Journal Pre-proof

Conversion of Au(III)-polluted Waste Eggshell into Functional CaO/Au nanocatalyst

for Biodiesel Production

Jiadi Liu, Minghuan Liu, Shaoyun Chen, Bingqing Wang, Jin Chen, Da-Peng Yang,
Shangzhou Zhang, Wenxiao Du

PII: S2468-0257(20)30119-9
DOI: https://doi.org/10.1016/j.gee.2020.07.019
Reference: GEE 280

To appear in: Green Energy and Environment

Received Date: 19 March 2020

Revised Date: 14 July 2020
Accepted Date: 22 July 2020

Please cite this article as: J. Liu, M. Liu, S. Chen, B. Wang, J. Chen, D.-P. Yang, S. Zhang, W. Du,
Conversion of Au(III)-polluted Waste Eggshell into Functional CaO/Au nanocatalyst for Biodiesel
Production, Green Energy & Environment, https://doi.org/10.1016/j.gee.2020.07.019.

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Graphical Abstract

Conversion of Au(III)-polluted Waste Eggshell into

Functional CaO/Au nanocatalyst for Biodiesel
Production
Jiadi Liu1,2, Minghuan Liu3, Shaoyun Chen3, Bingqing Wang3, Jin Chen4,

Da-Peng Yang3*, Shangzhou Zhang2*, Wenxiao Du1*

Waste eggshells were used to adsorb Au(III) in water and convert the Au(III)-polluted
eggshells into the functional nanocatalyst-CaO/Au for the transesterification reaction
between soybean oil and methanol to the preparation of biodiesel.
 1 Conversion of Au(III)-polluted Waste Eggshell into Functional

2 CaO/Au nanocatalyst for Biodiesel Production

3 Jiadi Liu1,2, Minghuan Liu3, Shaoyun Chen3, Bingqing Wang3, Jin Chen4,

4 Da-Peng Yang3*, Shangzhou Zhang2*, Wenxiao Du1*

1
5 College of life science, Yantai University, Yantai 264005, Shandong

6 Province, PR China
2
7 School of Nuclear Equipment and Nuclear Engineering, Yantai

8 University, Yantai 264005, Shandong Province, PR China

3
9 College of Chemical Engineering and Materials Science, Quanzhou

10 Normal University, Quanzhou 362000, Fujian Province, PR China

4
11 Clinical Center for Molecular Diagnosis and Therapy, the Second

12 Affiliated Hospital of Fujian Medical University, Quanzhou 362000, PR

13 China

14 *Corresponding authors.

15 Email address: duwenxiao2007@163.com (Wenxiao Du);

16 szzhangyt@163.com (Shangzhou Zhang); yangdp@qztc.edu.cn (Da-Peng

17 Yang).

18

19

20

21
22 Abstract
23 Developing an environmental-friendly and highly active catalyst in transesterification
24 for biodiesel production is of great importance for a more economic biodisel process.
25 Herein, we reported that waste eggshells were used to adsorb Au(III) in water and
26 convert the Au(III)-polluted eggshells into the functional nanocatalyst-CaO/Au for the
27 transesterification reaction between soybean oil and methanol to the preparation of
28 biodiesel. By coupling of CaO and Au nanoparticles, CaO/Au nanoparticles showed
29 superior catalytic activity for the transesterification reaction between soybean oil and
30 methanol. An optimum performance was observed over CaO/Au nanocomposites in a
31 methanol-oil molar ratio at 12: 1 with catalyst content of 1.0 wt% at 70 for 3 h.
32 Besides, the catalytic activity of CaO/Au nanocatalyst was almost unchanged after
33 recycling for 5 times and the yield of biodiesel still kept at 88.9%. The proof-of
34 concept study provided us a sustainable method for utilization of waste eggshells to
35 remedy the metal ions-polluted wastewater and the synthesis of functional
36 nanocomposite for biodiesel production, show great potential application of waste
37 eggshell in adsorption and catalytic reactions.
38

39

40

41

42 Keywords: CaO; Au; Eggshell; Biodiesel; Transesterification

43
44 1. Introduction
45 With the development of human society and the economy, petroleum and other fossil
46 resources are being continuously exhausted, and the supply of fuel has become
[1-5]
47 increasingly severe . At the same time, the consumption of fossil energy has
48 caused many environmental problems, threatening human health and living
[6]
49 environment . Therefore, the development of green, environmentally friendly and
50 renewable energy has become one of the most important topics for energy and
51 environment research in the 21st century. In the past decades, the development and
52 utilization of biodiesel have attracted worldwide attention owing to its excellent
[7] [8]
53 environmental protection , safety and renewability . Biodiesel primarily consists
54 of monoalkyl groups of unsaturated fatty acids, which contains about 77% carbon, 12%
[9-11]
55 hydrogen, 11% oxygen as well as trace amounts of sulfur and nitrogen . At
56 present, the preparation of biodiesel mainly included direct synthesis, microemulsion,
57 high-temperature thermal cracking and transesterification methods [12]. Among them,
58 transesterification reaction for the preparation of biodiesel, such as methanol or
59 ethanol reacted with vegetable oils, animal fats, edible waste fats or oils under the
60 action of catalysts, is regarded as an eco-friendly way and has attracted tremendous
61 attention.
62 Recently, lots of work has reported about the transesterification process by the use of
63 CaO as a basic catalyst, which facilitates the transesterification reaction at relatively
64 low temperature. Till now, much effort had been devoted to increase the yield of
65 biodiesel by using various kinds of CaO-based catalyst, such as the gel-combusted
66 CaO catalyst, the modified CaO catalyst and the supported CaO catalyst. For example,
67 Kambiz et al. used CaO/CuFe2O4 as an efficient catalyst to increase the yield of
[13]
68 biodiesel from chicken fat . Ch. Chingakham et al. prepared Fe3O4 nanoparticle
69 from eggshells as a new catalyst for the transesterification reaction for the preparation
[14]
70 of biodiesel . Liu et al. prepared a magnetic MgFe2O4/CaO nano-catalyst for
[1]
71 biodiesel production with a yield of 98.3% . Currently, intending to develop
72 renewable materials based processes, researchers are paying particular interest in solid
 [15-16]
73 waste, particularly bio-wastes for the value-added applications . Eggshell is an
74 economical and widely sourced agricultural by-product [17] and its unique hierarchical
[18]
75 porous structures , organic-inorganic composition, and surface geometry can
76 provide a higher specific surface area than artificial materials. Recent studies have
77 revealed that CaO catalysts can be prepared from waste eggshell under mild reaction
[19-20]
78 conditions , and shows its potentials in the application of environmental and
79 energy.
80 As previous work reported, the transesterification reaction usually was limited by the
81 diffusion resistance of the reactant, which was not helpful to the reaction. Au
82 nanoparticles as a popular catalyst with unique bio-compatibility, anti-oxidation
83 properties as well as excellent stability can significantly enhance the catalytic activity
[21]
84 and increase biodiesel production . Although only a few examples of Au or Ag
85 nanoparticles supported on eggshells had been reported, the as-prepared complex is
86 often made up of Au/CaCO3 or Ag/CaCO3[22-23]. In fact, CaCO3 can be further
87 converted into CaO under the high temperature (over 800 ℃). If we transferred the
88 CaCO3-based nanocomposite into CaO-based one, the enormous potential of novel
89 composite will be worthy of deep explorations, particularly Au/CaO in the
90 transesterification reaction [2].
91 On the other hand, with the development of modern industry, the recovery of heavy
92 metals from wastewater is very important to save the resources and protect the
[24]
93 environment . At present, there are many methods for treating heavy metals in
94 wastewater. Due to the strong ability to treat a variety of target pollutants, high
[25]
95 capacity, and fast speed, adsorption is widely used in wastewater treatment . For
96 the environmental application of adsorbents, the requirements of low-cost, abundant,
97 high-performance and available in nature should be fulfilled. As a porous material,
98 eggshell can act as functional support for effective adsorption of heavy metals in
99 wastewater. For example, Zhang et al. using eggshells to adsorb heavy metal Cd2+,
[26]
100 and the removal rate could reach more than 90% . They further explored the
101 adsorption of Cr3+ by eggshells, and the removal rate was close to 90%. Our group
102 found that Cu and Zn ions in wastewater can also be removed by eggshells
 [27]
103 simultaneously to form functional nanomaterials . All of these indicated that
[28-29]
104 eggshell was an excellent bio-adsorbent for metal ions . Therefore, the use of
105 agricultural waste, especially eggshell as an adsorbent to repair the pollution of heavy
[30]
106 metal ions are gradually recognized by the international community , since it not
107 only provides us a cheap and environmental-friendly raw material but also achieves
108 the goal of “waste control by waste” and value-added advantages [31-32].
109 Herein, we aimed to use eggshells to adsorb Au( ) in water and then calcined them to
110 obtain CaO/Au nanocomposite as catalysts for biodiesel production. The as-prepared
111 CaO/Au nanocomposite showed superior catalytic activity for the transesterification
112 reaction between soybean oil and methanol under an optimal condition. The work
113 provided us a sustainable and green approach for simultaneous disposal of waste
114 eggshell, the remedy of Au(III) pollution, and the highly-efficient production of
115 biodiesel.

116

117

118
119 2. Experimental Section
120 2.1 Materials
121 The eggshell used in the experiment was from the canteen of Quanzhou Normal
122 University (Quanzhou, Fujian Province, China). Chloroauric acid (AuCl3•HCl•4H2O)
123 was purchased from Sinopharm Group (Shanghai, China). Methanol was purchased
124 from Xilong Chemical Co., Ltd. (Shantou, Guangdong). Soybean oil bought was
125 called as fulinmen first-grade soybean oil. Hexane (C6H14, AR, 97%) was bought from
126 Macleans. Methyl salicylate (AR, 99%) was bought from Aladdin.
127 2.2 Preparation of Eggshell Powder
128 The collected waste eggshells were repeatedly washed by using the deionized water.
129 Then, they were immersed in water for 1 to 3 hours at room temperature and dried in
130 a dry box. The eggshell was broken with a pulverizer, sieved through 200 mesh and
131 soaked in NaOH solution for 10 to 30 minutes. Finally, the powder was washed with
132 deionized water for 3 to 5 times, and then dried to obtain the carrier eggshell.
133 2.3 Synthesis of CaO/Au nanocatalyst
134 A volume of 50 mL of chloroauric acid solution (10 mM) (used to simulate
135 wastewater) and 2 g of the pre-treated eggshell were mixed in a beaker. The mixture
136 was stirred at room temperature for 12 h to load the gold ions onto the eggshell carrier,
137 and then evaporated to dryness, calcined at 900 °C for 3 hours in a muffle furnace to
138 get the CaO/Au nanocatalyst. After calculation, the molar ratio of CaO to Au is 20:1.
139 2.4 Catalyst characterization
140 CaO/Au nanocatalyst is analyzed by X-ray diffractometer (XRD) (Bruker D8
141 Advanced, Germany) to detect the phase composition of the sample. The novel
142 nanocatalysts were analyzed by field-emission scanning electron microscopy
143 (FE-SEM, Zeiss, Germany) to observe the crystal structure and surface morphology,
144 and the type, content and distribution of the elements were detected by the synergistic
145 effect of the energy dispersive X-ray spectrometer (EDS) detector (Zeiss, Germany).
146 The morphology of the catalysts was characterized with transmission electron
147 microscope (FEI Tecnai 30 microscope (Philips, USA)). X-ray photoelectron
148 spectroscopy (XPS) analysis was conducted with a Kratos Axis Ultra DLD to examine
149 the peak of Au, C, Ca, and O.
150 2.5 Transesterification reaction
151 Soybean oil (8.8 g, 0.01 mol), 3.84 g of methanol (0.12 mol) as well as 88 mg of
152 CaO/Au nanocatalyst (1.0 wt% soybean oil) were added into a 50 ml three-necked
153 flask. The three-necked flask was placed in an oil bath and magnetically stirred at 70
154 for 3 h. The reacted suspension was centrifuged to separate the catalyst, and the
155 reaction solution was transferred to a separatory funnel. After standing to separate the
156 layers, the lower layer of the reaction solution was taken in a 50 ml round bottom
157 flask and the remaining methanol was removed in a rotary evaporator.
158 The obtained product was analyzed by gas chromatography-mass spectrometry
159 (GC-MS). GCMS-QP2020 instrument equipped with an AOC-20i auto-sampler
160 (Shimadzu, Kyoto, Japan) at full-scan mode were utilized for sample analyses. The
161 injection volume was 1 μL with a split ratio 100:1. Reaction products were separated
162 by a DB-5 capillary column (30 m×0.25 mm×1 μm, Agilent Technologies, Palo
163 Alto, CA). The flow rate of helium (carrier gas) was set at 40 cm/s. The oven
164 temperature was initially held at 120 ℃ for 1 min, increased to 220 ℃ by 20 ℃/min,
165 and ramped to 270 ℃ at 5 ℃/min, where it was held for 1 min. The inlet, ion source
[29]
166 and interface temperature were set at 265 ℃, 230 ℃ and 280 ℃, respectively .
167 Electron impact was employed as the ionization mode, and the voltage of the detector
168 was manipulated in accordance with the tuning results. Mass Scan was acquired from
169 m/z 55 to 550 with 3 min solvent delay. Compounds identification was based on the
170 commercially available libraries (NIST14, Gaithersburg, USA). Available reference
171 standards were used to confirm the identification results using the retention time,
172 retention index and mass spectra.
173 The calculation method of biodiesel yield is as following:
× ×
Yield = ≈
× × ×
≈ ≈ × 100%

174 In the above formula, mactual and mtheoretical are the actual mass and theoretical mass of
175 biodiesel. Cesters is the mass concentration of biodiesel. n represents the dilution factor
176 of biodiesel. moil is the quality of soybean oil. Vesters and Vesters are the volume of
177 biodiesel and the volume of soybean oil. is the density of soybean oil [1].
178

179 3. Results and Discussions

180 3.1 Characterization of Catalyst

181
182 Fig.1 XRD patterns of eggshell-derived CaO and CaO/Au nanocatalyst.
183

184 The phase constituents of eggshell-derived CaO/Au nanocatalyst and eggshell-derived

185 CaO were analyzed by XRD, as shown in Fig. 1. The diffraction peaks of the CaO/Au
186 nanocatalyst appeared at 38.178°, 44.373°, 64.558° and 77.543°, corresponding to the
187 (111), (200), (220) and (311) planes of Au, respectively (JCPDS PDF #89-3697),
188 while the diffraction peaks at 32.429°, 54.256° and 64.645° assigned to the (111),
189 (200) and (311) planes of CaO (JCPDS PDF # 74-1226). Interestingly, the diffraction
190 peaks at 37.376°, assigned to the (200) crystal plane of CaO, was not observed as
191 compared to bare CaO, due to the thick layer of Au NPs covered on the surface of
192 CaO. These results indicated that the CaO/Au composites had been successfully
193 prepared.
194
195 Fig.2 (a-b) SEM images of CaO / Au, (c-f) Element mapping images of C, O, Ca, and
196 Au by EDS, (g) TEM image of CaO / Au. Inset is the size distribution of Au
197 nanoparticles on eggshell support.
198

199 The SEM, TEM and EDX characterizations were carried out to inspect both the
200 morphology and microstructure of CaO/Au nanocomposites. The irregular rod-shaped
201 structure with macrochannel was observed from the SEM images of CaO/Au
202 nanocomposites, as shown in Fig. 2a-b. The EDS element mapping images
203 corresponding to the four elements C, O, Ca, and Au can be seen, in which Au
204 element was evenly distributed on the surface of CaO, indicated that many ultrasmall
205 Au nanoparticles supported on CaO were deposited with good dispersibility (Fig.
206 2c-f). It can be further observed that the particle size of Au nanoparticles is mostly
[33]
207 between 2-4 nm from the TEM image (Fig. 2g). As Ishida et al. Noted , Au with
208 sizes ranging from 2-5 nm had been proposed as active sizes of the Au species, also
209 depending on the type of support. Although the immobilization of active Au
210 nanoparticles on CaO support lost available surface area in part and a reduction of
211 catalysis active sites, some special sites between the interfaces of Au nanoparticle and
212 support CaO will be created, giving rise to additional activities. Charge transfer
213 between them can also change the electronic structure of Au nanoparticles, leading to
214 the enhanced catalytic activity for some reactions. These ultra-small and active Au
215 nanoparticles in our work would be beneficial to make full contact with the reactants
216 and promote the catalytic reaction.

217
218 Fig.3 XPS spectra of CaO/Au in full scan (a), C 1s region (b), O 1s region (c), Ca 2p
219 region (d), Au 4f region (e).
220 The different electronic states of CaO/Au, including Au, C, Ca and O elements, were
221 studied by XPS (Fig. 3). A full scan spectra of CaO/Au was obtained and four
222 characteristic peaks at 86.2, 287.6, 348.7, and 532.5 eV, attributed to C 1s, O1s, Ca 2p,
[34]
223 and Au 4f, respectively, were observed (Fig. 3a) . The XPS spectra in C 1s region
224 of CaO/Au exhibited two peaks at 285.0 and 289.5 eV, assignable to C-C and C=O,
225 respectively (Fig. 3b). Correspondingly, the peak at 532.5 eV, assignable to O2- in
226 Ca-O bonds, was also observed in the XPS spectra in O 1s region (Fig. 3c). Two
227 peaks at the 346.5 and 351.2 eV were observed, which attributed to Ca 2p3/2 and Ca
228 2p1/2 in CaO (Fig. 3d). The XPS spectra of CaO/Au nanocomposites further confirms
229 the presence of metallic Au by showing two peaks at a binding energy of 84.2 and
230 88.4 eV, assignable to Au0 4f7/2 and Au0 4f5/2 , respectively (Fig. 3e).
231

232
233 3.2 Performance of CaO/Au for transesterification reaction

234

235 Fig.4. GC-MS chromatogram of the end FAME (Fatty acid methyl ester) products
236 completed under an optimal condition.
237

238 Biodiesel is essentially a collective name for various types of fatty acid methyl esters
[35]
239 . The basic principle of the reaction between soybean oil and methanol to produce
240 biodiesel is as following: free fatty acids in soybean oil and methanol undergo a
241 transesterification reaction under an active catalyst to produce fatty acid methyl esters
[36]
242 . The performance of the as-obtained CaO/Au nanocomposites for the
243 transesterification reaction between soybean oil and methanol was investigated, which
244 was initially performed in an oil bath and magnetically stirred at 70 for 3 h and
245 analyzed by GC-MS. As shown in Fig. 4, the peak at 12.335 min was methyl
246 palmitate, the peak at 14.940 min was attributed to methyl stearate, the peak at 14.995
247 min was ascribed to methyl oleate, the peak at 15.065 min belonged to methyl
248 linoleate, the peak at 15.305 min was methyl linolenate. It can be proved that the
249 biodiesel product has been successfully obtained by using CaO/Au as catalyst.
250 3.3 Effects of reaction parameters
251

252 Fig.5 Influences of dosage of catalyst (a) reaction temperature (b) reaction time (c)
253 molar ratio of methanol to soybean oil (d) on biodiesel yield.
254 It is widely accepted that dosage of catalyst, reaction temperature, reaction time as
255 well as the amount of reactant play crucial roles in influencing catalytic performance.
256 Therefore, the following experiments were designed to further discuss the
257 performance of CaO/Au for the transesterification reaction between soybean oil and
258 methanol.
259 3.3.1 Influence of dosage of catalyst
260 The effects of different catalyst dosages taking up the proportions (0.25, 0.5, 1.0, 2.0,
261 3.0 wt%) to the weight of soybean oil, on the transesterification reaction was studied
262 with a molar ratio of methanol and oil at 12: 1 in an oil bath at 70 for 3 h. As shown
263 in Fig. 5a, the yield of biodiesel was increased with the dosage of the catalyst from
264 0.25 wt% to 1.0 wt%. Obviously, when the dosage of catalyst reached to 1.0 wt%, the
265 yield of biodiesel was the highest (94.69%). However, a further increase of the
266 catalyst dosages to 3.0 wt%, lead to a slightly reduce in the yield of biodiesel
267 (92.82%). This is probably ascribed to the total number of active sites increases,
268 which can promote the reaction and increase the yield of biodiesel. Along the
269 increasing dosage of the catalyst, the active sites of the catalyst were not increased
270 due to the occurrence of saturation state. Therefore, with the increase of dosage of
271 catalyst, the yield of biodiesel gradually declined. Moreover, the excess catalyst will
272 increase the viscosity of the system, which usually increases the mass transfer
273 resistance and cause a saponification reaction [37].
274 3.3.2 Influence of reaction temperature
275 The reaction temperature is one of the important factors for the transesterification
276 reaction. The effects of different reaction temperatures on the transesterification
277 reaction were studied. The transesterification reaction was carried out in a molar ratio
278 of methanol and oil at 12: 1 with a catalyst amount of 1.0 wt% under different
279 reaction temperatures (60, 70, 80, 90, 100 ) for 3 h. As shown in Fig. 5b, when the
280 reaction was carried out under 70 , the yield of biodiesel was the highest one.
281 However, the yield begins to decrease with the temperature increased. It may be
282 caused by the high-speed movement of molecules with the increase of temperature
283 leading to the diffusion resistance between the three phases of the
[38]
284 oil-methanol-catalyst decreases and thereby speeding up the reaction rate .
285 However, as the temperature exceeds 70 , the excessive temperature will cause the
286 loss of methanol evaporation and reduce the yield of biodiesel.
287 3.3.3 Influence of reaction time
288 The effect of reaction time ranging from 1-5 h on the transesterification reaction was
289 also investigated. The transesterification reaction was carried out in the molar ratio of
290 methanol and oil at 12: 1 with the amount of catalyst is 1.0 wt% in an oil bath at 70
291 (Fig. 5c). As the results showed, the yield of biodiesel increased rapidly at the first 1 h,
292 and the yield can reach 94.69% with extending the reaction time to 3 h. When
293 reaction time is over 3 h, the increase of biodiesel yield is not obvious, indicating that
294 the transesterification reaction had reached a reversible equilibrium point, and the
[39]
295 reaction rate has almost reached the kinetic equilibrium . If the reaction time
296 continued to be prolonged, emulsification may occur, which in turn affected the yield
297 of biodiesel.
298 3.3.4 Influence of molar ratio of methanol to soybean oil
299 The effects of different methanol-oil molar ratios (3: 1, 6: 1, 9: 1, 12: 1, 15: 1) on the
300 transesterification reaction were studied. The transesterification reaction was
301 performed in an oil bath at 70 with the amount of catalyst is 1.0 wt% for 3 h (Fig.
302 5d). Among five different methanol-oil molar ratios investigated, the highest yield
303 was obtained when the molar ratio of methanol to oil was 12: 1. It can be known from
304 the stoichiometric relationship that the transesterification reaction is a heterogeneous
305 reversible reaction with a molar ratio of methanol to oil of 3: 1. The mass transfer
306 resistance will significantly reduce the actual chemical reaction rate led to the adding
307 of excess methanol that can increase the yield of biodiesel. Therefore, increasing the
308 molar ratio of methanol and oil to 12:1, the yield of biodiesel increased. While
309 increase the molar ratio of methanol to oils equably, the yield of biodiesel decreased,
310 due to more and more catalyst and soybean oil are dissolved by methanol with the
311 methanol concentration increases, which inhibits the progress of the reaction, thereby
312 reducing the yield of biodiesel [34, 40].
313 3.4 Influence of Au content

314

315 Fig.6 Influence of different Au concentrations on biodiesel yield under an optimal

316 condition.
317

318 The optimal reaction conditions of this reaction were obtained through
319 above-mentioned experiments, and then the various concentrations of chloroauric acid
320 (1mM, 5 mM, 10 mM) were used to prepare CaO/Au nanocatalyst to explore the
321 effect of Au content on biodiesel yield. The results were shown in Fig. 6. Overall, as
322 the Au content increases, the biodiesel yield also increases. When the concentration of
323 Au is increased from 1 mM to 5 mM compared to from 5 mM to 10 mM, the increase
324 in biodiesel production is more obvious. It may be because the CaO-loaded Au NPs
325 have reached saturation, and increasing the gold content will not have a significant
326 impact on the increase in the yield of biodiesel.
327 3.5 Comparison of catalyst performance

328
329 Fig.7 Catalytic performances of CaO and CaO/Au catalysts under an optimal
330 condition.
331

332 The catalytic performances of CaO/Au and CaO, calcined from eggshell at 900 ,
333 were compared at a reaction temperature of 70 , a catalyst amount of 1.0 wt%, A
334 reaction time of 1-5 hours, and a molar ratio of methanol to oil of 12: 1. It can be seen
335 from Fig. 7, that no matter how long the reaction time is, the catalytic performance of
336 CaO/Au is better than pure CaO, and the yield of biodiesel has an enhancement about
337 10% within the first 3 hours. It can again be revealed that the performance of the
338 catalyst is greatly improved by supporting Au nanoparticles on the surface of CaO[41].
339 3.6 Reusability of catalyst
340
341 Fig.8 Cycling tests of CaO/Au nanocatalyst for five times under an optimal condition.
342

343 The reusability and stability of the catalyst are the key parameters to evaluate the
344 performance of a catalyst. No obvious loss of the activity of CaO/Au composite was
345 observed after five cycling tests and the yield of biodiesel still reached 88.9%,
346 indicating that the CaO/Au composite had good stability and reusability (Fig. 8). This
347 is because Au nanoparticles attached to the surface of the CaO matrix have a certain
348 hydrophobic ability, which can protect the CaO matrix avoiding the deterioration from
349 the water and glycerol generated by the reaction to a certain extent, and thus improve
350 the stability of CaO matrix [6].
351
352 4. Conclusions
353 This paper described the application of eggshell-derived CaO/Au composite in the
354 preparation of biodiesel from soybean oil. The eggshell was used to adsorb Au3+ in
355 chloroauric acid and then calcined to obtain a novel CaO/Au nanocatalyst. It was
356 found that CaO/Au nanocomposites showed superior catalytic activity for the
357 transesterification reaction between soybean oil and methanol via a successful
358 coupling of CaO with Au nanoparticles. The optimum performance was realized over
359 CaO/Au nanocomposites with a methanol-oil molar ratio at 12: 1 and catalyst content
360 of 1.0 wt% in an oil bath at 70 for 3 h. This proved that the CaO/Au nanocatalyst
361 had good catalytic performance for the biodiesel and showed the great potential
362 application of eggshell in catalytic reactions. It can be expected that the waste
363 eggshell would become an essential and environmentally friendly resources for
364 various applications in the industry.

365 Acknowledgments
366 This work was supported by the Orientative project funded by Fujian Provincial
367 Science and Technology Department (2019H0023), Quanzhou City Science &
368 Technology Program of China (2017G023), Fujian Educational Committee
369 (JAT160402) and Natural Science Foundation of Shandong Province, China (No.
370 ZR2019MEM012).

371

372
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Conflict of Interest

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be considered as
potential competing interests:

Jiadi Liu, Minghuan Liu, Shaoyun Chen, Bingqing Wang, Jin Chen, Shangzhou Zhang, Da-Peng Yang,
Wenxiao Du