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Tuning surface oxygen species via Mg-Ba co-doping on La2O3 to enhance oxidation coupling of methane performance
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Ke WANG1, 2, Qi ZHANG1, Pengyu NIU1, *, Minggui LIN1, *, Litao JIA1, Debao LI1, Riguang ZHANG2
Journal of Fuel Chemistry and Technology | 2026, 54(7) : 20250374-1273 - 20250374-1285
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Journal of Fuel Chemistry and Technology | 2026, 54(7): 20250374-1273-20250374-1285
• RESEARCH PAPER •
Tuning surface oxygen species via Mg-Ba co-doping on La2O3 to enhance oxidation coupling of methane performance
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Ke WANG1, 2, Qi ZHANG1, Pengyu NIU1, *, Minggui LIN1, *, Litao JIA1, Debao LI1, Riguang ZHANG2
Affiliations
  • 1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
  • 2State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
Published: 2026-07-10 doi: 10.1016/S1872-5813(26)60677-9
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Mg-, Ca-, Sr- and Ba-single-doped La2O3 as well as Mg-Ba co-doped La2O3 catalysts were synthesized via a hydrothermal method and evaluated for the oxidative coupling of methane (OCM). The experimental results revealed that the Mg-modified La2O3 catalyst activates O2 and CH4 effectively, yet achieves only moderate C2+ selectivity. Conversely, the Ba-modified analogue affords high C2+ selectivity, albeit at the expense of lower reaction activity. Notably, the Mg-Ba co-doped La2O3 catalyst strikes an effective balance between activity and selectivity, enhancing catalytic performance while maintaining a high C2+ selectivity. Specifically, at a Mg/Ba molar ratio of 1∶1 and 700 °C, it achieved a CH4 conversion of 29.5%, a C2+ selectivity of 54.5% and a corresponding C2+ yield of 16.1%.The characterization results indicate that Mg and Ba co-doped La2O3 catalysts promotes the formation of more ${\mathrm{O}}_2^- $ species on the catalyst surface, which in turn significantly enhances both the activity and selectivity of La2O3 catalysts.

oxidation coupling of methane  /  La2O3  /  Mg and Ba co-doped  /  ${\mathrm{O}}_2^- $ species
王珂, 张祺, 牛鹏宇, 林明桂, 贾丽涛, 李德宝, 章日光. Mg和Ba共掺杂调控氧化镧表面氧物种以增强其在催化甲烷氧化偶联反应中的性能. 燃料化学学报（中英文）, 2026 , 54 (7) : 20250374-1273 -20250374-1285 . DOI: 10.1016/S1872-5813(26)60677-9
Ke WANG, Qi ZHANG, Pengyu NIU, Minggui LIN, Litao JIA, Debao LI, Riguang ZHANG. Tuning surface oxygen species via Mg-Ba co-doping on La2O3 to enhance oxidation coupling of methane performance[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (7) : 20250374-1273 -20250374-1285 . DOI: 10.1016/S1872-5813(26)60677-9
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The increasing exploitation of unconventional natural gas resources, such as shale gas and coalbed methane, has investigated the demand for efficient, high-value utilization of methane (CH4)[1]. In general, CH4 conversion strategies are categorized into indirect and direct pathways. The indirect route typically involves the initial reforming of CH4 into synthesis gas (a mixture of CO and H2), which is then transformed into various high-value chemicals[2−4]. However, this multi-step process is often hampered by its complex infrastructure, high energy consumption, and suboptimal carbon atom economy. In contrast, the direct catalytic conversion of CH4 into target chemicals offers a more streamlined process with potentially higher efficiency and carbon utilization, presenting a promising frontier in catalysis[5]. Within this field, the oxidative coupling of methane (OCM) to C2+ hydrocarbons (C2+) has garnered significant research attention due to its conceptual simplicity and potential for direct production of valuable olefins and paraffins in a single step[6−8].
Since the seminal discovery of the OCM reaction in 1982, extensive research has been devoted to developing efficient catalytic systems[9−11]. These systems are broadly categorized into four categories: alkali metal/alkaline earth metal oxides (e.g., Li/MgO)[12], multi-component transition metal oxides (e.g., MnOx-Na2WO4/SiO2)[13−16], composite oxides (e.g., A2B2O7)[17−18], and rare earth oxides (e.g., La2O3)[19]. While Li/MgO catalysts offer the merits of compositional simplicity and high initial activity, they suffer from the volatility and leaching of lithium species, leading to rapid deactivation[20−21]. The benchmark MnOx-Na2WO4/SiO2 system delivers exceptional C2+ selectivity, but this performance typically requires reaction temperatures exceeding 800 °C. Under such harsh conditions, the sublimation of the Na2WO4 active component remains a critical challenge, severely limiting long-term stability[22−23]. Composite oxide catalysts exhibit superior structural and thermal robustness, resisting phase transitions at high temperatures. However, they are often hindered by lower C2+ selectivity due to a higher propensity for the complete oxidation of methane and desired C2 products[24−25]. In this landscape, rare earth oxides (particularly La2O3) have emerged as promising candidates. They present a balanced profile of high thermal stability and effective catalytic performance under comparatively milder conditions[26−29]. Nevertheless, achieving commercially viable C2+ yields over La2O3-based catalysts remains an ongoing research challenge, motivating further efforts in material design and optimization[30−32].
The OCM over La2O3 primarily involves two key steps: initial activation of CH4 on surface active sites to generate methane radicals (CH3·), followed by their gas-phase coupling to form C2+ hydrocarbon products. Studies have shown that surface oxygen species (such as O−, ${\mathrm{O}}_2^- $, ${\mathrm{O}}_2^{2-} $ and O2–) play a decisive role in directing activation of CH4 to form C2+ hydrocarbon products or COx[32−33]. Superoxide species (${\mathrm{O}}_2^- $) are recognized as crucial for selective C−H bond cleavage, directly abstracting a hydrogen atom from CH4 to yield methyl radicals[34−36]. This role of ${\mathrm{O}}_2^- $ has been corroborated in various catalytic systems, including barium halide-modified La2O3/CaO[37−38], La2Ce2O7[35] and Mn2O3-Na2WO4 supported on CexZr1−xO2[34]. When peroxide species (${\mathrm{O}}_2^{2-} $) interact with CH4, one of its oxygen atoms inserts directly into a C−H bond of CH4, forming a methanol intermediate[39]. However, under typical OCM reaction temperatures, methanol is very easily overoxidized to CO2, leading to complete oxidation via this pathway. Theoretical calculations by Wang et al.[39] suggest that the presence of peroxide species (${\mathrm{O}}_2^{2-} $) limits the C2+ selectivity on La2O3 to only 67%. Although not directly detected experimentally, atomic oxygen anions (O−) are theorized to form at defect sites on La2O3, though their precise role in CH4 oxidation remains ambiguous. Lattice oxygen (O2–) species on La2O3 generally exist in two forms: fully coordinated oxygen bound to lanthanum ions, and coordinatively unsaturated lattice oxygen. The interaction of CH4 with surface lattice oxygen (O2–) of the catalyst predominantly leads to the deep oxidation. Therefore, the regulation of oxygen species has become a focus in OCM. Doping L2O3 with foreign metals is an effective strategy to modulate oxygen species and enhance catalytic performance[40−41]. In particular, alkaline earth metal-doped lanthanum-based catalysts can significantly enhance their OCM reaction performance. Kiatsaengthong et al.[42] reported that Mg, Ca, Sr and Ba-activated La2O3 catalysts can boost the C2 selectivity by increasing the number of surface superoxide species (${\mathrm{O}}_2^{2-} $). Xiong et al.[43] studied the effects of Li, Mg, Zn and Ce-doped La2O3 nanorods on the OCM and found that Mg2+ doping generates oxygen vacancies, thereby promoting the formation of more surface oxygen species and enhancing C−C bond coupling.
Co-doping lanthanum oxides with multiple metals has recently emerged as a promising strategy to enhance catalytic performance for the oxidative coupling of methane (OCM) by harnessing synergistic effects between dopants. For instance, Ptrolini et al.[44] demonstrated in Mg- and Ce-modified La2(Ce1−xMgx)2O7-δ catalysts that Mg incorporation modulates reducibility, stabilizes Ce3+ species, and creates basic sites, collectivelyleading to superior C2+ selectivity at lower temperatures. Sollier et al.[45] reported that introducing Sr into LaxCeyOz solid solutions could promote the formation of structural defects, thereby enhancing the generation of superoxide species (${\mathrm{O}}_2^- $).This ultimately achieved a C2+ yield of 21.7% at 600 °C. Wu et al.[46] reported that co-doping of Ca and Sr in La2Ce2O7 could increase surface oxygen vacancies, which elevated the density of surface active oxygen species (${\mathrm{O}}_2^- $), resulting in a C2 product yield of 21.3% at 650 °C. However, the influence of alkaline-earth metal co-doping on OCM performance over lanthanum-based catalysts, as well as the underlying mechanism regulating the formation of superoxide species (${\mathrm{O}}_2^- $), remains inadequately understood.
In this work, a series of La2O3-based catalysts modified by single (Mg, Ca, Sr or Ba) and co-doping (Mg and Ba) were prepared by a hydrothermal method. The co-doping strategy, particularly the incorporation of Mg and Ba, was found to significantly enhance both the catalytic activity and C2+ selectivity for OCM. To gain mechanistic insights into this performance improvement, the structural and chemical properties of the catalysts were interrogated using a combination of characterization techniques. Specifically, O2/H2-TPR, in situ FT-IR and O2 pulse experiments were employed to systematically probe the dynamic activation of CH4 and O2 as well as the nature and evolution of surface oxygen species on catalysts under relevant conditions. This study clarifies the enhanced oxygen storage and activation behavior and elucidates the synergistic effect of Mg-Ba co-doping in La2O3, offering fundamental insights for the rational design of highly active and selective OCM catalysts.
1　Experimental
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1.1　Catalyst preparation
The La2O3 catalysts co-doped with Mg and Ba were synthesized via a hydrothermal-calcination method. Specifically, 18 g of NH4HCO3 was dissolved in 480 mL of ethylene glycol under vigorous stirring for 60 min. Separately, La(CH3COO)3, Ba(CH3COO)2 and Mg(CH3COO)2 (the molar ratio of La(CH3COO)3, Ba(CH3COO)2 and Mg(CH3COO)2 was 20∶0.5∶0.5, with a total amount of 0.04 mol) were dissolved in 480 mL of deionized water. This aqueous solution was then slowly added dropwise to the NH4HCO3/ethylene glycol solution. After stirring at 25 °C for 30 min, the mixture was transferred into a 200 mL Teflon-lined autoclave and maintained at 180 °C for 24 h. The resulting precipitate was collected by centrifugation, washed thoroughly with deionized water and absolute ethanol, and dried at 60 °C overnight. Finally, the dried precursor was calcined in air at 800 °C for 4 h to obtain the catalyst. After cooling to room temperature, the catalyst labeled as LaMg0.025Ba0.025 was obtained (subscripts represent the molar ratio of elements). In addition, catalysts with alternative La∶Mg∶Ba ratios of 20∶0.2∶0.8 and 20∶0.8∶0.2 were also synthesized, denoted as LaMg0.04Ba0.01 and LaMg0.01Ba0.04. A set of single M-doped La2O3 samples (M = Mg, Ca, Sr, Ba) were prepared with an M∶La molar ratio of 0.05∶1 and are labeled LaM0.05. Pure La2O3 (La) was obtained using the same procedure with only lanthanum acetate (0.04 mol).
1.2　Catalyst characterization
The morphology of the catalysts was characterized by scanning electron microscopy (SEM) on a JSM-7001F scanning electron microscope with a voltage of 5 kV.
The phase of the catalysts was determined by a PANalytical X'pert3 X-ray diffraction analyzer using a Cu target, Kα radiation (wavelength λ=0.154 nm), tube current of 50 mA, tube voltage of 50 kV, and a scanning rate of 10(°)/min.
Nitrogen adsorption-desorption isotherms of the catalysts were obtained on a Micromeritics ASAP 2460 physical adsorption analyzer.
XPS testing was performed using an AIX ULTRAADLD X-ray photoelectron spectrometer. The spectra were charge-corrected using the C 1s signal located at 284.5 eV. The O 1s spectra of all samples were fitted using XPSPEAK41 software, and the peaks were resolved using an 80% Gaussian-20% Lorentzian model function. The full width at half maximum (FWHM) of all O 1s spectra was approximately 2 eV.
O2/H2-TPR testing was conducted using an AMI300 fully automatic chemisorption analyzer. The sample (0.05 g) was first pretreated in a 10% H2/Ar (volume fraction) at 800 °C for 30 min, then exposed to a 10% O2/Ar (volume fraction) at 550, 650 or 750 °C for 30 min, subsequently cooled to 50 °C, switched to Ar purging, and finally heated to 850 °C in a 10% H2/Ar (volume fraction).
In situ DRIFT was performed on a Nicolet iS10 infrared spectrometer, collecting 128 scans at a resolution of 4 cm−1. The sample was pretreated in H2 at 680 °C for 10 min, then cooled to 550 °C in Ar. After 10 min, a background spectrum was collected in Ar. Then, a 5% O2/Ar (volume fraction) was introduced into the reaction cell, and infrared spectral signals were collected at 550 °C (infrared spectra were labeled as 0, 1, 2, 3, 4, 5 min according to sampling time). Subsequently, the sample was pretreated in H2 at 680 °C for 10 min, then cooled to 650 °C in Ar. After running in Ar for 10 min, a background spectrum was collected. A 5% O2/Ar gas mixture was introduced into the reaction cell, and spectra were collected at 650 °C(infrared spectra were labeled as 0, 1, 2, 3, 4, 5 min according to sampling time).
O2-TPD experiments were performed on AutoChem II chemisorption analyzer. The catalyst (0.1 g) was treated with 10% O2/Ar (volume fraction, 30 mL/min) at 800 °C for 30 min, and cooled to 50 °C in 10% O2/Ar. At 50 °C, the gas was switched to Ar and purged for 60 min to flatten the baseline. Finally, the temperature was raised to 800 °C under Ar. Results were recorded by a mass spectrometer (MS, IPI GAM200).
O2 pulse experiments were performed on AutoChem II chemisorption analyzer. The catalyst (0.1 g) was treated with H2 (30 mL/min) at 700 °C for 30 min to remove oxygen species, then switched to Ar for 30 min purging. Subsequently, 5% CH4 (volume fraction, 30 mL/min) was turned on, and 10 pulses of 5% O2 (volume fraction) were performed at 5 min intervals. Results were recorded by a mass spectrometer (MS, IPI GAM200).
1.3　Catalyst evaluation
The performance of the catalysts was evaluated in a fixed-bed quartz reactor (inner diameter 8 mm) with a feed gas of CH4∶O2=3∶1 (CH4 flow rate: 100 mL/min, O2/N2 flow rate: 66 mL/min) at a space velocity of 80000 mL/(g·h). 0.1 g of catalyst (40−60 mesh) and quartz sand were mixed uniformly to a volume of 0.5 mL and placed in the constant temperature zone of the reactor. Prior to the reaction, the catalyst was pretreated in N2 at 800 °C for 2 h, then cooled to 550 °C. Catalytic activity was measured while increasing the temperature from 550 to 800 °C. A chromatograph (Agilent 7890B) equipped with TCD and FID detectors was used for online analysis of feed gas and products.
CH4 conversion ($x_{{\mathrm{CH_4}}} $), O2 conversion ($x_{{\mathrm{O_2}}} $), C2+ selectivity ($s_{{\mathrm{C}}_{2+}} $), and C2+ yield ($Y_{{\mathrm{C}}_{2+}} $) were calculated with the following equations：
$ {{x}}_{{{\mathrm{CH}}_{\text{4}}}}=\frac{{\text{CH}}_{\text{4, in}}-{\text{CH}}_{\text{4,out}}}{{\text{CH}}_{\text{4,in}}}{\times 100\%} $
$ {{x}}_{{{\text{O}}_{\text{2}}}}=\frac{{\text{O}}_{\text{2,in}}-{\text{O}}_{\text{2,out}}}{{\text{O}}_{\text{2,in}}}{\times 100\%} $
${{s}}_{{{\text{C}}_{\text{2+}}}}\text=\frac{\rm{2 \times }\left({\rm{C}}_{\rm{2}}{\rm{H}}_{\rm{4}}\rm+{\rm{C}}_{\rm{2}}{\rm{H}}_{\rm{6}}\right)\rm{+3 \times }\left({\rm{C}}_{\rm{3}}{\rm{H}}_{\rm{6}}\rm+{\rm{C}}_{\rm{3}}{\rm{H}}_{\rm{8}}\right)\rm{+4 \times }\left({\rm{C}}_{\rm{4}}{\rm{H}}_{\rm{8}}\rm+{\rm{C}}_{\rm{4}}{\rm{H}}_{\rm{10}}\right)}{\rm{2 \times }\left({\rm{C}}_{\rm{2}}{\rm{H}}_{\rm{4}}\rm+{\rm{C}}_{\rm{2}}{\rm{H}}_{\rm{6}}\right)\rm{+3 \times }\left({\rm{C}}_{\rm{3}}{\rm{H}}_{\rm{6}}\rm+{\rm{C}}_{\rm{3}}{\rm{H}}_{\rm{8}}\right)\rm{+4 \times }\left({\rm{C}}_{\rm{4}}{\rm{H}}_{\rm{8}}\rm+{\rm{C}}_{\rm{4}}{\rm{H}}_{\rm{10}}\right)\rm{+CO+}{\rm{CO}}_{\rm{2}}} \times 100\% $
$ {{Y}}_{{{\text{C}}_{\text{2+}}}}={{x}}_{{{\text{CH}}_{\text{4}}}}{\times}{{s}}_{{{\text{C}}_{\text{2+}}}}\times 100\% $
2　Results and discussion
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2.1　Reaction performance
Figure 1 presents the OCM reaction performance of Mg, Ca, Sr and Ba doped La2O3 catalysts within the temperature range of 550−800 °C. The undoped La2O3 catalyst reaches its optimal performance at 750 °C, with CH4 and O2 conversions of 30.4% and 95.1%, respectively and a C2+ selectivity of 48.3%. For alkaline earth metal Mg, Ca, Sr and Ba doped La2O3 catalysts, a clear trend was observed: the light-off temperature gradually increased with the ionic radius of the dopant. At 600 °C, the order of activity for both O2 and CH4 conversion was LaMg0.05 > LaCa0.05 > LaSr0.05 > LaBa0.05. This sequence indicates that Mg doping significantly enhances the O2 activation capability of La2O3, leading to improved CH4 conversion. Conversely, the C2+ selectivity showed an opposite trend, increasing with the size of the dopant cation. LaBa0.05 exhibited the highest C2+ selectivity, which was 6.7% higher than that of undoped La2O3 catalyst at 750 °C. However, this gain in selectivity came at the cost of lower activity at 700 °C, LaBa0.05 showed conversions of only 20.2% for CH4 and 59.0% for O2. These results indicate that while Ba doping promotes C2+ formation, it concurrently weakens the catalyst's oxygen activation capacity, necessitating higher operating temperatures to achieve a competitive C2+ yield. Motivated by the complementary properties of Mg-doped La2O3 (strong O2 activation) and Ba-doped La2O3 (high C2+ selectivity), this study investigates the synergistic integration of both dopants into La2O3, aiming to concurrently achieve high CH4 conversion and C2+ selectivity under relatively mild reaction conditions. As illustrated in Figure 2, the catalytic properties showed a clear dependence on the Mg/Ba molar ratio. Specifically, with an increasing Mg/Ba molar ratio, the C2+ selectivity progressively increased, while the activation capability for both O2 and CH4 concurrently decreased. The catalyst with an equimolar Mg/Ba ratio (LaMg0.025Ba0.025) demonstrated balanced and superior performance at 700 °C, achieving a CH4 conversion of 29.5% and a C2+ selectivity of 54.5%. This represents a 6% enhancement in C2+ selectivity compared to the solely Mg-doped counterpart (LaMg0.05) and an 11% improvement in CH4 conversion relative to the solely Ba-doped catalyst (LaBa0.05) at the same temperature. Therefore, the synergistic co-doping of Mg and Ba into La2O3 successfully reconciled the trade-off between activity and selectivity at 700 °C, yielding a substantially higher C2+ yield. In addition, the long-term stability of the optimal LaMg0.025Ba0.025 catalyst was evaluated under industrially relevant, high-severity conditions (GHSV = 80000 mL/(g·h)). As shown in Figure 3(a), the catalyst maintained exceptionally stable CH4 conversion and C2+ selectivity over the 24 h test, showing its robustness, which is crucial for the OCM reaction.
The composition distribution of C2+ products over the LaMg0.025Ba0.025 catalyst was analyzed as a function of temperature (Figure 3(b)). Below 700 °C, the products were mainly C2 hydrocarbons (C2H4 and C2H6), with no C3+ products detected. As the temperature increased, longer-chain C3+ products began to form, and their selectivity gradually increased. The ratio of C2H4/C2H6 in C2 hydrocarbon products (Figure 3(c), (d)) continued to increase with temperature, indicating that higher temperatures promote the dehydrogenation of C2H6, thereby favoring the formation of the higher-value product, C2H4.
2.2　Catalyst structure
Figure 4 shows the XRD patterns of alkaline earth metal doped La2O3 catalysts. All diffraction patterns for both single-doped (Mg, Ca, Sr, Ba) and co-doped (Mg-Ba) catalysts correspond exclusively to the hexagonal phase of La2O3 (PDF#05-0602)[43]. No diffraction peaks corresponding to oxides or carbonates of the doped elements were observed, indicating high dispersion of the alkaline-earth metals within the La2O3. A comparison of the XRD patterns revealed that the diffraction peak of La2O3 (101) crystal plane corresponding to Mg and Ca single-doped La2O3 catalysts shifted toward higher angles. This shift results from the smaller ionic radii of Mg2+ (0.072 nm) and Ca2+ (0.100 nm) compared with La3+ (0.103 nm), which induce lattice contraction and a reduction in the interplanar spacing. In contrast, the (101) peak shifts to lower angles for the Sr- and Ba-doped samples due to the larger ionic radii of Sr2+ (0.118 nm) and Ba2+ (0.135 nm), leading to lattice expansion. The above analysis confirms that the successful incorporation of the dopant ions into the La2O3 lattice. Furthermore, the magnitude of the shift increased with the atomic radius of the dopant. A similar trend was observed in the co-doped samples, with LaMg0.025Ba0.025 exhibiting the most pronounced shift toward lower angles, suggesting the formation of a greater number of structural defects.
Figure 5 shows SEM images of La, LaMg0.05, LaBa0.05, LaMg0.04Ba0.01, LaMg0.01Ba0.04 and LaMg0.025Ba0.025 catalysts. The undoped La2O3 catalyst exhibited a well-defined triangular flake morphology. Upon doping with alkaline earth metals, all modified catalysts LaMg0.05, LaBa0.05, LaMg0.04Ba0.01, LaMg0.01Ba0.04 and LaMg0.025Ba0.025 retained the characteristic triangular lamellar morphology, indicating that alkaline earth metal doping treatment does not affect the fundamental morphology of the catalysts. However, the doped catalyst exhibited a more open, loosely packed lamellar structure with a developed microporous texture, which is expected to facilitate reactant diffusion and enhance mass transport during the reaction.
The specific surface area and pore volume of the catalysts were determined, and the results are shown in Table 1. Compared to pure La2O3, the alkaline-earth-metal-doped catalysts showed increased specific surface area and pore volume. A larger specific surface area can expose more surface active sites[46], which is beneficial for catalytic reactions.
2.3　Characterization of surface oxygen species
The reducibility of adsorbed oxygen species on Mg- and Ba-doped La2O3 catalysts was analyzed by O2/H2-TPR. All catalysts were first reduced in H2 to remove oxygen species adsorbed, followed by exposure to O2 at different temperatures (550, 650 and 750 °C) to (re)adsorb oxygen. Afterward, H2 temperature-programmed reduction was performed, and the amount of reducible oxygen species was quantified based on the H2 consumption peaks. The characterization results are shown in Figure 6. All catalysts showed three distinct H2 consumption peaks, corresponding to the reduction of different oxygen species: a low-temperature H2 consumption peak (200–300 °C) assigned to the reduction of oxygen species adsorbed on the catalyst surface; a medium-temperature H2 consumption peak (300–500 °C) attributed to the reduction of oxygen species oxygen migrating from the near-surface region; and a high-temperature H2 consumption peak above 500 °C associated with the reduction of bulk-phase oxygen species diffusing to the surface. With increasing O2 pretreatment temperature, the areas of the low- and medium-temperature H2 consumption peaks gradually increased, indicating that the number of reducible oxygen species on its surface and near-surface layer increased with O2 pretreatment temperature.
This trend indicates an enhanced ability of catalysts to adsorb and activate O2 at elevated temperatures. Moreover, this trend correlates well with the observed increase in O2 conversion with temperature, suggesting that the abundance of active oxygen species is a key factor governing O2 conversion, which in turn drives CH4 conversion. Furthermore, as the O2 treatment temperature increased, the high-temperature H2 consumption peak of the LaMg0.05 catalyst moved toward lower temperatures, suggesting that bulk phase oxygen migrated to the sub-surface layer and merged with near-surface oxygen species, which reflects its strong capacity for O2 dissociation and explains its highest O2 conversion at 600 °C. In contrast, the LaBa0.05 catalyst had a relatively weak ability to dissociate O2, thus resulting in the lowest O2 conversion at 600 °C. The relatively weak O2 dissociation capacity of the LaBa0.05 catalyst may be associated with enhanced C2+ selectivity, as dissociated oxygen species frequently lead to the complete oxidation of CH4[44]. In Mg and Ba co-doped La2O3 catalysts, as the O2 pretreatment temperature increased, the phenomenon of oxygen species in the bulk phase migrating to the sub-surface layer was also observed. Especially under the O2 pretreatment condition of 750 °C, the high-temperature H2 consumption peaks of LaMg0.04Ba0.01 and LaMg0.025Ba0.025 catalysts merged with the medium-temperature H2 consumption peaks. This feature indicates that LaMg0.04Ba0.01 and LaMg0.025Ba0.025 catalysts possess excellent capabilities in activating O2 and generating active oxygen species, thus enabling high O2 conversion and CH4 conversion at a reaction temperature of 700 °C.
The effects of single-doping (with Mg or Ba) and co-doping (with Mg and Ba) modifications on the surface oxygen species of La2O3 catalysts were investigated by O2-TPD, as shown in Figure 7. All catalysts displayed distinct O2 desorption peaks in the range of 200–300 °C, which are ascribed to chemisorbed oxygen species, such as superoxide (${\mathrm{O}}_2^{-} $) and peroxide (${\mathrm{O}}_2^{2-} $) ions[18,38,46]. Comparing the O2 desorption profiles of Mg and Ba single-doped and co-doped La2O3 catalysts, the O2 desorption peak of Mg-modified La2O3 was broad, suggesting the presence of multiple types of chemisorbed oxygen species on its surface. The Ba-modified sample presented a sharp desorption peak, indicating the formation of a more uniform type of chemisorbed oxygen species on its surface. When Mg and Ba were co-doped at a 1∶1 molar ratio (LaMg0.025Ba0.025), the desorption peak became broader and its intensity increased. Correlating with catalyst performance, the Mg and Ba co-doped LaMg0.025Ba0.025 catalyst achieved 96.3% O2 conversion at 700 °C, whereas LaMg0.05 and LaBa0.05 required 750 °C to exceed 95% O2 conversion. This indicates that the Mg and Ba co-doping enhanced the activation capacity for O2, significantly increasing both the type and quantity of surface chemisorbed oxygen species. It should be noted that the desorption peaks in this temperature regime may encompass both superoxide (${\mathrm{O}}_2^{-} $) and peroxide (${\mathrm{O}}_2^{2-} $) species, whose similar thermal stabilities make their precise deconvolution challenging[47].
The surface oxygen species distributions of La2O3 catalysts, modified by single (Mg or Ba) and co-doping (Mg-Ba), were analyzed via XPS, with results presented in Figure 8 and Table 2. The O 1s spectra can be deconvoluted into three characteristic peaks, corresponding to ${\mathrm{O}}_2^{-} $ (532 eV), ${\mathrm{CO}}_3^{2-} $ (531 eV), and O2− (529 eV) respectively[18,26,35]. Moreover, the quantitative results of surface oxygen species indicate that the concentration of ${\mathrm{O}}_2^{-} $ is significantly enhanced in Mg and Ba co-doped La2O3 catalysts, with the LaMg0.025Ba0.025 catalyst exhibiting the highest ${\mathrm{O}}_2^{-} $ concentration. However, XPS analysis cannot reflect the true surface state of the catalyst under high-temperature reaction conditions. Moreover, La-based catalysts easily adsorb CO2 and H2O to generate carbonates and hydroxyl groups, which seriously interfere with the O 1s signal and compromise the accuracy of active-oxygen quantification. Therefore, to investigate reactive oxygen species under reaction conditions, in situ DRIFT experiments were conducted.
In situ DRIFT was employed to further investigate the types of surface active oxygen species on La-based catalysts, and the results are shown in Figure 9. Both Mg and Ba single-doped and co-doped La2O3 catalysts exhibit an infrared band at approximately 1100 cm−1, which is assigned to surface superoxide species (${\mathrm{O}}_2^- $)[43]. In contrast, undoped La2O3 exhibits no detectable signal for surface superoxide species (${\mathrm{O}}_2^- $). As the temperature of the O2 treatment increased, the intensity of the band at 1100 cm−1 enhanced, indicating that the amount of superoxide species (${\mathrm{O}}_2^- $) generated on the catalyst increased with rising temperature. This trend correlates with the temperature-dependent increase in C2+ selectivity observed for these catalysts, further confirming that superoxide species (${\mathrm{O}}_2^- $) serve as the active oxygen species in the reaction. Specifically, for the LaMg0.025Ba0.025 catalyst, both the intensity of the ${\mathrm{O}}_2^- $ signal and the C2+ selectivity increased with temperature, with the latter rising from 3% to 52%. Doping with either Mg or Ba effectively promotes the formation of superoxide species (${\mathrm{O}}_2^- $) on the La2O3 surface. Notably, the signal for superoxide species (${\mathrm{O}}_2^- $) of LaBa0.05 was significantly stronger than that of LaMg0.05. This may be attributed to the strong charge-induced dipole interaction between Ba with a larger ionic radius and superoxide species (${\mathrm{O}}_2^- $), which can stabilize superoxide species (${\mathrm{O}}_2^- $)[48]. Importantly, compared to single-doped catalysts, the signal for superoxide species (${\mathrm{O}}_2^- $) was markedly enhanced in Mg and Ba co-doped La2O3 catalyst, demonstrating a synergistic effect of Mg and Ba in promoting the formation of superoxide species (${\mathrm{O}}_2^- $).
As evidenced by the O2/H2-TPR results, the co-doping of Mg and Ba significantly enhances the activation and dissociation of O2 on the La2O3 catalyst. Consequently, this co-doping strategy not only increases oxygen vacancies on the La2O3 catalyst, thereby promoting oxygen activation, but also significantly elevates the concentration of superoxide species (${\mathrm{O}}_2^- $) present on the catalyst surface. Combined with catalytic performance, the LaMg0.025Ba0.025 catalyst exhibited the highest C2+ selectivity of 52.4%, while the C2+ selectivity of other catalysts was lower than 50% at 700 °C. This indicates that the presence of superoxide species (${\mathrm{O}}_2^- $) is closely related to the C2+ selectivity.
2.4　Effect of surface oxygen species on OCM reaction
CH4/O2 pulse experiments were conducted to investigate the formation of surface oxygen species and their efficacy in activating CH4 to form C2H4. The variation in CH4 consumption under pulsed O2 at 700 °C is shown in Figure 10. Prior to O2 pulse, the catalyst was pretreated with H2 to remove adsorbed oxygen species. During the subsequent O2 pulses, oxygen species were progressively adsorbed, gradually establishing an equilibrium distribution between the surface and the bulk phase. All samples exhibited a similar two-stage response in CH4 signal intensity: as the number of O2 pulses increased, the CH4 signal intensity first gradually increased, and then tended to stabilize. The initial increase in CH4 signal intensity corresponds to the accumulation of surface active oxygen species on the catalyst, whereas the subsequent plateau of CH4 signal intensity indicates that adsorption equilibrium has been reached. LaBa0.05 required five O2 pulses to reach a stable CH4 signal, while La, LaMg0.05 and LaMg0.025Ba0.025 require three O2 pulses to achieve equilibrium CH4 signal intensity. The Mg and Ba co-doped catalyst LaMg0.025Ba0.025 achieved 86% of the equilibrium intensity in the CH4 signal during the first oxygen pulse, indicating that this catalyst promotes O2 activation and rapidly establishes adsorption equilibrium of oxygen species on both the catalyst surface and bulk phase.
The C2H4 generation profiles of the catalysts following O2 pulses at 700 °C is shown in Figure 11. The signal intensity of C2H4 also presented a trend of initial increase followed by stabilization as the number of O2 pulses increased. A detailed comparison revealed that the C2H4 signal for LaBa0.05 stabilized at the 4th O2 pulse, whereas that for LaMg0.05 required until the 5th pulse. Combined with in situ DRIFT (Figure 9) results, which showed a higher concentration of ${\mathrm{O}}_2^- $ species on LaBa0.05 than on LaMg0.05, this further supports the governing role of superoxide species (${\mathrm{O}}_2^- $) in the formation of C2+ products. Notably, no C2H4 was detected for LaBa0.05 and LaMg0.05 catalysts in the first O2 pulse. This is attributed to the limited amount of ${\mathrm{O}}_2^- $ available during the first pulse, which favors the complete oxidation of CH4 to CO2. The resulting CO2 is strongly adsorbed by the basic catalyst surface, explaining its absence in the gas-phase detection. It is worth noting that for the LaMg0.025Ba0.025 catalyst, the C2H4 signal intensity reached 81% of the equilibrium intensity during the first O2 pulse, which was significantly superior to other catalysts. This indicates that LaMg0.025Ba0.025 facilitates the generation of superoxide species (${\mathrm{O}}_2^- $) more readily, further verifying the in situ FT-IR results.
2.5　Activation of O2 and CH4 on La2O3 catalyst
The surface activation of O2 proceeds through reactive intermediates such as superoxide (${\mathrm{O}}_2^- $) and dissociated oxygen species (O− or O2−)[46]. Mg doped La2O3 promotes the activation of O2 on the catalyst surface. However, excessive O2 activation capacity led to the formation of a large quantity of dissociated oxygen species (O−), which promote the over-oxidation of CH4 to COx and consequently lower the C2+ selectivity. The Ba doped La2O3 catalyst possesses a weaker O2 activation ability, yet the dopant interacts favorably with superoxide species (${\mathrm{O}}_2^- $), stabilizing them on the surface. This results in a higher surface concentration of ${\mathrm{O}}_2^- $, which selectively promotes the formation of C2+ products. When Mg and Ba are co-doped, the activation of O2 toward superoxide species (${\mathrm{O}}_2^- $) is further enhanced, increasing the surface concentration of this selective oxygen species (Figure 12). Consequently, the Mg-Ba co-doped La2O3 catalyst achieves superior C2+ selectivity (54.5%) at a relatively mild temperature of 700 °C, outperforming both singly doped La2O3 catalysts.
3　Conclusion
Less
In this study, La2O3 catalysts single-doped with alkaline earth metals (Mg, Ca, Sr, Ba) and co-doped with Mg and Ba were prepared via a hydrothermal method, and their structure, catalytic performance, and oxygen species were systematically investigated. In situ DRIFTS revealed the presence of superoxide species (${\mathrm{O}}_2^- $) on the surface of both Mg- and Ba-doped catalysts, with the co-doped system exhibiting a significantly more intense signal for the superoxide species ${\mathrm{O}}_2^- $. This indicates a synergistic effect between Mg and Ba in promoting the formation and stabilization of these key reactive intermediates. O2/H2-TPR studies revealed that Mg and Ba co-doped La2O3 catalysts exhibit superior O2 activation capabilities compared to those doped with Mg or Ba alone. Furthermore, CH4/O2 pulse experiments revealed that the co-doped catalysts facilitate faster establishment of oxygen adsorption equilibrium, thereby enhancing CH4 activation and the subsequent formation of C2 products. This work establishes that co-doping La2O3 with Mg and Ba represents an effective strategy for improving catalytic performance in the oxidative coupling of methane (OCM), primarily by modulating the generation and stabilization of key active oxygen species.
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Year 2026 volume 54 Issue 7
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doi: 10.1016/S1872-5813(26)60677-9
  • Receive Date：2025-11-20
  • Online Date：2026-09-23
  • Published：2026-07-10
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  • Received：2025-11-20
  • Revised：2025-12-23
  • Accepted：2026-01-12
Affiliations
    1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
    2State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

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表12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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