Russian Science Foundation No. 22-29-20317 “Investigation of the sorption properties of Langmuir-Blodgett films based on graphene and its compounds by acoustoelectronic methods for the development of a carbon monoxide and dioxide sensor”
Head: PhD I.A. Gorbachev.
The aim of the project was to develop, form and study the gas-sensitive properties of hybrid Langmuir-Blodgett (LB) graphene films and its compounds to study their sorption properties and develop acoustoelectronic sensors of a new generation of carbon monoxide and carbon dioxide based on them.
To achieve this goal, the following tasks were solved over the course of two years:
Development of technology for the formation of highly ordered gas-sensitive LB films with modified graphene and its compounds and their transfer to solid piezoelectric substrates.
Investigation of the structural, morphological, and electrophysical properties of sensor coatings based on LB films with modified graphene and its compounds.
Investigation of sorption properties of formed films to carbon monoxide and dioxide using acousto-electronic technologies.
Development, creation and research of sensory properties of an acousto-electronic gas sensor to carbon monoxide and carbon dioxide.
To accomplish these tasks, the following works were carried out and the following results were obtained:
The process of formation and transfer of LB films of graphene and its compounds under various conditions is investigated. The effect of subphase temperature on the formation of Langmuir interlayers of graphene and graphene oxide has been studied. The temperature dependences of the compression modulus of graphene and graphene oxide monolayers are obtained in the subphase temperature range from 10 to 30°C. The maximum value of the compression modulus of graphene and graphene oxide monolayers is 1.91 mN/m and 1.18 mN/m at temperatures of 20 °C and 30 °C, respectively. The dependences of the compression modulus of graphene monolayer and graphene oxide are obtained with a change in acidity in the range from 4 to 12. The maximum compression modulus for graphene monolayer (pH = 7) and graphene oxide (pH=4) is 1.91 mN/m and 0.99 mN/m, respectively. A change in pH in the range from 4 to 12 leads to a monotonous decrease in the magnitude of the compression modulus of the graphene oxide monolayer from 0.99 mN/m to 0.41 mN/m.
– For the first time, the possibility of controlling the LB properties of graphene and graphene oxide monolayers directly during their creation using an electric field has been demonstrated. The presence of an external electric field leads to a decrease in the compression modulus of the graphene monolayer from 2.1 mN/m to 1.3 mN/m and a shift of the compression isotherm towards large areas. The presence of an electric field leads to a change in the compression modulus from 0.9 mN/m to 0.5 mN/m of the graphene oxide monolayer.
– The process of formation of hybrid monolayers and Langmuir-Blodgett films based on graphene, graphene oxide and oxide nanoparticles has been studied. The dependences of the compression modules of Langmuir monolayers of graphene, graphene oxide, and hydrophobic oxide nanoparticles are obtained. For a mixed monolayer of graphene and graphene oxide, the compression modulus increases from 1.1 mN/m to 2.5 mN/m and from 1.6 mN/m to 2.5 mN/m, respectively. The effect of the adsorption time of hydrophilic tin dioxide nanoparticles on the properties of Langmuir monolayers of graphene oxide and graphene has been studied. The adsorption of hydrophilic oxide nanoparticles by a graphene monolayer for 90 minutes leads to a decrease in its compression modulus from 0.7 mN/m to 0.5 mN/m. The adsorption of hydrophilic oxide nanoparticles by a graphene oxide monolayer leads to an increase in its compression modulus from 1.6 mN/m to 2 mN/m.
– The structural and morphological properties of LB films of graphene and its compounds obtained under various conditions of their formation have been investigated. It has been established that the most effective way to control the morphology of graphene-based Langmuir-Blodgett films is to change the temperature of the subphase during monolayer formation. Temperature variation in the range from 10 °C to 35 °C allows varying the coating thickness from 2.5 nm to 1.5 nm. The morphology of thin hybrid films of graphene and graphene oxide sensitized by oxide nanoparticles was studied. The film based on a monolayer of graphene oxide and hydrophobic oxide nanoparticles with an equi-volume ratio of components had the lowest surface roughness of 5 nm. An increase in the proportion of oxide nanoparticles in the monsol led to an increase in the film roughness to 15 nm. Hybrid films based on graphene and hydrophobic tin nanoparticles had a roughness in the range from 2 nm to 5 nm. The adsorption of hydrophilic oxide nanoparticles by a graphene oxide monolayer within 90 minutes leads to an increase in the surface area of the LB film obtained on its basis by 5%.
– The conductivity of LB films of graphene and graphene oxide obtained under various conditions of their formation has been investigated. Heating of the subphase from 20 °C to 35 °C leads to a decrease in the conductivity of the graphene oxide film from 0.9 Nm to 0.3 Nm. Cooling of the subphase to 10 ° C leads to a decrease in conductivity to 0.5 Nm. The conductivity of LB films of graphene oxide at a subphase acidity of PH =4 and a subphase temperature of 35C is 0.3 nCm and 0.7 nCm, respectively.
Test samples of piezo quartz sensors sensitive to carbon dioxide and carbon monoxide based on thin hybrid sensor films of graphene, graphene oxide and metal oxide nanoparticles have been obtained. Sensor coatings made of LB films of graphene oxide and hydrophilic nanoparticles of tin dioxide have a maximum sorption capacity of 47 ng/mcg to carbon dioxide. Coatings made of thin hybrid films of graphene oxide and hydrophobic nanoparticles of tin dioxide have the maximum sorption capacity (67 ng/mcg) for carbon monoxide. The coating of graphene oxide nanoparticles has a sorption capacity to carbon monoxide and carbon dioxide of 2 ng/mcg and 8 ng/mcg, respectively. Coatings formed on the basis of graphene and a hybrid film based on graphene and hydrophobic tin dioxide nanoparticles have minimal sorption capacity. The sorption capacity of graphene-based films to carbon dioxide and carbon monoxide is 4 ng/mcg and 6 ng/mcg, respectively. The sorption capacity of a hybrid film based on graphene and hydrophobic nanoparticles of tin dioxide is 2 ng/mcg for both gases.
Mockups of acoustoelectronic sensors for detecting carbon dioxide and carbon monoxide based on delay lines on a lithium niobate plate with a sensor layer of hybrid LB films of graphene and graphene oxide have been developed and created. The dependences of the S21 parameters of the acoustoelectronic sensors on the concentration of the detected gas in the total sample flow are obtained. A sensor based on a LB graphene oxide film has a maximum sensory response of 1.3 dB to carbon dioxide. The sensor with a sensor layer made of a hybrid film of graphene oxide and hydrophobic tin oxide nanoparticles has a sensory response value of 1.35 dB. The sensor layer formed on the basis of graphene oxide film has the maximum phase response (2.9°) to carbon dioxide. A layer of a hybrid film of graphene oxide and hydrophobic nanoparticles has a phase response of 2.5°. The graphene-based sensor layer has an amplitude response of 0.5 dB and a phase response of 1.5°. The LZ with a film of graphene oxide and hydrophobic tin dioxide nanoparticles has a maximum sensory response of 2 dB to carbon monoxide. Graphene oxide film has a sensory response value of 1.75 dB. The sensor layer formed on the basis of a graphene oxide film has a maximum phase response of 4° to carbon monoxide. The layer formed on the basis of a hybrid film of graphene oxide and hydrophobic nanoparticles has a phase response of 3.8°. The graphene-based sensor layer has an amplitude response of 0.5 dB and a phase response of 2.5 °.
The set goal of the project has been achieved. All the tasks set in the project have been completed in full. The results obtained during the implementation of the project tasks were published in journals included in Russian and international citation databases (Sensors, RENSIT). Some of the work was carried out with the consulting participation of Bulgarian colleagues working in the field of LB film production. The gas-sensitive properties of Langmuir-Blodgett hybrid films of graphene and graphene oxide were developed, formed and investigated. Their sorption properties have been investigated. A new generation acoustoelectronic sensor for carbon monoxide and carbon dioxide has been developed.
Publications:
- I. Gorbachev, A. Smirnov, G. R. Ivanov, T. Venelinov, A. Amova, E. Datsuk, V. Anisimkin, I.
Kuznetsova, V. Kolesov // Langmuir–Blodgett Films with Immobilized Glucose Oxidase
Enzyme Molecules for Acoustic Glucose Sensor Application // Sensors 2023, 23, 5290.
https://doi.org/10.3390/s23115290 - Горбачев И.А., Смирнов А.В. // Биосенсор на основе пленки Ленгмюра-Блоджетт с
ферментом алкогольоксидазы //RENSIT/РЭНСИТ | 2023 | ТОМ 15 | НОМЕР 3 С.307-316 - Горбачев И.А., Смирнов А.В., Кузнецова И.Е., Колесов В.В. // Влияние температуры на
формирование ленгмюровских монослоев с наночастицами Ni-арахиновой кислоты и
кластерами Ni-арахидата // RENSIT/РЭНСИТ | 2023 | ТОМ 15 | НОМЕР 3 С.295-306 - Горбачев И.А., Колесов В.В. Сенсорное покрытие на основе липидного ленгмюровского
монослоя с молекулами фермента глюкозооксидазы получена, прошла рецензирование,
принята к печати и будет опубликована в журнале РЭНСИТ: Радиоэлектроника.
Наносистемы. Информационные технологии, 2024, 16(1):117-126. DOI:
10.17725/rensit.2024.16.117 - Горбачев И.А., Колесов В.В. Морфология и электрофизические свойства
модифицированных ленгмюровских пленок оксида графена получена, прошла
рецензирование, принята к печати и будет опубликована в журнале РЭНСИТ:
Радиоэлектроника. Наносистемы. Информационные технологии, 2024, 16(1):109-116. DOI:
10.17725/rensit.2024.16.109 - И.А. Горбачев, А.В. Смирнов, В.В. Колесов, И.Е. Кузнецова // МОРФОЛОГИЯ И СЕНСОРНЫЕ
СВОЙСТВА ПЛЕНОК ЛЕНГМЮРА-БЛОДЖЕТТ С ИММОБИЛИЗОВАННЫМИ ФЕРМЕНТАМИ //
XXXV Сессия РАО, г. Москва, 13-17 февраля 2023 г.586-591 - Горбачев И.А., Смирнов А.В., Колесов В.В., Кузнецова И.Е. // Сенсорные покрытия на
основе пленок Ленгмюра — Блоджетт с иммобилизованными ферментами для создания
акустоэлектронного датчика глюкозы // СВЧ-техника и телекоммуникационные
технологии. 2023. Вып. 5. ISSN 2619-16281