Tech Science Press

DOI: 10.32604/jrm.2021.015952

ARTICLE

Preparation of Porous Materials Derived from Waste Mussel Shell with High
Removal Performance for Tableware Oil

Yi Yang1, Zhaodi Wu1, Lili Ji2, Shiyao Lu2, Hua Jing2, Jiaxing Sun2, Jian Guo1, Wendong Song3,
Yaning Wang2 and Lu Cai4,*
1
College of Food and Medical, Zhejiang Ocean University, Zhoushan, 316022, China
2
National Marine Facilities Aquaculture Engineering Technology Research Center, Zhejiang Ocean University, Zhoushan, 316022,
China
3
College of Petrochemical and Energy Engineering College, Zhejiang Ocean University, Zhoushan, 316022, China
4
Donghai Science and Technology College, Zhejiang Ocean University, Zhoushan, 316000, China
*
Corresponding Author: Lu Cai. Email: [email protected]
Received: 26 January 2021 Accepted: 23 March 2021

ABSTRACT
In this work, carbonized mussel shell powder (CMSP) was modified by alkyl polyglucosides (APG) and rhamno-
lipid (RL) to render porous biomass a lipophilic surface, which was innovatively utilized as an environmentally
friendly tableware cleaning material. The modified method was two-step hydrotherm-assisted synthesis. A contact
angle meter was used to determine the surface hydrophobic property of modified samples (MTAR). The pore and
the surface structure of CMSP and MTAR were characterized by BET, SEM, XRD, FTIR and XPS. The effect
of removing oil was tested by gravimetric method. The results showed that the surface of MTAR was more por-
ous and fluffier than CMSP, and the specific surface area is increased by 16.76 times. The results showed
that when calcining CMSP at 1000
C, the oil removal rate of the synthesized MTAR is the best, and the decon-
tamination rate can reach 87.05%. This research aims to develop a green and environmentally-friendly tableware
cleaning material, solve environmental problems, and make full use of waste, which is very conducive to envir-
onmental protection.

KEYWORDS
Calcined mussel shell; modified; tableware cleaning; surfactant

1 Introduction
Nowadays, dishwashing detergent has become an essential commodity in our daily life, which could
keep a clean kitchen environment. Usually, a typical dishwashing detergent consists of surfactants,
builders, emulsifiers and a few additives [1], which are basically chemicals, they can affect human health
and cause environmental pollution [2,3]. More seriously, long-term ingestion or exposure to these
ingredients will cause the accumulation of chemical toxins in the body, reduce the concentration of
calcium ions in the body’s blood, acidify the blood, reduce the detoxification function of the liver, and
increase liver cell disease, which is easy to induce cancer [4–7]. Currently, natural ingredients are
becoming a new trend in the detergent industry due to their environmentally friendly, low cost and easily

This work is licensed under a Creative Commons Attribution 4.0 International License, which
permits unrestricted use, distribution, and reproduction in any medium, provided the original
work is properly cited.
1870 JRM, 2021, vol.9, no.11

degradable, such as saponins [8], pineapple by-product [9], sapindus mukorossi [10], etc. However, few
natural ingredients are used in dishwashing detergent products, and the main ingredients of commercial
detergents are still chemicals.
The common components of household and municipal sewage consist of surfactants and other
components of detergents. They will enter the environment through the sewage system and cause harm to
aquatic organisms [11,12]. In addition, detergent ingredients can interact with other substances in the
water, causing toxicity and biodegradation [13]. Therefore, how to develop new cleaning materials
(degradable, pollution-free, and healthy) is a scientific problem that needs to be solved urgently.
In recent years, bio-based porous materials have attracted widespread attention from researchers due to
their abundant holes, excellent adsorb ability, non-toxicity, renewability and favorable stability, which have
been applied in many fields, such as dye wastewater treatment [14], heavy metal removal [15], oil adsorption
[16], etc. Among these, oil adsorption by bio-based porous materials has received much more attention. For
example, Zhao et al. [17] used waste peanut shells to prepare a biodegradable and super-wet separation layer,
which plays a very good role in oil-water separation. Xu et al. [18] used corn cobs and willows as materials,
first coagulated and precipitated the biomass solution with water, then freeze-dried to obtain porous
materials. These materials had effective adsorption capacity for methylene and oil. And a green sorbent
porous material was prepared with natural rubber and reduced graphene oxide, which was used in the
treatment of marine oil spills [19]. JO et al. [20] treated corncobs with acetic anhydride, which enhanced
its hydrophobicity and had good adsorption to crude oil. However, to the best of our knowledge, the
application of bio-based porous materials in the dishwashing detergent has not been reported yet.
Mussel shells are by-products of aquatic processing, accounting for about 70% of the biological weight
of mussels. Every year, a large number of shells are stacked in farmland or embankments as solid waste,
which not only occupies land resources, but also has a negative impact on the environment [21]. Under
the control of biological genetics, mussel shells present a “brick-mud” assembly structure that cannot be
synthesized by humans. In our previous studies, mussel shells have been prepared into various bio-based
materials as oil pollution adsorbent [22], photocatalyst carrier and photo catalyst [23], where mussel shell
porous material displays superior adsorption, dispersion, porousness and non-toxicity.
The purpose of this article is to use mussel shells as raw materials to obtain porous framework materials
by carbonization, and use this as a matrix to modify them with alkyl polyglucosides (APG) and rhamnolipid
(RL). Template method [24], chemical vapor deposition [25], hydrothermal [26] as well as chemical
activation [27] are widely used processes to synthesize porous framework materials. In recent years, other
new methods have been studied; Wang et al. [28] used freeze-drying method to prepare chitosan hybrid
sponge. Carbonization of biomass raw materials through high temperature pyrolysis is also one of the
methods [29,30]. Because it is calcined in the absence of oxygen, the carbon in the biomass does not
undergo a combustion process, and the resulting products include pyrolysis gas, bio-oil and bio-char.
Among them, the more valuable biochar is a black solid, which has the advantages of porosity, light
weight and high stability. In addition, other methods have some specific requirements for raw materials.
Carbonization can use many different types of feedstock, including agricultural waste, wood, animal
manure, etc. Hence, carbonization can be a waste-to-resource process, this is also a good realization of
the value-added utilization of agricultural waste.
As an emerging nonionic surfactant, APG possesses the advantage of low toxicity, high biodegradability
and good ecological compatibility [31]. The raw materials come from natural renewable resources, are non-
toxic and harmless, have excellent decontamination ability, and have a good synergistic effect with other
surfactants. In the 1920s, APG has been reported. It is now widely used in household detergents,
cosmetics and agricultural products [32]. RL is biodegradable, show low aquatic toxicity and can be
produced from renewable resources [33]. As a bio-surfactant, it can emulsify hydrophobic hydrocarbons,
JRM, 2021, vol.9, no.11 1871

making it easier to dissolve in water and reducing surface tension. In addition, compared with chemical
surfactants, bio-surfactants are less toxic and have higher biodegradability and surface activity [34]. The
raw materials for the production of the two surfactants are cheap and easily available, and the production
is relatively high. Considering that the porous materials in this article can be used as commercial cleaners
in the future, choosing these two surfactants will reduce production costs. The research is of great
significance for protecting health, environmental safety and waste utilization.
2 Materials and Methods
2.1 Materials
Mussel shells (genus: Mytilus Linnaeus) were obtained from Shengsi, Zhoushan, China. Alkyl
polyglucosides (APG, APG2000, 8−10 carbon alkyl chains) and rhamnolipid (RL, 98%) were purchased
from Fine Chemical, Shanghai, China. All chemical reagents were of analytical grade. Deionized water
was prepared in laboratory. All reagents were prepared with distilled water.

2.2 Preparation of Porous Materials

At room temperature, mussel shells were soaked in 1% HCl solution for 24 h to remove surface stains,
and then wash with distilled water until neutral (pH = 7), and then dried at 80
C in oven for 12 h. The mussel
shell samples were loaded into a tube furnace and heated to 800
C, 900
C, 1000
C and 1100
C at a rate of
10
C min−1 under nitrogen flow at 200 mL/min, respectively. And the calcination step was held for 2 h.
Finally, the calcined mussel shells were ground into powder with a mortar and sieved to < 100 μm mesh
particle size, the as-prepared samples were named as CMSP.

2.3 Modification of Shell Powder by Surfactants

2 g CMSP and 1 g alkyl polyglucosides (APG) were completely dissolved in 30 mL deionized water.
The solution was transferred into a high pressure reactor, which was heated to 120
C for 24 h. After
cooling to room temperature, the obtained composite was rinsed using deionized water, and the
composite was dried at 70
C for 8 h in an oven, the obtained sample was named Sample I. The Sample I
and 1 g Rhamnolipid (RL) were dissolved in 30 mL deionized water at a high pressure reactor, then
heated to 120
C for 12 h, collected and dried the synthetic sample at 70
C use the same method as
above. The synthetic sample was denoted as MTAR.

2.4 Characterization
The contact angle was measured by contact angle meter (CA, XG-CAMB, Xuanyichuangxi Indstrial
Equipment, Shanghai, China) at room temperature with the sessile drop method [35]. The volume of the
liquid used was 5 μL. All apparent water contact angles were measured three times, and an average value
was used. X-ray diffraction patterns (XRD, D/max 2500, Agilent, USA) of samples were recorded by
using a powder X-ray diffractometer at a setting of 40 kV and 30 mA. The surface chemical group of the
samples was investigated by Fourier transform infrared spectrometer (FTIR, Thermo Fisher Scientific,
USA) and X-ray photoelectron spectrometer (XPS, 5000C ESCA System, PHI, USA). The specific
surface area and pore-size distribution were performed on Quadrasorb SI instrument (Quantachrome,
USA) and calculated with the method of Brunauer-Emmett-Teller (BET). Scanning electron microscopy
(SEM, Hitachi S-4800, Tokyo, Japan) was employed to investigated microstructures and morphology of
samples.

2.5 Determination of Oil Removal Rate

0.5 g of CMSP and MTAR were put into 20 mL tap water respectively, and used as washing solution.
Rapeseed oil and peanut oil were mixed evenly in the ration of 1:1, and spread on the ceramic plate. The
ceramic plate was heated in the oven at 40
C for 20 min to make the oil solidify on it. The prepared
1872 JRM, 2021, vol.9, no.11

ceramic plates were placed in the above washing solutions for 1 min, and shook at a constant speed for 7 min
using an oscillator, respectively. Then removed the ceramic plate from the washing solution and dried them.
The measurements were repeated three times. The experiment also set a blank control group and a
commercially available detergent with tap water. The oil removal rate was calculated use the following
formula:
M1  M2
Dr ¼ 100% (1)
M1  M0
where M0 is the quality of the original ceramic plate, M1 is the quality of the stained ceramic plate, and M2 is
the quality of the washed and dried enamel sheet.

3 Results and Discussion

3.1 Contact Angle Measurement
Fig. 1 shows the contact angles of MTAR samples made from calcined mussel shell powder prepared at
different calcination temperatures. The contact angles of MTAR800
C, MTAR900
C, MTAR1000
C and
MTAR1100
C were 92.0°, 95.6°, 98.9° and 99.5°, respectively, which were all more than 90°, indicating
that the surface of samples were hydrophobic [36]. With the increase of the calcination temperature of
mussel shell powder, the contact angle of MTAR samples increased gradually. The reason is that the main
component of the mussel shell is calcium carbonate, but it contains a small amount of organic matter. The
organic matter will decompose as the temperature rises to form a regular pore structure. The rich pore
structure provides a large number of reaction sites for the surfactant and increases its hydrophobicity, so
the contact angle is increased [37]. Fig. 2 is the test graph of the contact angle.

Figure 1: Water contact angle value of as-prepared sample MTAR 800°C, MTAR 900°C, MTAR 1000°C
and MTAR 1100°C

But when the temperature reached 1000
C, the increase of contact angle tended to be slow down. This is
owing to the high calcination temperature could improve the quality of CaO in the shell. In the subsequent
hydrothermal process, CaO is converted into Ca(OH)2, which increased the content of hydroxide radical in
the compound and makes it easier to combined with the APG. In turn, the subsequent assembly with RL is
promoted. At the same time, CMSP samples calcined at different temperature were also measured under the
same conditions. The contact angle value of calcined mussel shell powder cannot be measured, because its
hydrophilicity is too strong. After contact with the sample surface, the water droplets are immediately
JRM, 2021, vol.9, no.11 1873

absorbed. Considering the material performance and energy saving, MTAR1000
C as the cleaning agent was
selected for follow-up experiments.

Figure 2: Water contact angle images of as-prepared sample MTAR 800°C (a), MTAR 900°C (b), MTAR
1000°C (c) and MTAR 1100°C (d)

3.2 Characterization of Morphology and Structure

3.2.1 SEM Analysis
SEM photographs of as-prepared samples CMSP1000
C and MTAR 1000°C were shown in Fig. 3. It
can be seen from Figs. 3a and 3c that CMSP1000
C has regular layered structure and no obvious pore
structure. Comparatively, the texture of MTAR1000
C is loose with a number of relative uniform pores.
This indicates that hydrothermal synthesis and surfactant modification [38] plays an active role in the
pore formation and its pore size is mainly mesoporous. Because after high temperature pyrolysis, the
smooth structure of the raw sample was broken down by devolatilization, condensation, dehydration, and
decarboxylation reactions [39].

(a) (b)

(c) (d)

Figure 3: SEM images of samples: (a, c) CMSP1000
C; (b, d) MTAR1000
C

1874 JRM, 2021, vol.9, no.11

3.2.2 BET Analysis

The specific surface area of two materials was measured via nitrogen adsorption-desorption. Fig. 4
shows two isotherm curves of nitrogen adsorption-desorption, according to the Brunauer classification
method, the curves shown in the figure all conform to the standard IV curve and the H3-type hysteresis
loops at relative pressure (P/P0) between 0 and 1.0, which indicates the presence of a mesoporous
structure in the sample [40,41]. Tab. 1 shows the calculated BET results of CMSP1000
C and MTAR
1000
C. The specific surface area of the MTAR1000
C and CMSP1000
C is about 49.9 and 2.98 m2g−1,
respectively. The specific surface area after modification by surfactants increased nearly 16.8 times, which
confirms that the surfactants (APG and RL) offer more active sites for the oil removal process. It can be
seen that the pore sizes are both concentrated in 2–10 nm, which indicates the catalyst includes rich
mesoporous.

Figure 4: N2 adsorption-desorption isotherm and pore size distribution of CMSP1000
C and MTAR1000
C

Table 1: The specific surface area and average pore size of different sample
Different sample CMSP1000
C MTAR1000
C
Specific surface area (m2/g) 2.98 49.9
Average pore size (nm) 9.40 9.13
pore volume (cm3/g) 0.00699 0.114

3.2.3 XRD Analysis

The crystallographic structures of the samples were characterized by X-ray diffraction analysis. As
shown in Fig. 5, the as-prepared composites with high crystallinity. The diffraction peaks of CMSP
located at 2θ = 32.20°, 37.34° and 53.85°, corresponding to the (111), (200) and (220) crystal planes of
CaO (JCPDS card number 37-1497). At the same time, the diffraction peaks of MTAR at about
2θ = 28.66°, 34.08°, 47.12°, 50.79° and 54.33° could be perfectly indexed to the (100), (101), (102),
(110) and (111) crystals planes of Ca(OH)2 (JCPDS card number 04-0733), respectively. Therefore, the
CMSP and MTAR is composed of CaO and Ca(OH)2, respectively. The calcium carbonate in the mussel
shell was decomposed at 1000
C and converted into calcium oxide [42], which was consistent with the
JRM, 2021, vol.9, no.11 1875

XRD test results. The existence of Ca(OH)2 crystal in MTAR 1000
C is due to the CaO reacts with H2O to
form Ca(OH)2 in Teflon-lined autoclave during the hydrothermal process.

Figure 5: XRD patterns of CMSP1000
C and MTAR1000
C

3.2.4 FTIR Analysis

The information on the chemical structure of the samples was investigated by FTIR spectra and
corresponding results were shown in Fig. 6. The peak at 876 cm−1 was both observed in the two
materials, this peak was corresponded to the out-of-plane bending vibration of CO32− [43,44]. The peak
near 3640 cm−1 was observed in the two spectrums of samples, which was owing to the stretching
vibration of O-H [45]. The O-H in MTAR may come from hydrothermal synthesis reaction, and APG and
RL, because the surface of two surfactants (APG and RL) is rich in O-H groups [46]. The weak peak
near 3640 cm−1 appeared in CMSP, which may be due to the samples absorbs water from the air. The
absorption peak at 2850 cm−1 and 2900 cm−1corresponded to the –CH2 stretching vibration [47]. The
absorption peak at 1420 cm−1 was corresponded to the C=O stretch from CaCO3 [46].

Figure 6: FTIR spectra of CMSP1000
C and MTAR1000
C

1876 JRM, 2021, vol.9, no.11

3.2.5 XPS Analysis

To further determine the surface composition and chemical states of the elements, the as-prepared CMSP
and MTAR samples were studies by XPS (Fig. 7a). The survey XPS spectra shows that the CMSP and
MTAR contain elements of C, N, O and Ca and the binding energies of C1 s, N1 s, O1 s and Ca2p were
at 284.2 eV, 483.2 eV, 531.1 eV and 346.4 eV, respectively. As shown in Fig. 7b, the XPS spectrums of
samples were similar, except for the peaks of C1 s. The C1 s high-resolution spectrum of CMSP could be
decomposed into three peaks at 288.6 eV (C1), 285.5 eV (C2) and 284.4 eV (C3), which were
characteristic of the O-C=O, C-O and the typical carbon atom peak [48–50]. The O-C=O and C-O in the
CMSP is mainly from CaCO3 which is probably derived from Ca(OH)2 produced by the reaction of CaO
in the shell with H2O and CO2 in the air [48–50]. In contrast, the C1 s high resolution spectrum of
MTAR 1000
C could be decomposed into three peaks at 289.4 eV (C1), 285.3 eV (C2) and 284.8 eV
(C3), which correspond to MCO3 [22], -C-OH and -CH2- [49], respectively. The peak intensity at
285.3 eV in MTAR may be attributed to the functional groups in APG and RL. Both APG and RL have a
large number of -C-OH functional groups [46], so the surfactants were successfully loaded on the surface
of calcined shell powder after two self-assembly reactions of hydrothermal synthesis.

Figure 7: XPS spectra of the CMSP1000
C and MTAR1000
C: (a) survey spectrum, (b) C1 s high-
resolution spectrum

3.3 Oil Removal Performance and Mechanism

The washing performance of the as-prepares materials was evaluated by the oil removal rate, and the oil
removal rate of series of MTAR and CMSP were shown in Fig. 8. The oil removal rate of surfactant modified
samples were extremely high than the unmodified samples. At the same time, the blank control group (tap
water) also showed slightly decontamination ability, the oil removal rate was 22.5%, which was caused by
the mechanical vibration of the oscillator. As the calcination temperature increased, the decontamination
rate of all samples increased. The decontamination rate of CMSP from 800°C to 1100°C is 35.14%,
43.34%, 48.84% and 50.26%. Under the same calcination temperature, the decontamination rate of
MTAR is higher than that of CMSP, which is 48.67%, 75.98%, 87.05% and 86.79%, respectively.
The oil removal rate values of samples were basically consistent with the contact angle results.
In comparison, a commercially available detergent (CAD) was selected for testing, and the
decontamination rate was 72.03%.
JRM, 2021, vol.9, no.11 1877

Figure 8: Oil removal rate of shell powder with different treatment methods

As shown in Fig. 9, the oil removal mechanism of as-prepared samples may be that the surfactant on the
surface of samples reduces the surface tension of oil, and the pore of samples is used to absorb the oil. At the
same time, mechanical vibration is also beneficial to the adsorption and removal of oil. The hydroxyl group
of APG is adsorbed on the surface of CMSP in the first step of hydrothermal reaction, and the intermediate
product with hydrophilic group on the surface is obtained. MTAR was formed by adsorption of surfactant RL
via its hydrophilic groups on the surface of intermediate product, leaving its hydrophobic group outwards.
Meanwhile, the surface of the as-prepared MTAR samples exhibited highly porous and dispersive
characteristic. The larger specific surface area increases the contact area of the dishwashing detergent with
oil, thus improving the oil removal efficiency. In addition, the calcium hydroxide in MTAR can make its
aqueous solution have certain alkalinity, which is conducive to the hydrolysis of tableware oil.

Figure 9: Mechanism diagram of MTAR in the process of removing kitchen oil

1878 JRM, 2021, vol.9, no.11

4 Conclusions
Novel materials MTAR with excellent removal performance for tableware oil were successfully
prepared and synthesized by two-step hydrotherm-assisted synthesis. Compared with CMSP, the surface
morphology of MTAR sample is highly dispersive and multihole. After two self-assembly of the
surfactant, the surface morphology of the shell powder has undergone great changes, which resulted in
the specific surface area increased by 16.76 times. In this work, MTAR 1000
C showed good cleaning
ability, the oil removal rate reached 87.05%, which was due to the big specific surface area, loose porous
structure and emulsion of surfactants. Particularly, the MTAR is from the organism, which is readily
available, renewable and biodegradable materials. This work provides a new idea and method to develop
a new kitchen cleaning materials by employing abandoned biomass as raw materials.
Funding Statement: This study was supported by scientific research fund of Zhejiang provincial education
department (Y201942627), Zhejiang Provincial Universities and Research Institutes (No. 2019J00025) and
Demonstration Project of Marine Economic Innovation and Development of Zhoushan City of China.
Conflicts of Interest: The authors declare that they have no conflicts of interest to report regarding the
present study.

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