Bioresource Technology 315 (2020) 123840

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Pyrolyzed fabrication of N/P co-doped biochars from (NH4)3PO4-pretreated T

coffee shells and appraisement for remedying aqueous Cr(VI) contaminants
⁎
Jianqiu Lia,1, Feifei Heb,1, Xiaoyang Shena, Dongwen Hua, Qiang Huanga,
a
School of Materials and Energy, Yunnan University, Kunming 650091, PR China
b
School of Agriculture, Yunnan University, Kunming 650091, PR China

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

Keywords: In this study, an agricultural residue-derived biochar was fabricated by pyrolyzing coffee shells using (NH4)3PO4
Agricultural residues pretreatment. The influence of pyrolysis temperature on the structure and properties of biochars was in-
Coffee shells vestigated. The elemental analysis, spectroscopic and textural studies showed that the biochars were endued
Biochar sufficient N and P co-doping and large specific surface area by (NH4)3PO4-pretreatment. The appraisement for
Heteroatom doping
remedying aqueous Cr(VI) contaminants demonstrated that the N/P co-doped biochars offered high efficiencies
Hexavalent chromium
above 95% for aqueous Cr(VI) removal. The mechanism investigation displayed that the adsorption and re-
duction of Cr(VI) were boosted by the synergistic effect between the hierarchical pore structure and the groups
related to oxygen, nitrogen and phosphorus. Moreover, the biochar can be readily regenerated by HCl solution
soaking for reuses several times. This work should permit for providing a convenient utilization of coffee shell
agricultural residues, and the coffee shell-derived biochars supplied potential for remedying Cr(VI) in effluents.

1. Introduction terms of environmental management, biochars based on agricultural

The disposal and resource utilization of agricultural residues are
issues of concern to governments and environmental organizations.
Although China is not a large coffee-growing country, its annual coffee
production has reached 150,000 tons, most of which is distributed in
the southwestern province of Yunnan. It is estimated that coffee shells
account for approximately 20% of the dry weight of coffee beans and
thus, about 30,000 tons of coffee shell wastes come into being every
year (Sun et al., 2019). Compared with the coffee residues from husks
and pulps, which can be used as raw material for the production of fuel,
animal feed additives, or nutritional supplements (Oliveira et al., 2009),
coffee shells lack effective utilization ways on a large scale, and most of
them are thrown in the fields. Not only does this cause environmental
damage, but it also wastes the valuable resource. Therefore, the de-
velopment of a practical method to process coffee shells on a large scale
is conductive to environmental management and resource utilization of
the agricultural waste.
It is cognizant that coffee shells are rich in cellulose and lignin
(Ioannidou and Zabaniotou, 2007), which can be acted as a high-
quality carbon source material with potential applications in battery
electrodes, energy storage and environmental remediation (Creamer
and Gao, 2016; Deng et al., 2016; Sun et al., 2019). Especially in the
waste have attracted much attention due to their renewability of
feedstock, low cost, simple processing and remarkable effects (Varma,
2019). Several groups have exhibited that fabrication of biochars from
coffee residues through pyrolysis offered economic and environmental
benefits for the removal of organic pollutants (e.g., dyes, formaldehyde
and phenols) and toxic heavy metals (e.g., Pb(II), Cd(II), Cu(II), Zn(II)
and Cr(VI)) (Ahmad and Rahman, 2011; Boudrahem et al., 2011;
Khenniche and Benissad-Aissani, 2011; Suganya and Senthil, 2018). In
order to achieve highly efficient removal of contaminants, an inde-
pendent two-step process of carbonization and activation was often
employed to increase the specific surface area in these previous works.
The activators generally involved chemical reagents such as ZnCl2,
KOH, and H3PO4. Among them, metal chloride activators are banned in
many countries due to severe corrosiveness, while strong base activa-
tors, although relatively less corrosive, cause a low carbon yield
(usually < 30%) (Mohammed et al., 2015; Cuong et al., 2019). As a
result, H3PO4 was regularly recommended as a suitable treatment agent
for pyrolysis of biomass (Kan et al., 2015; Chen et al., 2020a). Fur-
thermore, if the contaminants can be degraded during adsorption, this
will greatly avail the reduction of their toxicity. Many studies have
demonstrated that doping of N, P heteroatoms can provide biochars
extra adsorptive sites and strong delocalization of electrons to enhance

⁎
Corresponding author.
E-mail address: huangqiang@ynu.edu.cn (Q. Huang).
1
Li J. and He F. equally contributed to this work.

https://doi.org/10.1016/j.biortech.2020.123840
Received 1 June 2020; Received in revised form 8 July 2020; Accepted 10 July 2020
Available online 15 July 2020
0960-8524/ © 2020 Elsevier Ltd. All rights reserved.
J. Li, et al.
the reduction of aqueous Cr(VI) ions due to the supplied Lewis base
sites and improved hydrophilic surface (Chen et al., 2020a; Shin et al.,
2019; Valix et al., 2006). For this, Urea, ammonia and phosphates are
commonly used to introduce N, P heteroatoms into carbon networks
(Leng et al., 2020; Shin et al., 2019; Zhou et al., 2018). However, low
doping amount, serious corrosivity and high consumption limited their
practical application. Thus, it is significant to exploit a simple and ef-
fective method to introduce heteroatoms into biochars with high yield
and safety.
Ammonium phosphate ((NH4)3PO4), a nitrogen-phosphorus com-
pound fertilizer, can gradually generate H3PO4, and NH3 during heating
(Wang et al., 2013). It is well demonstrated that H3PO4 can assist the
dehydration, aromatization, crosslinking and porogenic effects of bio-
mass during carbonization (Valero-Romero et al., 2017; Chen et al.,
2020a). Moreover, the escaping nitrogen species can react with the
carbon substances to produce nitrogen-containing functional groups
during thermal process (Xia et al., 2017). Therefore, it is reasonable
that (NH4)3PO4 treatment should offer a simple yet efficient method to
simultaneously create N and P sources for N/P co-doping of biomass-
derived carbons, which can be easily scaled-up due to the gradualness
and safety afforded by the in-situ generation of the activators. In this
study, we reported a novel N/P heteroatom co-doped biomass-derived
porous carbon by directly pyrolyzing coffee shell feedstocks after
(NH4)3PO4 treatment. One-step activation-carbonization process assists
osmosis of (NH4)3PO4 into the cell walls of coffee shell that restrains
aggregation of neighboring walls during pyrolysis while evenly carbo-
nizes biomass materials. The obtained carbonaceous materials ex-
hibited features such as large specific surface area (1133 m2∙g−1),
hierarchical porous structures and sufficient N/P heteroatom co-
doping. The appraisement for remedying deleterious Cr(VI) ions
showed that the coffee shell-based carbons was endowed with highly
efficient adsorption/reduction of Cr(VI) to lower hazardous Cr(III). The
main objectives of current work are i) to render a method for mass
production of heteroatom-doped coffee-shell biochar, ii) to investigate
the adsorption performance and influence factors of aqueous Cr(VI)
removal, and iii) to identify the effect of N/P heteroatoms on the re-
duction of Cr(VI).
2. Materials and methods
2.1. Materials
Coffee (Coffea arabica L.) shell was a wet processed endocarp and
silverskin collected from Baoshan, Yunnan Province of China. Before
use, coffee shells were crushed to 18 mesh, washed and dried. All
chemicals used in the experiment were of analytical reagent (A.R).
Triammonium phosphate ((NH4)3PO4), potassium dichromate
(K2Cr2O7), sodium hydroxide (NaOH), hydrochloric acid (HCl), and
1,5-diphenylcarbazide (DPC) were purchased from Sinopharm
Chemical Reagent Co., Ltd (Shanghai, China). The experimental water
was self-made deionized water (DI water).
2.2. Preparation of coffee shell-derived carbons
Coffee shells of 10.0 g were well blended with 10.0 g (NH4)3PO4
using a pestle and mortar. DI water of 100 mL was added and the
mixture was sealed for 24 h at room temperature (16–28 °C). After the
mixture was heated to 110 °C to dry out free moisture, the resulted solid
was transferred into a ceramic crucible. The pyrolysis was completed in
a box-type furnace. Before heating the furnace, nitrogen gas was purged
to replace the air inside the chamber. The furnace was heated to 200 °C
at a heating rate of 5 °C/min and held at this temperature over 30 min
for volatile removal, then it was further increased to a set temperature
(600, 700 and 800 °C) at the same heating rate and kept at this tem-
perature for 120 min. The obtain solid was repeatedly washed with hot
DI water, dried at 110 °C for 8 h and then, stored in a desiccator to
2
Bioresource Technology 315 (2020) 123840
prevent moisture absorption. The biochars based on (NH4)3PO4-pre-
treatment under varying temperatures were denoted as NPBC600,
NPBC700 and NPBC800, respectively. For comparison, raw biochar
(RBC700) without (NH4)3PO4-pretreatment was prepared under 700 °C
with the similar procedure.
The yield of biochars was estimated by Eq. (1):
WBC
Y (%) = × 100
WCS (1)
where WBC and WCS are the weight of biochar and dried coffee shells
respectively.
2.3. Characterization
The elemental composition was determined by X-ray fluorescence
spectrometer (XRF, Rigaku ZSX100e, Japan). Thermogravimetric/dif-
ferential scanning calorimetry (TG/DSC, SDT Q600 America) was used
to analyze the thermal properties of coffee-shell powders pretreated by
(NH4)3PO4. Raman spectra (Renishaw inVia microscopic confocal
spectrometer system, UK) were recorded with Ar+ laser (514.5 nm)
excitation. Scanning electron microscopy (SEM, FEI Nova NanoSEM
450, US) was performed to take on the micrographs of biochars. Fourier
transform infrared spectroscopy (FTIR, Nicolet iS10, US) was recorded
to identify the surface functional groups in the wave number range of
400–4000 cm−1. X-ray photoelectron spectroscopy (XPS, Thermo
ESCALAB 250 US) was operated at 15 kV and 15 mA with an alumina
target (Al–Kα, hv = 1486.6 eV). The specific surface area and pore size
distribution were determined by nitrogen adsorption–desorption mea-
surements at 77 K (Micromeritics TriStar II 3020 US).
2.4. Batch experiment for Cr(VI) removal
Cr(VI) ions removal experiments were performed in a batch model.
The reaction flask was surrounded by a thermostatic water circulation
to maintain the temperature of 30 ± 1 °C. The stock solution
(1000 mg·L−1) of Cr(VI) was prepared by dissolving 1.00 g K2Cr2O7 in
1000 mL DI water, which was further diluted to the required con-
centration before use. The solution pH was adjusted by adding NaOH or
HCl sulotion (0.1 mol·L−1). In a typical experiment, 100 mL Cr(VI)
solution (50–300 mg∙L−1) was poured into a quartz flask with a fixed
amount of biochar (100 mg) and the flask was oscillated for 240 min. At
a certain interval, 5 mL of the suspension was withdrawn and cen-
trifuged quickly for solid–liquid separation. The total chromium con-
centration ([Cr]) in the supernatant liquid was measured by ICP ana-
lysis (ICP-AES1000, Shimadzu Japan). Residual Cr(VI) concentration
([Cr(VI)]) in liquid was analyzed by spectrophotometer (U-4100,
Hitachi Japan) using DPC as the complexing agent at a wavelength of
540 nm. The Cr(III) concentration ([Cr(III)]) was calculated by Eq. (2):
[Cr(III)] = [Cr] − −[Cr(VI)] (2)
The removal ratio of Cr(VI) ions was characterized by Eq. (3):
[Cr(VI)]0 − [Cr(VI)]
Removal ratio(%) = × 100
[Cr(VI)]0 (3)
And the reduced percent of Cr(VI) to Cr(III) in the solution was
denoted by the ratio of [Cr(III)] to [Cr] (Eq. (4)):
[Cr(III)]
Reduction ratio(%) = × 100
[Cr] (4)
3. Results and discussion
3.1. Synthesis and characterization of coffee shell-derived biochars
3.1.1. Elemental analysis
The elemental composition of biochar products under different
J. Li, et al. Bioresource Technology 315 (2020) 123840

Table 1
Composition of the raw materials and biochars.
Sample Ultimate analysis (wt% by dry basis) XRF analysis (wt%)

Moisture Volatile Fixed carbon Ash C O N P Metals

Coffee shells 5.61 47.22 45.36 1.81 / / / / /

RBC700 1.33 13.88 81.46 3.33 77.8 19.2 0.8 – 2.2
NPBC600 1.78 21.33 73.66 3.23 73.6 14 7.1 3.6 1.7
NPBC700 1.51 15.36 79.43 3.7 75.8 12.6 6.5 3.2 1.9
NPBC800 2.17 10.77 83.85 3.21 79.1 10.2 5.8 2.8 2.1

conditions is listed in Table 1. It can be found that with the increase of
pyrolysis temperature, the carbon content in products gradually in-
creased, while the content of other heteroatoms decreased. The ulti-
mate analysis also exhibited the similar tendency. The results reflected
the elimination of volatiles and deepening of carbonization. The yields
of RBC700, NPBC600, NPBC700 and NPBC800 were determined to be
33.7, 43.2, 40.3 and 37.8% respectively, which also clearly reflected
the decrease in raw material left caused by the increasing temperature.
It should be noted that although the pyrolysis temperature was the
same, the yield of RBC700 appeared to be less than that of NPBC700,
which may be due to the phosphoric acid released by (NH4)3PO4 to
prevent the generation of volatile carbonaceous substances (Valero-
Romero et al., 2017; Chen et al., 2020a). In addition, biochars contain a
small amount of metal elements (e.g. Ca, Fe, Al), which should be
brought by the raw materials. The ultimate analysis also found the
presence of small amounts of ash in biochars (3.21–3.33%). RBC700
contains a trace of nitrogen (0.8%), indicating that the feedstock itself
stores nitrogen, while phosphorus was only introduced after (NH4)3PO4
treatment. The content of these two elements were significantly in-
creased after treatment with (NH4)3PO4.
The TG curve gives a decreasing trend with the increasing tem-
perature (Supplementary Material). The residual amounts of feedstocks
at 600, 700, 800 °C was substantially equal to the yield pyrolyzed at the
same temperature. In the DSC curve (Supplementary Material), a sharp
endothermic peak about 200 °C corresponds to the decomposition of
(NH4)3PO4, and the broadened and strong endothermic band above
400 °C can be ascribed to the slow gasification and carbonization of
cellulose, lignin and other components in coffee shells, indicating a
progressive reaction that the evolution of volatiles and the rearrange-
ment of carbon occurred during the thermal treatment (Mohanty et al.,
2013).
3.1.2. Morphological and textural features
From the SEM images of biochars (Supplementary Material) it is
clear that these coffee shells-derived carbons have a honeycomb-like
porous structure. The visible pores vary in size, ranging from a few to
tens of microns. It can also be observed that NPBC800 sample appeared
richer and deeper pores, which may reflect the evolution of volatiles
and carbon consumption at the risen temperature. It is noted that the
raw biochar without (NH4)3PO4 treatment (RBC700) showed a rela-
tively smooth surface.
The textural properties were further analyzed by N2 adsorption-
desorption measurement. The main parameters are presented in
Table 2. It is clear that compared with NPBCs, RBC700 gave negligible
specific surface area (SSA) and total pore volume (Vtotal) values, fully
reflecting the activation of (NH4)3PO4 during pyrolysis. The tabulated
data also show that SSA and Vtotal increased with the rising pyrolysis
temperature, and the two values for NPBC800 reached 1133 m2∙g−1
and 0.59 cm3∙g−1, respectively. The ratio of the SSA for mesopores
(Smeso) to the SSA for micropores (Smicro) was calculated to be 0.096,
0.13 and 0.21 for NPBC600, NPBC700 and NPBC800, accordingly. The
gradually increasing ratio indicated that higher temperature enriched
the pore structures, which can boost the synergistic effects among pores
with different length scales and offer more channels for solute diffusion
(Chu et al., 2018; Hu et al., 2015). Noted the Vmeso of NPBC800 was
significantly reduced to compare with the biochars pyrolized at lower
temperatures. The most likely reason was considered the collapse of
mesoporous pores caused by high temperature or the fact that high
graphitization degree was not conducive to the construction of meso-
pores/macropores (Chu et al., 2018).
All three NPBCs represent I/IV-type adsorption-desorption iso-
therms with well-demarcated plateaus over the low pressure range
(Fig. 1a), revealing the emergence of high-density micropores. The
weak hysteresis loops that occur in the high pressure region are closely
related to mesopores and macropores (Song Yang et al., 2019). How-
ever, the isotherm provided by RBC700 is obviously different, which
belongs to the III-type without hysteresis loop (Fig. 1b). It also showed
the difference in their porous structures.
3.1.3. Spectral characteristics
FTIR, Raman and XPS analyses were applied to provide the spec-
troscopic characteristics of the biochar structures (Supplementary
Material). From the FTIR it can found that the biochars offered similar
IR spectra. The bands centered at 3430, 2918/2850, 1617 and
1388 cm−1 appeared due to the absorptions of –OH, –CH–/–CH2–,
aromatic C = O/C = C and C = N groups respectively. Besides, the
region below 1200 cm−1 was identified as functional segments corre-
sponding to C–O and C–N bonds (Chu et al., 2018; Zhou et al., 2018).
The peaks of phosphorus-containing groups were also discriminated in
this range, for example P–O–C and C–O–P = O from phosphates and
pyrophosphates linked with carbonaceous frameworks (Wang et al.,
2019). It was also found from the FTIR spectra that the absorptive in-
tensities for NPBC600, NPBC700 and NPBC800 are gradually de-
creased; implying that higher temperature treatment subtracted the
amount of asymmetric vibrational groups (Jin et al., 2016).
The Raman spectra of biochars displayed conspicuous peaks at 1358
and 1601 cm−1, which can be attributed to D-band and G-band of
carbons respectively. The D-band derives from the K-point phonons of
A1g symmetry of disordered carbon, whilst G-band is traceable to the
zone-center phonon of E2g symmetry of sp2 hybridized carbon (Chen

Table 2
Textural properties of the biochars obtained under different temperatures.
Sample SSA (m2∙g−1) Smicro N(m2∙g−1) Smeso (m2∙g−1) Vtotal (cm3∙g−1) Vmicro (cm3∙g−1) Vmeso (cm3∙g−1) Average pore size (nm)

NPBC600 787 706 68 0.448 0.264 0.124 2.28

NPBC700 825 743 96 0.464 0.269 0.141 2.25
NPBC800 1133 903 186 0.590 0.436 0.095 2.08
RBC700 2.63 – – 0.013 – – 1.98

3
J. Li, et al.
Fig. 1. (a) Porous size distribution of biochars prepared under different temperature with (NH4)3PO4-pretreatment: inset showing the N2 adsorption–desorption
isotherms at 77 K; (b) N2 adsorption–desorption isotherm of RBC at 77 K.
et al., 2019a; Hu et al., 2015). The intensity ratio of D-band to G-band
(ID/IG) was estimated to be 0.841, 0.826 and 0.819 for NPBC600,
NPBC700 and NPBC800 accordingly. The declining ID/IG values sug-
gested that a high pyrolysis temperature was more conducive to the
construction of ordered sp2 structure. The value of ID/IG for RBC700 is
0.845, which is greater than the ID/IG value provided by NPBC700,
indicating that the feedstocks treated with (NH4)3PO4 was more likely
to produce carbon with sp2 structure during pyrolysis. Furthermore, the
wider full width at half maxima (HWHM) of D-bands implied the di-
versity of disordered carbon structures (Hu et al., 2015).
The wide scan XPS detected C, O, N and P elements in NPBCs, while
the P element was not found in RBC700, and the content of N element
was also far less than NPBCs. The presence of the N and P elements
further illustrates that (NH4)3PO4 pre-treatment can introduce het-
eroatoms into the biomass-derived carbon backbones.
Based on the spectroscopic and textural analyses, it can be sum-
marized that (NH4)3PO4 played a role in at least two ways during coffee
shells pyrolysis: porogenic activator and supplier of N and P doping.
3.2. Aqueous Cr(VI) removal appraisement
3.2.1. Effect of solution initial pH
A laboratory prepared Cr(VI) solution was used to evaluate the
adsorption/reduction performances of the biochars. Many previous
studies have demonstrated that solution pH was a crucial factor on the
efficiency of aqueous Cr(VI) removal using biochars, which determined
the form of chromium species in the solution and affected the charge
distribution and functional group polarity of biochar surface (Chen
et al., 2020a; Suganya and Senthil, 2018).
Fig. 2 shows the Cr species removal ratios by the biochars under
initial pH range 2.0–7.0. The higher pH was not chosen to avoid pos-
sible precipitation of chromium ion. It is found that RBC700 offered an
inconsiderable Cr(VI) elimination, by which the removal and reduction
rates were below 20% over the tested pH range. For NPBCs, pH 2.0–3.0
is an available pH range, in which the removal and reduction of Cr(VI)
were over 95%. With the increase of pH, the removal ratio of Cr(VI)
showed a downward trend. At the intrinsic pH 5.3 of 100 mg∙L−1 Cr(VI)
solution, the removal rate dropped to about 80%. In addition, the Cr
(VI) reduced ratio at different pH also showed a similar trend, that is,
the reduction rate gradually decreased with increasing pH. Within the
low pH range (2.0–4.0), the reduction rate of Cr(VI) was almost equal to
the removal ratio, indicating that Cr(VI) was completely reduced to Cr
(III) during adsorption. In fact, many studies have exhibited that acidic
conditions favored Cr(VI) reduction due to the incremental Nernst
4
Bioresource Technology 315 (2020) 123840
potential with the growing H+ concentration to cause Cr(VI) the higher
oxidizing ability at lower pH (Chen et al., 2020a). It is also found that in
the high pH region (4.0–7.0), the downward of reduction rate was more
significant. For example, from pH 4 to pH 7, the removal rate of Cr(V)
by NPBC700 decreased from 94% to 63%, while the reduction rate
decreased from 90% to 42%. Overall, NPBC700 performed best in
NPBCs due to the relatively high removal rates and reduction rates
under various pHs.
The quantitative evaluation of Cr(VI) removal by NPBCs
(Supplementary Material) showed that the values of observed first-
order reaction rate constant (kobs) were estimated to be 0.0192, 0.0278
and 0.0219 min−1 for NPBC600, NPBC700 and NPBC800, respectively
(Fig. 3). This result reflected that the order of reaction rate was
NPBC700 > NPBC800 > NPBC600. It is noted that the order of SSA is
NPBC800 > NPBC700 > NPBC600, which is not completely con-
sistent with the reaction rate order. Therefore, it can be concluded that
the textural characteristics are not the only determinant of the removal
efficiency, and the functional groups on the surface of biochars should
be considered to play an important role. According to the FTIR and N2
adsorption–desorption analyses, the contents of polar functional groups
and mesopores/macropores in biochars were significantly decreased
under the higher pyrolysis temperature (800 °C), which may explain the
attenuation of NPBC800 reduction/adsorption activity. It was demon-
strated that abundant hierarchical pores and groups related to oxygen,
nitrogen and phosphorus were beneficial to Cr(VI) removal by biochars
(Xu et al., 2019; Zhang et al., 2018).
3.2.2. Adsorption isotherms
Langmuir, Freundlich, and Slips isotherm models (Supplementary
Material) were chosen to estimate the adsorption behaviors of Cr(VI)
solutions (50–300 mg∙L−1) by NPBC700 at different temperatures. The
obtained isotherm parameters are listed in Table 3. From the tabulated
parameters, it is obvious that Slips equation matched the experimental
data better due to the higher correlation coefficient (R2), suggesting
that chemisorption occurred. At low adsorbate concentrations Slips
model can effectively reduce to the Freundlich isotherm, whilst at the
higher concentration range it predicts a monolayer adsorptive char-
acteristic of the Langmuir isotherm (Zhang et al., 2018). Slips fitting
reflected the influence of solute concentration on the adsorption be-
havior.
Several studies have focused on coffee residues and the derived
carbonaceous materials for chromium pollution treatment. For ex-
ample, it was reported that the untreated coffee husk biosorbents can
remove heavy metals from aqueous solutions. The Langmuir maximum
J. Li, et al. Bioresource Technology 315 (2020) 123840

Fig. 2. Chromium species removal under various initial pH: (a) removal ratio, (b) reduction ration. [Dosage] = 1 mg∙mL−1, [Cr(VI)]0 = 100 mg∙L−1,
Temperature = 30 ± 1 °C, Time = 240 min.

corn straws has much higher Cr(VI) removal capacity (116.28 mg∙g−1)
than the untreated one (Zhao et al., 2017). By comparison, NPBC700
offered the largest Qm value, reaching 223.5 mg∙g−1. Not only that, the
aforementioned reports seldom mentioned the reduction of hexavalent
chromium. These advantages should benefit from the huge SSA of
NPBCs and the abundance of N/P heteroatoms co-doping. Or the bio-
mass feedstocks are also the reason for the difference in Cr(VI) removal
capacity.

3.2.3. Adsorption thermodynamics

Fig. 3. Kinetic plots under pH 3.0: inset showing the linear fits of ln([Cr(VI)]/
[Cr(VI)]0) to contact time t.
capacity (Qm) for Cr(VI) adsorption was determined to be 7.0 mg∙g−1 at
pH 4.0 (Oliveira et al., 2008). The coffee ground waste was found to
adsorb Cr(VI) corresponding to 87.7 mg∙g−1 of monolayer maximum
capacity under pH 2.0 (Cherdchoo et al., 2019). Suganya and Senthil
prepared activated carbon from coffee waste by a chemical activation
with H2SO4 and ultra-sonication (Suganya and Senthil, 2018). A Qm
value for remedying Cr(VI)-contained effluents was measured to be
156.7 mg∙g−1. Other research groups have also paid attention to the
remediation of aqueous Cr(VI) using biochars from other biomass
modified by P, N alone. N-doped magnetic biochar from ager powders
was proven 142.86 mg∙g−1 Cr(VI) capacity at pH 2 and excellent re-
collection ability (Mian et al., 2018). H3PO4 treated biochar based on
The isotherm data was also utilized to determine the thermo-
dynamic parameters of the adsorption process (Supplementary
Material). The obtained Gibbs free energy (ΔGo), standard enthalpy
change (ΔHo), and standard entropy change (ΔSo) were given in
Table 4. It can be seen that the values of ΔGo gradually decrease with
the rising temperature, but their absolute values gradually increase.
This result clearly illustrated that the adsorption process occurred au-
tomatically and a higher temperature favored the sorption of Cr(VI)
(Kera et al., 2017). The positive value of ΔSo suggested an endothermic
process and increased randomness over the solid/solution interface
during adsorption. Additionally, the ΔHo value was determined to be
20.3 kJ·mol−1 in this study. It has been denoted that the typical ΔHo
values is from 2.1 to 20.9 kJ·mol−1 for physical sorption while che-
misorption involving complexation is in the range of
20.9 ~ 418.4 kJ·mol−1 (Karthik and Meenakshi, 2014). The current
ΔHo value is just located on the critical region of the two adsorptions.
Combined with the isothermal analysis, it was recommended that
chemical adsorption with weak bonding forces such as electrostatic
interaction should occur at the solid/liquid interface (Hercigonja et al.,
2012).
3.3. Cr(VI) removal mechanism investigation
The analysis of Fig. 2 confirmed that Cr(VI) in the liquid phase was

Table 3
The main isotherm parameters from NPBC700 adsorbing different concentration Cr(VI) (50–300 mg∙L−1) at varying temperature (30–40 °C): [Dosage] = 1 mg∙mL−1,
pH = 3.0, Contact time = 240 min.
T (°C) Langmuir Freundlich Slips

Qm (mg∙g−1) KL (L∙mg−1) R2 KF (Ln∙mg1–n∙g−1) 1/n R2 Qm (mg∙g−1) KS (L∙mg−1) 1/nS R2

30 223.5 0.428 0.920 97.95 0.202 0.965 272.3 0.096 0.223 0.998
35 227.2 0.487 0.932 100.9 0.207 0.975 289.7 0.111 0.244 0.980
40 235.5 0.528 0.909 107.0 0.211 0.978 301.3 0.152 0.256 0.972

5
J. Li, et al. Bioresource Technology 315 (2020) 123840

Table 4 Table 5
Thermodynamic parameters for NPBC700 adsorbing Cr(V): XPS integration results for fresh biochar (NPBC700) and used biochar
[Dosage] = 1 mg∙mL−1, [Cr(VI)]0 = 300 mg∙L−1, initial pH = 3.0, Contact (NPBC700-Cr).
time = 240 min.
Sample Peak Position FWHM Atomic Assignment
T (°C) ΔGo (kJ·mol−1) ΔSo (kJ·mol−1·K−1) ΔHo (kJ·mol−1) Concentration

30 −2.81 0.0011 20.3 (eV) (eV) (%)

35 −3.13
40 −3.57 NPBC700 C1s C-1 288.24 6.40 24.7 O=C
C-2 285.42 2.35 37.1 C–O, C–P,
C–N
C-3 284.72 1.12 38.2 C = C, C–C
reduced to Cr(III) during sorption, so the removal mechanism of Cr(VI)
O1s O-1 535.17 4.00 11.8 −OH, H2O
was proposed considering the electrostatic attraction and coincident O-2 532.84 2.35 65.9 C-O, P-O
redox reaction. Within pH 2.0–4.0, the predominant Cr(VI) species in O-3 531.07 2.09 22.3 C = O, P = O
solution was defined as HCrO4− upon the present concentration range N1s N-1 403.59 2.01 9.3 N-X (oxides of
(50–300 mg∙L−1) according to our previous works (Chen et al., 2020a; N)
N-2 400.72 2.41 72.7 N-Q
Huang et al., 2019) and others (Karthik and Meenakshi, 2014; Zhang (quaternary
et al., 2018) through Visual MINTEQ simulation. While the protonated N)
surface of NPBC adsorbed negatively charged HCrO4− ions, a redox N-3 398.46 1.53 18.0 –N = C
reaction occurred within acidic solution. The generated Cr(III) and P2p P-1 134.31 2.36 35.3 P = O, P-O
P-2 133.39 2.24 64.7 C-P
NPBC adsorbent regained the adsorption–desorption equilibrium. The
NPBC700-Cr C1s C-1 287.89 5.94 22.6 O=C
reactions between NPBC and Cr(VI) can be described by Eqs. (5)–(7): C-2 285.41 2.33 38.6 C–O, C–P,
C–N
NPBC + HCrO4−→NPBCHCrO4− (5) C-3 284.76 1.12 38.8 C = C, C–C
− O1s O-1 534.14 3.02 31.6 –OH, H2O
NPBCHCrO4 +7H →(NPBC)*+Cr
+ 3+
+4H2O (6) O-2 532.75 2.40 39.4 C-O, P-O
O-3 531.16 2.26 30.0 C = O, P = O
HCrO4−+7H++3e−→Cr3++4H2Oφθ = 1.35 V (7)
N1s N-1 403.61 5.63 28.0 N-X (oxides of
N)
XPS spectroscopy was performed to detect the changes of chemical
N-2 400.75 2.40 55.4 N-Q
composition and valence on NPBC. To compare the core-level Cr2p (quaternary
spectra of the fresh biochar (NPBC700) and spent biochar (NPBC700- N)
Cr), it is detected that after the uptake of Cr(VI), two obvious peaks N-3 398.45 1.48 16.6 –N = C
appeared in the Cr2p region corresponding to Cr2p1/2 and Cr2p3/2 or- P2p P-1 134.27 2.40 54.5 P = O, P–O
P-2 133.2 2.25 45.5 C–P
bits, which can be separately resolved into two Gaussian bands
(Supplementary Material). The bands with larger binding energies at
592.25 and 582.34 eV was attributed to Cr(VI) while the smaller ones at biochar edge by the high potential Cr(VI). (Chen et al., 2020b; Mian
587.61 and 578.08 eV belong to Cr(III) (Zhou et al., 2016). The atomic et al., 2018; Wang et al., 2019). The content of heterocyclic nitrogen
ratios of Cr(III) were calculated to be more than 90%. This indicated was relatively stable, only decreased from 18.0% to 16.8%. Hetero-
that Cr species attacked to the surface of sorbent was trivalent form in a cyclic nitrogen was usually considered as active sites in heteroatom
great measure, further revealing the occurrence of redox reaction. doped carbon (Zhou et al., 2020; Zhu et al., 2018). But in the current
More details of XPS integration referred to Table 5. The high-re- case, the significant changes have not been detected for heterocyclic
solution C1s XPS showed that before and after use, the binding energies nitrogen, which may be due to the fact that the great mass of hetero-
and relative contents of carbon changed little, indicating that the che- cycles in the carbon networks was the relatively stable six-membered
mical state of C element in the biochar was relatively stable. However, ring, and the content of five-membered ring that was easily oxidized
the heteroatoms including O, N and P have been changed significantly. was limited (Navalon et al., 2017).
In the case of O1s, the proportion of groups –OH (534.14 eV), C = O In addition, C–P bond can also be considered as another electron-
and P = O (531.16 eV) has been raised after use, while the content of donating fragment. From the P2p changes it is detected that after
C–O and P–O (532.84 eV) decreased from 65.9% to 35.4%. The changes contacted with Cr(VI) solution the content of C–P band (133.39 eV) was
indicated that partial C–O and P–O were oxidized to form groups decreased from 64.7% to 45.5%, during which the content of O–P
containing C = O and P = O during reaction respectively. The groups (134.31 eV) was increased correspondingly (Chen et al., 2019b). The
of C–O and P–O were involved in the adsorption/reduction of Cr(VI) binding energy shifts reflected the direction of electron transfer in the
(Xu et al., 2019; Zhou et al., 2016). valent bond and thus, the changes of P2p resolution suggested that C–P
The role of N/P doping can also be defined in the high-resolved N1s bond was electron donors during Cr(VI) reduction. This result was
and P2p signals of the fresh NPBC700 and spent NPBC700 contributed to the electron cloud density of the P atom was increased,
(Supplementary Material). The N1s of NPBC700 was deconvoluted into causing an added binding energy bands detected (Chen et al., 2019b).
three bands of oxidized nitrogen (N-X, 403.59 eV), quaternary nitrogen
(N-Q, 400.72 eV) and heterocyclic nitrogens (–N = C, 398.46 eV) such
3.4. Regeneration
as pyridinic and pyrrolic (Mian et al., 2018). After Cr adsorbed, the
relative proportions of these nitrogenous groups have significantly al-
Regeneration is very important for the recovery and reuse of the
tered. Clearly, the atomic ratio of N-Q has dropped from 72.7% to
biochars. It can not only test the adsorption mechanism, but also relate
55.4%, while that of N-X increased from 9.3% to 28.0%. The results
to their economic performance. The mechanism investigation has
signified that the partial N-Q was oxidized to form N-X during Cr(VI)
shown that chromium species was immobilized on the surface of
uptake, supporting that quaternary nitrogens were closely connected to
NPBC700 in the form of trivalent cations. Therefore, high concentra-
the adsorption/reduction process of Cr(VI). In an acidic solution, the
tions of H+ should release Cr(III) through competitive substitution. For
edge N-Q can be protonated. The negative charged Cr(VI) was adsorbed
this, the spent biochars were immersed into a 0.1 M HCl solution under
by the formed positive charged groups and then, the electron-rich ni-
stirring for 240 min. The filtered solid was washed with DI water and
trogen moieties were easily oxidized to produce amine oxides on the
then dried at 110 °C. The recycled biochars were performed to remove

6
J. Li, et al.
Fig. 4. Regeneration of NPBC700.
Cr(VI) again. The results were shown in Fig. 4. It is clear that after five
cycles the removal rate of Cr(VI) by NPBC700 was gradually decreased
from 96% to 75%, reflecting the possibility to regenerate and reuse the
biochar several times. However, during the five cycles the kobs value has
dropped from 0.0278 min−1 of the fresh biochar to 0.0097 min−1,
almost only one third of the original. The result suggested that the
surface state of biochar underwent profound conversion during contact
with Cr(VI), resulting in a reduced reaction rate. Several reported
methods, such as adding metal chelating agent, microwave regenera-
tion and supercritical fluid regeneration, can enhance the regenerative
efficiency of biochars (Dai et al., 2019; Ifthikar et al., 2018; Xu et al.,
2019). Further studies can be implemented in the future.
4. Conclusions
In this study, agricultural residue-based biochar was fabricated from
coffee shells pretreated with (NH4)3PO4 by an in-situ pyrolyzed
method. The characterizations showed that (NH4)3PO4 acted as an ef-
fective activating agent and supplier of N and P elements. The obtained
biochars offered specific surface area as high as 1130 m2∙g−1 and
contained abundant N/P co-doping groups. The estimation for Cr(VI)
uptake demonstrated that the biochar remedied Cr(VI) pollutants from
water with high ratios more than 95% within a pH range of 2.0–3.0
and, also reduced Cr(VI) to Cr(III) with high reduction ratios. The
mechanism investigation showed that the O, N, P heteroatomic groups
played a crucial role on the adsorption/reduction of Cr(VI), which
conducted both adsorption active sites and electron donor moieties. The
current work provides a convenient processing and utilization route for
coffee shell agricultural residues, which is conductive to waste re-
cycling and environmental protection. In addition, the biochars derived
from coffee shells through (NH4)3PO4 treatment has outstanding po-
tential for the removal of Cr(VI) in effluents.
CRediT authorship contribution statement
Jianqiu Li: Investigation. Feifei He: Investigation. Xiaoyang Shen:
Investigation. Dongwen Hu: Data curation. Qiang Huang:
Conceptualization, Methodology.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
7
Bioresource Technology 315 (2020) 123840
Acknowledgements
The authors thank the financial supports from the National Natural
Science Foundation of China (No. 51964045) and the Innovation and
Entrepreneurship Training Program for college students
(201910673067, 201810673006).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biortech.2020.123840.
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