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Removal of Cr(VI) in wastewater by Fe–Mn oxide

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Cite this: RSC Adv., 2024, 14, 11746

loaded sludge biochar†
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ab *a
Chaoyang Yu and Jinyan Yang

Sludge biochar loaded with Fe–Mn oxides (FMBC) was prepared and employed to remove Cr(VI) from
wastewater. The influences of solution pH, co-existing ion, contact time, adsorption temperature and
Cd(VI) concentrations on removing Cr(VI) by FMBC were investigated. The Cr(VI) adsorption on FMBC had
strong pH dependence. Additionally, Na+, Mg2+, Ca2+, SiO32−, NO3− and Cl− ions exhibited no influence
on Cr(VI) removal efficiency for FMBC, whereas there were inhibition effects of Pb2+, Cu2+, Ni2+, CO32−,
SO42−, and PO43− on removing Cr(VI). The Cr(VI) adsorption from solution for FMBC was well described
by models of pseudo-second-order and Langmuir, and the largest Cr(VI) removal capacity of FMBC
reached 172.3 mg g−1. FMBC had good capacity for treating electroplating wastewater and mineral
Received 7th January 2024
Accepted 12th March 2024
dissolving wastewater containing Cr(VI). After five regenerations, the 50 and 5 mg L−1 Cr(VI) removing
efficiency of FMBC was 82.34% and 97.68%, respectively. The Cr(VI) removal for FMBC involved
DOI: 10.1039/d4ra00169a
adsorption-reduction and re-adsorption of Cr(III) generated by reduction. These results indicated that
rsc.li/rsc-advances FMBC has good prospects for remediating Cr(VI)-containing wastewater.

of biochar and its electrostatic attraction with anionic pollut-

1 Introduction ants was enhanced.10,11 While manganese oxides hold chemi-
Chromium (Cr) mainly exists in two valence states, Cr(VI) and cally stable and rich –OH functional groups, it is an adsorbent
Cr(III), of which Cr(VI) is highly toxic, difficult to biodegrade and material for efficient adsorption of contaminants in solution.12
easy to be enriched in the food chain.1,2 If Cr-containing However, in practical applications, the iron and manganese
wastewater is not treated properly, it will bring great harm to oxides exhibit insufficient mechanical strength, poor occula-
human beings and nature. Currently, the main method for tion and easy agglomeration.13 Biochar as a carrier could
Cr(VI) removal is reverse osmosis, ion exchange, oxidation effectively improve the agglomeration of Fe–Mn oxides. Aer
reduction, membrane separation and adsorption.3 Adsorption the introduction of Fe–Mn oxides, the amount of active site of
is considered to be a preferred method for treating Cr(VI) in biochar increased, and its removal performance for contami-
wastewater because of its simplicity, low cost and high effi- nants was greatly improved.14 Additionally, the multi-metal
ciency.4,5 Therefore, research and development of an econom- materials have synergistic adsorption and reduction effects,
ical, simple and efficient new adsorbent is of high application which can improve the effect of Cr(VI) treatment.13 Applying
value. composites to treat Cr(VI)-containing wastewater is expected to
Biochar prepared from waste biomass by pyrolysis has the achieve the dual purpose of waste biomass resource utilization
advantages of porous structure, rich oxygen-containing func- and Cr(VI) pollutant control.
tional groups, low cost and wide adaptability, which is consid- Hence, sludge biochar loaded with Fe–Mn oxides (FMBC)
ered as a good adsorbent material.6–8 However, the was employed to remove Cr(VI) from wastewater. The intentions
physicochemical properties of biochar, such as surface func- of this research were to: (i) investigate removal performance of
tional groups, porosity and specic surface area, have great FMBC for Cr(VI) in solution, (ii) elucidate the adsorption
inuence on removing Cr(VI).6,9 Therefore, the Cr(VI) removal mechanism of Cr(VI) by FMBC, and (iii) validate potential of
effect on biochar in water can be improved by modifying its FMBC for remediating electroplating wastewater and mineral
physicochemical properties and surface structure. Previous dissolving wastewater containing Cr(VI).
literature showed that iron oxides increased the positive charge

2 Materials and methods

a
College of Architecture and Environment, Sichuan University, Chengdu 610041, 2.1 Reagents
China. E-mail: [email protected]
b
Sichuan-Tibet Railway Co., Ltd, Chengdu 610041, China Ferric chloride (FeCl3$6H2O), manganese chloride (MnCl2-
† Electronic supplementary information (ESI) available. See DOI: $5H2O), sodium hydroxide (NaOH), hydrochloric acid (HCl),
https://doi.org/10.1039/d4ra00169a and potassium dichromate (K2Cr2O7) were purchased from

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Sinopharm Chemical Reagent Co. Ltd (Shanghai, China). Above adsorption. Adsorbent was added to 50 mL electroplating
reagent was of analytical reagent. Different concentration of wastewater or mineral dissolving wastewater, and the mixed
Cr(VI) solutions was obtained through K2Cr2O7 solids dissolu- solution was transferred to oscillator at 25 °C and 150 rpm to
tion. Dewatering sludge from Chengdu (Sichuan Province, adsorb 300 min. The electroplating wastewater came from
China) municipal wastewater treatment plant. Baohe swan electroplating plant (Chengdu, China) and mineral
dissolving wastewater originated during the construction of
2.2 Preparation of Fe–Mn oxide loaded sludge biochar railway tunnels in southwestern China. The properties of elec-
troplating wastewater and mineral dissolving wastewater were
Air-dried dry sludge was ground into powder by ball mill. Five
displayed in Table S1.†
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gram powdered dry sludges were incorporated into 100 mL

Repeatability experiments: 50 mg L−1 Cr(VI) solutions and
deionized water and homogenously stirred for 60 min. Mean-
0.4 g L−1 absorbent were added into a centrifuge tube, and pH
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while, 2 g of FeCl3$6H2O and 2 g of MnCl2$5H2O were incor-

of suspension was set to 3.0. Then suspension was transferred
porated into 100 mL deionized water. Above two solutions were
to a oscillator at 25 °C and 150 rpm to adsorb for 300 min. Aer
added to 500 mL conical ask and solution pH was adjusted to
reaction, the solution was ltered, and the absorbent was
10–11.0 by 0.1 mol L−1 NaOH solution. Subsequently, suspen-
collected on a nylon lter membrane. The sample was mixed
sion shake in a 25 °C thermostatic oscillator at 120 rpm for 12 h.
with 0.1 mol L−1 NaOH, and suspension pH was probably
And then, the solution was ltered through a 0.23 mm lter
around 10.0. The suspensions were shaken in oscillator (25 °C
membrane and the solids on membrane were assembled. Then,
and 150 rpm) for 12 h. Then suspension was ltered through
solids were dried in a thermostatic oven at 80 °C for 12 h.
0.45 mm nylon membrane lter and rinsed with ultrapure water
Thereaer, 5 g solid was placed on a ceramic boat and the boat
until the rinsing solution was neutral, and samples were dried
was pyrolyzed in a muffle furnace with N2 atmosphere at 450 °C
at 80 °C for 12 h. Repeatability experiment was repeated for 5
for 2 h. Aer pyrolysis, the black solid on the boat was washed
times with the regenerated absorbent and Cr(VI) adsorption
with ultrapure water and anhydrous ethanol for 3 times, and the
performances by FMBC for each regeneration were calculated.
obtained black solid was dried in a constant temperature oven
The total Cr contents of residual liquid were determined
at 80 °C for 12 h. The dried black solid was stored in a sealed bag
through an inductively coupled plasma optical emission spec-
and recorded as FMBC.
trometer (ICP-OES, FL1008M018, Cary, USA). The Cr(VI)
contents were determined through modied 1,5-diphe-
2.3 Batch adsorption experiment nylcarbazide method.10 The Cr(III) content was calculated by
Adsorption experiment performed in 100 mL polyethylene content difference between the total Cr and Cr(VI). The removal
centrifuge tube containing 50 mL of Cr(VI) solution. The solu- efficiency (eqn (1)) and adsorption capacity (eqn (2)) were
tion pH was adjusted by 0.1 mol L−1 HNO3 or NaOH. During the counted.
reaction, the centrifuge tubes was set into a shaker at 25 °C and C0  Ce
shaken at 150 rpm for 300 min. The effect of pH and co-existing R¼  100% (1)
C0
ion on removing Cr(VI) was researched.
Adsorption isotherm: 0.4 g L−1 adsorbent was added to Cr(VI) ðC0  Ce Þ  V
solution at concentrations of 50–150 mg L−1, and then solution qe ¼ (2)
m
pH set to 3.0. The suspension was placed into a temperature-
where R is the removal efficiency, %; C0 is the initial Cr(VI)
controlled shaker at multiple temperature (288 K, 298 K and
concentration, mg L−1; Ce is the Cr(VI) concentration aer
308 K) to reaction for 300 min. Langmuir, Freundlich, Temkin
adsorption equilibrium, mg L−1; qe is the Cr(VI) adsorption
and Sips model was employed to analyze experimental result
capacity of the adsorbent, mg g−1; V is the solution volume, L;
(ESI†).
and m is the mass of the adsorbent, g.
Adsorption kinetics: series of centrifuge tubes containing
50 mg L−1 Cr(VI) solution were set up according to the adsorp-
tion time, and 0.4 g L−1 of adsorbent was added to the tubes.
The solution pH was set to 3.0, and then adsorption experiment 3 Results and discussion
was carried out for 5–300 min in a thermostatic oscillator at 25 °
C. The data was analyzed by pseudo-rst-order kinetic model, 3.1 Characterization analysis
pseudo-second-order kinetic model, Elovich model, intra- BC and FMBC surface morphology structure was illustrated in
particle diffusion model and liquid lm diffusion model, Fig. S1.† The surface of BC was smooth and at as shown in
respectively (ESI†). Fig. S1a.† Nevertheless, the Fig. S1b† showed the presence of
To explore practicality of FMBC, Cr(VI) removal experiments ower-like structure on the FMBC surface, which indicated that
were carried out in electroplating wastewater and mineral dis- Fe–Mn compounds were successfully loaded on sludge biochar
solving wastewater. The content of Cr(VI) in electroplating surface. According to EDS analysis, the content of Fe and Mn on
wastewater and mineral dissolving wastewater were 40.21 and the FMBC surface was higher than that of BC. Furthermore,
1.35 mg L−1, respectively. Since pH of mineral dissolving Fig. S1c† showed that Fe and Mn were dispersed on FMBC
wastewater was 6.76, the mixed solution pH of mineral dis- surface, which also indicated that Fe–Mn oxide was loaded on
solving wastewater and adsorbent was adjusted to 3.0 before FMBC surface.

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The N2 adsorption–desorption curves of BC and FMBC are 1.02, respectively, and this result indicated that the graphiti-
displayed in Fig. 1a. Adsorption capacity of N2 by BC and FMBC zation of sludge biochar decreased aer loading with Fe–Mn
gradually increased with increasing relative pressure P/P0 and oxides. Furthermore, FMBC exhibited a new vibrational peak at
a hysteresis loop was formed, which suggested that N2 adsorp- 658 cm−1, which was considered to be the characteristic peak of
tion–desorption curves for BC and FMBC was categorized as MnFe2O4.17 The crystalline structures in BC and FMBC were
type IV isotherm.10,15 The non-coincidence in the second half of investigated through XRD technique and result are displayed in
the adsorption–desorption curves attributed to multilayer Fig. 1d. In XRD plot, the main substances in BC and FMBC were
lling inuence of capillary pore, suggesting that both micro- SiO2 and CaAl2Si2O8, which was in agreement with previous
pores and mesopores existed in BC and FMBC, but the material ndings.10,18 Moreover, the characteristic peak of Fe2O3 was
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was mainly mesoporous.16 The specic surface area of BC and detected in BC. Notably, new characteristic peaks in FMBC
FMBC was calculated as 25.28 m2 g−1 and 67.34 m2 g−1, appeared at 2q = 29.86°, 35.14° and 61.92°, which was specu-
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respectively. The pore width of BC and FMBC is displayed in lated that the new characteristic peaks may be caused by
Fig. 1b. The pore widths were concentrated in 2–50 nm, which MnFe2O4.19 In the FTIR prole of BC and FMBC (Fig. 1e), the
suggested that BC and FMBC were mesoporous material.3 broad band observed at 3300–3500 cm−1 was related to O–H
Moreover, the average pore size of BC and FMBC was calculated stretching vibration, and characteristic peak at 1620 cm−1 cor-
as 9.43 nm and 15.60 nm by methods, respectively. responded to the vibration of C]C/C]O deformation conju-
As shown in Fig. 1c, the Raman shi at 1358 cm−1 and gation vibration.9 The vibrational peak appearing at 1430 cm−1
1595 cm−1 was denoted as D peak and G peak, respectively.10 was considered to be due to the –COOH group, while the
The ID/IG ratio of BC and FMBC was calculated to be 0.98 and vibrational peak at 1070 cm−1 was considered to be due to the

Fig. 1 The spectra of N2 adsorption–desorption curves (a), pore size distribution (b), Raman (c), XRD (d), FTIR (e) and XPS (f) of BC and FMBC
sample.

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C–O group.20 Notably, the intensity of O–H, C]C/C]O, and – The contents of total Cr, Cr(III) and Cr(VI) in residual solution
COOH groups on FMBC were all enhanced upon loading of Fe– were determined. As solution pH rose from 2.0 to 10.0, the
Mn oxides, suggesting that the Fe–Mn oxide loading increased concentrations of total Cr and Cr(VI) rose from 2.84 and
the number of O-containing groups in the adsorbents.13 Addi- 0.83 mg L−1 to 44.79 and 44.79 mg L−1, respectively, whereas the
tionally, the vibrational peak at 531 cm−1 corresponded to Fe–O content of Cr(III) increased from 2.01 mg L−1 to 4.70 mg L−1 and
group in BC.19 Aer Fe–Mn oxide loading, the characteristic then decreased to under detect limit with increasing solution
peak at 531 cm−1 was shied to 539 cm−1, which may be caused pH, which indicated that FMBC reduced partial Cr(VI) to Cr(III)
by Fe/Mn–O characteristic peak formed by Fe–Mn oxide (Fig. 2c). More importantly, the Cr(III) concentrations were
loading.19 greater than that of Cr(VI) under acidic condition, while the
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According to the full spectrum analysis by XPS (Fig. 1f), the Cr(III) concentration were very low small or even below the
elements C, O, N and Fe appeared in the full XPS spectrum of detection value under alkaline condition, which indicated that
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BC, while the element Mn was found in FMBC. In the O 1 s it was difficult for FMBC to reduce Cr(VI) to Cr(III) on alkaline
proles of BC (Fig. S2a†) and FMBC (Fig. S2b†), O 1 s could be condition, whereas Cr(VI) ions were adsorbed through
classied into M–O (M denoted Fe or Mn), C]O and C–O adsorption-reduction on acidic condition.21
characteristic peaks. Aer loading Fe–Mn oxides, the relative The concentrations of Fe and Mn in solution aer equilib-
contents of Fe–O/Mn–O and C]O in FMBC increased from rium were determined (Fig. 2d). At pH 2.0, the leaching contents
6.04% and 0.72% to 21.68% and 3.02%, respectively, which of total iron ions were 2.34 mg L−1, and the contents of total Fe
demonstrated that Fe–Mn oxides effectively increased the and Fe(III) were substantially comparable, whereas the contents
number of O-containing groups on FMBC.13 In Fe 2p prole of of Fe(II) were small. This was partly due to the fact that Fe(II) will
BC (Fig. S2c†), The element Fe in BC existed as Fe(III) corre- be oxidized by dissolved oxygen, and partly owing to the ability
sponding to binding energies of 711.07 eV and 724.57 eV.21 This of Fe(II) to supply electron for reducing Cr(VI) and producing
was consistent with the results of the XRD analyses. Neverthe- Fe(III).22,23 Moreover, the change in Mn concentration decreased
less, elemental Fe in FMBC (Fig. S2d†) was present in the form gradually with increasing solution pH. To reduce leaching
of both Fe(II) and Fe(III), and the relative contents of Fe(II) and concentrations of Fe and Mn ions and at the same time to
Fe(III) were 44.74% and 55.26%, respectively.21 No characteristic ensure Cr(VI) adsorption performance for FMBC, solution pH of
peaks were detected in the ne XPS mapping of high-resolution 3.0 was selected as the initial pH in subsequent experiments.
Mn 2p in BC (Fig. S2e†). In Fig. S2f,† a distinct Mn 2p charac- To further investigate the inuences of coexisting ions on
teristic peak appeared in FMBC, and Mn 2p peaks existed in removing Cr(VI) for FMBC, effects of coexisting cations for Cr(VI)
both Mn(II) and Mn(III) valence states.12 The binding energies of removal were explored (Fig. 2e and f). Na+ ions did not have
Mn(II) and Mn(III) in the Mn 2p peaks were 640.76/652.28 eV and obvious inuence for removing Cr(VI) by FMBC. When concen-
642.72/653.88 eV, respectively, and the relative contents of trations of Ca2+ and Mg2+ rose from 0 mg L−1 to 50 mg L−1,
Mn(II) and Mn(III) were 64.28% and 35.72%, respectively.12 The Cr(VI) adsorption performance for FMBC decreased from
above analyses demonstrated that the loading of Fe–Mn oxides 93.24% to 92.34% and 91.14%, respectively, which suggested
provided developed pore structure and more O-containing that the presence of Ca2+ and Mg2+ exerted a slight inhibitory
groups for FMBC. inuence on removing Cr(VI) for FMBC. However, when the
concentrations of Pb2+, Cu2+ and Ni2+ were increased to
50 mg L−1, the Cr(VI) adsorption performance for FMBC
3.2 Inuence of solution pH and co-existing ion on decreased to 63.68%, 70.32% and 78.96%, respectively. This
removing Cr(VI) indicated that there was a serious inhibitory inuences of Pb2+,
Solution pH is one of crucial factor affecting contaminant Cu2+ and Ni2+ on removing Cr(VI). Among these three heavy
removal capacity by absorbent. The result indicated that solu- metal ions, the inhibitory effect of Pb2+ was more obvious.
tion pH obviously (p < 0.05) affected Cr(VI) adsorption perfor- According to previous ndings, oxygen-containing group had
mance for FMBC (Fig. 2a and b). The Cr(VI) adsorption a much higher affinity for Pb2+ than the other metal elements. It
capacities for FMBC were approximately 117 mg g−1 at solution was also possible that the competitive adsorption of Cr(VI) with
pH of 2.0 and 3.0, while Cr(VI) adsorption capacity by FMBC Pb2+, Cu2+ and Ni2+ would compete for active site on FMBC,
decreased to 1.03 mg g−1 with increasing solution pH to 10.0. resulting in decreasing Cr(VI) adsorption performance.10
The adsorption capacity of Cr(VI) by BC was considerably lower The inuences of different anions on removing Cr(VI) for
compared to FMBC (Fig. S3†). The Cr(VI) adsorption capacities FMBC were examined separately (Fig. 3f). SiO32−, NO−3 and Cl−
for BC were about 63 mg g−1 at solution pH of 2.0 and 3.0, and ions had no signicant inuences on removing Cr(VI) for FMBC
decreased to 0.7 mg g−1 as the solution pH increased to 10.0. when the ions concentrations rose to 50 mg L−1, and the
This result indicated the loading of Fe–Mn oxides improved the removal rate was maintained at 93%. Whereas, the co-existence
removal capacity of sludge biochar for Cr(VI).13 It was not diffi- of CO2-3 with Cr(VI) produced a slight inhibitory inuences and
cult to discover that the removal performance of Cr(VI) by FMBC Cr(VI) removal performance declined to 91.08%. However, there
was stronger on acidic condition. Furthermore, nal pH at was a signicant inhibitory effect of SO42− and PO43− on
adsorption equilibrium on acidic condition was greater than removing Cr(VI) for FMBC and the adsorption performance
initial solution pH, whereas nal pH was below initial pH on decreased to 75.62% and 68.96%, respectively. This may be due
alkaline condition. to the fact that sulfate and phosphate ions and HCr2O4− ions

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Fig. 2 Influence of solution pH on removing Cr(VI) for FMBC and solution pH after adsorption equilibrium (a), correlation between solution pH
and adsorption capacity (b), and the content of Cr, Fe and Mn in solution after adsorption equilibrium ((c) Cr and (d) Fe and Mn). Effect of co-
existing cation (e) and co-existing anion (f) on Cr(VI) removal by FMBC.

had similar chemical properties, which formed competitive Cr(VI) from solution to FMBC surface.24 The useable active site
relationship with each other to seize the active sites above on FMBC surface decreased dramatically during 30∼150 min,
FMBC.9 which led to slow increase in adsorption performance of Cr(VI)
for FMBC. In this stage, Cr(VI) would diffuse from the FMBC
3.3 Adsorption kinetics surface to the inside pore channels and be adsorbed in active
site of inside pore channels.25 The reaction reached equilibrium
The inuences of reaction time for removing Cr(VI) by FMBC are
when all the adsorption sites inside and outside the FMBC were
displayed in Fig. 3a. The Cr(VI) removal performance by FMBC
occupied by Cr(VI).
increased rapidly from 34.62% to 73.24% within 5–30 min, and
The Cr(VI) concentration declined rapidly from 50 mg L−1 to
Cr(VI) removal performance by FMBC increased to 92.03% at
4.86 mg L−1 in 0–30 min (Fig. 3b). In 30–120 min, the Cr(VI)
150 min, and then the removal efficiency stabilized at about
concentration decreased slowly to 1.38 mg L−1 and Cr(VI)
93% and reached equilibrium aer 150 min. This was attrib-
contents remained at about 1.2 mg L−1 aer 120 min. However,
uted to the fact that in the rst 30 min, the FMBC surface
the Cr(III) concentrations increased from 0 to 8.52 mg L−1 then
contained abundant useable active site and can rapidly adsorb

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Fig. 3 Influences of adsorption time on removing Cr(VI) for FMBC and change of solutions pH (a), influences of adsorption time on Cr
concentration in solution (b) and analysis of zeta potential value of MFBC (c).

decreased to 2.18 mg L−1, which indicated that the removal indicating that reduction reaction of Cr(VI) for FMBC was mainly
behavior belonged to the adsorption-reduction co-action.26 concentrated in early stage of removal process.
Notably, the solution pH (Fig. 3a) rst increased rapidly as To research removal process of Cr(VI) for FMBC, the pseudo
the reaction proceeded, and then the solution pH remained rst order kinetic model, pseudo second order kinetic model
around 5.0. Since solution pH affects presence pattern of and Elovich model were chosen to describe the experiment
pollutants and the electrical property of sorbent, the zeta results, and tting result is displayed in Fig. 4a and Table 1. The
potential value was used to represent the electrical properties of linear correlation coefficient of pseudo second order kinetic
FMBC at different pH, and the result is displayed in Fig. 3c. model (R2 = 0.997) was higher than that of pseudo rst order
Potentiometric analysis expressed that zeta potential value of kinetic model (R2 = 0.967) and Elovich model (R2 = 0.941).
FMBC shied from positive to negative with the increase of pH, Additionally, the difference between the theoretical adsorption
indicating that electrical property of FMBC shied from positive capacity (qe,cal) obtained from pseudo rst order kinetic model
to negative electricity.10 The zero potential point (pHpzc) of (114.00 mg g−1) and the actual adsorption capacity (qe,exp,
FMBC was 3.74. In aqueous solution, Cr(VI) exists mainly as the 116.48 mg g−1) was large, whereas the difference between the
anion HCr2O4− at solutions pH < 6.0, while Cr(III) exists as tted value from pseudo second order kinetic model (117.22 mg
Cr3+.27 This suggested that in the early stage of reaction, the g−1) and the qe,exp was small, which indicated that the pseudo
positively charged FMBC adsorbed Cr(VI) to the surface by second order kinetic model could better describe the Cr(VI)
electrostatic action, and then reduced Cr(VI) to cation Cr(III) by removal for FMBC than the pseudo rst order kinetic model.29
reducing substance, and due to electrostatic repulsion Cr(III) This expressed that the removal behavior of Cr(VI) for FMBC was
ions were released to aqueous solutions.28 During the Cr(VI) mainly controlled by chemisorption.30 Briey, the Cr(VI) removal
reduction, there were a continuous consumption of H+ in the behavior by FMBC was primarily controlled through chemical
solution, which was the reason for the increase in pH. When effects (e.g., complexation and electron transfer), while physical
solution pH outweighed pHpzc, FMBC adsorbed the cation Cr(III) effects (e.g., electrostatic effects and pore lling) were secondary
in solutions to surface by electrostatic action. Notably, the to controlling the reaction process.5,12
change in solution pH was mainly concentrated within 30 min, Ordinarily, diffusion behavior in removal process is deter-
mined by multiple mechanism. The intra-particle diffusion

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Fig. 4 The kinetic models for removing Cr(VI) by FMBC ((a) pseudo-first-order, pseudo-second-order and Elovich, (b) intra-particle diffusion
model and (c) liquid film diffusion model) and the adsorption isotherm for removing Cr(VI) by FMBC at different temperature (d).

Table 1 Adsorption kinetic model fitting parameters diffusion constants showed Kd1 > Kd2 > Kd3, and the boundary
layer constants showed C1 < C2 < C2, which showed that external
Fitting
diffusion dominated the removal behavior.10 The outcome of
Model Parameter result
lm diffusion is displayed in Fig. 4c and Table S2.† The
Experimental data qe,exp (mg g−1) 116.48 outcome indicated that liquid lm diffusion diagram held
Pseudo-rst-order qe,cal (mg g−1) 114.00 linear relationship, and R2 value (0.990) kept at a high level,
k1 (min−1) 0.086 which indicated that the liquid lm diffusion played a decisive
R2 0.967
role in the kinetic process.9 Briey, the removal behavior can be
Pseudo-second-order qe,cal (mg g−1) 117.22
k2 (g mg−1 min−1) 0.001 divided into the following step: liquid lm diffusion rst
R2 0.997 controlled adsorption behavior by removing Cr(VI) from liquid
Elovich a (mg g−1 min−1) 66.723 phase to outer surface of FMBC; then the entire removal pro-
b (g mg−1) 0.057 cessed were determined by intra-particle diffusion, and Cr(VI)
R2 0.941
entered into the inner pore structure and loaded into internal
active sites until adsorption saturation.

model and the liquid lm diffusion model were employed to

nd out the diffusion behavior and the rate control steps. The 3.4 Adsorption isotherm
curves of qt over t1/2 consisted of three linear segments (Fig. 4b), The Cr(VI) adsorption performance for FMBC rose rapidly as
indicating that Cr(VI) removal behavior by FMBC had multiple Cr(VI) concentration rose from 50 mg L−1 to 100 mg L−1, which
stage.9 In general, three stages were divided into external attributed to large Cr(VI) concentrations difference between
diffusion, internal diffusion and adsorption equilibrium. The solutions and FMBC, which created large mass-transfer resis-
curve of external diffusion stage had high slope (Kd1), indicating tance and allowed Cr(VI) to be adsorbed onto FMBC surface.
Cr(VI) ion in solutions transferred to outer surface. The second However, the Cr(VI) adsorption performance by FMBC did not
part of diffusion trend slowed down signicantly and belonged change much as concentration rose from 100 mg L−1 to
to the internal diffusion phase, where Cr ions diffused from the 150 mg L−1, because active sites on FMBC surface were
external surface into the internal structure of FMBC and were limited.29
subsequently adsorbed to internal adsorption site.23 The third To further understand the properties of the adsorption, four
part was equilibrium stages. Additionally, the Ci values (Table commonly isotherm models (Langmuir, Freundlich, Temkin
S2†) for all stages showed a tendency to deviate from 0, sug- and Sips models) were used in this work, and the result is
gesting that intra-particle diffusion was not the only controlling shown in Table 2 and Fig. 4d. The R2 (0.992–0.996) value of
factor in removal processes.31 Moreover, the intra-particle Langmuir model was signicantly greater than Freundlich

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Table 2 Adsorption isotherm fitting parameter of removing Cr(VI) for Table 3 Thermodynamic fitting parameter of removing Cr(VI) for
FMBC FMBC

Temperature T/K DG0 (kJ mol−1) DH0 (J k mol−1) DS0 (kJ mol−1)

Model Parameter 288 K 298 K 308 K 288.15 −7.864

298.15 −9.422 32.301 1.396
−1
Langmuir qmax (mg g ) 162.29 172.34 188.09 308.15 −10.650
KL (L mg−1) 0.369 0.700 0.832
R2 0.992 0.996 0.996
c2 0.132 0.485 0.632
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Freundlich Kf (mg1−n$Ln g−1) 65.47 89.18 83.50

n 4.593 5.317 4.919 Cr adsorbed on FMBC surface. According to the mapping
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R2 0.867 0.752 0.829 pattern of EDS, elemental Cr appeared on the FMBC surface
c2 22.485 12.364 36.95 aer adsorption, which demonstrated that Cr in the aqueous
Temkin bT (kJ mol−1) 92.77 95.54 97.47
solution was successfully removed by FMBC. The crystalline
AT (g−1) 9.599 21.853 24.827
R2 0.949 0.934 0.966 structure (Fig. 5c) of FMBC before and aer removal remained
c2 5.96 24.591 12.057 basically unchanged, and the main components were SiO2 and
Sips Qm (L mg−1) 62.27 124.92 152.19 CaAl2Si2O8.33,34 However, the characteristic peaks of MnFe2O4 at
Ks 0.959 0.911 0.862 29.86°, 35.14° and 61.92° showed different degrees of decrease
m 0.381 0.711 0.790
aer adsorption, which could be the involvement of MnFe2O4 in
R2 0.924 0.956 0.961
c2 8.317 6.214 5.938 Cr(VI) removal from aqueous solution.
To further illustrate mechanisms of Cr(VI) adsorption for
FMBC, the functional groups of FMBC were analyzed by FTIR
model (0.752–0.867), Temkin model (0.934–0.966) and Sips (Fig. 5d). Aer removal, the wavenumber of hydroxyl group –OH
at 3390 cm−1 in FMBC shi to 3420 cm−1, and the intensity of –
model (0.924–0.961), which indicated that Cr(VI) adsorption
processes for FMBC were homogeneous monolayer adsorp- OH vibrational peaks was weakened. Notably, the intensity of
tion.32 Additionally, the results of chi-square test (c2) showed vibrational peaks of –COOH group, C–O group and Mn/Fe–O
that Langmuir model could better describe Cr(VI) removal group in FMBC were all weakened or shied aer adsorption.
process for FMBC than the Freundlich, Temkin and Sips Most notably, the wavenumber of the –COOH group shied
model.12 The separation factor (RL) of Langmuir model from 1400 cm−1 to 1380 cm−1 aer the adsorption, and the
remained between 0 and 1 (Fig. S4a†), suggesting that Cr(VI) intensity of the vibrational peak of the –COOH group also
removal by FMBC was effective.10 Meanwhile, elevated temper- underwent a signicant weakening. The wavenumber of C–O
group was offset from 1040 cm−1 to 1030 cm−1. In addition, the
ature reduced the RL value, which indicated that high temper-
ature could promote Cr(VI) removal for FMBC.10 According to vibrational peak of Mn/Fe–O group could be observed to be
Langmuir model, the largest theoretical removal performance offset from 539 cm−1 to 526 cm−1 and the intensity of the peak
of FMBC at 303 K was 172.34 mg g−1. Temkin model (R2 > 0.93) appeared to be slightly reduced, which could be due to the
well described the experimental results, suggesting that there reduction caused by the dissolution of the Mn or Fe elements in
was strong intermolecular force between Cr in solution and the FMBC. These results indicated that the oxygen-containing
FMBC surface, which may be involved in the redox action and groups (e.g., –OH, –COOH, C–O, and Mn/Fe–O groups) on the
complexation. FMBC complex with negatively charged Cr(VI).13,25,35 Notably, the
vibrational peak of C]C groups at 1640 cm−1 was shied to
Based on the Van't Hoff equation, the ln K0 was used to plot
1/T (Fig. S4b†), and the slope and intercept of obtained straight 1610 cm−1, where the vibrational peaks were attributed to the
line were used to calculate the value of DH0 and DS0, and then C]C group on the carbon ring, which could be able to provide
the value of DG0 was calculated (Table 3). The DH0 was greater p-electrons as the adsorption site for contaminants and remove
than 0, which indicated that the removal reaction was a heat- contaminants from solution by cation–p interactions.32
absorbing reaction.9 The negative value of DG0 decreased with However, since Cr(VI) existed mainly as anion in solution, this
increasing temperatures, demonstrating that Cr(VI) removal could be the result of cationic–p interaction between Cr(III)
behavior for FMBC was spontaneous.16 DS0 was positive, sug- generated by reduction and C]C structure on FMBC during the
adsorption process.20 According to the previous ndings, the
gesting that Cr(VI) removal processes for FMBC were entropy-
driven, and degree of freedom at solid–liquid interface C]C group shied from 1640 cm−1 to 1610 cm−1 aer Cr(VI)
increased during removal process.20 removal from solution, which was also consistent with the
present study.1,22 These analysis showed that FMBC adsorbed
Cr(VI) on surface through complexation and electrostatic inter-
3.5 Reduction-adsorption mechanism actions, and Cr(VI) ion was reduced to cationic Cr(III), and then
The morphological features and surface element of FMBC were released cation Cr(III) into solutions by electrostatic repulsion.
analyzed by SEM-EDS (Fig. 5a and b). Aer adsorption, the When solution pH outweighed zero potential point of FMBC,
uneven surface became rougher than before adsorption and the negatively charged FMBC adsorbed the positively charged
massive small particles were attached, which may be due to that

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Fig. 5 The result of SEM-EDS (a and b), FTIR (c) and XRD (d) analysis for Cr(VI) removal by FMBC.

Cr(III) from the solution in the form of Cr(III)–p interaction, (Fig. 6d), the peaks were N–C (398.28 eV), N–H (399.58 eV) and
complexation and electrostatic interaction. N–O (402.20 eV).3 Aer Cr(VI) removal, the binding energy of N–
To gain deeper understanding of adsorption mechanism of C, N–H and N–O groups shied to 398.50 eV, 400.03 eV and
Cr(VI) for FMBC, the sample before and aer removal was 402.70 eV, respectively, suggesting that chemical reaction
analyzed through XPS. Fig. 6a showed full spectrum of FMBC between the N-containing groups in FMBC and Cr(VI) took
before and aer Cr(VI) adsorption, and Cr 2p peaks were place.3 Previous literature demonstrated the ability of N–C
detected on the full spectrum aer the removing Cr(VI), sug- groups in biochar to provide lone pair electrons for coordina-
gesting that Cr(VI) ions were successfully adsorbed in FMBC tion reactions with Cr(VI).37 Moreover, previous literature had
surface. The peak of Cr(III) and Cr(VI) appeared in Cr 2p3/2 ne also shown that the N–H group in biochar could act as an
spectra (Fig. 6b), further indicating that Cr(VI) ions were reduced electron donor triggering an electron transfer reaction to facil-
to Cr(III) by FMBC. The Cr(III) and Cr(VI) peaks correspond to itate the reduction of Cr(VI).38 The Fe 2p spectra (Fig. 6e) were
binding energies of 576.88 eV and 578.30 eV, respectively, the roughly classied into Fe(II) and Fe(III), and the relative amount
percentage of Cr(III) and Cr(VI) was 72.77% and 26.23%, of Fe(II) was reduced from 44.74% to 29.78% aer the reaction,
respectively. This result indicated that the vast majority of Cr(VI) while the content of Fe(III) in FMBC increased from 55.26%.
was removed through adsorption-reduction.24,28 The primary This result indicated that Fe(II) in FMBC could reduce Cr(VI) to
peak of O 1 s before removal in Fig. 6c were Mn/Fe–O (529.51 Cr(III).32 Similarly, in Mn 2p spectrum (Fig. 6f), the content of
eV), C–O (530.71 eV) and C]O (531.66 eV).10,19,36 The decreasing Mn(II) decreased from 64.28% to 60.50% aer the reaction,
peak areas of Mn/Fe–O/C–O and increasing peak area of C]O which also indicated the redox reaction between Mn(II) and
indicated that FMBC could be used as electrons transfer Cr(VI).19 The result demonstrated that Mn and Fe in FMBC could
medium and attend reactions through the gain and loss of reduce Cr(VI) to Cr(III). Meanwhile, the binding energies of both
electron by O-containing functional group.3 In addition, Mn and Fe shied to higher energy levels aer reaction, which
binding energy of C–O and C]O appeared to increase aer the further conrmed that Mn and Fe played a key role in removing
reaction, which was presumed to be due to the O-containing Cr(VI).13
groups in FMBC complexing with Cr(VI).23 In N 1 s spectra

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Fig. 6 XPS analysis of FMBC after Cr(VI) removal ((a) full spectrum, (b) Cr 2p3/2, (c) O 1s, (d) N 1s, (e) Fe 2p and (f) Mn 2p).

Thereby, removing Cr(VI) for FMBC consisted of complexa- 3.6 Performance in treating Cr(VI)-containing wastewater
tion containing O/N groups, cation–p interactions, electrostatic To explore practicality, the FMBC was employed to remove Cr(VI)
interactions, and reduction. The reduction process was shown from electroplating wastewater (Fig. 7a) and mineral dissolving
in the following equation:
wastewater (Fig. 7b). At dosage of 0.4 g L−1, Cr(VI) concentration
in both water samples decreased rapidly and the residual Cr(VI)
3Mn2+ + HCrO4− + 7H+ / 3Mn3+ + Cr3+ + 4H2O (3)
contents were higher than 0.2 mg L−1, and this result did not
3Fe2+ + HCrO4− + 7H+ / 3Fe3+ + Cr3+ + 4H2O (4) meet the discharge standard for Cr(VI)-containing wastewater
(0.2 mg L−1). To increase the removal rate, the dosage of FMBC
6Mn2+ + Cr2O72− + 14H+ / 6Mn3+ + 2Cr3+ + 7H2O (5) was increased to 1 g L−1, and FMBC was able to remove Cr(VI) to
less than 0.2 mg L−1 (Chinese Cr(VI) emission standard) in both
6Fe2+ + Cr2O72− + 14H+ / 6Fe3+ + 2Cr3+ + 7H2O (6) electroplating wastewater and mineral dissolving wastewater at
90 min and 30 min, respectively, which indicated that FMBC
Anionic Cr(VI) in solutions was adsorbed to FMBC surface by had potential to be applied to the treatment of real wastewater.
complexation containing N/O groups or electrostatic interac-
tion, and Cr(VI) ions on FMBC surface were reduced to positively
charged Cr(III) by reducing substances in FMBC (e.g., divalent
iron/manganese or reduced phenolic hydroxyl groups). The 3.7 Regeneration experiment
resulting cation Cr(III) with the positively charged FMBC would Aer each adsorption, the FMBC in aqueous solution was
undergo electrostatic repulsion and be released into the separated by magnet, then the adsorbed FMBC was regenerated
aqueous solution. Notably, the reduction reaction continued to by shock desorption for 12 h. In Fig. 7c, removal efficiency of
consume massive H+ in the aqueous solutions. When solutions Cr(VI) by FMBC declined with increasing number of regenera-
pH was higher than pHpzc, Cr(III) in the aqueous solution could tions when Cr(VI) contents were 50 mg L−1. However, Cr(VI)
be adsorbed onto the FMBC surface through the complexation removal performance by FMBC was still 82.34% in the h
of N/O groups, electrostatic interactions, and cation–p regeneration. When Cr(VI) contents were declined to 5 mg L−1
interactions. (Fig. 7d), the Cr(VI) removal efficiency for FMBC was still as high
as 97.68% aer ve regenerations. This result indicated that

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Fig. 7 Removing Cr(VI) in electroplating wastewater (a) and dissolved mineral wastewater (b) for FMBC. Regeneration experiment of Cr(VI)
removal by FMBC ((c) 50 mg L−1 and (d) 5 mg L−1).

FMBC exhibited excellent potential to treat Cr(VI)-containing Conflicts of interest

wastewater.
The authors declare that we have no competing nancial
interests.
4 Conclusion
In this research, Fe–Mn oxide loaded sludge biochar (FMBC) Acknowledgements
was prepared. The Cr(VI) removal processes for FMBC were in
accordance with pseudo-second-order kinetic and Langmuir This study was supported by Lithium Resources and Lithium
model, and largest removal performance of FMBC for Cr(VI) Materials Key Laboratory of Sichuan Province [LRMKF202309],
was 172.34 mg g−1. Additionally, the Cr(VI) adsorption and Sichuan Science and Technology Program (2022YFS0495).
processes for FMBC were a spontaneous, monolayer and
homogeneous chemical adsorption, and held obvious pH-
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