燃料化学学报（中英文）

Catalyst	t/min	t/°C	Catalyst amount/g	Sulfur removal/%	Ref.
[Bpy]PMoVn	480	110	0.02	65.5 (petroleum coke)	[42]
MoO₃/LaTiO_x	150	130	0.02	100 (4,6-DMDBT)	[43]
30%HPA-CeO₂	240	70	0.03	52.5 (petroleum coke)	[44]
Mo@CeO₂	480	100	−	61.2 (petroleum coke)	[45]
FeMoO_x/LaTiO_y	60	130	0.02	100 (4,6-DMDBT)	[46]
MoO₃/La₂O₂CO₃	120	130	0.04	100 (4,6-DMDBT)	[47]
VO_x/TiO₂	180	80	−	100 (4,6-DMDBT)	[48]
V₂O₅/TiO₂	120	120	0.02	100 (DBT)	[49]
Mn-Co-V-O	100	110	0.03	98 (DBT)	this work

Catalyst	t/min	t/°C	Catalyst amount/g	Sulfur removal/%	Ref.
[Bpy]PMoVn	480	110	0.02	65.5 (petroleum coke)	[42]
MoO₃/LaTiO_x	150	130	0.02	100 (4,6-DMDBT)	[43]
30%HPA-CeO₂	240	70	0.03	52.5 (petroleum coke)	[44]
Mo@CeO₂	480	100	−	61.2 (petroleum coke)	[45]
FeMoO_x/LaTiO_y	60	130	0.02	100 (4,6-DMDBT)	[46]
MoO₃/La₂O₂CO₃	120	130	0.04	100 (4,6-DMDBT)	[47]
VO_x/TiO₂	180	80	−	100 (4,6-DMDBT)	[48]
V₂O₅/TiO₂	120	120	0.02	100 (DBT)	[49]
Mn-Co-V-O	100	110	0.03	98 (DBT)	this work

Mn掺杂对Co-V-O二元金属氧化物结构和氧化脱硫性能的影响

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董哲涵 ¹ , 王泓力 ² , 李秀萍 ³ , 赵荣祥 ¹^,^*

燃料化学学报（中英文） | 2026,54(7): 20250372-1322-20250372-1332

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燃料化学学报（中英文） 2026 , 54 (7) : 20250372-1322 -20250372-1332

Mn掺杂对Co-V-O二元金属氧化物结构和氧化脱硫性能的影响

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董哲涵¹, 王泓力², 李秀萍³, 赵荣祥¹^,^*

作者信息

¹辽宁石油化工大学石油化工学院, 辽宁抚顺 113001

²山东金创金银冶炼有限公司, 山东烟台 265600

³辽宁石油化工大学理学院, 辽宁抚顺 113001

通讯作者:

赵荣祥

Effect of Mn doping on the structure and oxidative desulfurization properties of Co-V-O binary metal oxides

Zhehan DONG¹, Hongli WANG², Xiuping LI³, Rongxiang ZHAO¹^,^*

Affiliations

¹School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China

²Shandong Jinchuang Gold and Silver Smelting Co., Ltd. Yantai 265600, China

³School of Science, Liaoning Petrochemical University, Fushun 113001, China

Corresponding Author:

E-mail: zylhzrx@126.com

出版时间: 2026-07-10 doi: 10.1016/S1872-5813(26)60658-5

文章导航

摘要

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燃油中硫化物的燃烧排放是加剧大气污染的重要诱因之一。氧化脱硫技术因反应条件温和、对芳香族硫化物脱除效率优异，已成为传统加氢脱硫技术的重要补充手段。金属元素掺杂是精准调控催化剂电子结构、进而提升其催化性能的有效策略，本研究采用回流-高温煅烧耦合方法制备了锰掺杂钴钒复合金属氧化物（Mn-Co-V-O）；借助傅里叶变换红外光谱（FT-IR）、X 射线衍射（XRD）、扫描电子显微镜（SEM）、X 射线光电子能谱（XPS）及紫外-可见吸收光谱（UV-vis）等多种表征手段，分析了该催化剂的晶体结构、微观形貌及表面化学组成。以分子氧为氧化剂，本研究对Mn-Co-V-O催化剂的二苯并噻吩（DBT）氧化脱硫性能开展了评价。结果表明，相较于未掺杂的Co-V-O催化剂，Mn元素的引入可显著提升其催化活性；在优化反应条件下，DBT的直接脱除率可达81.6%，与萃取工艺联用后脱硫效率进一步提升至98.0%。机理探究结果表明，Mn掺杂可有效提升催化剂表面氧空位浓度，进而促进分子氧活化生成超氧自由基（${\cdot {\mathrm{O}}_2^- }$）；自由基捕获实验证实，${\cdot {\mathrm{O}}_2^- } $是实现DBT选择性氧化为二苯并噻吩砜（DBTO₂）的关键活性物种。本研究为深度氧化脱硫用高效金属氧化物催化剂的设计与开发提供了重要的理论依据与技术参考。

关键词

Co-V-O / 有氧氧化脱硫 / DBT / 氧空位 / 超氧自由基

Abstract

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The sulfur dioxide produced by the combustion of sulfur-containing aromatic compounds in fuels are a major contributor to atmospheric pollution. Due to its mild reaction conditions and excellent efficiency in removing aromatic sulfides, oxidative desulfurization has become a crucial complement to hydrodesulfurization technology. Metal doping represents an effective strategy for modulating the electronic structure of catalysts and enhancing their catalytic performances. In this study, Mn-doped Co-V-O metal oxide (Mn-Co-V-O) was successfully synthesized via a reflux method followed by high-temperature calcination. The structure, morphology, and surface chemical composition of Mn-Co-V-O were systematically characterized using FT-IR, XRD, SEM, XPS and UV-vis DRS. The oxidative desulfurization (ODS) performance of the catalyst toward dibenzothiophene (DBT) was evaluated using oxygen as a green oxidant. Results indicated that Mn doping significantly enhanced the ODS activity of Mn-Co-V-O compared to the undoped Co-V-O. Under optimized reaction conditions, the direct removal rate of DBT reached 81.6%. When combined with an extraction process, the desulfurization rate was further increased to 98.0%. Mechanistic studies revealed that Mn doping effectively increased the surface oxygen vacancy concentration, facilitating the activation of oxygen to generate superoxide radicals ($\cdot {\mathrm{O}}_2^- $). Free radical trapping experiments confirmed that $\cdot {\mathrm{O}}_2^- $served as the key active species responsible for the selective oxidation of DBT to DBTO₂. This study provides an important reference for the design of highly efficient metal oxide catalysts applicable to deep oxidative desulfurization in the future.

Key words

Co-V-O / aerobic oxidation desulphurization / DBT / oxygen vacancy / superoxide radical

引用本文

董哲涵, 王泓力, 李秀萍, 赵荣祥. Mn掺杂对Co-V-O二元金属氧化物结构和氧化脱硫性能的影响. 燃料化学学报（中英文）, 2026 , 54 (7) : 20250372-1322 -20250372-1332 . DOI: 10.1016/S1872-5813(26)60658-5

Zhehan DONG, Hongli WANG, Xiuping LI, Rongxiang ZHAO. Effect of Mn doping on the structure and oxidative desulfurization properties of Co-V-O binary metal oxides[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (7) : 20250372-1322 -20250372-1332 . DOI: 10.1016/S1872-5813(26)60658-5

正文

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Sulfur oxide emissions from fuel-powered vehicles significantly contribute to the atmospheric pollution^[1−2]. Accordingly, controlling sulfur-containing compounds at the source has become a global priority^[3−4]. In China, the National V standard for gasoline and diesel stipulates a sulfur content limit below 10 µg/g. Currently, hydrodesulfurization (HDS) remains the dominant technology in petroleum refining^[5−8], primarily owing to its high efficiency in removing aliphatic sulfur compounds. However, HDS operates under severe conditions (high temperature and pressure), requires highly active catalysts, and exhibits limited effectiveness toward aromatic sulfur compounds due to steric hindrance^[9]. These drawbacks have motivated extensive research efforts to develop alternative and more efficient desulfurization technologies.

Oxidative desulfurization (ODS) has emerged as a promising complementary technology to HDS, by virtue of its mild reaction conditions, low energy consumption, and notably high efficiency in removing aromatic sulfur compounds that are resistant to HDS^[10−11]. In ODS systems, both the oxidant and the catalyst play decisive roles in determining overall performance. Hydrogen peroxide is commonly employed as an oxidant due to its low cost, environmental compatibility, and the formation of water as the sole byproduct. Despite these advantages, its use is associated with practical challenges, such as equipment corrosion and potential explosion hazards. In contrast, molecular oxygen has attracted considerable interest as an alternative oxidant because of its abundance, low cost, intrinsic safety, and environmental benignity, with water typically being the primary oxidation product^[12−13]. However, activating the inherently stable triplet ground state of molecular oxygen under mild conditions remains a significant challenge, highlighting the critical need for the development of highly active and efficient catalysts for oxygen-mediated oxidative desulfurization.

In recent years, transition metal oxides have been widely investigated as catalysts for ODS due to their tunable oxidation states, structural stability, and ease of recovery^[14]. However, single-component metal oxides often suffer from limited catalytic activity. To enhance their performances, two primary strategies have been adopted: increasing the specific surface area and introducing heterometal ions into the catalyst structure. Such doping approaches can effectively modulate the electronic structure and surface physicochemical properties of the catalyst, thereby enhancing their performances. For example, Liu et al.^[15] incorporated Fe into MoO_x and demonstrated that Fe ions precisely regulated the electronic structure of Mo sites, significantly raising the surface oxygen vacancy concentration. After optimizing the dopant content, the catalyst exhibited excellent activity, achieving full conversion of various sulfur compounds. Uematsu et al.^[16] doped Mo ions into MnO₂ and observed that the introduction of high-valence transition-metal cations, particularly Mo⁶⁺, notably shortened the fiber length of MnO₂, leading to the formation of aggregates composed of ultrafine nanocrystals. This structural evolution increased the specific surface area and the number of exposed active sites, enabling efficient oxidation of various sulfides into the corresponding sulfoxides and sulfones. Similarly, An et al.^[17] reported that Mn doping effectively altered the electronic structure and surface atomic composition of NiMoO₄, resulting in an increased oxygen vacancy density and enhanced O₂ activation capability.

In the field of ODS, vanadium-based catalysts, such as 2D-2D V₂O₅/BNNS and V₂O₅, have shown promising desulfurization performance^[18−19]. Cobalt-based catalysts have also been extensively studied. For example, Murata et al.^[20] achieved 97% sulfur removal from diesel using cobalt acetate or cobalt chloride as catalysts, with aldehydes serving as sacrificial agents. Wei et al.^[21] synthesized a Co/KIT-6 catalyst, which reached a desulfurization rate of 98% in model oil with cyclohexanone peroxide employed as the oxidant. Similarly, Deng et al.^[22] prepared a Co/SBA-15 catalyst by loading cobalt oxide onto SBA-15 and achieved a notable sulfur removal efficiency of 99.5% at room temperature.

Considering that Co-V-O can be regarded as a composite metal oxide comprising of cobalt oxide and vanadium oxide, it is reasonable to expect that such materials to demonstrate favorable ODS activity. In this work, both Co-V-O and Mn-doped Co-V-O catalysts were synthesized via a reflux-calcination method. The crystalline structure, morphology, elemental valence states, and optical properties of the prepared catalysts were systematically characterized using XRD, SEM, XPS, FT-IR and UV-vis DRS. The results confirm the successful incorporation of Mn into the Co-V-O lattice. The ODS performance of the catalysts was evaluated using dibenzothiophene (DBT) in model oil as the substrate. The effects of Mn doping content, reaction temperature, catalyst dosage, oxygen flow rate, and different sulfur compounds on the desulfurization efficiency were investigated. Furthermore, the stability of the catalyst was examined, and a preliminary reaction mechanism for the ODS process was proposed.

1　Experimental

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1.1　Preparation of catalysts

Manganese(II) chloride tetrahydrate (MnCl₂·4H₂O, ≥99.0%), ammonium metavanadate (NH₄VO₃, ≥99.5%), cobalt(II) chloride hexahydrate (CoCl₂·6H₂O, ≥99.0%), hexamethylenetetramine (HMT, ≥99.5%), DBT (≥99.0%), 4,6-dimethyldibenzothiophene (4,6-DMDBT, ≥98.5%), and benzothiophene (BT, 98.0%) were purchased from Aladdin Reagent Co., Ltd. Decahydronaphthalene (≥98.0%), p-benzoquinone (≥99.0%), and isopropanol (≥99.7%) were obtained from Sinopharm Chemical Reagent Co., Ltd. Oxygen (≥99.99%) was supplied by Fushun Oxygen Plant.

The catalysts were synthesized through a typical procedure as follows: MnCl₂·4H₂O (0.03 g), NH₄VO₃ (2.32 g), CoCl₂·6H₂O (0.952 g), and hexamethylenetetramine (7.0 g) were dissolved in 160 mL of deionized water under stirring. The mixture was stirred at 80 °C for 4 h and then centrifuged. The precipitate was collected, washed three times with deionized water, dried at 100 °C for 4 h, and ground into a fine powder. Finally, the powder was calcined in a muffle furnace at 400 °C for 2 h to obtain the catalyst with a Mn-to-Co molar ratio of 1∶15, denoted as Mn-Co-V-O(1∶15). For comparison, Mn-Co-V-O(1∶10) and Mn-Co-V-O(1∶20) were synthesized by adjusting the amount of MnCl₂·4H₂O to 0.04 and 0.02 g, respectively. The Co-V-O catalyst was prepared under identical conditions without the addition of MnCl₂·4H₂O.

1.2　Characterization

Fourier transform infrared (FT-IR) spectra were recorded on a NEXUS 870 spectrometer (Thermo Nicolet, USA). X-ray diffraction (XRD) patterns were obtained using a D8 Advance diffractometer (Bruker, Germany). Scanning electron microscopy (SEM) was performed on a Philips XL 30 microscope (Philips, Netherlands). X-ray photoelectron spectroscopy (XPS) measurements were conducted with a K-Alpha spectrometer (Thermo Fisher Scientific, USA). UV-vis diffuse reflectance spectra (UV-vis DRS) were recorded on a TU-1901 spectrophotometer (Shanghai Yuanxi, China) in the range of 200–800 nm, with a scan step of 5 nm at room temperature, using barium sulfate as a reference. Electron paramagnetic resonance (EPR) spectra were measured on a Bruker EMXplus spectrometer. The sulfur content in oils was determined using a WK-2D coulometric analyzer (Jiangsu Jiangdian, China).

1.3　Catalytic evaluation

1.437 g of DBT was ultrasonically dissolved in 1000 mL of decahydronaphthalene to prepare a model oil with a sulfur content of 250 µg/g. The ODS experiments were carried out in a 250 mL three-necked flask equipped with a condenser. Typically, 20 mL of tetralin-based model oil and a predetermined amount of the Mn-Co-V-O catalyst were added to the reactor. The reaction was performed under a constant flow of oxygen at a specified temperature. During the process, 0.1 mL aliquots of the upper oil layer were collected at 20 min intervals. After reaction completion, all collected oil samples were centrifuged to remove residual catalyst particles. The sulfur content in the clarified samples was then quantified using a WK-2D coulometric analyzer. The desulfurization rate (η) was calculated using the following equation:

$ {\eta =[(A-B)/A]\times 100\% } $

(1)

where η is the desulfurization rate (%), and A and B represent the sulfur contents in the model oil at the initial time and at time t, respectively (µg/g).

2　Results and discussion

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2.1　Morphology, structure and composition characterization

The FT-IR spectra of the samples are shown in Figure 1(a). The absorption bands observed at 3448 and 1639 cm^‒1 are assigned to the O−H stretching and bending vibrations, respectively. Peaks located at 931 and 812 cm^‒1 correspond to the symmetric and asymmetric stretching vibrations of VO₄ units^[23], while the band at 653 cm^‒1 is attributed to the bending vibration of Co−O bonds^[24], and the band at 420 cm^‒1 arises from the Co−O stretching mode^[25]. It can be noted that the positions of these characteristic absorption bands remained largely unchanged after Mn doping; however, the band at 812 cm^‒1 becomes broader. This broadening indicates an increased structural disorder around the VO₄ tetrahedra, likely due to lattice distortion induced by the incorporation of Mn ions.

The XRD patterns of the samples are shown in Figure 1(b). All characteristic diffraction peaks can be indexed to Co₂V₂O₇ (PDF#29-0519) and Co₃V₂O₈ (PDF#16-0675), indicating that the samples exhibit a mixed-phase structure composed of these two crystalline phases. Furthermore, after Mn doping, the diffraction peak at 2θ ≈ 63.5° shifts to a lower angle, suggesting lattice expansion likely due to the incorporation of Mn ions into the host framework.

The morphological features of Co-V-O and Mn-Co-V-O(1∶15) were analyzed by SEM. As shown in Figure 2(a), Co-V-O exhibits a uniform assembly of block-like structures. The corresponding SEM image of Mn-Co-V-O(1∶15) in Figure 2(b) indicates that the overall morphology remains largely unchanged after Mn doping. Furthermore, elemental mapping results of Mn-Co-V-O(1∶15) presented in Figures 2(c)–(f), reveal a homogeneous spatial distribution of Mn, Co, V and O throughout the sample, confirming the successful incorporation of Mn into the Co-V-O framework.

The surface elemental composition and chemical states of Co-V-O and Mn-Co-V-O(1∶15) were further investigated by XPS spectra, as shown in Figure 3. The survey spectra in Figure 3(a) confirm the presence of Co, V and O in both samples, while Mn is detected exclusively in Mn-Co-V-O(1∶15), indicating the successful incorporation of Mn into the catalyst structure. Figure 3(b) presents the Mn 2p XPS spectrum of Mn-Co-V-O(1∶15). The peaks located at 653.2, 641.1 and 647.4 eV correspond to Mn 2p_1/2, Mn 2p_3/2 and satellite peaks (Sat), respectively. In the Mn-Co-V-O catalyst, Mn exhibits mixed valence states: the peaks at 655.01 and 644.1 eV are assigned to Mn⁴⁺, those at 653.5 and 642.4 eV to Mn³⁺, and those at 652.3 and 640.9 eV to Mn^2+[26]. The presence of Mn⁴⁺ can induce structural defects, thereby promoting oxygen mobility within the lattice, and thereafter enhancing the catalyst’s oxidative capability^[27].

The Co 2p XPS spectra are shown in Figure 3(c). Both Co-V-O and Mn-Co-V-O(1∶15) exhibit characteristic peaks corresponding to Co 2p_1/2, Co 2p_3/2, and two satellite peaks. For Mn-Co-V-O(1∶15), the fitted peaks at 796.6 and 780.5 eV are assigned to Co³⁺, those at 798.1 and 782.1 eV to Co²⁺, and the signals at 803.3 and 786.7 eV correspond to satellite peaks^[28]. Compared with Co-V-O, no significant peak shift in binding energy is observed for Mn-Co-V-O(1∶15), however, notable changes in peak areas are evident. Specifically, the Co³⁺/(Co²⁺+Co³⁺) ratio increases from 38.8% in Co-V-O to 46.8% in Mn-Co-V-O(1∶15), suggesting that Mn doping promotes electron transfer and lead to an elevated concentration of Co³⁺ species.

Figure 3(d) shows the V 2p XPS spectra. Both samples display characteristic peaks for V 2p_1/2 and V 2p_3/2. In Co-V-O, the fitted peaks at 524.2 and 516.7 eV are assigned to V⁴⁺ 2p_1/2 and 2p_3/2, respectively, while those at 524.8 and 517.5 eV correspond to V⁵⁺. For Mn-Co-V-O(1∶15), the V⁴⁺ 2p_1/2 and 2p_3/2 peaks are located at 524.0 and 516.8 eV and the V⁵⁺ peaks appear at 525.3 and 517.6 eV^[29], showing slight shifts compared to the undoped sample. The relative peak area of V⁴⁺ increases from 64.1% in Co-V-O to 69.5% in Mn-Co-V-O(1∶15), indicating that Mn doping promotes the formation and stabilization of V⁴⁺ species.

The O 1s XPS spectra are shown in Figure 3(e). For Mn-Co-V-O(1∶15), three peaks are observed at 530.1, 530.7, and 532.2 eV, which are assigned to lattice oxygen, oxygen vacancies, and adsorbed water species, respectively^[30]. In Co-V-O, these peaks are slightly shifted to 530.2, 530.8 and 532.5 eV. The relative content of oxygen vacancies increases from 21.49% in Co-V-O to 34.34% in Mn-Co-V-O(1∶15), indicating that Mn doping effectively enhances the concentration of oxygen vacancies. These vacancies are known to promote O₂ adsorption and facilitate the generation of superoxide radicals (

$\cdot {\mathrm{O}}_2^- $

) on the catalyst surface, which contributes to the improved ODS performance^[31].

The structural and optical properties of Co-V-O and Mn-Co-V-O(1∶15) were further examined by DRS over the wavelength range of 200–800 nm, as shown in Figure 4(a). Both Co-V-O and Mn-Co-V-O(1∶15) exhibit absorption in the ultraviolet and visible regions. Notably, Mn-Co-V-O(1∶15) shows a clear redshift along with enhanced absorption intensity relative to the undoped Co-V-O.

Figure 4(b) presents the band gap estimation for Co-V-O and Mn-Co-V-O(1∶15). The band gap of Mn-Co-V-O(1∶15) (1.62 eV) is lower than that of Co-V-O (1.94 eV). This reduction can be attributed to the increased free electron density and the formation of additional oxygen vacancies resulting from Mn doping^[32].

2.2　Oxidative desulfurization performances

The metal doping content is a key factor influencing the catalytic performance in heterogeneous catalysis. To examine the effect of Mn doping on desulfurization, experiments were conducted using 20 mL of DBT model oil under the following conditions: a catalyst dosage of 0.03 g, oxygen flow rate of 150 mL/min, and a reaction temperature of 110 °C. As shown in Figure 5(a), the undoped Co-V-O catalyst exhibited a DBT removal efficiency of only 60%. In contrast, when the Mn-to-Co molar ratio is 1∶15, the desulfurization rate increases significantly to 81.6%. However, both lower (1∶20) and higher (1∶10) doping levels result in reduced desulfurization efficiency. These results indicate that an appropriate Mn doping level can markedly enhance the catalytic desulfurization performance^[33].

At low doping levels, Mn may not be uniformly dispersed within the Co-V-O matrix, limiting its ability to effectively modulate the electronic structure and surface properties of the catalyst. Conversely, excessive Mn doping can lead to particle agglomeration, reducing the number of accessible active sites and consequently decreasing catalytic activity^[34]. Therefore, a Mn-to-Co molar ratio of 1∶15 was identified as optimal, and Mn-Co-V-O(1∶15) was selected as the catalyst for subsequent experiments.

Using Mn-Co-V-O(1∶15) as the catalyst, the influence of reaction temperature on DBT desulfurization was investigated under the identical experimental conditions (20 mL of DBT model oil, catalyst dosage of 0.03 g and oxygen flow rate of 150 mL/min).

The influence of reaction temperature on the DBT ODS performance of Mn-Co-V-O(1∶15) is shown in Figure 5(b). As the temperature increases from 100 to 110 °C, the desulfurization rate rises from 69.2% to 81.6%, which can be attributed to enhanced molecular collisions that facilitate the reaction and improve the desulfurization performance^[35]. However, when the temperature is further increased to 120 °C, the desulfurization rate declines to 60.0%. This is likely resulted from solvent volatilization, which compromises reaction stability, along with increased energy consumption^[36]. Consequently, 110 °C is identified as the optimal reaction temperature.

Under the optimized conditions (110 °C, oxygen flow rate of 150 mL/min), the influence of catalyst dosage on the desulfurization performance was studied using 20 mL of DBT model oil, as shown in Figure 5(c). As the catalyst amount increases from 0.02 to 0.03 g, the DBT removal efficiency after 100 min increases from 45.2% to 81.6%, owing primarily to the greater availability of active sites, which accelerates the ODS reaction^[37]. However, further increasing the catalyst loading to 0.04 and 0.05 g leads to reduced desulfurization efficiencies of 56.4% and 50.4%, respectively. This can be attributed to particle agglomeration at higher catalyst loadings, which diminishes the effective surface area, restricts contact with DBT molecules, and hampers the mass transfer of reactants and products^[38]. Therefore, the optimal catalyst dosage is determined to be 0.03 g.

The effect of oxygen flow rate on DBT removal was examined at 110 °C using, 0.03 g of Mn-Co-V-O(1∶15) and 20 mL of model oil, as shown in Figure 5(d). As the oxygen flow rate increases from 100 to 150 mL/min, the desulfurization rate increases from 51.6% to 81.6%. This improvement is attributed to enhanced gas-liquid mass transfer under moderate oxygen flow, which promotes the reaction between oxygen and DBT. However, further increasing the oxygen flow rate to 200 mL/min resultes in a decrease in the desulfurization rate to 36.4%. Excessive gas flow shortens the residence time, limiting sufficient oxygen dissolution and diffusion into the liquid phase, thereby reducing gas-liquid contact efficiency and the overall desulfurization performance^[39]. Therefore, an oxygen flow rate of 150 mL/min is determined to be optimal.

2.3　Effect of oxidation-extraction coupling on desulfurization rate

The desulfurization rate in the ODS process alone remains limited. To further improve sulfur removal, after the oxidation step, 5 mL of oxidized model oil was mixed with 5 mL of polyethylene glycol 200 (PEG-200) extractant and stirred at room temperature for 10 min. As shown in Figure 6(a), the desulfurization rate increases from 81.6% to 98.0%, in contrast to a mere 45.0% achieved by extraction alone. This result demonstrates that a synergistic oxidation-extraction strategy enables deep desulfurization.

Practical fuels typically contain various sulfur compounds. Following the oxidation step under optimized conditions, 5 mL of the oxidized upper oil layer was extracted with 5 mL of PEG-200 for 10 min. The sulfur content in the upper oil phase was subsequently determined. As shown in Figure 6(b), the desulfurization efficiencies of DBT, BT and 4,6-DMDBT are 98.0%, 60.0%, and 86.8%, respectively, indicating that the Mn-Co-V-O (1∶15) catalyst in the ODS-extraction system can effectively remove diverse sulfur species. The differences in removal efficiency are primarily due to differences in the electron cloud density at the sulfur atom and molecular steric hindrance. Generally, a higher electron cloud density facilitates sulfur removal^[40]. The electron cloud densities of 4,6-DMDBT, DBT and BT are 5.760, 5.758 and 5.739, respectively^[41]. BT, with the lowest electron cloud density, exhibits the poorest remove. Although 4,6-DMDBT possesses the highest electron density, the two methyl groups in its structure induce significant steric hindrance, which explains its lower desulfurization rate compared with DBT.

The presence of olefins and aromatics in real fuels may also influence the desulfurization process. Toluene and cyclohexene were used as representative compounds to investigate their effects on the removal of DBT. Under optimized reaction conditions, 1 mL of toluene or cyclohexene was added to the reaction mixture prior to extraction. As shown in Figure 6(c), the desulfurization efficiencies for DBT reach 79.2% and 98.8%, respectively. The lower efficiency observed in the toluene system may be attributed to competitive oxidation of toluene, which consumes a portion of the active oxidative species^[41]. Overall, the aerobic ODS system exhibits only limited interference from olefins and aromatics, demonstrating its potential for deep desulfurization of fuels containing such components.

Following the reaction, the catalyst was recovered by washing successively with distilled water and anhydrous ethanol, and then drying. The reusability of the recycled catalyst was evaluated under the optimal reaction conditions. As shown in Figure 6(d), the desulfurization rate decreases from 98.0% to 93.2% after repeated use. The observed decline in catalytic activity can be primarily attributed to a partial loss of catalyst material during the recovery process, as well as the adsorption or accumulation of oxidation products within the catalyst pores, which reduces the accessibility of the active sites.

The recovered catalyst was further analyzed by FT-IR spectroscopy. As shown in Figure 7(a), the characteristic absorption bands of the fresh and recovered catalysts are essentially identical, indicating that the catalyst framework remains intact after the reaction. However, additional absorption bands are observed at 1155 and 1251 cm^‒1, which correspond to dibenzothiophene sulfone (DBTO₂). This confirms the adsorption of sulfur-containing oxidation products on the catalyst surface. To remove these residual sulfur species, the recovered catalyst was calcined at 400 °C for 2 h and subsequently analyzed by XRD. The XRD pattern of the regenerated catalyst, shown in Figure 7(b), exhibits diffraction peaks that are highly consistent with those of the fresh catalyst. This demonstrates good structural stability of the catalyst throughout the reaction and regeneration processes.

The ODS performance of the catalyst was further benchmarked against previously reported systems. As summarized in Table 1, the present catalyst exhibits a comparatively high desulfurization rate under milder reaction conditions. Notably, it achieves efficient sulfur removal at lower temperatures and with shorter reaction times compared to other catalysts, underscoring its favorable energy efficiency and practical potential for industrial application.

2.4　Oxidation-extraction desulfurization mechanism

Radical trapping experiments were performed to identify the key active species in the aerobic ODS process. Under the optimized conditions, p-benzoquinone (BQ, 0.02 g) a superoxide radical (

$\cdot {\mathrm{O}}_2^- $

) scavenger, or isopropanol (IPA, 24 µL), a hydroxyl radical (·OH) scavenger, was separately added to the reaction system. As shown in Figure 8(a), the desulfurization rate drops sharply to 49.6% with BQ, whereas it remains almost unaffected (97.8%) with IPA. These results demonstrate that superoxide radicals (

$\cdot {\mathrm{O}}_2^- $

), rather than hydroxyl radicals (·OH), are the predominant active species driving the ODS reaction. Further confirmation was obtained from the EPR spectroscopy (Figure 8(b)), which displays characteristic signals attributable to

$ \mathrm{\cdot O}_2^- $

, directly evidencing its in situ generation during the reaction. The formation of these reactive oxygen species can be attributed to the enhanced activation of molecular oxygen over the Mn-doped Co-V-O catalyst, promoted by its high oxygen vacancy concentration and the synergistic redox cycling among Mn, Co and V species.

Figure 9 schematically illustrates the proposed desulfurization mechanism over the Mn-Co-V-O(1∶15) catalyst. The left part of the diagram depicts the oxidation process, while the right part illustrates the extraction step. During the oxidation stage, Mn³⁺ and Co²⁺ species in the Mn-Co-V-O (1∶15) catalyst are oxidized to Mn⁴⁺ and Co³⁺ via electron loss. Concurrently, molecular oxygen accepts these electrons and is activated to form superoxide radicals (

$\cdot {\mathrm{O}}_2^- $

) as reactive intermediates. These

$\cdot {\mathrm{O}}_2^- $

species then interact with the V active sites on the catalyst surface, promoting the conversion of V=O bonds into peroxovanadate intermediates. Such highly oxidative intermediates subsequently facilitate the stepwise oxidizing of DBT to its corresponding DBTO₂. The introduction of Mn dopants substantially increases the oxygen vacancy concentration, which enhances the adsorption and activation of molecular oxygen on the catalyst surface and promotes

$ \cdot\mathrm{O}_2^- $

formation. Consequently, the overall rate of aerobic ODS is significantly improved. In the extraction stage, based on the “like dissolves like” principle, polyethylene glycol (PEG) acts as an effective extractant to selectively transfer the polar oxidation product DBTO₂ from the oil phase into the extraction phase, thereby achieving deep desulfurization.

3　Conclusions

收起

In this study, Mn doping was introduced into the Co-V-O system to significantly enhance desulfurization performance by modulating the oxygen vacancy concentration and electronic structure. Experimental results demonstrated that under the optimal conditions of a reaction temperature of 110 °C, catalyst dosage of 0.03 g, oxygen flow rate of 150 mL/min and 20 mL of model oil, a desulfurization rate of 81.6% could be achieved. Notably, when oxidative desulfurization was combined with extraction, the removal efficiency of DBT was further increased to 98.0%, significantly surpassing that of the undoped Co-V-O catalyst. These results indicated that Mn doping effectively increased the concentration of oxygen vacancy, thereby improving the catalytic desulfurization performance. Radical trapping experiments further confirmed that

$\cdot {\mathrm{O}}_2^- $

are generated in the presence of the catalyst and molecular oxygen, which played a crucial role in the efficient oxidation of DBT to DBTO₂.

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2026年第54卷第7期

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doi: 10.1016/S1872-5813(26)60658-5

接收时间：2025-11-18
首发时间：2026-09-23
出版时间：2026-07-10

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收稿日期：2025-11-18
修回日期：2025-12-16
录用日期：2026-01-06

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¹辽宁石油化工大学石油化工学院, 辽宁抚顺 113001

²山东金创金银冶炼有限公司, 山东烟台 265600

³辽宁石油化工大学理学院, 辽宁抚顺 113001

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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