First virtual Bilateral Conference on Functional Materials (BiC-FM)

Biogenic synthesis of titanium dioxide: its composite with iron oxide and their potential biomedical application

Muhammad Azri Muhamad Yusop ^1,2, Che Azurahanim Che Abdullah ¹, Roshasnolyza Hazan ²

1-Department of Physics, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

2-Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor, Malaysia

muhammadazri0909@gmail.com

In recent years, biogenic synthesis of nanoparticles has received substantial attention owing to the ability in develop clean and safe chemicals, low-cost methods, eco – friendly and renewable materials. In the current study, the biogenic synthesis of TiO2 nanoparticles (TiO2NPs) is attained by a chemical and biosynthesized method by using the aqueous plant extract of Malaysian based agricultural. Iron oxide been produced via co-precipitation and alkaline fusion. The product (iron oxide) been doped with biogenic synthesized of titanium dioxide. TiO2 NPs pure and doped with iron oxide (composite) are characterized by FTIR, UV, and XRD. The antimicrobial activities of biosynthesized nanoparticles are examined using disc diffusion method. The TiONPs expected to show significant antimicrobial activity against all the tested microorganisms.

References:

[1] Muniandy, S. S., Kaus, N. H. M., Jiang, Z. T., Altarawneh, M., & Lee, H. L. (2017). Green synthesis of mesoporous anatase TiO 2 nanoparticles and their photocatalytic activities. RSC advances, 7(76), 48083-48094.

Topochemical transformations in MWCNTs-Si composites at high temperatures

Kuznetsov V.L.^1,2, Moseenkov S.I.¹, Zavorin A.V.^1,2, Tsendsuren Tsog-Ochir², Schmakov A.N.^1,2, Volodin V.A.^2,3.

1 – Boreskov Institute of Catalysis, Novosibirsk, Russia

2 – Novosibirsk State University, Novosibirsk, Russia

3 – Rzhanov Institute of Semiconductor Physics, Novosibirsk, Russia

zavorin@catalysis.ru

Multiwalled carbon nanotubes (MWCNTs) have unique physicochemical properties, allowing their use in a wide range of applications (composites, functional materials, electronics and others). One of the practical applications of carbon nanotubes is their use as part of an anode material in electrochemical power sources, where the addition of MWCNTs makes it possible to improve operational properties: maximum allowable charge-discharge currents, capacity and service life of lithium-ion power sources [1]. Another possible practical application of MWCNTs is their use as a reinforcing component of ceramic materials [2]. The introduction of MWCNTs in the composition of ceramics makes it possible to increase crack resistance, strength, improve tribological properties and achieve the appearance of electrical conductivity of such modified materials [3–4].

In this paper we study the high temperature initiated (700-1400 °C) topological transformation of MWCNTs-Si [5] composites produced by gas-phase deposition of silicon on the surface of nanotubes (at 500 °C). Si nanoparticles crystallization on MWCNTs surface and further topochemical reaction leading to SiC were studied using in-situ and ex-situ XRD and TEM, SEM, Raman spectroscopy. The data obtained were compared with results available after the study of macro Si-C systems. Industrial production of SiC regularly occurs at temperatures above 1500 °C. In the case of using the processes of decomposition of silicon organic compounds, the formation of SiC proceeds above 1100–1200 °C. In the case of MWCNTs-Si systems the formation of SiC began at temperatures of 700–800 °C. It was found that the topology of SiC particles is influenced by the sizes of the initial silicon particles. The kinetic parameters of the formation of silicon carbide in the MWCNTs-Si systems were also estimated.

Acknowledgement.Serkova A.N. for the study of MWCNTs-Si composites by the SEM method and Ishchenko A.V. and Chuvilin A.L. for the study of MWCNTs-Si composites by TEM.

References:

[1] N.Coppey et al., Chem. Eng. Res. Des., 12, P. 2491–2496, (2013).

[2] N.Song, H.Liu, J.Fang, Ceram. Int., 42, P. 351–356, (2016).

[3] А.Peigney, C.H.Laurent, Cambridge England, P. 309–333, (2006).

[4] S.Samal, S.Bal, Journal of Minerals & Materials Characterization & Engineering, 4, P. 355–370, (2008).

[5] A.Zavorin et al., J. Struct. Chem., 4, P. 617–627, (2020).

Enhanced imaging of single Si nanoparticles using non-reflective SWCNT membranes

Zhigunov D.M.¹, Shilkin D.A.², Kokareva N.G.², Bessonov V.O.^2,3, Dyakov S.A.¹, Chermoshentsev D.A.^1,4, Mkrtchyan A.A.¹, Gladush Yu.G.¹, Fedyanin A.A.², Nasibulin A.G.^1,5

1 – Skolkovo Institute of Science and Technology, Moscow, Russia

2 – Faculty of Physics, M. V. Lomonosov Moscow State University, Moscow, Russia

3 – Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Russia

4 – Moscow Institute of Physics and Technology, Russia

5 – Department of Chemistry and Materials Science,Aalto University, Finland

d.zhigunov@skoltech.ru

We demonstrate that single-walled carbon nanotube (SWCNT) membranes can be successfully utilized as nanometer-thick substrates for enhanced visualization and facilitated study of individual nanoparticles. As the model objects, optically resonant 200 nm silicon nanoparticles are transferred onto pristine and ethanol-densified SWCNT membranes by the femtosecond laser printing method. The nanoparticles are imaged by scanning electron and bright-field optical microscopy, and characterized by linear and Raman scattering spectroscopy. Using a pristine SWCNT membrane, an order-of-magnitude enhancement of the optical contrast of the nanoparticle bright-field image is achieved, as compared to the case of a glass substrate (Fig. 1). The observed optical contrast enhancement is in agreement with the spectrophotometric measurements showing an extremely low total reflectance of the pristine membrane (<1 %). Owing to the high transparency, negligibly small reflectance and thickness, SWCNT membranes offer a variety of perspective applications in nanophotonics, bioimaging and synchrotron radiation studies.

Fig. 1. Proof-of-concept demonstration of bright-field optical microscope image contrast enhancement using 200 nm Si nanoparticles (Si NP) transferred on a cover glass (left) and SWCNT membrane (right).

SYNTHESIS, CHARACTERIZATION AND TOXICITY STUDIES OF GOLD NANOPARTICLES FOR BIOMEDICAL APPLICATIONS

Siti Nadiah Zulkifli¹, Manali Haniti Zahid², Iskandar Zulkarnain Alias^2, Che Azurahanim Che Abdullah¹

¹Institute of Advanced Technology (ITMA), Universiti Putra Malaysia, 43400 Serdang, Selangor

² Department of Chemical Pathology, School of Medical Sciences, Health Campus, Universiti Sains Malaysia, 16150 Kubang Kerian, Kelantan

sitinadiahzulkifli@gmail.com

Gold nanoparticles (AuNPs) is chosen for this project due to the fact that it is widely used in a variety of applications as well as straightforward synthesis methods that allow the fast and cheap production of AuNPs. Comparative analysis on characterization between two methods have been studied. One step synthesis method can reduce metal ions to nanoparticles. Both approaches chemical and green synthesis were successfully synthesized by using modified Turkevich method. The prepared samples were analyzed using ultraviolet and visible spectrophotometry (UV–Vis), Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS). X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy have been used to study their structural phase composition and their functional group. The toxicity of AuNPs was then tested on brine shrimp. The nanoparticles produced will offer a potential materials for biomedical application.

Acknowledgement.This work was supported by Universiti Sains Malaysia under Research University Grant (Project Grant No. 1001/PPSP/8012296).

Abstracts of Participants

Enhanced Electrochemical Performance of TiO₂ Modified LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Material via Atomic Layer Deposition

Zahra Ahaliabadeh¹, Tanja Kallio¹

1 – Department of Chemistry and Materials Science (CMAT), Aalto University, School of Chemical Engineering, 02150, Espoo, Finland

Zahra.ahaliabadeh@aalto.fi

Developing high-energy and high-power lithium-ion batteries (LIBs) is a key challenge to meet the demands for practical applications in electric vehicles. These demands have driven the recent studies on positive electrode materials. Ni-rich layered lithium transition metal oxides are promising positive electrode material for the next generation high energy density LIBs because of their good electrochemical stability, comparatively low cost, low toxicity, and high capacity. However, high Ni content leads to severe side reactions at positive electrode/electrolyte interface and secondary particle cracking during cycling which significantly degrade the electrochemical performance of this material [1]. Improving the performance of positive electrode by using surface coatings has proven to be an effective method for developing LIBs, while a high-quality film satisfying all requirements of electrochemical issues, chemical stability, and lithium ion conductivity is yet to be implemented [2]. Recently, surface modification via atomic layer deposition (ALD) has gain attention as an effective strategy to enhance the electrochemical performance of high-specific-capacity electrode materials [3]. In this study, we reported a strategy that employed metal oxides (TiO₂) coating by ALD technique, in order to improve the bulk integrity, structure, and interfacial stability of the LiNi_0.6Co_0.2Mn_0.2O₂ (NMC622) and, hence, the long-term cycling capability. By varying the ALD parameters such as cycle number, mass of the substrate and precursor, an optimal ALD coating was achieved. The effects of TiO₂ coating on the surface states, crystal structure and electrochemical performances of NCM622 material are studied in detail. All characterizations results confirm the coating layer on the surface of NMC622 particles. The electrochemical characterization results indicated that the coating of TiO₂ ALD improved the cycling stability of NMC622 based electrodes by suppressing side reactions between the electrolyte and electrode. The improved electrochemical performance is ascribed to the high conformal and ultrathin TiO₂ coating, which enhances the kinetics of Li⁺ diffusion and stabilizes the electrode/electrolyte interface.

References:

1. Croy, Jason R., Brandon R. Long, and Mahalingam Balasubramanian. "A path toward cobalt-free lithium-ion cathodes." Journal of Power Sources 440 (2019): 227113.

2. Liu, Siyang, et al. "Comparative studies of zirconium doping and coating on LiNi0. 6Co0. 2Mn0. 2O2 cathode material at elevated temperatures." Journal of Power Sources 396 (2018): 288-296

3. Zhu, Wenchang, et al. "Ultrathin Al2O3 coating on LiNi0. 8Co0. 1Mn0. 1O2 cathode material for enhanced cycleability at extended voltage ranges." Coatings 9.2 (2019): 92.

Development of ceramic composites based on hydroxyapatite and carbon nanomaterials

Ávila E.S.¹, Antônio L.M. ¹, Ladeira L.O. ¹, Barabás R.²

1 – Universidade Federal de Minas Gerais, Escola de Engenharia Química, Belo Horizonte – MG – Brasil.

2 – Universitatea Babeș-Bolyai, Facultatea de Chimie și Inginerie Chimică, Cluj-Napoca – Romania.

erickavila@gmail.com

Graphene oxide has been studied ^1–4 as an alternative instead graphene because the presence of carboxylic and hydroxyl functional groups, it has excellent mechanical properties and biocompatibility.

Carbon nanotubes (CNT) were first synthesized by Iijima in 1991⁵. The great potential of applications of CNT are their physical and chemical properties and the possibility production of new biomaterials and composites ^1,6,7.

Hydroxyapatite is one ceramic material produced using calcium phosphate and is good candidate already widely used as artificial bone in orthopedic or maxillofacial surgeries to repair bone defects, on the olther hand, present fragility and other imperfections ^8,9. The ideal bone substitute must be biocompatible and gradually replaced the new bone tissue, need to have osteoinductive or osteoconductive properties ².

The production of ceramic nanocomposites based in hydroxyapatite and carbon nanomaterials can be the solution of join the better qualities of each separate materials.

This work is one study of the composites production based on graphene oxide, carbon nanotubes and hydroxyapatite with possibilities of application in engineering of bone tissues, mainly for the clinical treatments of bone defects caused by trauma, cancer, infection or congenital deformity also in dental restoration and implant processes field ¹⁰.

Acknowledgement.This work was supported by the Erasmus Mundus Program.

References:

[1] G. M. Neelgund. Et al, J. Colloid Interface Sci. 484, 2016, 135.

[2] P. Yu, Et al, Carbohydrate Polymers 155, 2017, 507.

[3] Y. Liu, J. Huang, H. Li, J. Mater. Chem. B 1, 2013,1826.

[4] Y. Bai, Et al., J Alloys Compd 688, 2016, 657.

[5] S. Iijima, Nature 354, 1991, 56.

[6] R. Barabás, Et al., Ceram. Int. 41, 2015, 12717.

[7] L. Costatini, Et al., J. Adv. Ceram. 5, 2016, 232.

[8] M.Czikó, Et al., Rev. Roum. de Chimie 59, 2014, 353.

[9] B. Cengiz, Et al., Colloids Surf A Physicochem Eng Asp 322, 2008, 293.

[10] R.Barabás, Et al., Arabian J. for Science and Eng. 45, 2020, 219.

About the intercalation of carbon dioxide molecule into the BC₅ nanotube

Zaporotskova I.V.¹, Boroznin S.V.¹, Zaporotskov P.A.¹, Boroznina N.P.¹

1 – Volgograd State University, Volgograd, Russia

boroznin@volsu.ru

The article is devoted to the study of methods of catching СО₂ molecules using boroncarbon nanotubes of type ВС₅. The paper considers the capillary method of filling nanotubes with a carbon dioxide molecule. The main method used in the work is the density functional theory (DFT) method within the B3LYP functional. As a result of the work, the most likely method of catching carbon dioxide molecules using boroncarbon nanotubes was established and the physicochemical characteristics of these phenomena were determined.

It was found that upon penetration into the cavity of the nanotube, the molecule is forced to overcome the potential energy barrier. This barrier was identified with the activation energy of this process. The calculated activation energy turned out to be less than 1 eV. This value indicates that the implementation of this mechanism has a high degree of probability. Accordingly, these nanostructures can be used as filters to trap harmful molecules from the atmosphere.

Acknowledgement.This work was supported by Russian Foundation for Basic Research and the government of Volgograd region, grant № 19-43-340005 r_a, by Russian President's grant № 798.2019.1, by Russian President's grant № MK-1758.2020.8.

On the possibility of creating a highly efficient sensor based on carbon nanotubes for determining air quality

Boroznina N.P.¹, Zaporotskova I.V.¹, Boroznin S.V.¹, Zaporotskov P.A.¹, Ivanov I.I.¹, Petrov P.P.²

1 – Volgograd State University, Volgograd, Russia

boroznin.natalya@volsu.ru

The presented article conducts a theoretical study of the possibility of interaction of substances that affect the quality of inhaled air – carbon dioxide and sulfur dioxide – with carbon nanotubes modified by the functional amine group. The article analyzed the results of addition and carried out a comparative analysis of sorption interaction of the nanosystem with molecules of carbon dioxide (CO2) and sulfur dioxide (SO2). Recommendations are given for further use of the results as a basis for creating a new generation of highly sensitive sensor device for detecting micro-quantities of substances. The calculations were carried out by the DFT method.

Our research will allow us to create instruments that can conduct a more efficient and more subtle study of air quality. They will allow detecting micro amounts of harmful substances to prevent pollution in a timely manner. A sensor based on modified carbon nanotubes will respond to the presence of ultra-small amounts of substances. This allows us to judge the prospects of its use in the field of chemistry, biology, medicine, etc.

Acknowledgement.The reported research was funded by Russian Foundation for Basic Research and the government of Volgograd region, grant № 19-43-340005 r_a, by Russian President's grant № 798.2019.1, by Russian President's grant № MK-1758.2020.8.

Doping of inner and outer surface of single-walled carbon nanotubes

Anastasia E. Goldt¹, Orysia Zaremba¹, Mikhail O. Bulavskiy¹, Fedor S. Fedorov¹,

Konstantin V. Larionov^2,3, Alexey P. Tsapenko¹, Zakhar I. Popov^2,4, Pavel Sorokin²,

Anton S. Anisimov⁵, Albert G. Nasibulin^1,6

1 – Skolkovo Institute of Science and Technology, Nobel str. 3, 121205 Moscow, Russian Federation

2 – National University of Science and Technology “MISiS”, Leninsky prospect 4, Moscow 119049, Russian Federation

3 – Moscow Institute of Physics and Technology, Institutskiy lane 9, Dolgoprudny, Moscow region 141700, Russian Federation

4 – Emanuel Institute of Biochemical Physics RAS, Moscow 119334, Russian Federation

5 – Canatu Ltd., Konalankuja 5, 00390 Helsinki, Finland

6 – Aalto University, 00076 Espoo, Finland

mikhail.bulavskiy@skoltech.ru

An increasing growth of flexible electronics market facilitates the development of new generation of materials that to be employed as flexible transparent conducting films (TCF) [1]. Even though, single-walled carbon nanotube (SWCNT) films are considered the most promising candidates for flexible TCFs, they still cannot meet the demanded characteristics [2]. Thus, the existing approaches to doping need a revision or improvement to allow SWCNTs achieve optoelectrical properties required for application as new generation TCFs.

In this work, we have utilized and investigated the new approach, which comprises the thermal treatment of SWCNTS in ambient air atmosphere with subsequent doping in ethanol solution of HAuCl₄. We have shown that thermal treatment at temperatures higher than 300 ^oC leads to the SWCNT cap’s removal. Consequently, such opening of nanotubes is responsible for the more efficient doping of the treated films due to providing an additional inner surface doping when compared to the untreated samples. Stronger level of p-doping effect of opened via thermal treatment SWCNT films in comparison to pristine ones were confirmed by DFT-calculations and open circuit potential (OCP) measurements during the doping procedure. The utilized approach has allowed us to achieve the record equivalent sheet resistance value of 31 ± 4 Ω/sq for the SWCNT films treated at 400 ^oC.

Acknowledgement.This work was supported by the Russian Science Foundation, grant No. 17-19-01787.

References:

[1] S. Zhang, N. Nguyen, B. Leonhardt, C. Jolowsky, A. Hao, J.G. Park, R. Liang, Adv. Electron. Mater., 5 (6), 1800811 (2019)

[2] Y. Zhou, R. Azumi, Sci. Technol. Adv. Mater., 17 (1), 493–516 (2016)

Influence of boron atoms in surface-carboxylated boron-carbon BC₃ and BC₅ nanotubes in the creation of sensory devices

Zaporotskova I.V.¹, Dryuchkov E.S.¹, Vilkeeva D.E. ¹, Elbakyan L.S. ¹

1 – Volgograd State University, Volgograd, Russia

dryuchkov@volsu.ru

In this article, discusses the possibility of the fabrication of a highly sensitive sensor based on single-walled boron-carbon BC₅ nanotubes surface modified with functional carboxyl groups (-COOH) and a comparative analysis of the sensory properties of BC₃ [1] and BC₅ single-walled boron-carbon nanotubes surface-modified with a functional carboxyl group (-COOH) was carried out. The potential of the sensor for detecting alkali (lithium, potassium and sodium) metals was investigated. Results of computer simulation of process of sensor interaction with arbitrary surface of modified tube containing atoms of analysed metals are presented. The effect of boron atoms on the sensory properties of the obtained systems is concluded. Calculations were carried out as part of the Density Functional Theory (DFT) method using a molecular cluster model. Surface-modified boron-carbon nanotubes according to the carboxyl group have been shown to exhibit high sensitivity to the metal atoms under study and can be used as a sensor device. However, modification of the surface of the nanotube BC₃ leads to a better result relative to BC₅: this system has the maximum energy of sensory interaction, which suggests that an increase in the number of boron atoms in the nanotubular system improves its sensory properties.

Acknowledgement.The research was carried out with the financial support of the RFBR and The administration of the Volgograd region in the framework of the scientific project no.19-43-340005 r_a.

References:

[1] N.P. Boroznina, I.V. Zaporotskova, S.V. Boroznin, L.V.Kozhitov, A.V. Popkova, On the Practicability of Sensors Based on Surface Carboxylated Boron-Carbon Nanotubes, Russian Journal of Inorganic Chemistry, 64 (2019) 74–78.