najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2025-16-6-865-871najo-1625Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХMicrowave-assisted synthesis of M/TiO₂/C (M=Ni, Cu, Ni–Cu) photocatalysts for CO₂ reduction: structural evolution and photocatalytic propertiesСинтез фотокатализаторов M/TiO₂/C (M=Ni, Cu, Ni-Cu) для восстановления CO₂ с помощью микроволнового излучения: структурная эволюция и фотокаталитические свойстваhttps://orcid.org/0009-0002-9103-3977КашанскийВ. С.KashanskyV. S.

Vladislav S. Kashansky

 420008, Kazan

vladkashansky@gmail.comhttps://orcid.org/0000-0001-8481-8544СуховА. В.SukhovA. V.

Alexander V. Sukhov

420088, Kazan

alex.suhoff@rambler.ruhttps://orcid.org/0000-0003-3908-1963ЖуренокА. В.ZhurenokA. V.

Angelina V. Zhurenok

 630090, Novosibirsk

angelinazhurenok@gmail.comhttps://orcid.org/0000-0001-8822-5148МищенкоД. Д.MishchenkoD. D.

Denis D. Mishchenko

630559, Kol’tsovo

q14999@yandex.ruhttps://orcid.org/0000-0003-3107-5251СофьичеваО. С.SofichevaO. S.

Olga S. Soficheva 

 420088, Kazan

olga.soficheva@iopc.ruhttps://orcid.org/0000-0001-8944-7666КозловаЕ. А.KozlovaE. A.

Ekaterina A. Kozlova

630090, Novosibirsk

kozlova@catalysis.ruhttps://orcid.org/0000-0002-2241-9764СиняшинО. Г.SinyashinO. G.

Oleg G. Sinyashin

420088, Kazan

oleg@iopc.ruhttps://orcid.org/0000-0002-3906-8841ЯхваровД. Г.YakhvarovD. G.

Dmitry G. Yakhvarov

420088, Kazan

yakhvar@iopc.ruArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center RAS; A. M. Butlerov Institute of Chemistry, Kazan Federal UniversityRussian FederationBoreskov Institute of Catalysis SB RASRussian FederationSynchrotron Radiation Facility SKIF, Boreskov Institute of CatalysisRussian FederationArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center RASRussian Federation202506012026166865871Copyright © Kashansky V.S., Sukhov A.V., Zhurenok A.V., Mishchenko D.D., Soficheva O.S., Kozlova E.A., Sinyashin O.G., Yakhvarov D.G., 20262026Кашанский В.С., Сухов А.В., Журенок А.В., Мищенко Д.Д., Софьичева О.С., Козлова Е.А., Синяшин О.Г., Яхваров Д.Г.Kashansky V.S., Sukhov A.V., Zhurenok A.V., Mishchenko D.D., Soficheva O.S., Kozlova E.A., Sinyashin O.G., Yakhvarov D.G.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/1625

This study presents the synthesis of a TiO2-based composite material with transition metal (Ni, Cu) nanoparticles using microwave radiation. The obtained materials were characterised using X-ray powder diffraction, and the size of the nanoparticles was determined using the Scherrer equation. The photocatalytic activity of the synthesised composites was studied in reaction of CO2 reduction to CO and CH4 under the visible light with a wavelength of 400 nm. Microwave treatment of a mixture of TiO2 with transition metal salts (Ni, Cu) and graphite was founded to decrease a photocatalytic activity in CO2 reduction reaction, while a mechanical mixture of TiO2 and graphite, not subjected to microwave treatment, demonstrated increased catalytic activity compared to unmodified TiO2 Evonik P25. The decrease in catalytic activity of the case of microwave-treated samples is associated with an irreversible phase transition of the photoactive anatase phase into the catalytically inert rutile phase and formation of TiO2−x phases. This process is induced by overheating during microwave synthesis, where graphite (Cg) acts as an effective microwave absorber and a reducing agent for Ti4+ cations in TiO2. The obtained results are interesting for the development of efficient TiO2-based photocatalysts for CO2 reduction.

Методом микроволнового синтеза получены композиты на основе TiO2, модифицированные наночастицами переходных металлов (Ni, Cu). Структура полученных материалов охарактеризована с помощью рентгеновской порошковой дифракции, а размер кристаллитов оценен по уравнению Шеррера. Фотокаталитическая активность синтезированных композитов исследована в реакции восстановления CO2 до CO и CH4 при облучении светом с длиной волны 400 нм. Показано, что микроволновая обработка смеси TiO2 с графитом (Cg) и солями переходных металлов приводит к снижению фотокаталитической активности. В то же время механическая смесь TiO2 и графита, не подвергавшаяся микроволновому воздействию, проявляет более высокую активность по сравнению с немодифицированным TiO2 Evonik P25. Снижение активности у обработанных образцов обусловлено необратимым фазовым переходом фотоактивной фазы анатаза в каталитически инертную фазу рутила, а также образованием фаз TiO2-x. Причиной является перегрев в ходе синтеза, при котором Cg выступает в роли эффективного поглотителя микроволнового излучения и восстановителя катионов Ti4+ в структуре TiO2. Полученные результаты важны для разработки эффективных фотокатализаторов на основе TiO2 для восстановления CO2.

диоксид титанафотокатализнаночастицы переходных металловвосстановление диоксида углеродарентгеновская дифракциязелёная химияtitanium dioxidephotocatalysistransition metal nanoparticlescarbon dioxide reductionX-ray diffractiongreen chemistryThis research was funded by the grant of the Ministry of Science and Higher Education of the Russian Federation for large scientific projects of the priority areas of scientific and technological development (Nr. 075-15-2024-646). The photocatalytic activity tests of the obtained materials were carried out under the government contract at Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences (project FWUR-2024-0033). The XRD studies were performed using the equipment of the Multiaccess Centre “National Centre for Catalyst Research” of the Institute of Catalysis, Siberian Branch, Russian Academy of Sciences.ReferencesJeffry L., Ong M.Y., Nomanbhay S., Mofijur M., Mubashir M., Show P.L. Greenhouse gases utilization: A review. Fuel, 2021, 301, 121017.Jeffry L., Ong M.Y., Nomanbhay S., Mofijur M., Mubashir M., Show P.L. Greenhouse gases utilization: A review. Fuel, 2021, 301, 121017.Yoro K.O., Daramola M.O. CO2 emission sources, greenhouse gases, and the global warming effect. Advances in carbon capture. Woodhead Publishing, 2020, P. 3–28.Yoro K.O., Daramola M.O. CO2 emission sources, greenhouse gases, and the global warming effect. Advances in carbon capture. Woodhead Publishing, 2020, P. 3–28.Zlotin S.G., Egorova K.S., Ananikov V.P., Akulov A.A., Varaksin M.V., Chupakhin O.N., Charushin V.N., Bryliakov K.P., Averin A.D., Beletskaya I.P., Dolengovski E.L., Budnikova Y.H., Sinyashin O.G., Gafurov Z.N., Kantyukov A.O., Yakhvarov D.G., Aksenov A.V., Elinson M.N., Nenajdenko V.G., Zolotukhina A.V. The green chemistry paradigm in modern organic synthesis. Russ. Chem. Rev., 2023, 92 (12), 5104.Zlotin S.G., Egorova K.S., Ananikov V.P., Akulov A.A., Varaksin M.V., Chupakhin O.N., Charushin V.N., Bryliakov K.P., Averin A.D., Beletskaya I.P., Dolengovski E.L., Budnikova Y.H., Sinyashin O.G., Gafurov Z.N., Kantyukov A.O., Yakhvarov D.G., Aksenov A.V., Elinson M.N., Nenajdenko V.G., Zolotukhina A.V. The green chemistry paradigm in modern organic synthesis. Russ. Chem. Rev., 2023, 92 (12), 5104.Alekseev R.F., Saraev A.A., Kurenkova A.Y., Kozlova E.A. Heterostructures based on g-C3N4 for the photocatalytic CO2 reduction. Russ. Chem. Rev., 2024, 93 (5), 5124.Alekseev R.F., Saraev A.A., Kurenkova A.Y., Kozlova E.A. Heterostructures based on g-C3N4 for the photocatalytic CO2 reduction. Russ. Chem. Rev., 2024, 93 (5), 5124.Kozlova E.A., Lyulyukin M.N., Kozlov D.V., Parmon V.N. Semiconductor photocatalysts and mechanisms of carbon dioxide reduction and nitrogen fixation under UV and visible light. Russ. Chem. Rev., 2021, 90 (12), P. 1520–1543.Kozlova E.A., Lyulyukin M.N., Kozlov D.V., Parmon V.N. Semiconductor photocatalysts and mechanisms of carbon dioxide reduction and nitrogen fixation under UV and visible light. Russ. Chem. Rev., 2021, 90 (12), P. 1520–1543.Jeon J.P., Kweon D.H., Jang B.J., Ju M.J., Baek J.B. Enhancing the photocatalytic activity of TiO2 catalysts. Advanced Sustainable Systems, 2020, 4 (12), P. 1–19.Jeon J.P., Kweon D.H., Jang B.J., Ju M.J., Baek J.B. Enhancing the photocatalytic activity of TiO2 catalysts. Advanced Sustainable Systems, 2020, 4 (12), P. 1–19.Song H., Tan Y.C., Kim B., Ringe S., Oh J. Tunable product selectivity in electrochemical CO2 reduction on well-mixed Ni–Cu alloys. ACS Applied Materials and Interfaces, 2021, 13 (46), P. 55272–55280.Song H., Tan Y.C., Kim B., Ringe S., Oh J. Tunable product selectivity in electrochemical CO2 reduction on well-mixed Ni–Cu alloys. ACS Applied Materials and Interfaces, 2021, 13 (46), P. 55272–55280.Du Y.R., Li X.Q., Yang X.X., Duan G.Y., Chen Y.M., Xu B.H. Stabilizing high-valence copper(I) sites with Cu–Ni interfaces enhances electroreduction of CO2 to C2+ products. Small, 2024, 20 (42), 2402534.Du Y.R., Li X.Q., Yang X.X., Duan G.Y., Chen Y.M., Xu B.H. Stabilizing high-valence copper(I) sites with Cu–Ni interfaces enhances electroreduction of CO2 to C2+ products. Small, 2024, 20 (42), 2402534.Jun M., Kundu J., Kim D.H., Kim M., Kim D., Lee K., Choi S.I. Strategies to modulate the copper oxidation state toward selective C2+ production in the electrochemical CO2 reduction reaction. Advanced Materials, 2024, 36 (21), 2313028.Jun M., Kundu J., Kim D.H., Kim M., Kim D., Lee K., Choi S.I. Strategies to modulate the copper oxidation state toward selective C2+ production in the electrochemical CO2 reduction reaction. Advanced Materials, 2024, 36 (21), 2313028.Qiu J., Zhu H., Chen B., Jing W., Zhou W., Bai Y., Xu L. Scalable development of photocatalysis-mediated aquatic habitat restoration devices based on TiO2/graphene/BiVO4 and the application in black-odorous river treatment. J. of Environmental Chemical Engineering, 2024, 12 (5), 113414.Qiu J., Zhu H., Chen B., Jing W., Zhou W., Bai Y., Xu L. Scalable development of photocatalysis-mediated aquatic habitat restoration devices based on TiO2/graphene/BiVO4 and the application in black-odorous river treatment. J. of Environmental Chemical Engineering, 2024, 12 (5), 113414.Toby B.H., Von Dreele R.B. GSAS-II: The genesis of a modern open-source all purpose crystallography software package. J. of Applied Crystallography, 2013, 46 (2), P. 544–549.Toby B.H., Von Dreele R.B. GSAS-II: The genesis of a modern open-source all purpose crystallography software package. J. of Applied Crystallography, 2013, 46 (2), P. 544–549.Pentsak E.O., Gordeev E.G., Ananikov V.P. Noninnocent nature of carbon support in metal/carbon catalysts: Etching/pitting vs nanotube growth under microwave irradiation. ACS Catalysis, 2014, 4 (11), P. 3806–3814.Pentsak E.O., Gordeev E.G., Ananikov V.P. Noninnocent nature of carbon support in metal/carbon catalysts: Etching/pitting vs nanotube growth under microwave irradiation. ACS Catalysis, 2014, 4 (11), P. 3806–3814.Gouma P.I., Mills M.J. Anatase-to-rutile transformation in titania powders. J. of the American Ceramic Society, 2001, 84 (3), P. 619–622.Gouma P.I., Mills M.J. Anatase-to-rutile transformation in titania powders. J. of the American Ceramic Society, 2001, 84 (3), P. 619–622.Shannon R.D., Pask J.A. Kinetics of the anataserutile transformation. J. of the American Ceramic Society, 1965, 48 (8), P. 391–398.Shannon R.D., Pask J.A. Kinetics of the anataserutile transformation. J. of the American Ceramic Society, 1965, 48 (8), P. 391–398.Bouzoubaa A., Markovits A., Calatayud M., Minot C. Comparison of the reduction of metal oxide surfaces: TiO2-anatase, TiO2-rutile and SnO2-rutile. Surface Science, 2005, 583 (1), P. 107–117.Bouzoubaa A., Markovits A., Calatayud M., Minot C. Comparison of the reduction of metal oxide surfaces: TiO2-anatase, TiO2-rutile and SnO2-rutile. Surface Science, 2005, 583 (1), P. 107–117.Zhurenok A.V., Kurenkova A.Y., Zazulya A.E., Vasilchenko D.B., Mishchenko D.D., Lomakina V.A., Gerasimov E.Y., Markovskaya D.V., Kozlova E.A. Heterostructures based on reduced graphene oxide and graphitic carbon nitride for visible light-induced photocatalytic production of H2. Russian Chemical Bulletin, 2025, 74 (3), P. 733–741.Zhurenok A.V., Kurenkova A.Y., Zazulya A.E., Vasilchenko D.B., Mishchenko D.D., Lomakina V.A., Gerasimov E.Y., Markovskaya D.V., Kozlova E.A. Heterostructures based on reduced graphene oxide and graphitic carbon nitride for visible light-induced photocatalytic production of H2. Russian Chemical Bulletin, 2025, 74 (3), P. 733–741.

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