction peak decreased (Ji, 2013). After the reaction, the
9 characteristic peaks of Fe3O4 and Fe2O3 were detected at the diffraction angles of 35.4°
10 and 35.6°, indicating that Fe0 was corroded and transformed into Fe3O4 and Fe2O3
11 during the reaction.
12 3.2 Adsorption experimental results
13 3.2.1 Selection of load ratio
14 EaB-Fe/Ni had a significant effect on the removal of 2,4,6-TCP (Fig. 1 a). Among
15 the tested materials, EaB-Fe/Ni with the load ratios of 1:1, 1:2, 1:4 had the best effect
16 on the removal of 2,4,6-TCP. After 240 minutes, the removal rate of 2,4,6-TCP in the
17 solution was above 90%. In contrast, EaB-Fe/Ni with a load ratio of 2:1 had the lowest
18 removal efficiency. The possible mechanism is that the nano Fe/Ni occupies the
19 adsorption point on the surface of the biochar and the dispersibility of the nano Fe/Ni is
20 not good when the load ratio is 2:1.
21 The amount of Cl- in the solution represented the amount of Cl removed from the
22 structure of 2,4,6-TCP by EaB-Fe/Ni at 120 minutes in the reaction (Fig. 1 b).
23 EAB-Fe/Ni with a load ratio of 1:4 has a removal rate of 100% at 120 minutes.
24 However, the effect of EaB-Fe/Ni with the load ratio of 1:4 on the removal of Cl was
25 not superior compared with that with the load ratios of 1:2 and 1:1. The possible reason
26 is that the nano-iron/nickel in the composite material with the load ratio of 1:4 does not
27 completely cover the surface of the echinacea biochar. When the load ratio is 1:4, there
28 is rare iron/nickel to react with the adsorbed 2,4,6-TCP in some of the exposed biochar
29 pores. The results indicate that the biochar of Eupatorium adenophorum only plays a
30 role in dispersing and adsorbing in the process of 2,4,6-TCP removal. The reduction
31 reaction of the adsorbed 2,4,6-TCP is induced by the nano-Fe/Ni. The best removal rate,
32 namely 100%, could be obtained when the load ratios were 1:1 and 1:2. Based on the
33 production yield of Cl-, a higher removal efficiency, namely 71.6%, was obtained when
34 the load ratio was 1:2, which was similar to the results obtained by Devi in the study of
35 removing pentachlorophenol (Devi & Saroh, 2014). Lin S.-J et al. have reported using
36 cobalt ruthenium bimetallic composite oxide to degrade 2,4,6-TCP. In their study, under
37 the same ambient temperature and pH conditions, the degradation rate of 2,4,6-TCP was
38 22.4% after adding the material for 6 h (Lin et al,2017). Choi, J.-H & Kim, Y.-H have
39 reported degrading 2,4,6-TCP by Pd / Zn, Ni / Zn, Cu / Zn, and Pt / Zn. Their results
40 showed that 2,4,6-TCP degradation occurred within 6 h and the rate was lower than 25%
41 (Choi, J.-H & Kim, Y.-H 2009). In comparison, the degradation rate of EaB-Fe/Ni for
 1 TCP reached 39.7%-71.6% under different load ratio conditions.
2 3.2.2 Effect of concentration of 2,4,6-trichlorophenol
3 The removal rates of 2,4,6-TCP at 240 minutes were 100%, 100%, 95.5%, 75.8%,
4 44.5% along with the concentration of 2,4,6-TCP increased from 10 mg/L to 200 mg/L
5 (Fig. 1 c). At 120 minutes, the removal rates of Cl were 88.5%, 73.3%, 55.8%, 26.3%,
6 14% along with the increase of 2,4,6-TCP concentration (Fig. 1 d). The gradual increase
7 of the concentration of 2,4,6-TCP caused that the removal efficiency of 2,4,6-TCP by
8 EaB-Fe/Ni gradually decreased while the total removal amount increased. When the
9 dosage of EaB-Fe/Ni was constant, the total effective adsorption area and reactive site
10 were fixed. As the concentration of 2,4,6-TCP increased, the gradual decrease of
11 effective reaction site along with the increase of 2,4,6-TCP concentration was caused by
12 the occupation of part of the adsorption area and reaction site. Besides, as the adsorption
13 and reduction processes went on, the surface passivation layer was formed, which result
14 in the decrease of active point of EaB-Fe/Ni and the degradation efficiency.
15 3.2.3 Effect of pH of the solution
16 The pH of the solution had a significant effect on the removal of 2,4,6-TCP by
17 EaB-Fe/Ni (Fig. 1 e,f). As the pH increased from 3 to 11, the removal rate of 2,4,6-TCP
18 decreased from 100% to 12.3% at 240 minutes. At 120 minutes, the dechlorination
19 efficiency decreased from 93% to 4%. When the pH of the solution was 3, EaB-Fe/Ni
20 could completely remove 2,4,6-TCP within 90 minutes. The reaction rate was faster
21 when the acidity of the solution was higher. This phenomenon is possibly because there
22 is a large amount of H+ in the reaction system under acidic conditions, which promotes
23 the corrosion of nanoscale zero-valent iron to produce a large amount of H2. In the
24 reaction system, Ni has a strong adsorption effect on H2 and can convert the adsorbed
25 H2 into strongly reducible H* as a good catalyst, which can have the
26 hydrodechlorination reaction with 2,4,6-TCP and promote the degradation of 2,4,6-TCP.
27 In addition, a large amount of H+ in the reaction system under acidic conditions can
28 dissolve the passivation layer on the surface of EaB-Fe/Ni particles in time, which
29 facilitates the nanoscale zero-valent iron to contact with 2,4,6-TCP. The corrosion of
30 acid can continue to produce H2. Taken together, the acidic condition is more favorable
31 for the reductive dechlorination reaction of 2,4,6-TCP.
32 When the pH values of the solution were 9 and 11, the removal rates of 2,4,6-TCP
33 at 240 minutes were 22.3% and 12.3%, respectively. The stronger basicity of the
34 solution was more unfavorable for the reaction. Under alkaline conditions, OH- reacts
35 with Fe2+ and Fe3+ to form precipitates, which cover the surface of nanoscale
36 zero-valent iron and hinder the corrosion of nano-zero-valent iron. It can reduce the
37 contact points between the nano-zero-valent iron on EaB-Fe/Ni particles and 2,4,6-TCP.
38 Besides, 2,4,6-TCP is an ionizable organic substance, which is prone to deprotonation
39 under negative conditions and negatively charged (Yang et al., 2004). The acidic
40 functional groups (-COOH, -OH) on the surface of the biochar of Eupatorium
41 adenophorum dissociate to form -COO- or -O- under alkaline conditions, which
 1 weakens the hydrogen bonding between biochar and organic matter. The electrostatic
2 repulsion between EaB-Fe/Ni and 2,4,6-TCP results in lower removal efficiency of
3 2,4,6-TCP by EaB-Fe/Ni under alkaline conditions. When Mubarik S et al. used the
4 biochar of sugarcane bagasse to remove 2,4,6-TCP, the removal rate was about 88%-93%
5 under acidic conditions (Mubarik S et al., 2016). However, in this study, the 2,4,6-TCP
6 removal rate by EaB-Fe/Ni can reach 100% under acidic conditions.
7 3.2.4 Effect of coexisting ions
8 All of the coexisting ions, including HCO3-, SO42-, and NO3-, inhibited the removal
9 of 2,4,6-TCP by EaB-Fe/Ni. The degree of influence of these coexisting ions can be
10 arranged as the following order: NO3-> HCO3-> SO42- (Fig. 1 g,h). When a large amount
11 of SO42- was present in the reaction system, the removal rate of 2,4,6-TCP by
12 EaB-Fe/Ni decreased, which may be caused by the presence of Fe(OH)ads on the surface
13 of the reacted material. Fe(OH)ads can react with 2,4,6-TCP to form hydrogen bonds.
14 The OH- of Fe(OH)ads on the surface of the material was easily replaced by SO42- to
15 form a Fe(OH)ads, which has low affinity for 2,4,6-TCP (Yu et al., 2012). Therefore, the
16 presence of SO42- can inhibit the reduction of 2,4,6-TCP, which is consistent with the
17 inhibition effect of SO42- on the reduction of tetracycline in water by PVP-K50-loaded
18 nanoscale zero-valent iron (Chen et al., 2011).
19 When a large amount of HCO3- was present in the reaction system, the removal
20 rate of 2,4,6-TCP in the solution by EaB-Fe/Ni was reduced because the reaction
21 between Fe2+ produced by the corrosion of nanoscale zero-valent iron and CO32- ionized
22 from HCO3- can form a poorly soluble salt of FeCO3. The FeCO3 precipitates deposited
23 on the surface of zero-valent iron and hindered the zero-valent iron to contact with
24 2,4,6-TCP and be corroded. As a result, the removal efficiency of 2,4,6-TCP goes down
25 as the presence of a large amount of HCO3-.
26 As an oxidizing ion, NO3- can easily react with nanoscale zero-valent iron that is
27 very reductive. When NO3- and 2,4,6-TCP were present in the reaction system,
28 EaB-Fe/Ni had a simultaneous chemical reaction with both substances. Thus, there was
29 a competition between NO3- and 2,4,6-TCP in the reaction system for the adsorption
30 sites on the surface of EaB-Fe/Ni. As a result, the adsorption sites for 2,4,6-TCP
31 decreased. Chang J et al. have reported using oleic acid-coated nanoscale
32 palladium/zero-valent iron alginate beads to remove TCP (Chang J et al, 2015). With the
33 same concentration of NO3-, the material removal efficiency was reduced by 50%. In
34 comparison, the removal rate by EaB-Fe/Ni was affected less by NO3-.
35 3.3 Reaction kinetics of the removal of 2,4,6-trichlorophenol by EaB-Fe/Ni
36 The removal of 2,4,6-TCP by the EaB-Fe/Ni material was fitted with the L-H
37 model. The correlation coefficient (Table. 1) R2 was 0.9864, which demonstrated that
38 the experimental results were consistent with the fitting results of the L-H model. The
39 removal of 2,4,6-TCP was a combined result affected by both adsorption and reduction.
40 The reaction rate constant k1 between EaB-Fe/Ni and 2,4,6-TCP was 51.02 mg/(L min).
41 The adsorption constant k2 was 0.023 L/mg. k1 was much larger than k2, which
 1 indicated that the reduction played a dominant role while the adsorption controlled the
2 reaction rate.
3 3.4 Analysis of reaction pathways
4 The reaction pathway was obtained from the detection and analysis of the reaction
5 products (Fig. 2). At the beginning of the reaction, 2,4,6-TCP was reduced to
6 2,4-dichlorophenol, 2,6-dichlorophenol, 2-chlorophenol, 4,-chlorophenol and phenol.
7 After 120 minutes, the removal rate of 2,4,6-TCP gradually decreased and reached 71.6%
8 at 240 minutes. The concentration of the intermediate products, including
9 2,4-dichlorophenol, 2,6-dichlorophenol, 2-chlorophenol and 4,-chlorophenol, increased
10 at the beginning of the reaction, reached a maximum at 60 minutes, and then decreased
11 until completely reduced. The yield of the product phenol changed slowly at the
12 beginning of the reaction, and the growth rate became faster after 60 minutes. At 240
13 minutes, the yield of phenol reached 59.7 μmol/L. The mass loss of the reaction system
14 was about 5%, which might be caused by the adsorption by nano-Fe/Ni.
15 Therefore, the degradation process of 2,4,6-TCP by EaB-Fe/Ni is a reductive
16 dechlorination process, which is consistent with the XPS characterization of EaB-Fe/Ni.
17 Based on the intermediates, there are three possible reduction pathways: (1) The
18 substance 2,4,6-TCP was first reduced to 2,6-dichlorophenol, then 2-chlorophenol, and
19 finally phenol. (2) The substance 2,4,6-TCP was first reduced to 2,4-dichlorophenol,
20 then 2-chlorophenol, and finally phenol. (3) The substance 2,4,6-TCP was first reduced
21 to 2,4-dichlorophenol, then 4-chlorophenol, and finally phenol. The priority of
22 dechlorination is p-chloro > o-chloro, which is consistent with the previous studies (Wei
23 & Sun, 2014; Sun et al., 2019).
24 3.5 Calculation of density functional model
25 The main parameters of the geometric configuration of each resident substance in
26 the reaction were calculated by Gaussian 09 software. In the figure, a, b and c represent
27 the reactants, transition state, and product, respectively. The H2 produced by the
28 corrosion of the zero-valent iron was adsorbed by Ni to form a V-type structure. The
29 bond length of Ni-H was 1.4414 Å. The original bond length of the hydrogen molecule
30 was 0.74 Å, while the bond length of H-H was enlarged to be 1.7915 Å after activated
31 by Ni.
32 In the reactant NiH2, the Ni-H bond length was 1.4414 Å. In the 2,4,6-TCP, the
33 C-Cl bond length was 1.7788 Å. In the transition state, the Ni-H bond length increased
34 to 1.5074 Å and the C-Cl bond length increased to 1.9808 Å, which indicated that the
35 bond energy of Ni-H and C-Cl was weakened and both bonds (Ni-H and C-Cl) appeared
36 to dissociate in the transition state.
37 Based on the calculated and optimized geometry model, the PCM model (Scalmani
38 & Frisch, 2010) was used to calculate the total energy of each substance in the reaction
39 in aqueous solution. The correlation energy parameters and activation energy data of
40 each substance in the reaction are shown in Fig. 3. The activation energy of the reaction
41 between EaB-Fe/Ni and 2,4,6-TCP was 109.5 kcal/mol, which indicated that the
 1 reaction was relatively easy to take place.

2 4. Conclusions

3 EaB-Fe/Ni is highly effective in degrading and removing 2,4,6-TCP from water.

4 Both the removal effect of 2,4,6-TCP and the dechlorination effect reach the best ones
5 when the load ratio of EaB-Fe/Ni is 1:2. The composite material has a better effect on
6 the removal of the low concentrated solution of 2,4,6-TCP under acidic condition. As a
7 large amount of Eupatorium adenophorum waste is produced in the process of
8 ecological restoration and treatment of the invasive species Eupatorium adenophorum,
9 the utilization of Eupatorium adenophorum as a biochar raw material can achieve the
10 comprehensive purpose of both waste utilization and water pollution control.
11
12 Acknowledgements
13 We greatly acknowledged the financial support from the Independent Research
14 Program by the State Key Laboratory of Geohazard Prevention and Geoenvironment
15 Protection. Chengdu University of Technology (SKLGP2016Z008). The Key Research
16 and Development Project of Sichuan Science and Technology Department
17 (2017SZ0177), Key Research and Development Program of Sichuan Province of Oiina
18 (2018SZ0321) and the Teacher Development Research Startup Fund of Chengdu
19 University of Technology (10912-2019KYQD07360).

20 Appendix A. Supplementary data

21 E-supplementary data of this work can be found in online version of the paper.
22
23 1.Arnold, W. A., & Roberts, A. L. 2000. Pathways and Kinetics of Chlorinated Ethylene
24 and Chlorinated Acetylene REaBction with Fe(0) Particles. Environmental Science &
25 Technology, 34(9), 1794–1805.
26 2.Ahmad, M., Lee, S. S., Dou, X., Mohan, D., Sung, J.-K., Yang, J. E., & Ok, Y. S. 2012.
27 Effects of pyrolysis temperature on soybEaBn stover- and pEaBnut shell-derived
28 biochar properties and TCE adsorption in water. Bioresource Technology, 118, 536–544.
29 3.Alvarez-Ramirez, J., Femat, R., Meraz, M., & Ibarra-Valdez, C. 2015. Some remarks
30 on the Langmuir–Hinshelwood kinetics. Journal of Mathematical Chemistry, 54(2),
31 375–392.
32 4.Barik, A. J., & Gogate, P. R. 2018. Hybrid trEaBtment strategies for
33 2,4,6-trichlorophenol degradation based on combination of hydrodynamic cavitation
34 and AOPs. Ultrasonics Sonochemistry, 40, 383–394.
35 5.Clark, C. J., Rao, P. S. C., & Annable, M. D. 2003. Degradation of perchloroethylene
36 in cosolvent solutions by zero-valent iron. Journal of Hazardous Materials, 96(1),
37 65–78.
38 6. Choi, J.-H., & Kim, Y.-H. 2009. Reduction of 2,4,6-trichlorophenol with zero-valent
39 zinc and catalyzed zinc. Journal of Hazardous Materials, 166(2-3), 984–991.
 1 7. Christoforidis K C , Serestatidou E , Louloudi M , et al. 2011. Mechanism of catalytic
2 degradation of 2,4,6-trichlorophenol by a Fe-porphyrin catalyst[J]. APPLIED
3 CATALYSIS B, 101(3-4):417-424.
4 8.Chen, H., Luo, H., Lan, Y., Dong, T., Hu, B., & Wang, Y. 2011. Removal of
5 tetracycline from aqueous solutions using polyvinylpyrrolidone (PVP-K30) modified
6 nanoscale zero valent iron. Journal of Hazardous Materials.
7 9. Chang J , Woo H , Ko M S , et al. 2015 Targeted removal of trichlorophenol in water
8 by oleic acid-coated nanoscale palladium/zero-valent iron alginate
9 beads11Abbreviations: CP – chlorophenol; DCP – dichlorophenol; MCP –
10 monochlorophenol; n-ZVI – nanoscale zero-valent iron; Pd/nZVI – nanoscale palladium
11 zero-valent iron; Pd/nZVI-A – nanoscale palladium zero-valent iron alginate beads;
12 Pd/nZVI-A-O – oleic acid-coated nanoscale palladium zero-valent iron alginate beads;
13 SRHA – Suwannee River humic acid; TCP – trichlorophenol.[J]. Journal of Hazardous
14 Materials, 293:30-36.
15 10.Danis, T. G., & Albanis, T. A. (1996). Analysis of Phenolic residues in soil as free
16 and acetylated derivatives by capillary gas chromatography equipped with fid, ECD and
17 MSD. Toxicological & Environmental Chemistry, 53(1-4), 9–18.
18 11.Devi, P., & Saroha, A. K. 2014. Synthesis of the magnetic biochar composites for use
19 as an adsorbent for the removal of pentachlorophenol from the effluent. Bioresource
20 Technology, 169, 525–531.
21 12.Dong, j, Ren, L.-M, Chi, Z.-F, Hu W.-H. 2017. Analysis of XPS in the Removal of
22 Cr(Ⅵ) from Groundwater with rGO-nZⅥ. Spectroscopy and Spectral Analysis |
23 Spectrosc Spect Anal, 37(01): 250-255.
24 13.Ghauch, A., Abou Assi, H., & Bdeir, S. 2010. Aqueous removal of diclofenac by
25 plated elemental iron: Bimetallic systems. Journal of Hazardous Materials, 182(1-3),
26 64–74.
27 14.Godlewska, P., Schmidt, H. P., Ok, Y. S., & Oleszczuk, P. 2017. Biochar for
28 composting improvement and contaminants reduction. A review. Bioresource
29 Technology, 246, 193–202.
30 15.Gao, Y.-Y, 2017. Degradation of nitrate in groundwater by Rhamnolipid modified
31 Nano-scale zero valent iron/ nano-scale carbon composite. Chengdu University of
32 Technology.
33 16.Hay, P. J., & Wadt, W. R. 1985. Ab initio effective core potentials for molecular
34 calculations. Potentials for K to Au including the outermost core orbitals. The Journal of
35 Chemical Physics, 82(1), 299–310.
36 17.Hammes, K., Schmidt, M.W.I., 2009. Changes of biochar in soil. In: Lehmann,
37 J.,Joseph, S. (Eds.), Biochar for Environmental Management: Science and Technology.
38 EaBrthscan, London.
39 18.Hall, K. E., Spokas, K. A., Gamiz, B., Cox, L., Papiernik, S. K., & Koskinen, W. C.
40 2017. Glyphosate sorption/desorption on biochars - interactions of physical and
41 chemical processes. Pest Management Science, 74(5), 1206–1212.
42 19.Ji, Z.-F. 2013. Preparation of Nano Pd/Fe Bimetallic Particles and Its Application in
43 Reductive Dechlorination of Chlorophenolic Compounds. Nanjing Normal University.
 1 20.Jiang, Bini;Lin, Yunqin;Mbog, James Carl. 2018. Biochar derived from swine
2 manure digestate and applied on the removals of hEaBvy metals and antibiotics.
3 Bioresource Technology.2018：603-611.
4 21.Kim, Y.-H., & Carraway, E. R. 2000. Dechlorination of Pentachlorophenol by Zero
5 Valent Iron and Modified Zero Valent Irons. Environmental Science & Technology,
6 34(10), 2014–2017.
7 22.Kameyama, K., Miyamoto, T., Iwata, Y., & Shiono, T. 2016. Influences of feedstock
8 and pyrolysis temperature on the nitrate adsorption of biochar. Soil Science and Plant
9 Nutrition, 62(2), 180–184.
10 23.Lang, Y.-H, Liu W, Wang H, 2014. Adsorption efficiencies of pentachlorophenol
11 from aqueous solution onto biochars. China Environmental Science , 34(08):
12 2017-2023.

13 24.Lin S.-J, Zhang L, Dong L.-G, et al.2017, Catalytic Dgradation of 2，4，6

14 Trichlorophenol by Cobalt-Cerium Complex Oxides. Chemical Industry and
15 Engineering
16 25.Lee, D.-J., Cheng, Y.-L., Wong, R.-J., & Wang, X.-D. 2018. Adsorption removal of
17 natural organic matters in waters using biochar. Bioresource Technology, 260, 413–416.
18 26.Liu, Y., Lonappan, L., Brar, S. K., & Yang, S. 2018. Impact of biochar amendment in
19 agricultural soils on the sorption, desorption, and degradation of pesticides: A review.
20 Science of The Total Environment, 645, 60–70.
21 27.Mohan, D., Sarswat, A., Ok, Y. S., & Pittman, C. U. 2014. Organic and inorganic
22 contaminants removal from water with biochar, a renewable, low cost and sustainable
23 adsorbent – A critical review. Bioresource Technology, 160, 191–202.
24 28.Mubarik S , Saeed A , Athar M M , et al. 2016.Characterization and mechanism of
25 the adsorptive removal of 2,4,6-trichlorophenol by biochar prepared from sugarcane
26 baggase[J]. Journal of Industrial & Engineering Chemistry, 33:115-121.
27 29.Mishra, A., Sharma, M., Mehta, A., & Basu, S. 2017. Microwave TrEaBted
28 Bentonite Clay Based TiO2 Composites: An Efficient Photocatalyst for Rapid
29 Degradation of Methylene Blue. Journal of Nanoscience and Nanotechnology, 17(2),
30 1149–1155.
31 30.Sayles, Gregory D.;You, Guanrong. 1997.DDT,DDD and DDE dechlorination by
32 zero-valent iron..Environmental Science and Technology. Vol.31(NO.12)：3448-3448.
33 31.Song, H., Carraway, E. R., Kim, Y. H., Batchelor, B., Jeon, B.-H., & Kim, J. 2008.
34 Amendment of hydroxyapatite in reduction of tetrachloroethylene by zero-valent zinc:
35 Its rate enhancing effect and removal of Zn(II). Chemosphere, 73(9), 1420–1427.
36 32.Sohi, S. P., Krull, E., Lopez-Capel, E., & Bol, R. 2010. A Review of Biochar and Its
37 Use and Function in Soil. Advances in Agronomy, 47–82.
38 33.Scalmani, G., & Frisch, M. J. 2010. Continuous surface charge polarizable
39 continuum models of solvation. I. General formalism. The Journal of Chemical Physics,
40 132(11), 114110.
 1 34.Shi, X.-Z, 2011,Analysis and characterization of several nanomaterials synthesized
2 by electrochemical and liquid method. Lanzhou University
3 35.Sun, Y., Liu, Z., Fei, Z., Li, C., Chun, Y., & Zhang, A. 2019. Synergistic effect and
4 degradation mechanism on Fe-Ni/CNTs for removal of 2,4-dichlorophenol in aqueous
5 solution. Environmental Science and Pollution ResEaBrch.
6 36.Van Poucke, R., Ainsworth, J., Maeseele, M., Ok, Y. S., Meers, E., & Tack, F. M. G.
7 2018. Chemical stabilization of Cd-contaminated soil using biochar. Applied
8 Geochemistry, 88, 122–130.
9 37.Wang, W.-M, 2013. Removal of 2,4-Dichlorophenol from Aqueous Solution using
10 Organic Vermiculite and Vermiculite-supported Pd/Fe nanoparticles. South China
11 University of Technology
12 38.Wei, X.-F, Sun, Z.-R. 2014. Reductive dechlorination of 2,4,6-TCP on Pd/Ti
13 electrode: parameters optimization and degradation pathway. China Environmental
14 Science, 34(09): 2285-2291.
15 39.Wan, J.-J. 2014, Preparation of Si02-coated Iron Nanoparticles and Degradation of
16 2,4-DCP of Refractory Organics. South China University of Technology
17 40.Wu, C; Liu, X.-G; Wu, X.-H. 2019.Sorption, degradation and bioavailability of
18 oxyfluorfen in biochar-amended soils.Science of the total enviornment.2019：87-94.
19 41.Xu, X.-Y. 2015. The sorption and transformation of inorgaing contaminants by
20 biochars and the underlying mechanisms. Shanghai Jiao Tong University.
21 42.Yan, X.-L, Shou, H.-Y, Ma, J.-S, 2012. The Problem and Status of the Alien Invasive
22 Plants in China . Plant Diversity and Resources Plant Diver Resour, 34(03): 287-313.
23 43.Yak, H. K., Wenclawiak, B. W., Cheng, I. F., Doyle, J. G., & Wai, C. M. 1999.
24 Reductive Dechlorination of Polychlorinated Biphenyls by Zerovalent Iron in
25 Subcritical Water. Environmental Science & Technology, 33(8), 1307–1310.
26 44.Yang, Y., Chun, Y., Sheng, G., & Huang, M. 2004. pH-Dependence of Pesticide
27 Adsorption by WhEaBt-Residue-Derived Black Carbon. Langmuir, 20(16), 6736–6741.
28 45.Yu, J., Liu, W., Zeng, A., Guan, B., & Xu, X. 2012. Effect of SO on
29 1,1,1-Trichloroethane Degradation by Fe in Aqueous Solution. Ground Water, no–no.
30 46.Yan, W., Lien, H.-L., Koel, B. E., & Zhang, W. 2013. Iron nanoparticles for
31 environmental clEaBn-up: recent developments and future outlook. Environ. Sci.:
32 Processes Impacts, 15(1), 63–77.
33 47.Zhang, P., Tao, X., Li, Z., & Bowman, R. S. 2002. Enhanced Perchloroethylene
34 Reduction in Column Systems Using Surfactant-Modified Zeolite/Zero-Valent Iron
35 Pellets. Environmental Science & Technology, 36(16), 3597–3603.
36 48.Zhu, D., Kwon, S., & Pignatello, J. J. 2005. Adsorption of Single-Ring Organic
37 Compounds to Wood Charcoals Prepared under Different Thermochemical Conditions.
38 Environmental Science & Technology, 39(11), 3990–3998.
39 49.Zhou, Z., Ruan, W., Huang, H., Shen, C., Yuan, B., & Huang, C.-H. 2016.
40 Fabrication and characterization of Fe/Ni nanoparticles supported by polystyrene resin
41 for trichloroethylene degradation. Chemical Engineering Journal, 283, 730–739.
1 50.Zhang, X., Fu, W., Yin, Y., Chen, Z., Qiu, R., Simonnot, M.-O., & Wang, X. 2018.
2 Adsorption-reduction removal of Cr(VI) by tobacco petiole pyrolytic biochar: Batch
3 experiment, kinetic and mechanism studies. Bioresource Technology, 268, 149–157.
 Figure captions

Fig.1 Effect of load ratio (a, b); 2,4,6-trichlorophenol concentration (c, d); pH(e, f) and

coexisting ions (g, h); Experimental condition: a, b: pH=6, temperature =20 ℃, Material

dosage=1 g/L, C0=20 mg/L; c, d: pH=6, temperature=20 ℃, Material dosage=2 g/L; e, f:

temperature=20 ℃, Material dosage=2 g/L. C0= 20 mg/L; g, h: pH=6, temperature =20 ℃,

Material dosage=2 g/L, C0= 20 mg/L

Fig.2 Reduction of 2,4,6-trichlorophenol by nano-Fe/Ni

Fig.3 Schematic diagram of potential energy surface of 2,4,6-TCP catalytic reduction

dechlorination
Fig.1

100
a b
100
90

80
80

Cl-(solution)/Cl-(total)(%)
70
（ C0-C） /C0(%)

60 60

50
Fe/Ni:EaB=2:1
40
Fe/Ni:EaB=1:1 40
Fe/Ni:EaB=1:2
30
20
Fe/Ni:EaB=1:4
EaB 20
Fe/Ni
0 10

0
0 50 100 150 200 250 Fe/Ni 2:1 1:1 1:2 1:4 EaB
t (min)

100
c d
100

80
80
Cl-(solution)/Cl-(total)(%)
（ C0-C） C0（ %）

60 60

40
10mg/L 40
20mg/L
20 50mg/L
100mg/L 20
200mg/L
0

0
0 50 100 150 200 250 10mg/L 20mg/L 50mg/L 100mg/L 200mg/L
t/min

100
e f
100

80
80
Cl-(solution)/Cl-(total)(%)

pH=3
（ C0-C） /C0(%)

60 pH=5 60
pH=7
pH=9
40 pH=11 40

20
20

0
0 50 100 150 200 250 PH=3 PH=5 PH=7 PH=9 PH=11
t (min)
 100
g
100 h

80
80

Cl-(solution)/Cl-(total)(%)
（ C0-C） /C0(%)

60 60

40 Blank
40
SO42-
HCO3-
20
NO3- 20

0
0 50 100 150 200 250
Black SO42- HCO3- NO3-
t (min)
Fig. 2

100

2,4,6-Trichlorophenol 2,6-Dichlorophenol
80 2,4-Dichlorophenol 2-monochlorophenol
4-monochlorophenol Phenol
Material Balance
c（ μmol/L）

60

40

20

0 50 100 150 200 250

t/min
Fig. 3
 Table captions

Table.1 Fitting parameters of L-H model for the removal of 2,4,6-trichlorophenol using

EaB-Fe/Ni
Table.1

Correlation
Kinetic model Parameter
coefficient (R2)

K1(mg/(L·min)) K2(L/mg)

Langmuir-Hinshelwood 0.9864
51.02 0.023
Removal of 2,4,6-trichlorophenol from water by Eupatorium

adenophorum biochar-loaded nano-iron/nickel

Guo Liua,b,c*1，Haoran Tanga,b,c,1，Jiajun Fana,b,c，Zhihao Xiea,b,c，Tianyu Hea,b,c，Rui Shia,b,c，Bing Liaoa,b,c
a. State Key Laboratory of Geohazard Prevention and Geoenvironment Protection，Chengdu,610059,.China
b. State Environmental Protection Key Laboratory of Synergetic Control and Joint Remediation for Soil&Water
Pollution SEKL-SW，Chengdu,610059,China
c. Chengdu University of Technology, College of Environment and Ecology,Chengdu,610059,China

Graphical abstract: