Preparation of silica nanoparticles from geothermal sludge via sol-gel method

S. N. Aisyiyah Jenie, Almira Ghaisani, Yudia P. Ningrum, Anis Kristiani, Fauzan Aulia, and Himawan T. M. B.
Petrus

Citation: AIP Conference Proceedings 2026, 020008 (2018); doi: 10.1063/1.5064968

View online: https://doi.org/10.1063/1.5064968
View Table of Contents: http://aip.scitation.org/toc/apc/2026/1
Published by the American Institute of Physics

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AIP Conference Proceedings 2026, 020009 (2018); 10.1063/1.5064969
Preparation of Silica Nanoparticles from Geothermal Sludge
via Sol-Gel Method

S. N. Aisyiyah Jenie1, a), Almira Ghaisani1), Yudia P. Ningrum1), Anis Kristiani1),

Fauzan Aulia1 ), and Himawan T.M.B. Petrus2)
1
Research Centre for Chemistry, Indonesian Institute of Sciences, Kawasan Puspiptek, Building 452, Serpong,
Tangerang Selatan, Banten 15314 Indonesia
2
Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika Utara 1,
Sekip, Yogyakarta 55283 Indonesia
a)
Corresponding author: siti045@lipi.go.id

Abstract. Silica geothermal is abundantly available as side products or waste from the production of energy from
Geothermal Power Plants. These inexpensive waste materials was used to produce silica nanoparticles which in return
increased the value of silica geothermal. The purpose of this research is to synthesize nanoparticle silica from
geothermal waste following the sol-gel method. This was conducted by reacting silica waste with NaOH 1.5 N and
subsequently the addition of 2N HCl solution to form a gel at pH 5. The ageing time of the gel were varied from 18 to 72
hours and the specific surface area were characterized by the Brauner Emmett Teller (BET) Adsorption. Aging time at 18
hours showed the highest specific surface area of 289 m2/g. The surface chemistry of the silica nanoparticles were
performed using Fourier Transform Infra Red (FTIR) which showed that silanol dan siloxane groups were prominent. In
contrast with its precursor, the silica geothermal waste, which was in its amorphous phase, the X-Ray Diffraction (XRD)
of the silica nanoparticles showed high crystallinity.

INTRODUCTION
Geothermal in the form of water vapor can be used as a source of renewable energy. This geothermal energy
production generates waste in the form of sludge and brine [1]. Sludge is derived from sediments in liquid waste
processing (geothermal brine) while silica crust is produced from the geothermal plant installation pipes. This solid
waste contains metallic elements, some of which are heavy metals such as Cu, Pb, Zn, Mn, Fe, Cd, As, Sb, Au, Ag,
Hg, Se. This solid waste also contains high amount of silica [1]. Geothermal waste contains about 90 to 98% of
amorphous silica and some traces of metallic compound, hence geothermal waste is very potential to be used for the
preparation of silica nanoparticles.
Silica nanoparticles have several properties such as large surface area, good heat resistance, high mechanical
strength and inert which can be used as catalyst precursors, adsorbents and composite filters [2]. Silica nanoparticles
can also be applied for latent fingerprint identification, as it has the ability to attach to the fatty deposit which is a
major component of a fingerprint [3].
Various methods have been developed for the synthesis of nanoparticles. The most common method is the sol-
gel method due to its simple and ease of preparation of the nano-sized metal oxide materials [4]. Kusumastuti et al
(2017) has synthesized silica nanocomposites from geothermal waste by sol-gel method, modified with chitosan,
gelatin, and pectin. The results showed that silica based nanocomposites can be obtained from geothermal waste by
optimizing the components of the composites [5]. The sol-gel method have been proven as the method of choice for
the preparation of silica nanoparticles from waste. Previous works by Rafiee et al (2012) and Le et al (2013) has

2nd International Conference on Chemistry, Chemical Process and Engineering (IC3PE)

AIP Conf. Proc. 2026, 020008-1–020008-5; https://doi.org/10.1063/1.5064968
Published by AIP Publishing. 978-0-7354-1746-5/$30.00

020008-1
showed that rice husk ash, a common agricultural waste, can be utilized as percusors for silica nanoparticles,
resulting in size as low as 3 nm [6,7]. Herein, the preparation and characterization of silica nanoparticles via sol-gel
method was conducted. The geothermal waste was used as the source of silica.

EXPERIMENTAL

Materials
Geothermal sludge, as the source of silica, was collected from PLTP Geodipa Dieng, Central Java, Indonesia.
Sodium hydroxide (NaOH) was purchased from Merck Chemicals. Hydrochloric acid (HCl) 37% was an analytical
grade from Merck Chemicals. All chemicals were used without further purification. Deionized water was used for
all synthesis.

Synthesis of Silica Nanoparticles

As shown in Scheme 1, a total of 20 g of washed silica powder was mixed with 800 ml of 1.5 N sodium
hydroxide (NaOH) in a beaker glass to form sodium silicate (Na2SiO3). The mixture was then stirred using a
magnetic stirrer with constant heating maintained at 90ºC for 60 minutes. Subsequently, the mixture was filtered
through filter paper to separate the solution with solids. The sodium silicate solution was titrated with 2 N HCl to
form the gel at pH 5 and then allowed to stand for various ageing times, which includes 18, 43 and 72 hours. The gel
formed was filtered with filter paper and washed with aquadest until neutralized. The neutralized gel was dried
overnight in an oven at 100 ºC. The resulting solid samples were identified as the silica nanoparticles (SiNP).

Characterization of Silica Nanoparticles

X-Ray Diffraction (XRD) analysis were carried out for crystallographic phases identification of the Silica
Nanoparticles samples usis a Phillip PW 1710 diffractometer, using Cu Kα radiation at 40 kV and 30 mA, and a
secondary graphite monochromator.
Nitrogen adsorption-desorption isotherms were measured on Micromeritics TriStar II 3020 porosimeter at 77 K.
Prior to each measurement all samples were degassed at 110 ºC and 10-4 Torr pressure to evacuate the physisorbed
moisture The specific surface area of the particles was determined by Brunauer–Emmett–Teller (BET) method.
Fourier Infrared Spectroscopy (FTIR) spectra were were recorded on a FTIR Prestige-21 (Shimatzu, Japan), in
transmittance mode, at 16 cm-1 resolution, over the range of 300-400 cm-1 with an accumulating average of 10 scans.
The software used to generate the spectra was IR Solution (Shimatzu).
Transmission Electron Microscopy (TEM) images were obtained with TEM Tecnai G-20 S-Twin (FEI, USA)
scanning TEM instrument (200 kV accelerating voltage) equipped with Tungsten cathode and an Eagle CCD
camera. For TEM measurement, a suitable amount of ethanolic solution of SiNP was dropped onto a porous carbon
film on a copper grid and then dried in vacuum.

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 Scheme 1. Flowchart of the preparation of SiNP from geothermal silica

RESULTS AND DISCUSSION

Particle Size and Morphology

The silica nanoparticles were fabricated using the common approach of sol-gel process using silica obtained
from the side product of geothermal plant [8] as precursor, which until now has not been reported elsewhere.
Transmission electron micrographs of the prepared SiNP are shown in Fig. 1. The morphology of the SiNP was
observed to be in the spherical crystal structure with the size 10-20 nm. The silica nanoparticles investigated in this
study was derived from amorphous geothermal silica. From the BET adsorption-desorption, the average particle size
was calculated as 20.7447 nm, which corroborates the results from TEM images.

FIGURE 1. Representative TEM images showing the nanostructures of SiNP at aging time of 18 hours

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 The details of specific surface area is given in Table 1. From the BET results, it can be seen that the increase of
ageing time from 18 hours to 72 hours resulted in a smaller surface area from 289 g/m2 to 15 g/m2, respectively.
SiNP samples that underwent 18 hours of ageing time gave the optimum specific surface area of 289 g/m2, which
is 60% and 5% higher than that of ageing time of 43 hours and 72 hours, respectively. This indicates that there is
influence of ageing time on surface area. This may be explained that the higher the ageing time, the stronger the
bonding of the gel resulting in the pores shrinkage and lower specific surface area [9].

TABLE 1. Specific surface area of the Silica Nanoparticles

Aging Time (hours) Surface Area (g/m2)

18 289

43 175

72 15

Crystal Phase
X-Ray Diffraction pattern for the formation of crystalline SiNP are shown in Fig. 2. The raw silica geothermal
and after washing with aquadest showed that the silica is in its amorphous phase. After ageing time of 18 hours and
43 hours, the XRD spectra showed that the silica nanoparticles were in the crystalline form. The XRD peaks in
pattern SiNP 18 h showed 2θ at 27.95º and 32.27º which indicates the formation of SiO2 and Sodium Silicate
crystallite according to Joint Committee on Powder Diffraction Standard (JCPDS). However, the intensity of these
peaks decreased when the ageing time was extended to 43 hours.

FIGURE 2. XRD pattern of samples Fresh Si Geo, Washed Si Geo, SiNP Geo 18 h, and SiNP Geo 43h

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 Surface Chemistry
The presence of silica functional groups and peak shifts are identified in the samples before and after sol-gel
modification through FTIR spectra, as shown Fig. 3. The corresponding peaks of silica for Si-O, Si-OH, Si-O-Si, Si-
O, O-H Silanol, O-H (water molecule) were found in the regions of 493 cm-1, 802 cm-1, 1056 cm-1, 1624 cm-1, 3047
cm-, respectively. The peaks between the two FTIR spectra were observed at the same wavenumbers, however the
intensity of O-H from the silanol groups and Si-O-Si of the silica nanoparticles increased compared to that of the
raw materials, indicating that at the surface of the SiNP, both silanol and siloxane groups were prominent.

3047 1624
1056 802
493

FIGURE 3. FTIR spectra of Silica geothermal as the raw material (red) and Silica nanoparticles ageing time 18 h (blue)

ACKNOWLEDGMENT
The authors would like to acknowledge the Ministry of Research, Technology and Higher Education for the
research funding. This research was supported by Department of Chemistry, Gajah Mada University for the FTIR
analysis and Research Center of Physics, Indonesian Institute of Sciences (LIPI) for the XRD and TEM analysis.

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