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Article

Oxidation of 4-Methylpyridine on Vanadium-Based Catalysts Modified with Titanium and Manganese

by
Kairat Kadirbekov
1,*,
Nurdaulet Buzayev
1,2,*,
Yersin Tussupkaliyev
1 and
Mels Oshakbayev
1
1
A.B. Bekturov Institute of Chemical Sciences, Almaty 050010, Kazakhstan
2
Department of Physical Chemistry, Catalysis and Petrochemistry, Al-Farabi Kazakh National University, Almaty 050040, Kazakhstan
*
Authors to whom correspondence should be addressed.
Catalysts 2025, 15(7), 625; https://doi.org/10.3390/catal15070625
Submission received: 12 May 2025 / Revised: 10 June 2025 / Accepted: 19 June 2025 / Published: 25 June 2025
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Abstract

Current research on the synthesis of isonicotinic acid (INA) has focused on the development of catalysts by mixing transition metal oxides such as vanadium, titanium and zirconium in the desired molar ratio. These materials have good catalytic activity (CA) but have drawbacks, including low resistance to deactivation and limited ability to control reaction selectivity. In the present study, two- and three-component catalysts containing vanadium were successfully synthesized and their compositions and properties were studied. The experimental results showed that the efficiency of V-Ti-Mn-O catalyst was superior to V-Ti-O. Selectivity analysis showed that V-Ti-Mn-O was the most efficient catalyst, reaching a maximum value of 67.17% at 320 °C. Scanning electron microscope (SEM), Raman spectroscopy and X-ray diffraction (XRD) were used to characterize the catalysts. The corresponding experimental results showed that the superior performance of the V-Ti-Mn-O catalyst was attributed to both the smaller size of the catalyst particles and their more uniform distribution. In the oxidation of 4-methylpyridine (4-MP), the V-Ti-O catalyst showed lower CA and stability compared to the V-Ti-Mn-O catalyst, which can be attributed to its limited CA and potential deactivation at higher temperatures, probably due to excessive oxidation.

Graphical Abstract

1. Introduction

The development of better catalysts for selective oxidative processes is a big challenge in green chemistry and sustainable industrial production. A process of this kind is the oxidation of 4-MP (4-methylpyridine), which is of key importance because it is used in the synthesis of INA, an important intermediate for producing the tuberculosis drug isoniazid [1]. INA is synthesized by liquid phase oxidation of 4-MP and its methyl derivatives with nitric acid [2]. At present, the most efficient method of preparing INA is gas phase catalytic oxidation of 4-MP with oxygen (air) over oxide catalysts [3,4]. It allows valuable target products to be obtained from raw materials in a single stage.
The oxidation of 4-MP has been traditionally carried out using catalytic systems, which are simply physically mixed components [5,6,7,8]. The flexibility of their structure, the ability to introduce alloying additives for the improvement of performance, and their recognized properties of redox activity make them good candidates. Vanadium oxide is widely used as an active oxide component for oxidation processes [9]. However, this application is restricted by low selectivity and poor thermal stability with a tendency to sinter. Other metal oxides coexisting in the catalyst system may form additional phases, enhancing the chemical stability and altering the activity and selectivity through interaction [10]. It has been established that elements, like chromium, titanium and iron, when present in combination can alter the CA, stability, and selectivity of the catalysts [11,12,13]. The alloying additives modify the electronic structure, enhance oxygen mobility and improve the thermal stability of the catalysts [14,15] and thus are promising for application in oxidation processes.
In studies [7,8], the effects of reaction temperature, loading, water content and oxide promoters on the catalytic properties were analyzed. It was found that the use of acidic promoters increases catalyst efficiency, while the addition of alkaline oxides decreases its activity. According to the patent [16], INA with 18–38% yield was obtained by oxidation of 4-MP on a vanadium-titanium catalyst containing vanadium and titanium oxides in mass ratios (%):V2O5:TiO2(anatase) = (5–50):(95–50).
In the above-mentioned works traditional vanadium-based catalysts have shown high CA in the oxidation of 4-MP. Nevertheless, conventional catalysts are usually characterized by low stability and inhomogeneous phase composition [5,7,17], which deteriorate their performance and therefore call for the development of new approaches to catalyst design and optimization. The review of the works on gas-phase oxidation of 4-MP with the use of modified vanadium oxide catalysts displays that such systems can enhance the yield of target products. Moreover, vanadium pentoxide has its drawbacks, for instance, it tends to sinter with increasing load, which decreases its activity by 15–20% during the first 50 h of operation [18].
The Pechini method, based on the use of complexing agents to obtain oxide materials with a high degree of homogeneity, represents a promising approach to the synthesis of catalysts with improved characteristics. This method allows the morphology and textural properties of the catalysts to be controlled [19], which is particularly important for gas-phase oxidation processes. There are data in [20,21] on the successful application of the Pechini method for the synthesis of nanopowders of oxide materials with high CA.
Thus, the synthesis of catalysts by the Pechini method and their application in the oxidation of 4-MP are a relevant area of research aimed at improving the efficiency of the process. In this paper, the CA, structural properties and stability of three mixed oxide systems based on vanadium V-Ti-O and V-Ti-Mn-O in the oxidation of 4-MP will be studied. XRD, SEM and Raman spectroscopy were used to establish structure–activity relationships and identify the most efficient catalyst for the selective synthesis of INA.

2. Results and Discussion

2.1. Structural Characterization of Catalysts

XRD analysis results are presented in Figure 1. The peaks were compared to standard reference patterns for known crystalline phases. Figure 1a demonstrates the structure of the V-Ti-O, which have two prominent peaks at diffraction peaks 27.622, 41.435, 54.561 and 36.235 and has crystal levels ((110), (111), (211) and (101) respectively), where we notice good agreement between the results obtained experimentally with the international standards PDF #77-0332 (TiVO4) and PDF #89-4920 (V2O5) [22]. This indicates the presence of a titanium dioxide phase with a rutile structure. The dominance of the rutile phase aligns with studies of vanadium catalysts supported on TiO2, which have shown that rutile TiO2 provides a stable support matrix [23]. Additional weak peaks at 15.683 (200), 20.377 (001), 21.549 (101), 26.132 (110), 31.058 (400), 64.587 (103) and 69.302 (303) are attributed to V2O₅ (JCPDS No. 41-1426), corroborating previous findings [24], where such phases exhibited enhanced activity in selective oxidation reactions. The XRD pattern of the V-Ti-Mn-O catalyst (Figure 1b) reveals three primary peaks corresponding to titanium vanadate (TiVO4, PDF #77-0332) rutile-phase TiO2 (PDF #99-0090), manganese vanadate (Mn2V2O7, PDF #73-1806), Mn3O4 (ICDD No. 80-0382) and MnO2 (JCPDS No. 44-0141).
Peaks at 2θ = 27.579, 54.458, 69.171 and 36.216 are typical reflections of rutile TiO2 and TiVO4 [25], confirming the presence of titanium-based crystalline compounds. Peaks at 2θ = 29.293, 34.431 and 59.23 indicate the formation of manganese vanadate (Mn2V2O7). Peaks located at (101), (200), (220), (105) and (400) match well with ICDD No. 80-0382, indicating the presence of tetragonal hausmannite Mn3O4 with a spinel structure. Moreover, peaks corresponding to (301), (420) and (600) planes align with the tetragonal α-MnO2 phase, in accordance with JCPDS No. 44-0141, highlighting the successful incorporation of Mn into the mixed oxide matrix. The dominance of titanium in the structure emphasizes its role as a stable carrier for mixed oxide catalysts. The incorporation of manganese into the vanadium oxide matrix to form Mn2V2O7 is consistent with findings [26] that demonstrate its superior performance in redox and oxidative catalytic reactions. These results underscore the role of the crystalline structure and phase composition in determining catalytic properties, with mixed oxide systems providing enhanced structural stability and CA. The synergy between components, such as Mn, Ti and V, in the catalyst matrix contributes to improved performance in oxidation reactions.

2.2. Surface Morphology and Textural Properties

SEM was used to investigate the size and morphology of the synthesized catalysts. Figure 2 shows SEM images of the same heterogeneous and irregular surface morphology of the two samples. In both cases, all elements are uniformly distributed in the compound, which is also confirmed by the XRD results, indicating that the samples have a good crystalline structure and are free of impurities. The morphology of the V-Ti catalyst (Figure 2a) is characterized by the presence of large particles with wide variation in size and shape compared to the V-Ti-Mn catalyst (Figure 2b), where a uniformly distributed flake-like structure with micro- and nanoparticles with an average microparticle size of 1–52 μm and nanoparticles in the range of 500–900 nm is seen. Adding manganese significantly affects the morphology of the material, reducing the particle size and ensuring their more uniform distribution. Manganese probably acts as a structure-forming agent, promoting controlled particle growth. Thus, its presence increases the homogeneity of the material, which can have a positive effect on the CA due to an increase in the specific surface area and an optimal distribution of active sites.
To further assess the textural characteristics, BET surface area analysis was performed. The V-Ti-Mn-O catalyst exhibited (Table 1) a BET surface area of 44.6 m2/g, which decreased to 40.72 m2/g (8.7%) after the reaction. The V-Ti-O catalyst, by comparison, had a much lower initial surface area of 2.05 m2/g and slightly declined to 1.82 m2/g (11.2%) after use. These results confirm that the V-Ti-Mn-O catalyst not only has a higher initial surface area but also maintains its textural properties more effectively during the reaction. The modest reduction in surface area for both catalysts suggests limited structural changes sintering or pore blockage, with the V-Ti-Mn-O catalyst showing better morphological stability over time.

2.3. Analysis of Bonding and Oxide Phases

Raman spectra of the catalysts (Figure 3) exhibit intense bands in the regions of 990 cm−1 and 994 cm−1, which are attributed to the V=O stretching modes. These bands serve as key identifiers for catalytic regions associated with activity. They indicate the presence of vanadium pentoxide (V2O5) or similar oxo-vanadium compounds within the catalyst matrix [27]. Broad bands below 405 cm−1 are associated with lattice defects and oxygen vacancies, which enhance oxygen adsorption and transfer on the catalyst surface. For the manganese-containing catalyst (Figure 3b), peaks at 699 cm−1 and 523 cm−1 were observed, corresponding to Mn-O stretching vibrations. These bands confirm the presence of manganese oxides, such as MnO2 or Mn3O4 [28]. This observation is in good agreement with the XRD results, which also indicate the coexistence of multiple manganese and vanadium oxide phases within the catalyst. Furthermore, the peak at 523 cm−1 also corresponds to Ti-O stretching vibrations, indicating the incorporation of titanium dioxide (TiO2) into the catalyst. The alignment of TiO2 with the anatase phase is typical for V-Ti-O systems [29]. The V-Ti-O catalyst displays several characteristic features in its Raman spectrum. A peak near 516 cm−1 (Figure 3a), associated with Ti-O stretching vibrations, confirms the presence of titanium dioxide (TiO2) in the anatase phase. It is known for its superior photocatalytic properties compared to other TiO2 polymorphs [30]. The structure of anatase provides a favorable environment for catalytic reactions due to its electronic properties and surface characteristics. Moreover, the integration of vanadium into the TiO2 lattice can further enhance the catalytic efficiency by introducing additional active centers and changing the electronic environment of the catalyst. The mixed oxide phases in the V-Ti-O system, including V=O and Ti-O bonds, are responsible for structural stability and redox properties [31]. These mixed oxides play a crucial role in stabilizing the catalyst structure and enhancing oxygen mobility, which significantly improves its redox performance. These findings underline the importance of structural features and mixed oxide phases in the catalytic performance of the studied systems, highlighting the synergistic effects of the incorporated elements on redox and catalytic properties.
It should be noted that the study of the phase composition of the V-Ti-O and V-Ti-Mn-O catalysts using X-ray diffraction and Raman spectroscopy yielded results that may seem contradictory at first glance. According to X-ray diffraction data, titanium oxide in the samples under study is present exclusively in the rutile phase, while Raman spectroscopy demonstrates the presence of only the anatase phase. However, a detailed analysis suggests that this discrepancy is due to the objective features of the methods used and does not indicate a contradiction.
Firstly, a key role is played by the different sensitivities of the methods to TiO2 phases. X-ray diffraction has a high sensitivity to bulk crystalline structures, such as rutile, especially if they are localized deep in the sample [32]. At the same time, Raman spectroscopy is more sensitive to the surface layers of the material, where anatase predominates [33]. This explains why the two methods detect different phases of titanium oxide.
Secondly, the spatial distribution of the phases also affects the analysis results [34]. It is assumed that anatase is predominantly concentrated on the catalyst surface, which makes it easily detectable by Raman spectroscopy. In contrast, rutile is probably localized in deeper layers, where its presence is better detected by XRD due to the greater penetration depth of X-ray radiation [35].
In addition, it is impossible to exclude the possibility of overlapping rutile signals in the Raman spectrum with more intense bands of other phases, such as manganese or vanadium compounds, which can mask its presence [36]. It is also necessary to take into account the incomplete phase transition of anatase into rutile during heat treatment, which leads to the coexistence of both phases in the material [36].
The presence of TiVO4 and Mn2V2O7 phases in the catalysts suggests possible redox activity, which may influence catalytic performance. Previous studies [37,38] have shown that metal oxides exhibit distinct XRD and Raman signatures depending on their oxidation states. The V4+/V5+ ratio in vanadium-based catalysts significantly affects the redox properties and catalytic activity, with an optimal ratio facilitating efficient oxidation reactions [39]. The critical role of the V5+/V4+ redox couple in catalytic cycles has also been highlighted [40]. Regarding manganese species, Mn3+ centers are known to enhance the catalytic activity by providing redox flexibility, with Mn3+/Mn2+ transitions playing a key role in oxygen evolution reactions and related oxidation processes [41,42]. These findings support the notion that manganese incorporation in V-Ti-Mn-O catalysts introduces additional redox-active sites, potentially improving catalytic performance.

2.4. Catalytic Performance

V-TI and V-Ti-Mn catalysts were investigated for the 4-MP oxidation and performed under consistent conditions, with a water feed rate of 1.79 g/h, a feedstock rate of 0.35 g/h and an air feed rate of 4.2 L/h, while the temperature was varied between 280 °C and 380 °C. The relevant results are presented in Table 2, as well as in Figure 4 and Figure 5. Figure 4 and Figure 5 show the time dependence of 4-MP conversion and the selectivity of INA as a function of time on the V-Ti-O and V-Ti-Mn-O catalysts, respectively. Both catalysts exhibit a positive correlation between temperature and conversion up to approximately 360 °C, beyond which a slight decline in performance is observed. The V-Ti-O catalyst exhibits the lowest conversion over the entire temperature range, starting at 74.66% at 280 °C and gradually increasing to a maximum of 80.26% between 360 °C and 380 °C. In comparison, the V-Ti-Mn-O catalyst exhibits higher conversion, starting at 75.24% at 280 °C and increasing significantly to 82.23% at 360 °C, with a slight decrease to 81.97% at 380 °C. Figure 5 illustrates the temperature-dependent selectivity of INA in the oxidation of 4-MP over 2 catalysts: V-Ti-O and V-Ti-Mn-O. Above 320 °C, both catalysts show a decrease in selectivity for 4-MP, which suggests this temperature as the optimum temperature to obtain INA with high specificity. The V-Ti-Mn-O catalyst shows the highest selectivity among these samples. The selectivity starts from 65.25% at 280 °C, increases to a maximum of 67.17% at 320 °C and decreases to 63.88% at 380 °C. Notably, the incorporation of manganese in the V-Ti-Mn-O catalyst shifts the temperature for optimal conversion from 360 °C in the V-Ti-O catalyst to 340 °C in the V-Ti-Mn-O catalyst, suggesting that manganese enhances catalytic activity at relatively lower temperatures. According to the XRD results, we can find that the crystal structure and phase composition play a key role in determining the catalytic performance, with mixed oxide systems providing enhanced structural stability and CA. Furthermore, the SEM results suggest that smaller particle size was obtained in V-Ti-Mn-O, which is also useful to enhance the CA. The V-Ti-Mn-O catalyst shows the highest selectivity among these samples. The selectivity starts from 65.25% at 280 °C, increases to a maximum of 67.17% at 320 °C and decreases to 63.88% at 380 °C. The improved performance can be attributed to the synergistic effect of manganese, which improves oxidation precision and suppresses side reactions.

3. Materials and Methods

3.1. Materials

The starting materials were titanium (III) chloride solution (10–15% TiCl3 basis), vanadyl sulfate trihydrate (VOSO4 × 3H2O), manganese sulfate monohydrate (MnSO4 × H2O), citric acid (C6H8O7) and ethylene glycol (C2H6O2), with a high purity of about 97%. All reagents were of analytical grade and employed in their original form without any additional purification.

3.2. Catalyst Synthesis

The V-Ti and V-Ti-Mn catalysts were synthesized using the Pechini method, ensuring precise control over the molar ratios of the components. Initially, 0.5 moles of citric acid (CAc) were dissolved in 100 mL of distilled water in a 500 mL beaker, with constant stirring at 70 °C until fully dissolved. Afterward, 0.05 mole each of the metal precursors was added to the CAc solution to form the catalyst mixtures. For the V-Ti and V-Ti-Mn catalysts, the respective metal salts and complexes were carefully introduced, ensuring complete dissolution and uniform mixing to create a homogeneous solution. Next, ethylene glycol (EG) was added in a 1:1 molar ratio with CAc (0.5 moles). The solution was heated to 90 °C to evaporate excess water, forming a resin, which was then dried at 120 °C for 12 h. The dried material was heated at 400 °C for 4 h to remove organic components and then calcined at 800 °C for 4 h to yield the final catalysts.

3.3. Experimental Procedure

Experimental procedures and catalyst characterization were performed as in our previous works [43], with the oxidation of 4-MP carried out in a fixed-bed flow reactor, consisting of a 120 cm long, 20 mm diameter stainless steel reaction tube. The reactor was packed with 100 mL of catalyst particles, ranging in size from 3 to 5 mm. The air flow was carefully regulated using a rheometer, and a syringe device was used for continuous reagent delivery. To heat the reactor to the required temperature, a LATR was used. Water was pumped through a steel tube into the furnace, where it was mixed with air and the initial 4-MP, creating a reagent flow with a molar ratio of 1:10.5:26.2 at the entrance of the catalyst bed. The experiments were performed under consistent conditions, with a water feed rate of 1.79 g/h, a feedstock rate of 0.35 g/h, and an air feed rate of 4.2 L/h, while the temperature varied between 280 °C and 380 °C. The reaction products were captured in air-lift scrubbers, which were irrigated with water.

3.4. Characterization

The reaction products were collected in air-lift scrubbers, which were irrigated with water. The starting materials, 4-MP, pyridine-4-carbaldehyde and pyridine, were analyzed using chromatography with a flame ionization detector. INA was quantified by titration with KOH, using a pH-150MI pH meter (LLC “Izmeritelnaya Tekhnika”, Moscow, Russia). Chromatographic analysis of 4-MP oxidation products was conducted using a Cvet-106 chromatograph (USSR). The structural characterization of the samples was carried out with a Solver Spectrum Raman spectrometer (NT-MDT) (NT-MDT, Zelenograd, Russia). The surface morphology of the catalyst was examined using a Quanta 200i 3D SEM (FEI Company, Hillsboro, OR, USA). Furthermore, XRD analysis was performed using a DW 27 mini X-ray diffractometer (Dandong Aolong Radiative Instrument Group Co., LTD, Dandong, China) to investigate the crystalline structure of the catalyst.

4. Conclusions

The study comprehensively investigated the catalytic activity, structural characteristics and stability of V-Ti-O and V-Ti-Mn-O catalysts in the oxidation of 4-MP, revealing critical insights into their performance and structure–activity relationship. The results of CA and selectivity emphasize the advantages of including manganese in the catalytic system, which can be attributed to several factors. First, these results emphasize the crucial role of crystal structure and phase composition in determining the catalytic properties. In the second, the synergy between the components, Mn, Ti and V, in the catalyst matrix contributes to improved performance in oxidation reactions. Manganese increases the number of active centers, improving oxygen mobility in the catalytic structure. This synergistic interaction between the metal oxides stabilizes the catalyst and promotes more efficient oxidation of 4-MP, resulting in higher conversion rates and improved selectivity for INA. However, the V-Ti-O catalyst showed lower catalytic stability compared to V-Ti-Mn-O catalysts, which may be because excessive temperatures lead to side reactions and catalyst deactivation.

Author Contributions

K.K.: Conceptualization, Funding acquisition, Project administration, Resources, Supervision, Writing—review & editing; N.B.: Conceptualization, Formal analysis, Investigation, Methodology, Visualization, Writing—original draft; Y.T.: Data curation, Formal analysis, Resources, Validation, Methodology, Visualization; M.O.: Data curation, Resources, Validation, Methodology, Writing—review & editing. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the A.B. Bekutrov Institute of Chemical Sciences under the program of targeted funding of scientific research for 2023–2025, implemented by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan, under project No. BR21882220.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Acknowledgments

The authors are grateful to the “National Nanotechnological Open-Type Laboratory” for providing SEM and Raman spectroscopy data critical to this research.

Conflicts of Interest

The authors declare no conflicts of interest.

Abbreviations

The following abbreviations are used in this manuscript:
INAIsonicotinic Acid
CACatalytic Activity
XRDX-ray Diffraction
SEMScanning Electron Microscopy
4-MP4-methylpyridine
EGEthylene Glycol
CAcCitric Acid

References

  1. Isoniazid. In Dictionary of Toxicology; Springer: Singapore, 2024; p. 530. [CrossRef]
  2. Everett, H.M.; Barker, R.S. Process for Preparing Isonicotinic Acid. U.S. Patent Application No. US2748137A, 29 May 1956. Available online: https://patents.google.com/patent/US2748137A/en (accessed on 4 April 2023).
  3. Suvorov, B.V.; Bukeykhanov, N.R. Oxidation Reactions in Organic Synthesis. In Khimiya; Chemistry: Moscow, Russia, 1978; Volume 200. [Google Scholar]
  4. Chuk, R. Technology development in nicotinate production. Appl. Cat. A Gen. 2005, 280, 75–82. [Google Scholar] [CrossRef]
  5. Vorobyev, V.B.; Mikhaylovskaya, T.P.; Yugai, O.K.; Serebryanskaya, A.P.; Kurmakyzy, R. Vapour-phase oxidation of 3- and 4-methylpyridines on vanadium oxide catalysts modified by titanium and chromium oxides. Chem. J. Kaz. 2019, 1, 113–124. [Google Scholar]
  6. Sembaev, D.K.; Vorobyov, P.B.; Kurmakizy, R.; Nikitina, A.I.; Serebryanskaya, A.P. Catalytic oxidation of 3- and 4-methylpyridines. In Proceedings of the International Scientific Conference “Chemistry and Applications of Natural and Synthetic Biologically Active Compounds”, Almaty, Kazakhstan, 16–17 October 2004; pp. 215–217. [Google Scholar]
  7. Vorobyev, P.; Mikhailovskaya, T.; Yugay, O.; Serebryanskaya, A.; Chukhno, N.; Imangazy, A. Catalytic oxidation of 4-methylpyridine on modified vanadium oxide catalysts. Iran. J. Chem. Chem. Eng. 2018, 37, 81. Available online: https://www.researchgate.net/publication/330874472_Catalytic_Oxidation_of_4-Methylpyridine_on_Modified_Vanadium_Oxide_Catalysts (accessed on 4 April 2023).
  8. Vorobyev, P.B.; Gabdrakipov, V.Z.; Mikhaylovskaya, T.P.; Sembaev, D.K. Reactivity of isomeric picolines under oxidative ammonolysis on a vanadium oxide catalyst. Rus. J. Gen. Chem. 2001, 71, 650–652. [Google Scholar] [CrossRef]
  9. Langeslay, R.R.; Kaphan, D.M.; Marshall, C.L.; Stair, P.C.; Sattelberger, A.P.; Delferro, M. Catalytic Applications of Vanadium: A Mechanistic Perspective. Chem. Rev. 2018, 119, 2128–2191. [Google Scholar] [CrossRef]
  10. Védrine, J.C. Gas phase heterogeneous partial oxidation reactions. In Metal Oxides in Heterogeneous Catalysis; Elsevier: Amsterdam, The Netherlands, 2018; pp. 211–286. [Google Scholar] [CrossRef]
  11. Guerrero-Pérez, M.O. V-Containing Mixed Oxide Catalysts for Reduction–Oxidation-Based Reactions with Environmental Applications: A Short Review. Cat. 2018, 8, 564. [Google Scholar] [CrossRef]
  12. Wang, N.L.; Qiu, J.E.; Wu, J.; You, K.Y.; Luo, H.A. A Comparison of the Redox Properties of Bulk Vanadium Mixed Oxide Catalysts. Cat. Lett. 2015, 145, 1792–1797. [Google Scholar] [CrossRef]
  13. Benavente, E.; Aliaga, J.; González, G. Vanadium Oxides in Photocatalysis, Including Bare Oxides and VOx-based Organic–Inorganic Nanocomposites. In Vanadium Catalysis; Royal Society of Chemistry: Cambridge, UK, 2020; pp. 340–373. [Google Scholar] [CrossRef]
  14. Monfort, O.; Petrisková, P. Binary and Ternary Vanadium Oxides: General Overview, Physical Properties, and Photochemical Processes for Environmental Applications. Processes 2021, 9, 214. [Google Scholar] [CrossRef]
  15. Wachs, I.E. Catalysis Science of Supported Vanadium Oxide Catalysts. Dalton Trans. 2013, 42, 11145–11160. [Google Scholar] [CrossRef]
  16. Hoelderich, W. Verfahren Zur Herstellung von Isonikotinsaeure. Germany Patent Application No. DE10146088A1, 19 September 2001. Available online: https://patents.google.com/patent/DE10146088A1/de (accessed on 13 March 2023).
  17. Yugay, O.; Mikhailovskaya, T.; Sembaev, D.; Vorobyev, P. Oxidation of 3- and 4-methylpyridines on vanadia-anatase and vanadia-rutile catalysts. Eur. Chem. Tech. 2012, 1, 337–342. [Google Scholar] [CrossRef]
  18. Vorobyev, P.B.; Saurambayeva, L.I.; Mikhailovskaya, T.P.; Yugay, O.K.; Serebryanskaya, A.P.; Shlygina, I.A. Vapor-phase oxidation of β-picoline to nicotinic acid over V2O5 and modified vanadium oxide catalysts. J. Appl. Chem. 2014, 87, 894–901. [Google Scholar]
  19. Dimesso, L. Pechini Processes: An Alternate Approach of the Sol–Gel Method, Preparation, Properties, and Applications. In Handbook of Sol-Gel Science and Technology; Springer: Cham, Switzerland, 2016; pp. 1–22. [Google Scholar] [CrossRef]
  20. Sunde, T.O.L.; Grande, T.; Aksnes, M.A. Modified Pechini Synthesis of Oxide Powders and Thin Films. In Handbook of Sol-Gel Science and Technology; Springer: Cham, Switzerland, 2016; pp. 1–30. [Google Scholar] [CrossRef]
  21. Hajizadeh-Oghaz, M.H.; Razavi, S.R.; Estarki, L.M. Estarki, Large-scale synthesis of YSZ nanopowder by Pechini method. Bull. Mat. Sci. 2014, 37, 969–973. [Google Scholar] [CrossRef]
  22. Gawande, M.B.; Pandey, R.K.; Jayaram, R.V. Role of Mixed Metal Oxides in Catalysis Science: Versatile Applications in Organic Synthesis. Cat. Sci. Tech. 2012, 2, 1113–1125. [Google Scholar] [CrossRef]
  23. Reddy, C.V.; Reddy, I.N.; Koutavarapu, R.; Reddy, K.R.; Saleh, T.A.; Aminabhavi, T.M.; Shim, J. Novel edge-capped ZrO2 nanoparticles onto V2O5 nanowires for efficient photosensitized reduction of chromium (Cr (VI)), photoelectrochemical solar water splitting, and electrochemical energy storage applications. Chem. Eng. J. 2022, 430, 132988. [Google Scholar] [CrossRef]
  24. Chen, S.; Xiong, F.; Huang, W. Surface Chemistry and Catalysis of Oxide Model Catalysts from Single Crystals to Nanocrystals. Surf. Sci. Rep. 2019, 74, 100471. [Google Scholar] [CrossRef]
  25. Inumaru, K.; Misono, M.; Okuhara, T. Structure and Catalysis of Vanadium Oxide Overlayers on Oxide Supports. Appl. Cat. A Gen. 1997, 149, 133–149. [Google Scholar] [CrossRef]
  26. Zhao, L.; Lin, S.; Bi, K.; Liang, C.; Du, Y.; Liu, J.; Yang, H.; Fan, D.; Wang, Y.; Lei, M. Manganese vanadium oxide hollow microspheres: A novel electrocatalyst for oxygen reduction reaction. J. Solid State Electrochem. 2017, 21, 1743–1749. [Google Scholar] [CrossRef]
  27. Sandhya, G.L.; Dhananjaya, M.; Prakash, N.G.; Lakshminarayana, A.; Rosaiah, P.; Hussain, O.M. Structural and Supercapacitive Performance of V2O5 Thin Films Prepared By DC Magnetron Sputtering. IOSR J. Appl. Chem. 2017, 10, 64–69. [Google Scholar] [CrossRef]
  28. Post, J.E.; McKeown, D.A.; Heaney, P.J. Raman spectroscopy study of manganese oxides: Layer structures. Am. Mineral. 2021, 106, 351–366. [Google Scholar] [CrossRef]
  29. Nuguid, R.J.G.; Ferri, D.; Marberger, A.; Nachtegaal, M.; Kröcher, O. Modulated-Excitation Raman Spectroscopy of V2O5/TiO2: Mechanistic Insights into the Selective Catalytic Reduction of NO by NH3. ACS Cat. 2019, 9, 6814–6820. [Google Scholar] [CrossRef]
  30. Gupta, S.K.; Desai, R.; Jha, P.K.; Sahoo, S.; Kirin, D. Titanium dioxide synthesized using titanium chloride: Size effect study using Raman spectroscopy and photoluminescence. J. Raman Spectrosc. 2009, 40, 1401–1407. [Google Scholar] [CrossRef]
  31. Carvalho Costa, R.C.; de Sá Oliveira, F.M.; Ferreira, A.P.; Cappa de Oliveira, L.F. Raman microscopy as a tool for the surface characterization of V2O5/TiO2 catalysts before and after reaction with H2O2. Quarks Braz. Electron. J. Phys. Chem. Mater. Sci. 2019, 1, 1–10. [Google Scholar] [CrossRef]
  32. Zhang, H.; Banfield, J.F. Understanding Polymorphic Phase Transformation Behavior during Growth of Nanocrystalline Aggregates: Insights from TiO2. J. Phys. Chem. B. 2000, 104, 3481–3487. [Google Scholar] [CrossRef]
  33. Ohsaka, T.; Izumi, F.; Fujiki, Y. Raman spectrum of anatase, TiO2. J. Raman Spectrosc. 1978, 7, 321–324. [Google Scholar] [CrossRef]
  34. Diebold, U. The surface science of titanium dioxide. Surf. Sci. Rep. 2003, 48, 53–229. [Google Scholar] [CrossRef]
  35. Holmgren Rondahl, S.; Pointurier, F.; Ahlinder, L.; Ramebäck, H.; Marie, O.; Ravat, B.; Delaunay, F.; Young, E.; Blagojevic, N.; Hester, J.R.; et al. Comparing results of X-ray diffraction, µ-Raman spectroscopy and neutron diffraction when identifying chemical phases in seized nuclear material, during a comparative nuclear forensics exercise. J. Radioanal. Nucl. Chem. 2018, 315, 395–408. [Google Scholar] [CrossRef]
  36. Li, G.; Richter, C.P.; Milot, R.L.; Cai, L.; Schmuttenmaer, C.A.; Crabtree, R.H.; Brudvig, G.W.; Batista, V.S. Synergistic effect between anatase and rutile TiO2 nanoparticles in dye-sensitized solar cells. Dalton Trans. 2009, 45, 10078–10085. [Google Scholar] [CrossRef]
  37. Gargasya, Y.; Gish, M.K.; Nair, V.V.; Johnson, J.C.; Law, M. Evaluation of nanostructured β-Mn2V2O₇ thin films as photoanodes for photoelectrochemical water oxidation. Chem. Mater. 2021, 33, 7743–7754. [Google Scholar] [CrossRef]
  38. Risch, M.; Stoerzinger, K.A.; Han, B.; Regier, T.Z.; Peak, D.; Sayed, S.Y.; Wei, C.; Xu, Z.; Shao-Horn, Y. Redox processes of manganese oxide in catalyzing oxygen evolution and reduction: An in situ soft X-ray absorption spectroscopy study. J. Phys. Chem. C. 2017, 121, 17682–17692. [Google Scholar] [CrossRef]
  39. Yan, Y.; Mao, L.; Zhao, X.; Xiao, Y.; Dong, G. A relationship between the V4+/V5+ ratio and the surface dispersion, surface acidity, and redox performance of V2O5–WO3/TiO2 SCR catalysts. RSC Adv. 2018, 8, 31081. [Google Scholar] [CrossRef]
  40. Koust, S.; Reinecke, B.N.; Adamsen, K.C.; Beinik, I.; Handrup, K.; Li, Z.; Moses, P.G.; Schnadt, J.; Lauritsen, J.V.; Wendt, S. Coverage-dependent oxidation and reduction of vanadium supported on anatase TiO2(101). J. Catal. 2018, 360, 118–126. [Google Scholar] [CrossRef]
  41. Chan, Z.M.; Kitchaev, D.A.; Weker, J.N.; Schnedermann, C.; Lim, K.; Ceder, G.; Tumas, W.; Toney, M.F.; Nocera, D.G. Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts. Proc. Natl. Acad. Sci. USA 2018, 115, E5261–E5268. [Google Scholar] [CrossRef]
  42. Han, S.J.; Ameen, M.; Hanifah, M.F.R.; Aqsha, A.; Bilad, M.R.; Jaafar, J.; Kheawhom, S. Catalytic evaluation of nanoflower structured manganese oxide electrocatalyst for oxygen reduction in alkaline media. Catalysts. 2020, 10, 822. [Google Scholar] [CrossRef]
  43. Buzayev, N.A.; Kadirbekov, K.A.; Tolemisova, D.K.; Basbayeva, G.S. Oxidation of 4-methylpyridine on V-Cr-O catalyst. Chem. J. Kaz. 2024, 3, 114–123. [Google Scholar] [CrossRef]
Catalysts 15 00625 g001
Figure 1. XRD patterns of synthesized catalysts: (a) V-Ti-O and (b) V-Ti-Mn-O.
Figure 1. XRD patterns of synthesized catalysts: (a) V-Ti-O and (b) V-Ti-Mn-O.
Catalysts 15 00625 g001
Catalysts 15 00625 g002
Figure 2. SEM characterization (1000×) of catalysts: (a) V-Ti-O and (b) V-Ti-Mn-O.
Figure 2. SEM characterization (1000×) of catalysts: (a) V-Ti-O and (b) V-Ti-Mn-O.
Catalysts 15 00625 g002
Catalysts 15 00625 g003
Figure 3. Raman spectra of catalysts: (a) V-Ti-O and (b) V-Ti-Mn-O.
Figure 3. Raman spectra of catalysts: (a) V-Ti-O and (b) V-Ti-Mn-O.
Catalysts 15 00625 g003
Catalysts 15 00625 g004
Figure 4. Time dependence of 4-MP conversion achieved on V-Ti-O and V-Ti-Mn-O.
Figure 4. Time dependence of 4-MP conversion achieved on V-Ti-O and V-Ti-Mn-O.
Catalysts 15 00625 g004
Catalysts 15 00625 g005
Figure 5. Selectivity of INA obtained as a function of time on V-Ti-O and V-Ti-Mn-O.
Figure 5. Selectivity of INA obtained as a function of time on V-Ti-O and V-Ti-Mn-O.
Catalysts 15 00625 g005
Table 1. BET surface area and pore properties of the catalysts before and after reaction.
Table 1. BET surface area and pore properties of the catalysts before and after reaction.
CatalystsV-Ti-O
(Fresh)		V-Ti-O
(Used)		V-Ti-Mn-O
(Fresh)		V-Ti-Mn-O
(Used)
Parameter
BET surface area, m2/g2.051.8244.6040.72
Table 2. Oxidation of 4-MP on (a) V-Ti-O and (b) V-Ti-Mn-O catalysts.
Table 2. Oxidation of 4-MP on (a) V-Ti-O and (b) V-Ti-Mn-O catalysts.
Temperature, °CConversion,
%		INA Selectivity, %Oxidation Products
PyridinePyridine-4-CarboxaldehydeOthers
(a)
28074.6662.1012.075.4910.74
30077.5564.0012.375.649.91
32079.3964.5912.695.4010.01
34080.0864.0313.045.949.83
36080.2663.2113.796.289.46
38080.2661.8513.956.2810.39
(b)
28075.2465.2510.654.7610.74
30078.7466.5111.645.269.47
32081.2167.1711.955.409.32
34082.1965.7112.115.5210.56
36082.2364.3413.635.869.83
38081.9763.8813.825.899.90
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Kadirbekov, K.; Buzayev, N.; Tussupkaliyev, Y.; Oshakbayev, M. Oxidation of 4-Methylpyridine on Vanadium-Based Catalysts Modified with Titanium and Manganese. Catalysts 2025, 15, 625. https://doi.org/10.3390/catal15070625

AMA Style

Kadirbekov K, Buzayev N, Tussupkaliyev Y, Oshakbayev M. Oxidation of 4-Methylpyridine on Vanadium-Based Catalysts Modified with Titanium and Manganese. Catalysts. 2025; 15(7):625. https://doi.org/10.3390/catal15070625

Chicago/Turabian Style

Kadirbekov, Kairat, Nurdaulet Buzayev, Yersin Tussupkaliyev, and Mels Oshakbayev. 2025. "Oxidation of 4-Methylpyridine on Vanadium-Based Catalysts Modified with Titanium and Manganese" Catalysts 15, no. 7: 625. https://doi.org/10.3390/catal15070625

APA Style

Kadirbekov, K., Buzayev, N., Tussupkaliyev, Y., & Oshakbayev, M. (2025). Oxidation of 4-Methylpyridine on Vanadium-Based Catalysts Modified with Titanium and Manganese. Catalysts, 15(7), 625. https://doi.org/10.3390/catal15070625

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