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Review on Biochar as an adsorbent material for removal of dyes from

waterbodies

Article in International journal of Environmental Science and Technology · June 2022

DOI: 10.1007/s13762-022-04364-9

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International Journal of Environmental Science and Technology
https://doi.org/10.1007/s13762-022-04364-9

REVIEW

Review on biochar as an adsorbent material for removal of dyes

from waterbodies
S. Dwivedi1 · S. Dey1

Received: 18 January 2022 / Revised: 10 April 2022 / Accepted: 17 June 2022

© The Author(s) under exclusive licence to Iranian Society of Environmentalists (IRSEN) and Science and Research Branch, Islamic Azad University 2022

Abstract
Biochar has emerged as a potential candidate with a multi-faceted application in recent times. Abundant availability, high sur-
face area coupled with porosity, and low cost have transformed biochar into a sustainable candidate for versatile applications
such as wastewater treatment, soil nutrient enrichment, and many more. A growing number of researches have been exercised
to produce biochar and composites derived thereof. This review article presents an in-depth discussion of biochar including
its synthesis via hydrothermal and pyrolysis methods, elemental composition, role of O/C ratio, structural characteristics,
physicochemical properties, and applications in dye removal from simulated and contaminated water. Role of diversified
feedstock on the efficiency of biochar is presented. Physiochemical properties of biochar such as pH, water holding capacity,
specific surface area, and stability have been illustrated in detail. The effect of operational parameters such as pH, tempera-
ture, dose, and nature of dyes on the adsorption has been thoroughly discussed. A comparative study on adsorption kinetics
reveals that the pseudo-first-order and pseudo-second-order are the most followed ones. Adsorption capacities of differently
prepared biochar suggest a wide range of effectiveness, starting from 30.03 mg/g up to as high value of 12,501.98 mg/g.
Mechanistic interpretation of dye binding with biochar has been proposed to be a combination of electrostatic interaction,
hydrogen bonding, π-π interaction, etc. Economic viability of biochar in soil quality improvement and water detoxification
has been outlined. Waste management covering the safe disposal and utilization as building blocks is proposed.

Keywords Biochar · Feedstock · Pyrolysis · Dye · Adsorption · Kinetics · Mechanism

Introduction It is prepared by pyrolysis or by heating organic material

and biomass in the absence or limited supply of air. Hydro-
Rapid industrialization coupled with increased water thermal carbonization and hydrothermal liquefaction have
demand seriously creates problems for the environment been exercised in detail. Various pyrolysis techniques are
and humans. Increased use of dyes and heavy metals make commercially available that yield different proportions of
water bodies and soil contaminated thereby decreasing their biochar and bioenergy products such as bio-oil and syngas.
potability. While heavy metals are not biodegradable, dyes The gaseous bioenergy products are typically wont to gen-
impart serious deterioration in water quality leading to a erate electricity; the bio-oil could even be used directly for
threat to aquatic biota. Thus, an urgent need arises to search low-grade heating applications and potentially as a diesel
for cost-effective techniques to decontaminate water. Recent substitute after suitable treatment.
years witnessed a surge in the preparation and utilization Biochar has recently grabbed the focus of researchers for
of biochar as an alternative adsorbent for water treatment. environmental remediation and removal of industrial waste
Biochar is a highly porous and high-carbon form of charcoal. from water (Thines et al. 2017). The characteristic of biochar
depends on the nature of biochar feedstock, the condition in
which it has been prepared, and the method of synthesis or
Editorial responsibility: Iskender Akkurt.
the technique which has been followed for the preparation.
* S. Dey These factors affect various elemental properties namely the
soumen.dey@cuj.ac.in surface functional group, charge on the surface, pH, porous
nature, and specific surface area. All these factors are largely
1
Department of Chemistry, Central University of Jharkhand, responsible for the adsorption efficiency. By the virtue of
Ranchi 835205, India

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Vol.:(0123456789)
 International Journal of Environmental Science and Technology

these factors, biochar is regarded as a cost-efficient treat- in the use of raw material; more precisely as the raw mate-
ment and an effective technique for the removal of water rial changes, the nature of biochar also changes. Scheme 2
contaminants. (Praveen et al. 2022). represents various synthetic routes for biochar preparation.
The key objective of this review paper is to provide a clear
understanding of different feedstock, operational parameters, Hydrothermal carbonization
physicochemical properties, and a detailed investigation of
kinetic and isotherm study followed by adsorption efficiency. This method is used to produce structured carbon like char-
The mechanism involved in the adsorption of dye and regen- coal, biochar, etc., from biomass.(Yusuf et al. 2020) As in
eration of biochar is discussed. Environmental and economic the case of a fossil fuel where it is formed at high tempera-
advantages are also studied regarding the implementation of ture and pressure over thousands of years using biomass,
biochar on a broad scale. The manuscript also implied the the same as in the case of hydrothermal carbonization, but
future prospective, especially regarding its application on the product is achieved in a shorter duration of time. For
the industrial scale. hydrothermal carbonization, a mixture of biomass like
animal waste and/or plant waste/litter is taken along with
Date and location of the research water under a pressure vessel which is heated at the tem-
perature range of 180–250 °C and pressure of about 10 bars
Date: May–July 2021, location: as provided in the author or more(Ischia and Fiori 2021).
affiliation. Although there is no such clear-cut classification avail-
able for hydrothermal carbonization, based on acting tem-
Biochar preparation methods perature it can be broadly classified into two categories. One

In earlier days, it was not known chemically what does bio-

char means, and hence Jones back in 1997 came across this
problem in all biochar-related literature and proposed the
Hydrothermal
guideline. (Hedges et al. 2000)A close inspection of the O/C carbonization
molar ratio reveals that in the graphite, O/C molar ratio is 0,
showing that no oxygen is there in their structure. In soot,
the ratio ranges between 0–0.2, in charcoal, it is 0.2–0.5,
whereas in char it is > 0.5. So, char is the name given to the
material ranges between 0.4 to about 0.6. Biochar usually
has a O/C ratio of more than 0.6. Summing up, the biochar Synthetic
routes
spans multiple divisions in the black C continuum. However,
it is noteworthy that biochar has no separate division though
the property may vary with the oxygen and carbon ratio.
Hydrothermal
Scheme 1 represents the variation of oxygen to carbon molar Pyrolysis
liquefaction
ratio in various carbon forms. This was used to differentiate
between different black carbons and biochar.
Several synthetic routes that are available for biochar
preparation are hydrothermal carbonization (Niinipuu
et al. 2020), hydrothermal liquefaction (Li et.al. 2020), and
pyrolysis (Shen et. al. 2020). These three processes differ Scheme 2  Synthetic routes for biochar preparation

Soot Char

Graphite Charcoal Biomass

Scheme 1  Oxygen and carbon ratio for different carbon varieties (from Jones and Chaloner, 1991; Goldberg, 1985)

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International Journal of Environmental Science and Technology

is high temperature (300–800 °C) and the other is the low using water as a solvent, bio-oil is most likely to form, as
temperature (< 300 °C). High-temperature range is used for water does not support polymerization reaction leading to
the synthesis of graphitic carbon material, carbon nanotube, biochar. Alcohol shows a significant advantage as a solvent
and activated carbon material, whereas in the case of low- in the following ways they support better reaction condi-
temperature, effective carbon content elevates and the con- tion and helps to release hydrogen which is important for
tent of oxygen and mineral decreases in the carbonization stabilization purpose.(Cui et al. 2020) So, from the above
process. (Salvador et al. 2007; Yoganandham et al. 2020)The discussion, it can be concluded that biochar formed by
product obtained by hydrothermal carbonization is called hydrothermal liquefaction can act as a biocatalyst for heavy
hydrochar instead of biochar. Although the properties and metal adsorption.
the condition followed during hydrothermal carbonization
make hydrochar different from biochar, they are prepared Pyrolysis
from the same raw material (Fregolente et al. 2019). Hydro-
char prepared by the hydrothermal carbonization has rela- Pyrolysis is a process in which carbons are formed using
tively low organic content, and less mobility of heavy metals different biomass feedstock under high temperatures and
and this is what makes hydrochar ideal for soil amendment inert conditions. It is interesting to highlight here that bio-
(L. Wang et al. 2019). Adding hydrochar to soil improves oil which is formed by pyrolysis can be upgraded into high-
water retention capacity, nutrient holding capacity, etc. quality fuel which has a lot of applications. (Shen et al.
(Maniscalco et al. 2020), and hence, it can be concluded that 2020) Biochar obtained from pyrolysis has applications in
the biochar formed via hydrothermal carbonization would be many fields such as catalyst, super capacitor, soil amend-
best fitted for soil amendment and partially in water treat- ment, carbon sequestration, removal of dye from wastewater,
ment purposes (Niinipuu et al. 2020). climate change mitigation, and many more. Scheme 3 high-
lights the feedstock, and how they are converted into bio-
Hydrothermal liquefaction char after carrying out pyrolysis along with two by-products
namely bio-oil and biogas. (Srivastava et al. 2020) The broad
In the case of hydrothermal liquefaction employing thermal category of feedstock is there out of which wood feedstock
de-polymerization, wet biomass is converted into a variety of contains chipped, shaved, bark, peeled, etc., agriculture
final products including bio-oil and biochar. At temperatures waste feedstock includes corn, wheat straw, rice straw and
ranging from 250–550 °C and pressure 5–25 MPa, wet bio- husk, potato, coconut husk, soybean, sugarcane bagasse,
mass is exposed for a set time. During hydrothermal lique- cotton, orange, grape, peanut, and rapeseed/straw. Similarly
faction, several chemical processes happen on biomass such animal waste and industrial waste include paper mill sludge,
as aromatization, dehydration, re-polymerization, hydroly- cattle, and dairy manure, horse/pig manure, swine manure,
sis, and fragmentation (Khan et al. 2020). This leads to the poultry manure and litter, fish scales, bio-solids, and so on.
formation of biochar along with some other by-products. (H. (Ippolito et al. 2020) Pyrolysis is an industrially preferred
Liu et al. 2017) Biochar thus produced depends on several method over hydrothermal carbonization and hydrothermal
factors such as feedstock, temperature, pressure, residence liquefaction because it can be used for a broad range of bio-
time, etc. (Sun et al. 2017). Though at high temperatures, mass and waste, for the production of biochar. (Elkhalifa
residence time has been found to have limited effects. Based et al. 2019), and hence, the following discussion is primarily
on different studies, it was noted that the main constituents focused on pyrolysis. It is noteworthy that pyrolysis tempera-
of biomass are lignin, cellulose, and hemicellulose which ture affects the quality of biochar and possible applications
plays the important role in the formation and properties of originating thereof (Zhang et al. 2020a, b). Fast, intermedi-
biochar. Out of this three, lignin is the major contributor. At ate, and slow pyrolysis has been demonstrated well (Asensio
a very high temperature, lignin gets degraded, and hence, et al. 2013; Meier et al. 2013).
it does not lead to the conversion of biomass feedstock into In the above topic, we have discussed different tech-
biochar. In most of the studies, it has been seen that the niques used to synthesize biochar and it has been con-
biochar which is produced by hydrothermal liquefaction dif- cluded that the yield of the product form after different
fers in the physical properties like specific surface area and techniques depend upon residence time, and temperature.
volume of biochar as compared to those which are produced Table 1 represents the yield of the product based on dif-
by the pyrolysis. On the other hand, biochar obtained from ferent physical parameters. It can be concluded from
hydrothermal liquefaction are good at heavy metal adsorp- Table 1 that as the rate of pyrolysis increases, the cor-
tion and also acts as a biological catalyst. (Muppaneni et al. responding yield of biochar increases, and the yield of
2017) It has been observed that alcohol such as methanol, bio-oil decreases. Comparing slow and fast pyrolysis, the
butanol, etc. improves the quality of biochar in the case of residence time can be set as desired. For slow pyrolysis,
hydrothermal liquefaction. (Ponnusamy et al. 2020) On biochar feedstock should be treated for a longer residence

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 International Journal of Environmental Science and Technology

Biochar feedstock

Wood Animal Agricultur Food Sewage Industrial Forestry

chips wastes al waste wastes sludge wastes waste

Pyrolysis

Bio-oil Biochar Bio gas

Scheme 3  Representative feedstock along with products and byproducts of pyrolysis

Table 1  The yield of biochar, bio-oil, and syngas under various conditions
Technique Temperature Residence time Bio-oil (%) Biochar (%) Syngas (%) References

Fast pyrolysis Moderate tempera- Short hot vapor 75 12 13 Asensio et al. 2013;
ture–600 °C residence time Meier et al. 2013
Intermediate Low moderate Hot vapor resi- 50 25 25 Asensio et al. 2013;
pyrolysis temperature dence time Meier et al. 2013
(300 °C)
Slow pyrolysis Low moderate Long residence 30 35 35 Asensio et al. 2013;
temperature, time Meier et al. 2013
Gasification High temperature Long vapor resi- 5 10 85 Asensio et al. 2013;
(> 700 °C) dence time Meier et al. 2013
Hydrothermal Elevated Elevated pressure Not readily avail- Not readily avail- Not readily avail- Asensio et al. 2013;
carbonization temperature able able able Meier et al. 2013
(200–250 °C)
Flash carboni- (350–650 °C) residence time Not readily avail- 50 50 Asensio et al. 2013;
zation (350– below 30 min able Meier et al. 2013
650 °C)

time and at a low temperature. In this case, the amount and biochar is needed. In fast pyrolysis, bio-oil becomes
is also high compared to fast pyrolysis and intermediate the major product whereas in slow pyrolysis biochar is
pyrolysis. Intermediate pyrolysis is generally taken into the major product.
consideration when a balanced ratio of bio-oil, syngas,

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International Journal of Environmental Science and Technology

Structure, elemental composition, Physicochemical properties of biochar

and physicochemical properties of biochar
pH
The composition and structure of a substance important
parameters to determine its characteristics and designing an Biochar is generally basic, as this is mainly related to the
application. Likewise, the structural feature and composi- inorganic metal carbonates and phosphates, and the ash
tion of biochar are one of the most important reasons for its which has been formed during pyrolysis and carbonization.
dynamic application in diverse fields. (Yuan et al. 2011) This is also influenced by the factors like
raw material and carbonization temperature. If the pyroly-
Structural characteristics of biochar sis temperature is changed, the pH generally increases as
the temperature increases, this is due to the decomposition
Biomass is transformed into carbon-rich microporous material of acidic functional groups, such as carboxyl and phenolic
through pyrolysis and carbonization. The material has a well- hydroxyl, and the volatilization of organic acids. (Zhao et al.
developed porous structure and a high degree of aromatiza- 2015).
tion. (Lehmann & Joseph 2017) The condition of pyrolysis
and carbonization is closely related to the property of biochar. Specific surface area
(W. Chen et al. 2019a, b) The nanoporous size of rice husk
biochar possesses a volume of 2.1 cm3 g−1 which is about 12.35 Various studies suggest that the specific surface area of bio-
times greater than the biochar obtained from sludge. (W. Chen char generally lies within the range of 1.5–500 m2 ∕g . (Li
et al. 2019a, b) According to different researchers, the tem- et al. 2018) Researchers have reported that sugarcane bio-
perature of pyrolysis is also a very important factor affecting char has a comparatively higher pore size as compared to
the biochar structure. It has been seen that upon increasing the coconut shell biochar. Sugarcane biochar has a pore size of
temperature, the aromatization and also the nanoporous size 0.1 ­m2/g and a specific surface area of 253.2 ­m2/g whereas
of the biochar increase. However, on increasing the tempera- coconut shell-derived biochar has a pore size of 0.1 ­m2/g
ture above 700 °C, some of the microporous structures seem and specific surface area of 25.8 ­m2/g (Kajina and Rous-
to destroy, and when the temperature is further increased to set 2018). As the temperature increases, the surface area
800 °C, the carbon skeleton structure of the biochar may get also increases within a certain range. (Ahmad et al. 2017)
unstable.(Intani et al. 2018). At relatively low temperatures the volatiles, tars, and other
products, from the thermal decomposition of biomass fill
Elemental composition of biochar the internal pore structure of biochar, and therefore reduce
the specific surface area to some extent. Upon increasing
Biochar generally consists of elements including C, H, O, N, the temperature, these substances decompose which allows
S, P, K, Ca, Mg, Na, and Si, of which carbon has the highest the volatile gases to escape which in turn further reduces the
content (above 60%), followed by H and O, with the minerals/ pore size but dramatically increases in the number of pores
elements mainly exists in ash.(Intani et al. 2018) The carbon in in the biochar. On increasing the temperature to the critical
biochar is mainly aromatic, and it is deposited in an irregular value, the surface area decreases as the temperature increase,
stack of stable aromatic rings. Nitrogen is specifically present which might be due to the destruction of microporous struc-
on the surface of biochar within a C–N heterocycle. But the tures and the enlargement of micropores.
available nitrogen content is invariably very low in the biochar.
Similarly, the content of P is low in biochar. The availability Water‑holding capacity
of P varies with the pyrolysis temperature; it varies inversely
with the pyrolysis temperature. Content of K, Ca, Mg, and Biochar derived from different sources exhibits different
Na is different in different kinds of biochar, metal ion having water-holding capacities. As the temperature increases, the
low valence are more available than the high-valence metal degree of aromatization and hydrophobicity of biochar also
ions such as Al, Ca, and Mg in biochar. In a general sense, the increases or is enhanced, resulting in the decreased number
elemental composition and activity of biochar are related to of functional groups containing O and N, and the water-
raw materials, conditions of the pyrolysis process, and pH.(Y. holding capacities of biochar decline steadily (Yu et al.
Yao et al. 2018). 2013). Water holding capacity in biochar has been shown to
affect soil quality. It has been seen that most of the biochar
are hydrophobic in nature having few polar components.
Such observation indicates that such biochar having a large
polar group enhances water retention efficiency. (Batista
et al. 2018).

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 International Journal of Environmental Science and Technology

Scheme 4  Some representative

applications of biochar
Removal of
organic waste

Energy
generation & Soil
storage improvement
Application of
Biochar

Climate change
Building sector
mitigation

Stability Dyes

The stability of biochar is the main reason why it is used Dyes are molecules that connect themselves to the fabric
as an efficient alternative for reducing greenhouse gases. surface to impart a permanent color (Yagub et al. 2014).
Biochar eventually decays so as any other organic mat- Nowadays, dyes are used in various industries such as tex-
ter, but the major difference is that it decays much more tiles, food, paint, paper, pulp, leather treatment, jute, wool,
slowly, and may leave some unwanted materials. One of and personal care products. They possess an aromatic
the primary reasons for the stability of biochar in soils is structure and are recalcitrant to biodegradation due to their
their chemical recalcitrance which is due to the presence xenobiotic nature. Discharge of waste dyes to water bodies
of aromatic structures of varying properties that are sub- results in considerable environmental and health problems.
ject to the current investigation. (Leng et al. 2019) High (Ramalingam and Jonnalagadda 2017; Song et al.; Mishra
stability can also be explained by a high degree of car- et al. 2019) It drastically decreases oxygen concentration
boxylate esterification and aromatization structure, high in the waterbody and restricts the passage of light through
carbon content, low solubility, high stability, high boiling the waterbody. Dyes can remain in the environment for an
point, and strong resistance to physical, chemical, and bio- extended period because of high thermal and photo-stability
logical decomposition. (W. Chen et al. 2019a, b) The sta- against biodegradation. The greater environmental concern
bility of biochar is an important concern for dye removal with dyes is their absorption and reflection of sunlight enter-
in-field application. ing the water. High concentrations of dyes in water bod-
ies stop the re-oxygenation capacity of the receiving water
and cut-off sunlight, thereby upsetting biological activity in
aquatic life and also influencing the photosynthesis process
Application of biochar of the aquatic plants or algae. The polluting effects of dyes
on the aquatic environment can be due to their prolonged
Scheme 4 shows some major applications of biochar. A exposure in the environment, accumulation in sediments
broad range of environmental applications made biochar especially in fishes or other aquatic life forms, decomposi-
a suitable candidate for water treatment, energy genera- tion of pollutants in carcinogenic or mutagenic compounds,
tion, soil quality up-gradation, and many more. As this and also low aerobic biodegradability. (S. Khan & Malik
paper is focused on the major applications of biochar in 2014)Many dyes and their breakdown product are carcino-
the removal of organic dyes from water by adsorption genic and mutagenic, hence toxic for living creatures. (Altin-
technique, a brief description of the dye and adsorption tig et al. 2018) The presence of very small amounts of dyes
phenomenon is presented below (Scheme 4). in the water is highly visible, and seriously affects the quality

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International Journal of Environmental Science and Technology

and transparency of water bodies such as lakes, rivers, and of –COO- anion and –OH functional groups on the bio-
others, leading to damage to the aquatic environment. char surface also increases and hence there is an increase
in the negatively charged sites. (A. Ahmad et al. 2020a)
Method for treating effluents In a similar research work based on Remazol Black B and
Caulerpa scalpelliformis (marine seaweeds) biochar as an
Several chemicals, biological, and physical methods have adsorbent, it has been seen that pH plays an important
been developed for the removal of dyes from the water bod- role and if it is not optimized properly, it can influence the
ies. This review is focused on the removal of dye using bio- percentage of dye removal. As the biochar surface consists
char as an adsorbent. Adsorption is considered to be one of lignocelluloses which contain amine group, carboxyl
of the best techniques. It offers advantages such as easy group, and sulfate so as the pH decreases removal effi-
operation technique, high separation efficiencies, and cost- ciency will increase. The presence of these functionalities
effectiveness.(Afroze & Sen 2018; Dey et al. 2020; Qaiyum will increase the electrostatic interaction between biochar
et al. 2022; Mohanta et al. 2020; Ali 2012; Manippady et al. and the dyes and in turn, will increase the removal effi-
2020). ciency. In this case, also it has been seen that increase
in the temperature of pyrolysis will increase the sorption
Biochar as an adsorbent capacity and hence increase the removal percentage. But
carrying out pyrolysis at a high temperature of 45 °C will
Being environmentally friendly and extremely versatile, bio- increase the cost also so the reaction has been carried out
char becomes a potential material to treat dye-containing at 35 °C which is room temperature. (Gokulan et al. 2021).
wastewater. However, successful removal of dyes depends From the above studies, it can be concluded that the
on several operational factors such as solution pH, adsorbent nature of dye plays an important role in adsorption effi-
dose, working temperature, the concentration of dye, agita- ciency. It was also discussed that pH and adsorption are
tion speed in batch, etc. interdependent and a large number of factors are responsi-
ble for different trends. Scheme 5 represents dye adsorption
using biochar involving several interactions. Activation of
Effect of operational parameters biochar leads to an increase in surface area and pore size
which in turn acts as a better adsorbent. Possible modes of
Biochar works well in a specific condition as an adsorbent. interaction have also been presented.
Some factors which play important role in determining the In a study related to anionic dye methyl orange (MO)
efficiency of biochar are the concentration of dye and nature with date palm fronds biochar as an adsorbent, it has been
of biochar, working temperature, and solution pH.(H. Wang seen that the adsorption capacity of dye decrease with an
et al. 2020). increase in the amount of biochar dosage but after a limit
In a study related to the removal of Methylene Blue of dosage it shows no decrease on an increasing amount of
(MB) by using rice straw as an adsorbent, in this case, the biochar. In this case, the maximum adsorption capacity
corresponding biochar was obtained at temperatures of was found to be 63.5 mg/g. It can be explained by the fact
300, 500, and 700 °C. This was done to know the effect that at a low adsorbent dosage adsorption capacity is high
of pyrolysis temperature on the adsorption capacity of because the ratio of dye to adsorbent molecule increases
dye. It has been seen that at elevated temperature pore and this, in turn, increases adsorption capacity. If we keep
size is large and hence higher surface area can be seen. on increasing biochar dosage keeping dye concentration
Hence in this case pore size increased from 0.051–0.064 constant, this may result in overlaying of the binding site,
to 0.171–0.299 cm3 ∕g as the temperature increased from and in this case, dye availability will be less for active sites
300–700 °C in the case of rice straw. In the same study, pH so, this will also result in low adsorption capacity. (Zubair
was taken in the range of 2.0–10.0, and in this pHzpc was et al. 2020a) similar study based on rice husk biochar as an
found to be 6.9 for the rice straw. From different studies, adsorbent it has been seen that the biochar dosage range
it has been seen that theoretically charge of the biochar lies between 0.5–5.0 g/100 mL and in this case, it has been
surface is positive if the case is below pHzpc, but if the seen that maximum adsorption capacity was observed at
pH is more than pHzpc the biochar surface turns out to be 5.0 g/100 mL. In this case, the removal efficiency was found
negative. So, in this case, the adsorption of MB increase to be 96.92% and hence this case increase in dye removal
as the solution pH increases. Maximum uptake has been has been observed with an increase in biochar dosage. In
observed at pH 7.0 which was up to 91–95%, in the case the case of magnetic wakame biochar as an adsorbent tak-
of rice husk. It can be explained by electrostatic attraction ing methylene Blue as a dye, the removal took place with
between the positively charged dye and negatively charged an adsorption capacity of 117.58 mg/g.(X. Yao et al. 2020)
biochar surface. As the solution pH increases the number From the above study it can be concluded that operation

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 International Journal of Environmental Science and Technology

Scheme 5  Dye adsorption mechanism onto biochar

parameter plays an important role to know the adsorption value for pseudo-second-order kinetics was found to be more
process. than is ­R2 = 0.984 and in the case of pseudo-first-order it was
found to be 0.927, slightly less which shows that pseudo-
second-order fits more. Based on the kinetic model, it can
Adsorption kinetics be stated that a chemical reaction is taking place. These two-
model mentioned above are not efficient to explain variation
For understanding the rate of adsorption and mechanism, in the rate of adsorption in every case, hence intra-parti-
kinetic studies have been conducted by many researchers. cle-diffusion is used to explain the kinetics of adsorption.
Widely used models are pseudo-first-order, pseudo-second- (B. Zhang et al. 2020a, b) In a study related to Eucalyptus
order, and intra-particle-diffusion models. Based on correla- camdulensis biochar for removing crystal violet, it has been
tion coefficient ­R2, the best-fitted model is generally selected seen that pseudo-second-order was the best-fitted one which
(J. Wang & Guo 2020). describes chemisorptive behavior of adsorption of dye on the
The Study of adsorption kinetics help to identify the biochar. In this case, it has been observed that the beginning
physicochemical interaction between the dye and the bio- uptake rate of dye increased from 16 to 40.6 mg-g−1 ­min−1
char as an adsorbent, along with predicting the adsorption for crystal violet dye. Here non-linear approach of Elovich
mechanism. In a study related to date palm fronds, biochar kinetic models has also been found to be the best fitted one.
as an adsorbent and methylene orange as a dye; different (Amin et al. 2021a)In the study based on algae D. antarctica
kinetic studies have been performed like pseudo-first-order, based biochar where the researcher took methylene blue as
second-order, and Elovich intra-particle-diffusion and based a dye, pseudo-first-order kinetics have been used to explain
on kinetic studies it has been derived that pseudo-second- the progress of the complete adsorption process and to know
order kinetics was best fitted one. (Zubair et al. 2020a) again about the initial phase whereas pseudo-second-order has
a study carried out with corn husk biochar pseudo-second- been used to know the type of adoption taking place that is
order was found to be best fitted.(Mishra et al. 2019)In a chemisorption. Then based on different kinetic data it has
similar kinetic study performed for the adsorption of methyl been concluded that pseudo-second-order and Elovich have
orange dye on pomelo peel waste, it has been seen that out of a high connection and hence they can be used to describe the
pseudo-first-order and pseudo-second-order kinetics the ­R2

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International Journal of Environmental Science and Technology

mechanism of adsorption of methylene blue dye on biochar. such as Langmuir, Freundlich, Temkin, and Pyzhev equa-
(Guarín et al. 2018). tions. Depending upon different evaluated parameters, it
Thus, from the above discussion, it can be concluded that has been concluded that both Freundlich and Langmuir are
the pseudo-second-order kinetics is the most followed kinet- found to be best fitted. Langmuir led to the conclusion that
ics which shows in the majority of cases chemisorption is adsorption is even, homogeneous and Freundlich indicates
the key adsorption that is happening between adsorbent and that adsorption is heterogeneous. Corresponding ­R2 values
adsorbate. Apart from these kinetic studies helps researchers for Freundlich, and Langmuir are found to be 0.987, and
to know the progress of the adsorption process, the type of 0.959 respectively. Since the correlation coefficient value
adsorption process, and the initial phase, and most important of the Freundlich isotherm is closer to unity, Freundlich is
deduce the mechanism. Although, it is not always possible to more accepted.(Acemioğlu 2019) For chitosan-tapioca peel
deduce the mechanism by kinetic studies as dye gets adsorb biochar which was used for the removal of Malachite Green,
on the biochar by hydrogen bonding interaction too. So, it the correlation coefficient was found higher for Langmuir
may not be possible to get complete information regarding isotherm as compared to Freundlich isotherm so Langmuir
the mechanism just by performing the kinetic studies. (Tran isotherm was considered the best-fitted one. For Lang-
2020). muir isotherm, the adsorption efficiency was found to be
Table 2 illustrates different kinetic studies studied in 53.35 mg/g (Vigneshwaran et al. 2021). In a similar study
adsorptive removal of dye using biochar. This comparative related to weed biochar where methylene blue has been
table also shows that the majorly of the processes followed taken as a dye, Langmuir isotherm fitted the best. In this
by the kinetic model are pseudo-second-order. case, it has been observed that with the increase in tem-
perature adsorption density increased. Besides, there seems
to operate a chemical interaction between dye and adsor-
Adsorption isotherm studies bent. (Güzel et al. 2017) In a study based on municipal solid
waste as an adsorbent when the isotherm studies have been
Adsorption isotherm provides useful information about: (i) performed Temkin model is closely fitted. (Agarwal et al.
an equilibrium relation between adsorbate and adsorbent 2015) From the above discussion, it can be concluded that
which can be used in understanding equilibrium; (ii) an idea an isotherm study is very important to know the type of
about the biochar-dye interactions; iii) the affinity between interaction taking place between dye and adsorbent. Table 3
biochar and dye; (iv) the maximum adsorption capacity of summarizes some selected isotherm constants related to dye
the biochar in a specific condition; (v) the amount of biochar removal using biochar prepared from the different feedstock.
which should be used for the removal of a certain quantity of Based on the kind of feedstock taken and the mechanism
dye from an effluent; and vi) the effect of the experimental involved in the process of adsorption, different isotherms
conditions on the equilibrium. are followed.
To ascertain the best-fitted model, various isotherms such
as Langmuir, Freundlich, Dubinin-Radushkevich, Redlich-
Peterson, and Temkin isotherms have been investigated. Mechanistic interpretation of adsorption
Biochar prepared from activated peanut taking up remazol onto biochar
orange RGB as a dye, the isotherm study has been per-
formed at different dye concentrations such as 20,50,75,100 The adsorption mechanism of a dye onto biochar involves
150 mg/L, the temperature was set to 50 °C and the opti- electrostatic interaction, weak hydrogen bonding, and ion
mized pH is 3. Various isotherm study has been performed exchange. Besides, nitrogen functional groups may initiate

Table 2  Correlative kinetics Adsorbent Adsorbate Application kinetic model Reference

parameters for different dyes
adsorption onto biochar Soybean dreg Methylene blue Pseudo-second-order (Ying et al. 2021)
Cornstalk Biochar Methylene blue Pseudo-second-order (Nizam et al. 2021)
Rice Straw Basic Red 46 Pseudo-second-order (Sackey et al. 2021)
Cornstalk biochar Methylene blue Pseudo-second-order (Ranzi et al. 2018)
Corncob biochar Brilliant green (BG) dye Pseudo-second-order (Giri et al. 2020)
Algae D. Antarctica biochar Methylene blue Pseudo-second-order (Guarín et al. 2018)
Calciumrich biochar Congo red Pseudo-second-order (Dai et al. 2018b)
wood residues biochar Indosol Black NF1200 dye Pseudo-second-order (Kelm et al. 2019)
Lychee seed Methylene blue Pseudo-second-order (Sahu et al. 2020)

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 International Journal of Environmental Science and Technology

Table 3  Adsorption isotherm constants for various dye adsorbent onto biochar
Adsorbent Adsorbate Isotherm models studied References

Cow Dung biochar Methylene blue Langmuir (A. Ahmad et al. 2020)
Sludge and rice husk biochar Acid Orange II Langmuir, Freundlich (S. Chen et al. 2019a, b)
Bael shell (Aegle marmelos)biochar Patent Blue (PB) Freundlich isotherm (Roy et al. 2018)
Alginate-kelp biochar Crystal violet Langmuir, Freundlich, and (Ohemeng-Boahen et al. 2019)
Redlich-Peterson
Bamboo biochar Acid black 172 Freundlich (Yang et al. 2014)
Corn straw-derived biochar Malachite green Langmuir (Eltaweil et al. 2020)
Wodyetiabifurcata biochar Methylene blue Freundlich and Sips (Santos et al. 2019)

n-π type interaction. In general, dye adsorption onto biochar Regeneration and reuse of biochar
involves several steps. The first step is regarded as physical
adsorption wherein dye settles on the biochar surface. In The adsorption capacity of the biochar surface is limited;
the second step, dyes get deposited on the biochar’s sur- in other words there is a fixed number of sites available for
face and the third and last step involves the condensation the adsorption and hence protract exposure of biochar with
of dyes into the pores of the biochar (adsorbent).(Fagbo- dye results in the establishment of equilibrium between the
hungbe et al. 2017) The first stage involves the initiation biochar and dye. Hence there is a need arises to regenerate
of adsorption, hence regarded as a clean zone. The second and reuse biochar or simply decompose it. Once the bio-
stage is regarded as a mass transfer zone. In the third stage, char surface gets saturated with the adsorbate, desorption
equilibrium is reached and hence called an exhausted zone. has been performed with solutions of ­NaNO3, ­KNO3, and
During the completion of the process, the exhausted zone ­HNO3 at different concentrations. The low pH of the desorb-
increases whereas the clean zone decrease steadily.(Zubair ing solution is used to replace heavy metal ions efficiently.
et al. 2020a, b) With increasing adsorbate concentration, (Sounthararajah et al. 2015)Several techniques can be used
the mass transfer zone gets affected significantly. This trend to regenerate fixed-bed columns that are partial pressure
is followed until and unless the adsorbent surface gets satu- reduction, a heat treatment that can be done using an inert
rated, that point is called the breakthrough point. Table 4 gas, and changing chemical states such as pH. The solvent
presents the adsorption capacities of various biochar-based which has been demonstrated to regenerate modified biochar
adsorbents for the removal of different dyes. From Table 4 is acetic acid, NaOH, EDTA, HCl, and NaCl. The efficiency
it has been seen that calcium-rich biochar from crab shells of regenerated biochar by different organic solvents has
shows the highest adsorption capacity of 12,501.98 mg/g been examined in several studies. It was found that metha-
whereas oil palm waste-derived biochar shows the least nol, ethanol, and acetone show high regeneration capacity
adsorption capacity of 24.00 mg/g. Mentha plant biochar is by separating dyes from biochar. (Y. di Chen et al. 2018).
also a frontline with an adsorption capacity of 322.58 mg/g. Regenerated materials have been tested for multi-cycle reuse
and found promising.

Table 4  Adsorption capacities of various biochar-based adsorbents for the removal of different dyes from wastewater
Adsorbent Adsorbate Dose (g/L) Contact Adsorption pH Ref
time (min) capacity (mg/g)

Mentha (mint) plant biochar Malachite green 3.0 45 322.58 10 (Rawat& Singh, 2018)
Oil palm waste-derived biochar Methylene blue 5.0 90 24.00 2 (Baloo et al. 2021)
Magnetic biochar Acid orange 7 2.0 200 110.27 2–10 (Santhosh et al. 2020)
Chitosan Beads Tartrazine 0.72 120 30.03 3 (Pal & Pal 2019)
Pecan nutshell Reactive Red 141 0.05 240 130 3 (Zazycki et al. 2018)
Lignin-derived porous biochar Methylene blue 123.8 240 248.96 11 J. Liu et al. 2021)
Fe2O3 biochar nanocomposite Methylene blue 0.5 30 20.53 8 (Chaukura et al. 2017)
Calcium-rich biochar from Crab Shell Malachite green 0.5 150 12,501.98 7 (Dai et al. 2018a)
Modified (biochar) from pea shells Malachite green 0.5 120 277.77 – (Darama & Çoruh,
2020)

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International Journal of Environmental Science and Technology

The setback of using biochar and exhausted biochar should be treated with intense care
as an adsorbent by following standards of hazardous waste treatment for
avoiding further pollution. Nowadays, fly-ash bricks are
Till now the ability of biochar for dye removal is dis- becoming popular for relatively cost-effective building
cussed, but it is important to know the challenges involved construction. Exhausted biochar may be mixed in appro-
also to proceed with the further experiment to avoid cer- priate proportion to reduce the cost further with a goal
tain experimental errors. Some polyaromatic hydrocarbon of waste utilization. Although more study in the field of
(PAH) may be formed during the preparation of biochar stability factors, major secondary pollution, and economi-
which may be detrimental to the environment.(Liang et al. cal feasibility is still needed, the search is on but requires
2021) Biochar may also augment growth factor change in more research.
plants and crop production when disposed of in soil.(Spo-
kas et al. 2012) Biochar works well with some specific
conditions of dosage, temperature, pH, etc. Hence an extra Economic potential
optimization step needs to be performed for the removal
of biochar from the wastewater which in turn increases Biochar has huge application in the removal of dye from
treatment cost. In a few studies, it has been seen that the wastewater but before applying it on a broad scale it is
efficiency of biochar after prolonged use gets decreased. important to optimize key parameters such as biochar feed-
(Oladipo and Ifebajo 2018) Biochar derived from cer- stock, the temperature of pyrolysis, availability of industrial-
tain sources contains traces of heavy metals which may scale reactor, method of regeneration, and a lifetime of the
increase the risk of additional pollution.(Odinga et al. biochar to enhance the economic feasibility of the entire
2020; Q. Zhang et al. 2020a, b) At a certain temperature, process. (Oni et al. 2019) It was observed that the average
the heavy metals may start diffusing in the surrounding harvesting and collection cost of biomass made up of wood
environment which is wastewater. It has been observed like loblolly pine and eucalyptus approximated $24.80/ton.
that at high operational temperatures heavy metals start Dragging and transportation costs are depended on the dis-
volatilizing. At temperatures beyond 500 °C volatility tance covered for the delivery and the density of biomass
of cadmium increases more as compared to other heavy which is estimated as $0.26/mile for switchgrass and $0.64/
metals. This is a point of concern as cadmium is a major mile for poplar wood(Kung et al. 2013). It has been observed
source of pollution. Despite having a plethora of applica- by (Y. Dai et al. 2019) that during the production of biochar
tions of biochar in a different fields, it still possesses some through slow and fast pyrolysis, the cost came out to be
threat to environmental pollution if not used appropriately. 18.30 and 8.14 US$/ton. Also, based on the international
Suitable methods need to be adopted to restrict such occur- survey conducted by the International Biochar Initiative
rences. Moreover, the safe disposal of spent biochar should (IBI) in the year 2013, it has been reported that at sellers'
be considered an integral part of any upcoming studies. companies, internationally the average biochar price lies in
Adsorption is a contaminants transferring process and the range of 80.00 US$/ton to 13,480.00 US$/ton. Based on
hence used biochar can be hazardous waste. Depending the recent report made by (Y. Dai et al. 2019), the Interna-
on the type of impurity biochar is loaded with- different tional Biochar Initiative and the European Biochar Certifi-
techniques are used for regeneration or desorption. Specifi- cate set up a standards chart for the development of biochar.
cally, if the used biochar is loaded with phosphate, nitrate, Although research based on the market price of biochar is
ammonium, and no other hazardous pollutants, it can be at its initial state, further research is required so that the
used as a fertilizer which in turn uplifts the fertility of analysis of biochar can be done in a better way to economic
the soil. Whereas if the biochar is used for the removal benefits so that it can be applied at the industrial scale for
of organic waste like the removal of dye from wastewater the removal of dye from wastewater and in other potential
has to handle with intense care. Based on different stud- application.
ies, it has been concluded that if U(VI) is adsorbed in the
process so for desorbing loaded biochar should undergo a
four-time sorption cycle by the use of 0.05 molL− 1 HCl. Biochar: holistic approach to economic
(Z. bin Zhang et al. 2013) Results based on different stud- and environmental sustainability
ies indicate that biochar which is made up of food waste
can be used again and again without much loss in the Biochar is a resource material that is regarded as waste
capacity of adsorption in the case of dye. Also, if biochar before going through any thermochemical process, but
has undergone several sorption cycles and exhibits less changing the frame of reference can be regarded as a poten-
adsorption is due to its high toxicity. This toxic biochar tial solution to waste management which can be imple-
mented in rural areas to manage agricultural waste. It can

13
 International Journal of Environmental Science and Technology

boost the source of income and help in developing that area 2. A model is required for the adsorption mechanism of
by assisting small scale and medium scale industries with modified biochar. As it would be good to modify the
the production of energy. Agricultural and animal feedstock biochar surface according to the application using a
in huge quantities can be efficiently converted to biochar and different process like surface oxidation, amination, sul-
can be commercialized. This will help in developing a model fonating, and modification of pores structure. By doing
where one industry can act as a feedstock or input for the this, selective biochar materials can be made which can
other industry. It will bring positive consequences at a differ- considerably enhance the adsorption efficiency of bio-
ent level and help in developing a circular economy. Biochar char.
can also be used for the preparation of bricks in associa- 3. Before implementing the use of biochar on a large scale-
tion with fly ash. This will reduce the cost of construction regeneration, the standard method of operation for the
provided the quality is not compromised. Strategies may removal of dye pollutants from wastewater, and cost-
be made to maintain coordination between the economic effectiveness should be monitored carefully to assess the
as well as the technical aspect. An integrated system has to cost of production and usage.
be developed which will bring balance between the way it 4. Pre-treatment of biochar for removing toxicity or toxic
has to be used, energy optimization, and controlled drain or elements and successive biological way of treatment
discharge. needs more research before implementing it on large
scale.
5. For the fast removal of dye from wastewater optimiza-
Conclusion and future Perspective tion of adsorption dosage and standard method of bio-
char production will be helpful.
From the exhaustive discussions presented above, it can 6. Heavy metals, aromatic hydrocarbon, and metalloids
be concluded that biochar is an outstanding alternative as are associated with the biochar which is supposed to
an adsorbent for the removal of dye from wastewater. Out be toxic. So, before moving further to use it on a broad
of various techniques for preparing biochar, pyrolysis is aspect negative effect which is associated with the use
regarded as the most preferred one to process various types of biochar it has to be taken into consideration.
of feedstock such as agricultural waste, algae biomass, 7. Regeneration and reusability of biochar need focused
sludge, plant residue, animal waste, etc., for the production comparative research so that biochar can be imple-
of biochar. Biochar is eco-friendly adsorbing material by the mented on large scale without producing potential sec-
virtue of its large surface area, presence of surface functional ondary pollutants. To avoid this knowledge gap, biochar
group, and porous nature. It shows the high capability of made from different feedstock should undergo security
removal of dye from wastewater which involves different checks under different circumstances and should be
mechanisms including but not limited to electrostatic inter- explored on a broad time scale.
action, weak hydrogen bonding, ion exchange precipitation,
surface adsorption, and pore-filling. Performance depends
on the different physicochemical parameters including the Author contribution S. Dwivedi has reviewed the literature, drafted
the original manuscript, and prepared the graphics/schemes/figures.
temperature of pyrolysis, pH, and biochar dosage. Biochar S. Dey has originated the idea, edited and revised the manuscript, and
also has the potential to minimize the bioavailability and supervised.
mobility of pollutants and this can be implemented when
the concentration of the contaminant is high. Hence, this Funding The authors did not receive support from any organization
review suggests that biochar can be used as a low-cost and for the submitted work.
environment-friendly adsorbent that can also be used for a
Availability of data and material Not applicable.
socioeconomic benefit which will further lead to environ-
mental and economic sustainability.
Different studies regarding the effect of different feed-
Declarations
stock on the quality of biochar and physicochemical prop- Conflict of interest The authors have no relevant financial or non-fi-
erties affecting the adsorption efficiency of biochar suggest nancial interests to disclose.
that these are still in their initial phase. Following are some
areas where more focus should be given in the future: Ethical approval This article does not contain any studies with human
participants or animals performed by any of the authors.

1. Chemically activated biochar shows high performance as

compared to nano-activated biochar, although detailed
mechanisms needs to be investigated further for broad-
scale application.

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International Journal of Environmental Science and Technology

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