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Article

Ozone-Oxidation of Glucose to Formic Acid over Polyoxmetalates

by
Xia Yu
1,
Qiwen Wang
2,*,
Haiyan Li
1,
Tong Liu
1,
Mengxue Xiu
1,
Baiji Xue
1 and
Linghe He
1,*
1
Pharmaceutical Research and Development Center, Baicheng Medical College, Baicheng 137000, China
2
College of Resources and Environment, Jilin Agricultural University, Changchun 130118, China
*
Authors to whom correspondence should be addressed.
Molecules 2026, 31(3), 467; https://doi.org/10.3390/molecules31030467
Submission received: 9 November 2025 / Revised: 26 January 2026 / Accepted: 26 January 2026 / Published: 29 January 2026
(This article belongs to the Section Inorganic Chemistry)
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Versions Notes

Abstract

The efficient oxidation of glucose to formic acid (FA) has emerged as a sustainable method for biomass utilization. Herein, we developed a new approach to fulfill oxidation of glucose to formic acid using a polyoxometalate (POM) K10SiW9Mn3IIO37/O3 system, and its high efficiency was presented with 79.3% yield of FA at 82.1% conversion at room temperature for 3 h. As evidenced by experiments, the components in Mn-POMs significantly influenced glucose conversion due to their effect on generating reactive oxygen species (ROSs) from O3, which was essential for FA production.

1. Introduction

Polyoxometalates (POMs) are classic metal–oxide clusters, which show great potentials in catalysis [1,2,3], especially in biomass utilization [4]. In recent years, many efforts have been made in the conversion of biomass into value-added fine chemicals to replace petroleum-based chemicals in industry [5]. In particular, the production of formic acid (FA) from monosaccharides or polysaccharides over POMs has attracted significant attention due to its wide applications in chemicals, pharmaceutical and textile industries [6,7,8]. H5PV2Mo10O40 was the first catalyst for the oxidation of biomass to FA using O2 as an oxidant [9]. Subsequently, H8PMo7V5O40 was used as a homogeneous catalyst to produce FA from glucose with 2 MPa of O2, wherein an 85% yield was achieved using a long-chain primary alcohol as an extractant [10]. The use of an extracting agent not only isolated the produced FA, but also limited the decrease in pH, which favored the enhancement of FA selectivity. However, the main challenge in the field lay in increasing FA selectivity and preventing over oxidation to CO2 and H2O [11,12]. Furthermore, Wu et al. developed a new looping oxidant process using H8PMo7V5O40 as an oxygen carrier [13,14], wherein a 95.4% yield of FA was achieved in the oxidation of glucose. This success was attributed to the separated processes for glucose oxidation and regeneration of reduced H8PMo7V5O40. To date, there have been few reports on the development of more POMs for the oxidation of glucose to FA (Table S1) [15,16,17,18,19,20,21,22,23,24,25,26]. Transition metal (TM)-substituted POMs could provide a greater chance of developing new oxidative catalysts suitable for production of FA from mono- or polysaccharides, using oxygen or other oxidants.
To date, catalytic ozonation (CO) has attracted significant attention in pollutant abatement [27], whereas less attention has been paid to organic transformation [28,29,30]. By now, some metal catalysts including Mn, Fe oxides or complexes had been developed for ozonation of organic pollutants. To the best of our knowledge, there are currently no reports on ozonation based on POMs. Due to the incorporation effect of TM on vacant POMs, Mn-substituted POMs including Kx[SiW12−nMnnmO(40−n)] (abbreviated as SiW12−nMnnm, n = 1–3, m = II–IV) [31,32,33,34,35,36,37] could be easily synthesized to control the compositions of Mn in POMs. As such, SiW12−nMnnm might provide some new concepts for oxidation in the presence of ozone.
Herein, we developed POMs containing Mn including Kx[SiW12−nMnnmO(40−n)], which showed activity in glucose oxidation to FA in the presence of O3. An 82.1% conversion and 79.3% yield were achieved at room temperature for 3 h in water. And the mechanism study demonstrated that reactive oxygen species (ROSs) were generated during ozonation, which contributed to high conversion of monosaccharides as well as cellulose. These results have great potential in FA production, as well as the application of O3 in the industry for POMs. This work also provides valuable insights into the application of POMs in catalytic ozonation of glucose or other saccharides into FA.

2. Results and Discussion

Firstly, we screened the catalytic activity of various Mn-POMs in ozonation of glucose under the following reaction conditions: 100 mg of glucose, 10 mg of catalyst, 10 mL of water, an O3 flow rate of 30 mL/min, for 3 h at room temperature (Figure 1). Without any catalyst, O3 oxidized glucose to 50.6% conversion, but only 46.8% selectivity to FA. This indicates the high oxidative ability of O3 for glucose oxidation, but with lower selectivity. It was observed that Mn-POMs exhibited catalytic activity in the ozonation of glucose in the order of SiW12 (51.3%) < SiW9 (54.4%) < SiW11MnII (69.3%) < SiW10Mn2II (76.6%) < SiW9Mn3II (82.1%). This indicated that Mn-POMs could catalyze O3 to oxidize glucose at room temperature, and their activity depended on the Mn substitution of W. In contrast, silicotungstate SiW12 did not show any activity in the ozonation of glucose, indicating the essential role of Mn in POMs for this reaction. Furthermore, the activity of Mn-POMs relied on the account of Mn components in POMs, with SiW9Mn3II showing the highest activity among all Mn-POMs. Compared with Mn(OAc)2, SiW9Mn3II presented enhanced activity, which was attributed to the effect of polyanion. To investigate this, we checked the activity of SiW12−nMnnIII with a higher valence state in ozonation of glucose. It was observed that MnIII-POM showed relatively lower activity than MnII-POM did. This implied that MnII-POM was first oxidized by O3 to MnIII-POM, and the oxidized form then reacted with glucose to cleave C-C or C-O bonds. During this process, MnIII-POM was reduced back to the original MnII-POM to complete the catalytic cycle. The lower activity of MnIII-POM was likely because the ozonation of MnIII-POMs to MnIV-POMs might be more difficult compared to the oxidation between MnII-POMs to MnIV-POMs, which induced the lower activity for MnIII-POMs compared to MnII-POMs [38]. Meanwhile, the oxidation of MnIV-POMs to high-valence MnV became more difficult [39].
For the undecatungstosilicate, Mn could be coordinated with mono-lacunary SiW11 to form SiW11MnII, which was oxidized by O3 or K2S2O8 to SiW11MnIII and SiW11MnIV. The catalytic activity followed the order of 69.3%(SiW11MnII) > 67.4% (SiW11MnIII) > 61.1% (SiW11MnIV) in ozonation of glucose. Based on these results, we assumed the mechanism was as follows: (1) O3 reacted with SiW11MnII to [SiW11MnIII-O3·] via oxidation–reduction [40]; (2) release one O2 molecule to [SiW11MnIII-O·]; (3) coupled with a H+ to [SiW11MnIII-·OH] [41]; (4) finally ·OH was removed from [SiW11MnIII-·OH] to SiW11MnIII, and ·OH oxidized glucose; and (5) SiW11MnIII participated the oxidation of glucose, while SiW11MnIII accepted 1e− to fresh SiW11MnII. The relevant equations are listed as follows:
SiW11MnII + O3 → SiW11MnIII-O3·
SiW11MnIII-O3· → SiW11MnIII-O· + O2
SiW11MnIII-O· + H+ → SiW11MnIII-·OH
SiW11MnIII-·OH → SiW11MnIII + ·OH
glucose + ·OH + SiW11MnIII → FA + SiW11MnII + H2O
Based on the above results, SiW11MnII appears to be the most active among SiW11MnII, SiW11MnIII and SiW11MnIV, whereas SiW11MnIV was difficult to oxidize to high-valence Mn in POMs using O3. This hypothesis was further verified by a reactive oxygen species (ROS) quenching test. As shown in Figure 2, isopropanol (i-PrOH), sodium azide (NaN3) and p-benzoquinone (BQ) were employed as scavengers to trap ·OH, 1O2 and ·O2−, respectively. It was observed that the conversion of glucose was significantly inhibited by addition of i-PrOH, whereas NaN3 and BQ had a negligible influence on catalytic activity of SiW9Mn3II. This indicated that ·OH was the primary ROS during the ozonation process in the presence of Mn-POMs. Minor amounts of ·O2− and 1O2 also contributed to the reaction involving O3 and ·OH [30]:
O3 + ·OH → HO2· + ·O2−
And ·O2− dismutated into 1O2 [42]:
2·O2− → 1O2 + O22− + 3O2
The generation of ·OH was dependent on the species of Mn POMs (Figure 3). Notably, SiW9Mn3II exhibited the highest activity in generating ·OH, which is consistent with its superior performance in glucose conversion. Furthermore, ·OH radical production correlated with the amount and valence of Mn, following the trend: SiW9Mn3II > SiW10Mn2II > SiW11MnII and SiW9Mn3II > SiW9Mn3III. Consequently, SiW9Mn3II effectively induced the decomposition of O3 to generate ·OH, along with ·O2− and 1O2, confirming that ·OH played a pivotal role in glucose oxidation.
Furthermore, Electron Paramagnetic Resonance (EPR) spectroscopy was employed to confirm the production of ROSs in the presence of O3 and SiW9Mn3II. 5,5-Dimethyl-1-pyrroline N-oxide (DMPO) and 2,2,6,6-tetramethylpiperidine (TEMP) were used as spin traps to distinguish ·OH and ·O2− (in water or methanol) [43] and 1O2 (in water) [44], respectively (Figure 4). Characteristic signals corresponding to DMPO-·OH, DMPO-·O2− and TEMP-1O2 adducts were all observed in the EPR spectra of the SiW9Mn3II/O3 system. These results indicate that ·OH, ·O2− and 1O2 were generated during ozonation, contributing to the rapid oxidation of glucose at lower temperatures.
Meanwhile, to determine interaction between SiW9Mn3II/SiW9Mn3III with O3 or glucose, the UV-Vis spectra were obtained (Figure 5). It was observed that a new peak at approximately 500 nm, attributed to [SiW9Mn3III-·O3], appeared in the SiW9Mn3II/O3 system, while a peak at ~450 nm, assigned to [SiW9Mn3IV-·O3] [35,36], appeared in the SiW9Mn3III/O3 system. The appearance of these peaks in the Mn-POMs/O3 system confirmed the initial interaction between the POMs and O3. Furthermore, the UV-Vis spectra of SiW9Mn3II/SiW9Mn3III with glucose at room temperature showed no new peaks, indicating that SiW9Mn3II and SiW9Mn3III exhibited low activity in oxidizing glucose under these conditions (Figure S1). Consequently, the Mn-POMs likely activated O3 to generate ROS via Equations (1)–(7), thereby contributing to glucose oxidation.
The ozonation of glucose resulted in a high yield of formic acid (FA) (Figure 1). Among all Mn-POMs, catalyst SiW9Mn3II exhibited the highest FA yield of 79.3%, which was consistent with the conversion trend. The reaction products were identified as gluconic acid, xylose, glycolic acid (GA) and FA (Figure S2), with FA being the predominant product after 3 h.
Based on the product distribution, it was proposed that glucose was initially oxidized by ROS to gluconic acid, followed by C1-C2 bond cleavage to yield xylose and FA. Subsequently, xylose was degraded to FA and glycolic acid (GA), with the final cleavage of GA to FA occurring in the presence of ·OH (Scheme 1).
Finally, the reaction conditions were optimized to 100 mg of glucose, 10 mg of SiW9Mn3II, 10 mL of H2O and an O3 flow rate of 30 min/min (Figure S3, Figure S4, Figure S5 and Figure S6). Catalyst SiW9Mn3II was separated via decantation using methanol for subsequent reuse. The regenerated SiW9Mn3II was collected by centrifugation with a recovery rate of 99.3%. Catalyst SiW9Mn3II could be reused for at least six cycles; during this period, the glucose conversion decreased from 82.1% to 79.3%, and FA yields decreased from 76.5% to 71.6%. The total loss of SiW9Mn3II relative to the fresh catalyst was approximately 6.0% (Figure S7). Moreover, IR, UV-Vis and XPS analyses of Mn-POMs before and after glucose oxidation revealed no significant changes, confirming the excellent stability of these catalysts under the reaction conditions (Figure S8, Figure S9 and Figure S10).
Furthermore, VOSO4 (0.0034 mmol), identified as the optimal homogeneous catalyst in Table S1, was selected for the ozonation of glucose. Under identical reaction conditions, VOSO4 achieved a glucose conversion of 75.4% with a formic acid (FA) yield of 65.8%. In comparison, catalyst SiW9Mn3II exhibited superior performance in the ozonation of monosaccharides.
We further extended the application of the SiW9Mn3II/O3 system to cellulose conversion (Figure 6). A cellulose conversion of 75.6% was achieved at room temperature with a formic acid (FA) yield of 69.8%. This result was of significant value for the conversion of cellulosic polysaccharides into FA under mild reaction conditions.

3. Experimental Section

3.1. Chemicals and Measurements

All chemicals and solvents used in this work were of AR grade or better and used without further purification. The syntheses of Kx[SiW12−nMnnmO(40−n)] were carried out based on relevant reported procedures (see Supporting Information). The products were characterized by elementary analysis (Table S2), FTIR spectroscopy, TG/DTG, EPR [45,46] and mass spectrum (Figure S8, Figure S9, Figure S10, Figure S11, Figure S12, Figure S13, Figure S14 and Figure S15).
Elemental analyses were performed using a Leeman Plasma Spec (I) ICP-ES (Hudson, NH, USA) and a PerkinElmer 2400 CHN elemental analyzer (Shelton, CT, USA). IR spectra (4000–400 cm−1) were recorded as KBr pellets on an Agilent Cary 630 spectrometer (Santa Clara, CA, USA). X-ray photoelectron spectroscopy (XPS) was conducted on a Thermo ESCALAB 250X photoelectron spectrometer (Waltham, MA, USA) using an Al Kα source (1200 eV). EPR spectra were collected using a JES-FA 300 spectrometer (JEOL, Tokyo, Japan) operating at 9.05 GHz with a microwave power of 0.998 mW. UV-Vis diffuse reflectance spectra were recorded on a Cary 500 UV-Vis-NIR spectrophotometer. The concentrations of glucose and xylose (Xyl) were determined by HPLC (Shimadzu LC-16A, Kyoto, Japan) equipped with RID and UV detectors and an NH2 column. The mobile phase consisted of acetonitrile and water (volume ratio 4:1) at a flow rate of 1.0 mL/min. The column temperature was maintained at 25 °C, and the injection volume was 20 µL. Additionally, an ion chromatography system (ICS-930, Metrohm, Herisau, Switzerland) was employed to quantify the final oxidation products of glucose. The mobile phase was 0.5 mM H2SO4 at a flow rate of 0.5 mL/min, with an injection volume of 20 µL.

3.2. Oxidation of Glucose

3.2.1. Oxidation of Glucose with O3

Glucose (100 mg), distilled water (10 mL) and the catalyst (10 mg) were added to a glass reactor equipped with an ozone bubbling device. The reaction was initiated by introducing O3 into the magnetically stirred mixture at a flow rate of 30 mL/min. After a reaction time of 3 h, the mixture was analyzed by HPLC and IC to quantify the concentration of glucose and FA. The catalyst was subsequently recovered using methanol.

3.2.2. Quenching Experiments

Radical species generated during the oxidation process were identified under optimal conditions. Initially, different scavengers (i-PrOH [47], NaN3 [48] and BQ [44]) were added to 10 mL of water containing 100 mg of glucose and 10 mg of catalyst at a scavenger-to-catalyst molar ratio of 1:10. Subsequently, ozone was introduced at a flow rate of 30 mL/min for 3 h at room temperature. The role of reactive oxygen species (ROS) was evaluated by determining the conversion and yield of glucose.

3.2.3. Oxidation of Cellulose with O3

The oxidation of cellulose was performed by mixing 100 mg of cellulose with 10 mg of catalyst in 10 mL of H2O. The mixture was stirred at 500 rpm for 9 h at room temperature with an O3 flow rate of 30 mL/min.

4. Conclusions

Mn-containing polyoxometalates (SiW12−nMnnm, n = 1–3, m = II–IV) with different valence states were found to be active in activating O3 to generate reactive oxygen species (ROSs), demonstrating efficient ozonation activity in glucose oxidation. The catalytic activity was influenced by both the Mn content and its valence state, and a higher Mn loading and the presence of low-valent Mn(II) played pivotal roles. The initial interaction between SiW9Mn3III and O3 to form [SiW11MnIII-O3·] contributed to the generation of ROSs including ·OH, ·O2− and 1O2, which were identified by UV-Vis, EPR spectroscopy and quenching experiments. A 79.3% yield of formic acid (FA) was achieved from glucose via this ROS-mediated process, while a 69.8% yield was obtained directly from cellulose at room temperature. This work provides new insights into the application of POMs/O3 systems in biomass conversion.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/molecules31030467/s1, Preparation of Compounds; Table S1: Catalytic oxidation of glucose to FA using different types of catalysts in presence of O2; Figure S1: UV-Vis spectra of SiW9Mn3II and SiW9Mn3III with glucose; Figure S2: Product distribution in ozonation of glucose; Figure S3: Influence of ozone concentration on ozonation of glucose; Figure S4: Influence of glucose amount on glucose ozonation; Figure S5: Influence of catalyst amount on ozonation of glucose; Figure S6: Influence of reaction time on glucose ozonation; Table S2: The elemental analysis of Kx[SiW12-nMnnmO(40−n)] (SiW12−nMnnm, n = 1–3, m = II–IV); Table S3: The elemental analysis of K10SiW9Mn3IIO37 (1st and 2nd syntheses), (NH4)10SiW9Mn3IIO37 and (C16H36N)10SiW9Mn3IIO37; Figure S7: Recyclability of K10SiW9Mn3IIO37 in glucose ozonation; Figure S8: IR spectra of Mn-POMs before (black) and after (red) the ozonation reaction; Figure S9: IR spectra of K10SiW9Mn3IIO37 (1st and 2nd syntheses), (NH4)10SiW9Mn3IIO37 and (C16H36N)10SiW9Mn3IIO37. Figure S10: UV-Vis spectra of Mn-POMs before (black) and after (red) the ozonation reaction; Figure S11: XPS of SiW9Mn3II (a) and SiW9Mn3III (b) before and after the reaction, and results of two repeated syntheses (c); Figure S12: XRD spectra of K10SiW9Mn3IIO37 (1st and 2nd syntheses), (NH4)10SiW9Mn3IIO37 and (C16H36N)10SiW9Mn3IIO37; Figure S13: TG/DTG curves of K10SiW9Mn3IIO37·8H2O; Figure S14: EPR spectra of K10SiW9Mn3IIO37 and (C16H36N)10SiW9Mn3IIO37; Figure S15: ESI-MS of K10SiW9Mn3IIO37.

Author Contributions

Writing—original draft, methodology, data curation, X.Y.; writing—review and editing, writing—original draft, data curation, Q.W.; investigation, data curation, H.L.; writing—original draft, data curation, T.L.; writing—original draft, methodology, investigation, M.X.; software, methodology, B.X.; software, methodology, investigation, L.H. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the National Natural Science Foundation of China (Grant No. 51978134 and 32130073), the Jilin Provincial Science and Technology Department (Grant No. YDZJ202201ZYTS521 and YDZJ202301ZYTS192), the Research Project of Jilin Provincial Department of Education (Grant no. JJKH20261798KJ and JJKH20261786KJ) and the Fundamental Research Funds for the Central Universities (2412022ZD042).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The original contributions presented in this study are included in the article and Supplementary Materials. Further inquiries can be directed to the corresponding authors.

Conflicts of Interest

The authors declare no conflicts of interest.

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Molecules 31 00467 g001
Figure 1. Catalytic activity of various catalysts. Reaction conditions: 100 mg glucose, 10 mg catalyst, 10 mL water, O3 flow rate of 30 mL/min for 3 h at room temperature.
Figure 1. Catalytic activity of various catalysts. Reaction conditions: 100 mg glucose, 10 mg catalyst, 10 mL water, O3 flow rate of 30 mL/min for 3 h at room temperature.
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Molecules 31 00467 g002
Figure 2. Quenching experiments for SiW9Mnnm (valence of m, n = 2, 3) in the ozonation of glucose. Reaction conditions: 100 mg glucose, 10 mg catalyst, 10 mL water, O3 flow rate of 30 mL/min for 0.5 h at room temperature.
Figure 2. Quenching experiments for SiW9Mnnm (valence of m, n = 2, 3) in the ozonation of glucose. Reaction conditions: 100 mg glucose, 10 mg catalyst, 10 mL water, O3 flow rate of 30 mL/min for 0.5 h at room temperature.
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Molecules 31 00467 g003
Figure 3. Influence of i-PrOH in the ozonation activity of Mn-POMs. Reaction conditions: 100 mg of glucose, 10 mg of catalyst, 1 mg of i-PrOH, 10 mL H2O, room temperature, O3 flow rate of 10 mL/min, for (a) 0.5 h and (b) 1.0 h.
Figure 3. Influence of i-PrOH in the ozonation activity of Mn-POMs. Reaction conditions: 100 mg of glucose, 10 mg of catalyst, 1 mg of i-PrOH, 10 mL H2O, room temperature, O3 flow rate of 10 mL/min, for (a) 0.5 h and (b) 1.0 h.
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Molecules 31 00467 g004
Figure 4. EPR spectra of DMPO-·OH (*) in water, DMPO-·O2− (△) in methanol and TEMP-1O2 (▽) in water. Reaction condition: 10 mg SiW9Mn3II, 50 mM DMPO or TEMP, 10 mg/L O3 and room temperature.
Figure 4. EPR spectra of DMPO-·OH (*) in water, DMPO-·O2− (△) in methanol and TEMP-1O2 (▽) in water. Reaction condition: 10 mg SiW9Mn3II, 50 mM DMPO or TEMP, 10 mg/L O3 and room temperature.
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Molecules 31 00467 g005
Figure 5. UV-Vis spectra of SiW9Mn3II (a)/SiW9Mn3III (b) in the presence of O3. Reaction conditions: 10 mg of catalyst, 10 mL of water, O3 flow rate of 30 mL/min for 1 h at room temperature.
Figure 5. UV-Vis spectra of SiW9Mn3II (a)/SiW9Mn3III (b) in the presence of O3. Reaction conditions: 10 mg of catalyst, 10 mL of water, O3 flow rate of 30 mL/min for 1 h at room temperature.
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Molecules 31 00467 sch001
Scheme 1. The possible pathway for glucose conversion over SiW9Mn3II/O3.
Scheme 1. The possible pathway for glucose conversion over SiW9Mn3II/O3.
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Figure 6. Catalytic activity of SiW9Mn3II in ozonation of cellulose. Reaction conditions: 100 mg cellulose, 10 mg SiW9Mn3II, 10 mL water, O3 flow rate of 30 mL/min, 9 h, room temperature.
Figure 6. Catalytic activity of SiW9Mn3II in ozonation of cellulose. Reaction conditions: 100 mg cellulose, 10 mg SiW9Mn3II, 10 mL water, O3 flow rate of 30 mL/min, 9 h, room temperature.
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Yu, X.; Wang, Q.; Li, H.; Liu, T.; Xiu, M.; Xue, B.; He, L. Ozone-Oxidation of Glucose to Formic Acid over Polyoxmetalates. Molecules 2026, 31, 467. https://doi.org/10.3390/molecules31030467

AMA Style

Yu X, Wang Q, Li H, Liu T, Xiu M, Xue B, He L. Ozone-Oxidation of Glucose to Formic Acid over Polyoxmetalates. Molecules. 2026; 31(3):467. https://doi.org/10.3390/molecules31030467

Chicago/Turabian Style

Yu, Xia, Qiwen Wang, Haiyan Li, Tong Liu, Mengxue Xiu, Baiji Xue, and Linghe He. 2026. "Ozone-Oxidation of Glucose to Formic Acid over Polyoxmetalates" Molecules 31, no. 3: 467. https://doi.org/10.3390/molecules31030467

APA Style

Yu, X., Wang, Q., Li, H., Liu, T., Xiu, M., Xue, B., & He, L. (2026). Ozone-Oxidation of Glucose to Formic Acid over Polyoxmetalates. Molecules, 31(3), 467. https://doi.org/10.3390/molecules31030467

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