zldmЗаводская лаборатория. Диагностика материаловIndustrial laboratory. Diagnostics of materials1028-68612588-0187ООО «Издательство «ТЕСТ-ЗЛ»10.26896/1028-6861-2025-91-4-5-11zldm-2455Research ArticleАНАЛИЗ ВЕЩЕСТВАSUBSTANCES ANALYSISИзучение замещения лантана стронцием в ферритах лантана для газочувствительных сенсоров методом рентгенофлуоресцентного анализа с полным внешним отражениемStudy of lanthanum substitution by strontium in lanthanum ferrites for gas-sensitive sensors by total reflection X-ray fluorescenceФилатоваД. Г.FilatovaD. G.

Дарья Геннадьевна Филатова,

119991, Москва, Ленинские горы, д. 1, стр. 3.

Daria G. Filatova,

1-3, Leninskie gory, Moscow, 119991.

gak1.analyt@gmail.comПлатоновВ. Б.PlatonovV. B.

Вадим Борисович Платонов,

119991, Москва, Ленинские горы, д. 1, стр. 3.

Vadim B. Platonov,

1-3, Leninskie gory, Moscow, 119991.

МалининН. М.MalininNikolai M.

Николай Михайлович Малинин,

119991, Москва, Ленинские горы, д. 1, стр. 73.

Nikolai M. Malinin,

1-73, Leninskie gory, Moscow, 119991.

ТроицкийА. А.TroitskiyA. A.

Артем Александрович Троицкий,

119334, Москва, Ленинский просп., д. 49.

Artem A. Troitskiy,

49, Leninsky prosp., Moscow, 119334.

РумянцеваМ. Н.RumyantsevaM. N.

Марина Николаевна Румянцева,

119991, Москва, Ленинские горы, д. 1, стр. 3.

Marina N. Rumyantseva,

1-3, Leninskie gory, Moscow, 119991.

Химический факультет Московского государственного университета имени М. В. ЛомоносоваРоссияFaculty of Chemistry, Lomonosov Moscow State UniversityRussian FederationФакультет наук о материалах Московского государственного университета имени М. В. ЛомоносоваРоссияFaculty of Materials Science, Lomonosov Moscow State UniversityRussian FederationИнститут металлургии и материаловедения имени А. А. Байкова Российской академии наукРоссияBaikov Institute of Metallurgy and Materials ScienceRussian Federation202525042025914511Copyright © Филатова Д.Г., Платонов В.Б., Малинин Н.М., Троицкий А.А., Румянцева М.Н., 20252025Филатова Д.Г., Платонов В.Б., Малинин Н.М., Троицкий А.А., Румянцева М.Н.Filatova D.G., Platonov V.B., Malinin N.M., Troitskiy A.A., Rumyantseva M.N.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.zldm.ru/jour/article/view/2455

Разработан подход к совместному определению La, Fe и Sr в растворах и суспензиях композитов (La, Sr)FeO3 методом РФА ПВО для изучения влияния замещения лантана стронцием на сенсорные свойства ферритов лантана. В качестве внутреннего стандарта для определения элементов использовали раствор галлия с концентрацией 50 мг/л. Правильность полученных результатов подтверждали для растворов образцов методом атомно-эмиссионной спектрометрии с индуктивно-связанной плазмой (ИСП АЭС). Согласно полученным данным не отмечено межэлементных влияний для La, Fe и Sr при совместном присутствии в растворах. Воспроизводимость результатов определения (Sr) методом РФА ПВО составила 0,04, 0,05, 0,06 для La, Fe и Sr соответственно. Полученные воспроизводимые результаты для суспензий связаны с малым размером частиц (15 – 17 нм) и равномерным распределением внутреннего стандарта в аликвоте при выбранном способе пробоподготовки. Установлено, что все образцы имеют единственную фазу, соответствующую чистому ферриту лантана с орторомбической кристаллической решеткой (ICDD 37-1493). Отсутствие посторонних рефлексов на дифрактограмме свидетельствует об успешном внедрении катионов Sr2+ в позиции La3+. Показано, что введение стронция в состав феррита лантана позволило повысить чувствительность материалов к CO, NH3, метанолу и ацетону, а также снизить оптимальную рабочую температуру сенсора на 50 – 150 °C. При этом самые лучшие сенсорные свойства проявляют нановолокна феррита лантана с минимальной концентрацией, введенного Sr (0,01 % ат.). При этом отсутствие чувствительности материалов к метану и бензолу обусловлено большей стабильностью этих молекул по отношению к кислотно-основным активным поверхностным центрам La1 – xMexFeO3.

An approach for the simultaneous quantification of La, Fe, and Sr in solutions and suspensions of (La, Sr)FeO3 composites by the TXRF method has been developed to study the effect of lanthanum substitution with strontium on the sensory properties of lanthanum ferrites. A gallium solution with a concentration of 50 mg/liter was used as an internal standard for the determination of the elements. The validity of the obtained results was confirmed for sample solutions by inductively coupled plasma atomic emission spectrometry (ICP AES). No interelement effects were observed for La, Fe, and Sr when present together in solutions. The precision of the results of the determination (Sr) by the TXRF was calculated as 0.04, 0.05, 0.06 for La, Fe, and Sr, respectively. The results obtained for suspensions are caused to the small particle size (15 – 17 nm) and the uniform distribution of the internal standard in the aliquot with the chosen sample preparation method. It is shown that all samples have a single phase corresponding to pure lanthanum ferrite with an orthorhombic crystal lattice (ICDD 37-1493). The absence of extraneous reflexes on the diffractogram indicates the successful incorporation of Sr2+ cations into the La3+ positions. It is shown that the doping of strontium into lanthanum ferrite made it possible to increase the sensitivity of materials to CO, NH3, methanol and acetone, as well as to reduce the optimal operating temperature of the sensor by 50 – 150°C. At the same time, the best sensory properties were found for lanthanum ferrite nanofibers with a minimum concentration of introduced Sr (0.01 % at.). The absence of sensitivity of materials to methane and benzene is due to the greater stability of these molecules with respect to the acid-base active surface centers of La1 – xMexFeO3.

рентгеновская флуоресценция с полным внешним отражением (РФА ПВО)определениестронцийлантан(LaSr)FeO3феррит лантанаtotal reflection X-ray fluorescence (TXRF)determinationstrontiumlanthanum(LaSr)FeO3lanthanum ferriteИспользование РФА ПВО спектрометра S2 PICOFOX поддержано программой развития Московского Государственного Университета имени М. В. Ломоносова. Работа выполнена при финансовой поддержке гранта РНФ № 23-73–01093.ReferencesSong P., Zhang H., Han D., et al. Preparation of biomorphic porous LaFeO3 by sorghum straw biotemplate method and its acetone sensing properties / Sens. Actuators, B. 2014. Vol. 196. P. 140 – 146. DOI: 10.1016/j.snb.2014.02.006Song P., Zhang H., Han D., et al. Preparation of biomorphic porous LaFeO3 by sorghum straw biotemplate method and its acetone sensing properties / Sens. Actuators, B. 2014. Vol. 196. P. 140 – 146. DOI: 10.1016/j.snb.2014.02.006Alharbi A., Sackmann A., et al. A highly selective sensor to acetylene and ethylene based on LaFeO3 / Sens. Actuators, B. 2020. Vol. 303. 127204. DOI: 10.1016/j.snb.2019.127204Alharbi A., Sackmann A., et al. A highly selective sensor to acetylene and ethylene based on LaFeO3 / Sens. Actuators, B. 2020. Vol. 303. 127204. DOI: 10.1016/j.snb.2019.127204Hu J., Chen X., Zhang Y. Batch fabrication of formaldehyde sensors based on LaFeO3 thin film with ppb-level detection limit / Sens. Actuators, B. 2021. Vol. 349. 130738. DOI: 10.1016/j.snb.2021.130738Hu J., Chen X., Zhang Y. Batch fabrication of formaldehyde sensors based on LaFeO3 thin film with ppb-level detection limit / Sens. Actuators, B. 2021. Vol. 349. 130738. DOI: 10.1016/j.snb.2021.130738Hao P., Qu G.-M., Song P., et al. Synthesis of Ba-doped porous LaFeO3 microspheres with perovskite structure for rapid detection of ethanol gas / Rare Met. 2021. Vol. 40. P. 1651 – 1661. DOI: 10.1007/s12598-020-01672-2Hao P., Qu G.-M., Song P., et al. Synthesis of Ba-doped porous LaFeO3 microspheres with perovskite structure for rapid detection of ethanol gas / Rare Met. 2021. Vol. 40. P. 1651 – 1661. DOI: 10.1007/s12598-020-01672-2Zhu L., Wang J., Liu J., et al. Designing highly sensitive formaldehyde sensors via A-site cation defciency in LaFeO3 hollow nanofbers / Appl. Surf. Sci. 2022. Vol. 590. 153085. DOI: 10.1016/j.apsusc.2022.153085Zhu L., Wang J., Liu J., et al. Designing highly sensitive formaldehyde sensors via A-site cation defciency in LaFeO3 hollow nanofbers / Appl. Surf. Sci. 2022. Vol. 590. 153085. DOI: 10.1016/j.apsusc.2022.153085Aranthady Ch., Jangid T., Gupta K., et al. Selective SO2 detection at low concentration by Ca substituted LaFeO3 chemiresistive gas sensor: A comparative study of LaFeO3 pellet vs thin film / Sens. Actuators, B. 2021. Vol. 329. 129211. DOI: 10.1016/j.snb.2020.129211Aranthady Ch., Jangid T., Gupta K., et al. Selective SO2 detection at low concentration by Ca substituted LaFeO3 chemiresistive gas sensor: A comparative study of LaFeO3 pellet vs thin film / Sens. Actuators, B. 2021. Vol. 329. 129211. DOI: 10.1016/j.snb.2020.129211Dash S., Mojumder S., Das T., et al. Highly sensitive and selective rGO-LaFeO3 nanocomposite based formaldehyde sensors towards air quality monitoring / Chemosphere. 2024. Vol. 367. 143499. DOI: 10.1016/j.chemosphere.2024.143499Dash S., Mojumder S., Das T., et al. Highly sensitive and selective rGO-LaFeO3 nanocomposite based formaldehyde sensors towards air quality monitoring / Chemosphere. 2024. Vol. 367. 143499. DOI: 10.1016/j.chemosphere.2024.143499Fu B., Bi L., Lin J., et al. Low-temperature detection and excellent selectivity of ethanol using LaFeO3 gas sensors with dual regulation of doping and non-stoichiometry / J. Alloys Compd. 2025. Vol. 1013. 178590. DOI: 10.1016/j.jallcom.2025.178590Fu B., Bi L., Lin J., et al. Low-temperature detection and excellent selectivity of ethanol using LaFeO3 gas sensors with dual regulation of doping and non-stoichiometry / J. Alloys Compd. 2025. Vol. 1013. 178590. DOI: 10.1016/j.jallcom.2025.178590Takalkar G., Bhosale R. R., AlMomani F., et al. Thermochemical splitting of CO2 using solution combustion LaMO3 (M = Co, Fe, Mn, Ni, Al, Cr, Sr) / Appl. Surf. Sci. 2020. Vol. 509. 144908. DOI: 10.1016/j.apsusc.2019.144908Takalkar G., Bhosale R. R., AlMomani F., et al. Thermochemical splitting of CO2 using solution combustion LaMO3 (M = Co, Fe, Mn, Ni, Al, Cr, Sr) / Appl. Surf. Sci. 2020. Vol. 509. 144908. DOI: 10.1016/j.apsusc.2019.144908Shikha P., Kang T. S., Randhawa B. S. Effect of different synthetic routes on the structural, morphological and magnetic properties of Ce doped LaFeO3 nanoparticles / J. Alloys Compd. 2015. Vol. 625. P. 336 – 345. DOI: 10.1016/j.jallcom.2014.11.074Shikha P., Kang T. S., Randhawa B. S. Effect of different synthetic routes on the structural, morphological and magnetic properties of Ce doped LaFeO3 nanoparticles / J. Alloys Compd. 2015. Vol. 625. P. 336 – 345. DOI: 10.1016/j.jallcom.2014.11.074Gluchowski P., Oganisian K., Tomala R., et al. Optical, dielectric and magnetic properties of La1 – xNdxFeO3 powders and ceramics / Ceramics. 2019. Vol. 2. P. 1 – 12. DOI: 10.3390/ceramics2010001Gluchowski P., Oganisian K., Tomala R., et al. Optical, dielectric and magnetic properties of La1 – xNdxFeO3 powders and ceramics / Ceramics. 2019. Vol. 2. P. 1 – 12. DOI: 10.3390/ceramics2010001Doshi J., Reneker D. Electrospinning process and applications of electrospun fibers / J. Electrost. 1995. Vol. 35. P. 151 – 160. DOI: 10.1016/0304-3886(95)00041-8Doshi J., Reneker D. Electrospinning process and applications of electrospun fibers / J. Electrost. 1995. Vol. 35. P. 151 – 160. DOI: 10.1016/0304-3886(95)00041-8Samanta P., Bagchi S., Mishra S. Synthesis and Sensing Characterization of ZnO Nanofibers Prepared by Electrospinning / Mater. Today: Proc. 2015. Vol. 2. P. 4499 – 4502. DOI: 10.1016/j.matpr.2015.10.061Samanta P., Bagchi S., Mishra S. Synthesis and Sensing Characterization of ZnO Nanofibers Prepared by Electrospinning / Mater. Today: Proc. 2015. Vol. 2. P. 4499 – 4502. DOI: 10.1016/j.matpr.2015.10.061Kim J.-H., Mirzaei A., Kim H. W., Kim S. S. Synthesis and Sensing Characterization of ZnO Nanofibers Prepared by Electrospinning / Sens. Actuators, B. 2019. Vol. 284. P. 628 – 637. DOI: 10.1016/j.snb.2018.12.120Kim J.-H., Mirzaei A., Kim H. W., Kim S. S. Synthesis and Sensing Characterization of ZnO Nanofibers Prepared by Electrospinning / Sens. Actuators, B. 2019. Vol. 284. P. 628 – 637. DOI: 10.1016/j.snb.2018.12.120Laia T.-Y., Fang T.-H., Hsiao Y.-J., Chan Ch.-A. Characteristics of Au-doped SnO2 – ZnO heteronanostructures for gas sensing applications / Vacuum. 2019. Vol. 166. P. 155 – 161. DOI: 10.1016/j.vacuum.2019.04.061Laia T.-Y., Fang T.-H., Hsiao Y.-J., Chan Ch.-A. Characteristics of Au-doped SnO2 – ZnO heteronanostructures for gas sensing applications / Vacuum. 2019. Vol. 166. P. 155 – 161. DOI: 10.1016/j.vacuum.2019.04.061Wang T., Xu J., Li F., et al. Perovskite-structured LaFeO3 gas sensor modified by polyoxometalate electron acceptor with high sensitivity and low detection limit for acetone gas / J. Rare Earths. 2024. DOI: 10.1016/j.jre.2024.11.006Wang T., Xu J., Li F., et al. Perovskite-structured LaFeO3 gas sensor modified by polyoxometalate electron acceptor with high sensitivity and low detection limit for acetone gas / J. Rare Earths. 2024. DOI: 10.1016/j.jre.2024.11.006Bohlen A., Fernández-Ruiz R. Experimental evidence of matrix effects in total-reflection X-ray fluorescence analysis: Coke case. / Talanta. 2020. Vol. 209. 120562. DOI: 10.1016/j.talanta.2019.120562Bohlen A., Fernández-Ruiz R. Experimental evidence of matrix effects in total-reflection X-ray fluorescence analysis: Coke case. / Talanta. 2020. Vol. 209. 120562. DOI: 10.1016/j.talanta.2019.120562Allegretta I., Gattullo C. E., Renna M., et al. Rapid multi-element characterization of microgreens via total-reflection X-ray fluorescence (TXRF) spectrometry / Food Chem. 2019. Vol. 296. P. 86 – 93. DOI: 10.1016/j.foodchem.2019.05.187Allegretta I., Gattullo C. E., Renna M., et al. Rapid multi-element characterization of microgreens via total-reflection X-ray fluorescence (TXRF) spectrometry / Food Chem. 2019. Vol. 296. P. 86 – 93. DOI: 10.1016/j.foodchem.2019.05.187Pashkova G. V., Aisueva T. S., Finkelshtein A. L., et al. Quantitative approaches to the determination of elements in lake sediments by total reflection X-ray fluorescence / Microchem. J. 2018. Vol. 143. P. 264 – 271. DOI: 10.1016/j.microc.2018.08.020Pashkova G. V., Aisueva T. S., Finkelshtein A. L., et al. Quantitative approaches to the determination of elements in lake sediments by total reflection X-ray fluorescence / Microchem. J. 2018. Vol. 143. P. 264 – 271. DOI: 10.1016/j.microc.2018.08.020Allegretta I., Giannelli R., Grisorio R., et al. Chemical analysis of cesium lead-halide perovskite nanocrystals by total-reflection X-ray fluorescence spectroscopy / Spectrochim. Acta, Part B. 2020. Vol. 164. 105750. DOI: 10.1016/j.sab.2019.105750Allegretta I., Giannelli R., Grisorio R., et al. Chemical analysis of cesium lead-halide perovskite nanocrystals by total-reflection X-ray fluorescence spectroscopy / Spectrochim. Acta, Part B. 2020. Vol. 164. 105750. DOI: 10.1016/j.sab.2019.105750Samoilova A. A., Petrakova N. V., Andreeva N. A., et al. Quantification of Calcium, Phosphorus, and Cerium in Novel Biocompatible Materials by Total Reflection X-Ray Fluorescence Spectroscopy / Inorg. Mater. 2024. Vol. 60. P. 33 – 37. DOI: 10.1134/S0020168524700055Samoilova A. A., Petrakova N. V., Andreeva N. A., et al. Quantification of Calcium, Phosphorus, and Cerium in Novel Biocompatible Materials by Total Reflection X-Ray Fluorescence Spectroscopy / Inorg. Mater. 2024. Vol. 60. P. 33 – 37. DOI: 10.1134/S0020168524700055Filatova D. G., Bogdanova A. P., Krivetskiy V. V., et al. Quantification of Si Dopant in β-Ga2O3-Based Semiconductor Gas Sensors by Total Reflection X-Ray Fluorescence Spectroscopy (TXRF) / Inorg. Mater. 2023. Vol. 59. P. 1433 – 1436. DOI: 10.1134/S0020168523140066Filatova D. G., Bogdanova A. P., Krivetskiy V. V., et al. Quantification of Si Dopant in β-Ga2O3-Based Semiconductor Gas Sensors by Total Reflection X-Ray Fluorescence Spectroscopy (TXRF) / Inorg. Mater. 2023. Vol. 59. P. 1433 – 1436. DOI: 10.1134/S0020168523140066Dhara S., Misra N. L. Elemental characterization of nuclear materials using total reflection X-ray fluorescence spectrometry / TrAC: Trends Anal. Chem. 2019. Vol. 116. P. 31 – 43. DOI: 10.1016/j.trac.2019.04.017Dhara S., Misra N. L. Elemental characterization of nuclear materials using total reflection X-ray fluorescence spectrometry / TrAC: Trends Anal. Chem. 2019. Vol. 116. P. 31 – 43. DOI: 10.1016/j.trac.2019.04.017Villoria J. A., Alvarez-Galvan M. C., Navarro R. M., et al. Zirconia-supported LaCoO3 catalysts for hydrogen production by oxidative reforming of diesel: Optimization of preparation conditions / Catalysis Today. 2008. Vol. 138. P. 135 – 140. DOI: 10.1016/j.cattod.2008.06.016Villoria J. A., Alvarez-Galvan M. C., Navarro R. M., et al. Zirconia-supported LaCoO3 catalysts for hydrogen production by oxidative reforming of diesel: Optimization of preparation conditions / Catalysis Today. 2008. Vol. 138. P. 135 – 140. DOI: 10.1016/j.cattod.2008.06.016Zhilicheva A. N., Pashkova G. V., Karkhova A. V., et al. Determination of S, Ni, Cu in cooper-nickel sulfide ores by total reflection X-ray fluorescence analysis: experience of participation in the interlaboratory comparisons / Industr. Lab. Mater. Diagn. 2024. Vol. 90. No. 7. P. 8 – 16. DOI: 10.26896/1028-6861-2024-90-7-8-16Zhilicheva A. N., Pashkova G. V., Karkhova A. V., et al. Determination of S, Ni, Cu in cooper-nickel sulfide ores by total reflection X-ray fluorescence analysis: experience of participation in the interlaboratory comparisons / Industr. Lab. Mater. Diagn. 2024. Vol. 90. No. 7. P. 8 – 16. DOI: 10.26896/1028-6861-2024-90-7-8-16

The authors declare that there are no conflicts of interest present.