Low-temperature Oxidation Research Articles

Experimental and kinetic modeling study of 1,3,5-trimethylbenzene oxidation at elevated pressure

This work presents the experimental and modeling results of 1,3,5-trimethylbenzene (T135MB) oxidation in a jet-stirred reactor at equivalence ratios (Φ) of 0.4 and 2.0, temperature range of 660–1020 K and pressure of 12.0 atm. 5 aromatic compounds, 5 oxygenated species and 6 light hydrocarbons were identified and quantified using GC and GC-MS. Compared with previous oxidation studies, 1-ethyl-3,5-dimethylbenzene, 3,5-dimethylbenzaldehyde, 3,5-dimethylphenol, ethylene and acetylene were newly detected. A detailed chemical kinetic model involving 911 species and 5370 reactions was developed and validated against experimental results of T135MB oxidation speciation at jet-stirred reactor and shock tube, laminar burning velocities and ignition delay times. Rate-of-production analysis shows that the dominant consumption channel of T135MB is H-abstraction by OH radicals on methyl sites, and 3,5-dimethylbenzaldehyde is a key intermediate in the oxidation of T135MB. Compared with atmospheric pressure, sharp consumption of T135MB was observed (the fuel conversion rate changes from 25 % at 838 K to 95 % at 839 K) under fuel-lean condition at 12 atm, which results from the rapid growth of OH radicals controlled by H2O2(+M) = 2OH(+M). Sensitivity analysis reveals that H-abstraction reactions of T135MB by OH and H on methyl sites are the most inhibiting reactions at Φ = 0.4 and 2.0, respectively, when T135MB conversion rate is 25 %. However, these two reactions become promoting at 95 % T135MB conversion. The H-abstraction reaction of T135MB with O2 on methyl sites is the most promoting at 25 % T135MB conversion, shifting to an inhibiting reaction at 95 % conversion.Novelty and significance statement: The novelty of this research is that high-pressure and low-temperature oxidation experiment of T135MB covering both fuel-lean and fuel-rich conditions was first reported in this work with abundant intermediates information. Rapid consumption of T135MB under fuel-lean condition was observed, and new intermediates such as 3,5-dimethylbenzaldehyde were detected which plays an important role in the fuel conversion. Additionally, a comprehensive kinetic model for T135MB was developed, which well predicts speciation, ignition delay times and laminar flame speeds under wide range of conditions. It is significant because the high pressure data is very important for the model validation since it is more close to the real engine-operating conditions. Moreover, the model provides insight on the high pressure chemical kinetics of the aviation surrogate fuel consumption and deepens the understanding of low-temperature oxidation of alkyl aromatics.

The effects of grafted multiple phenolic antioxidants onto polymethacrylate type pour point depressants on the low-temperature flowability and oxidation stability of biodiesel blends

The enhancement of cold flow properties (CFPs) and oxidative stability (OS) in biodiesel-diesel blends typically involves the use of pour point depressants and antioxidants. However, a scant number of additives are capable of manifesting both pour point depression and antioxidant functionalities concurrently. This study explored the grafting of syringic acid (SA), 3,5-di-tert-butyl-4-hydroxybenzoic acid (DTBHA), and gallic acid (GA) onto polymethacrylate (PMA) type copolymers, culminating efficacious copolymers, namely PTG-SA, PTG-DTBHA and PTG-GA. The findings reveal that with the addition of 1500 ppm of PTG-GA, the CFPP and PP of B20 (20 vol% soybean biodiesel+80 vol% diesel) decrease by 10 and 18 °C respectively, and with the addition of 2000 ppm, the induction period (IP) of B20 can be extended from 1.34 to 8.69 h. In contrast, the application of PTG-SA and PTG-DTBHA to B20 led to inferior OS and CFPs as compared to PTG-GA. The inherent scientific mechanism that underlies this performance discrepancy was thoroughly investigated, scrutinizing it through the lens of co-crystallization and nucleation processes. This research underscores the potential of post-modification of PMA type pour point depressants with antioxidants, a strategy that not only bolsters the CFPs of B20 but also confers antioxidant attributes to the pour point depressants.

Experimental and kinetic modeling study of iso-propylamine oxidation with SVUV-time of flight mass spectrometry

Atmospheric oxidation experiments of iso-propylamine (IPA) were conducted in a jet-stirred reactor over the temperature range from 550 to 870 K at fuel-equivalence ratios of 0.5 and 2.0. A combination of synchrotron vacuum ultraviolet (SVUV) photoionization and time-of-flight mass spectrometry (TOFMS) was utilized to identify and quantify oxidation products and intermediates. Compared to the previous n-propylamine (NPA) low-temperature oxidation [Proc. Combust. Inst., 39 (2023) 295–303.], some intermediates and products were newly observed among the 34 detected species, including nitrosyl hydride, methylamine, acetonitrile, nitrous oxide, ethyl isocyanide, propanenitrile, 2-propanimine, n-methylformamide and 2-methylallylamine. A kinetic model consisting of 815 species and 4402 reactions was developed based on the iso-propanol model [Prog. Energy Combust. Sci. 67 (2018) 31–68.] and an ethylamine model [Prog. Energy Combust. Sci. 44 (2014) 40–102.]. The onset temperature of IPA and O2 consumption is 750 K under both lean and rich conditions. Rate-of-production (ROP) and sensitivity analyses were performed at 800 K to illustrate the reacting paths from parent fuel to major intermediates and products, and identify the most sensitive reactions. H2O2(+M) = 2OH(+M) is the most sensitive reaction with a promoting effect on IPA consumption while 2HO2 = H2O2+O2 is the most inhibiting one. Important N-containing pollutants like NH3, NOx, HCN, CH3NH2 and so on were analyzed with respect to their reaction routes. (CH3)2CNH is abundant due to the H-abstraction reactions between tC3H6NH2 radical with O2. This work was made for gaining a more comprehensive insight into the oxidation of IPA and make a foundation for further exploring amine chemistry.

Influence of mudstone on coal spontaneous combustion characteristics and oxidation kinetics analysis

To explore the spontaneous combustion characteristics and hazards of the low-temperature oxidation (LTO) stage in the process of spontaneous combustion of coal and mudstone, the pore structure, spontaneous combustion characteristic parameters, and exothermic characteristics of coal and mudstone were tested and studied, and the oxidation kinetic parameters were calculated. The results show that mudstone has a larger specific surface area and pore volume than coal. From the fractal characteristics, the pore structure of mudstone is more complex than that of coal. According to the comparison of theoretical and actual gas generation and oxygen consumption rate curves, it is found that there is an interaction between coal and mudstone in the LTO process. With the increase of mudstone mass ratio, gas production, and its oxygen consumption rate increase. Among them, CM-4 (Coal:Mudstone = 1:1) has the highest exothermic intensity and the exothermic factor (A) and fire coefficient (K) increase with the increase of mudstone content. The apparent activation energy of the mudstone sample is lower than that of the raw coal, indicating that the sample after adding mudstone is more likely to have spontaneous combustion in the LTO stage.

Promoting intermediates transformation by boosting H2O dissociation over core-shell Pd@CoO Janus for acetone efficacious oxidation

Reactivity loss by intermediates aggregation and water vapor inhibition are two major and longstanding challenges for the noble-metal-based catalysts in oxygenated volatile organic compounds (OVOCs) oxidation. Herein, the core-shell Pd@CoO Janus sites are creatively designed and stabilized over the HSAPO-34 support. Quasi in situ XPS spectra reveal that the strong interactions in Pd@CoO Janus sites promote the charge redistribution and electron back-donation through Pd-O-Co coordination. Therefore, abundant positively charged Pd2+ sites are formed and oxygen species transformation is facilitated, which significantly promote the low-temperature efficiency of acetone oxidation. Furthermore, the Pd@CoO/HSAPO-34 catalyst facilitates H2O molecules dissociation and produce reactive OHTer and OHTri species, which considerably promotes the rapid decomposition of aldehyde intermediate via attacked CH2O* group, ensuring low-temperature oxidation of acetone. This work provides valuable guidance to develop specific catalysts with functional active sites for rationally utilizing H2O molecules to improve low-temperature performance and modulate reaction pathways during OVOCs oxidation.

Synthesis and Catalytic Performance of High-Entropy Rare-Earth Perovskite Nanofibers: (Y0.2La0.2Nd0.2Gd0.2Sm0.2)CoO3 in Low-Temperature Carbon Monoxide Oxidation.

This study investigated the catalytic properties of low-temperature oxidation of carbon monoxide, focusing on (Y0.2La0.2Nd0.2Gd0.2Sm0.2)CoO3 synthesized via a glycothermal method using 1,4-butanediol and diethylene glycol at 250 °C. This synthesis route bypasses the energy-intensive sintering process at 1200 °C while maintaining a high-entropy single-phase structure. The synthesized material was characterized structurally and chemically by X-ray diffraction and SEM/EDX analyses. The material was shown to form nanofibers of (Y0.2La0.2Nd0.2Gd0.2Sm0.2)CoO3, thereby increasing the active surface area for catalytic reactions, and crystallize in the model Pbnm space group of distorted perovskite cell. Using a custom setup to investigate catalytic properties of (Y0.2La0.2Nd0.2Gd0.2Sm0.2)CoO3, the CO oxidation behavior of those high-entropy perovskite oxide was investigated, showing an overall conversion of 78% at 50 °C and 97% at 100 °C. These findings highlight the effective catalytic activity of nanofibers of (Y0.2La0.2Nd0.2Gd0.2Sm0.2)CoO3 under mild conditions and their versatility in various catalytic processes of robust CO neutralization. The incorporation of rare-earth elements into a high-entropy structure could impart unique catalytic properties, promoting a synergistic effect that enhances performance.

Efficient simultaneous removal of diesel particulate matter and hydrocarbons from diesel exhaust gas at low temperatures over Cu–CeO2/Al2O3 coupling with dielectric barrier discharge plasma

Diesel particulate matter (DPM) and hydrocarbons (HCs) emitted from diesel engines have a negative affect on air quality and human health. Catalysts for oxidative removal of DPM and HCs are currently used universally but their low removal efficiency at low temperatures is a problem. In this study, Cu-doped CeO2 loaded on Al2O3 coupled with plasma was used to enhance low-temperature oxidation of DPM and HCs. Removals of DPM and HCs at 200 °C using the catalyst were as high as 90% with plasma but below 30% without plasma. Operando plasma diffuse reflectance infrared Fourier transform spectroscopy coupled with mass spectrometry was conducted to reveal the functional mechanism of the oxygen species in the DPM oxidation process. It was found that Cu–CeO2 can promote the formation of adsorbed oxygen ( – ) and terminal oxygen (M=O), which can react with DPM to form carbonates that are easily converted to gaseous CO2. Our results provide a practical plasma catalysis technology to obtain simultaneous removals of DPM and HCs at low temperatures.

PH-responsive HMDS terminated m-Cresol for inhibiting the spontaneous combustion in different-rank coals

In this study, pH responsiveness of 1, 1, 1, 3, 3, 3-hexamethyldisilazane terminated m-Cresol (HTMC) in different-rank coals was investigated, and its inhibition performance regarding the spontaneous combustion of coal was explored. First, color changes in the deprotection reaction of HTMC under different acidic conditions were analyzed. Then, surface microstructures of these coals and pH values of their filtrates were tested. Subsequently, experiments were performed on different coal samples for grasping their low-temperature oxidation characteristics, weight loss rates, pore characteristics, and free radical variations. The experimental results show that HTMC can effectively protect phenolic hydroxyl groups in inhibitors, and the acidity of coal can promote the conversion rate of its deprotection reaction. For instance, in XAM coal (pH ≈ 6), sufficient H+ stimulates HTMC to release massive m-Cresol which contains highly reactive phenolic hydroxyl, thereby effectively suppressing increases of the concentration and type of free radicals. The crossing point temperature (177.2 °C) and inhibition rate at 110 °C (75.9 %) of the HTMC-inhibited XAM sample are 33.1 °C and 17.9 % higher than those of the m-Cresol-inhibited one, respectively. This study confirms the applicability of pH-responsive HTMC to different-rank coals and may lay a theoretical foundation for the design of efficient reactive inhibitors.

Mn-Based Mullites for Environmental and Energy Applications.

Mn-based mullite oxides AMn2O5 (A = lanthanide, Y, Bi) is a novel type of ternary catalyst in terms of their electronic and geometric structures. The coexistence of pyramid Mn3+-O and octahedral Mn4+-O makes the d-orbital selectively active toward various catalytic reactions. The alternative edge- and corner-sharing stacking configuration constructs the confined active sites and abundant active oxygen species. As a result, they tend to show superior catalytic behaviors and thus gain great attention in environmental treatment and energy conversion and storage. In environmental applications, Mn-based mullites have been demonstrated to be highly active toward low-temperature oxidization of CO, NO, volatile organic compounds (VOCs), etc. Recent research further shows that mullites decompose O3 and ozonize VOCs from -20°C to room temperature. Moreover, mullites enhance oxygen reduction reactions (ORR) and sulfur reduction reactions (SRR), critical kinetic steps in air-battery and Li-S batteries, respectively. Their distinctive structures also facilitate applications in gas-sensitive sensing, ionic conduction, high mobility dielectrics, oxygen storage, piezoelectricity, dehydration, H2O2 decomposition, and beyond. A comprehensive review from basic physicochemical properties to application certainly not only gains a full picture of mullite oxides but also provides new insights into designing heterogeneous catalysts.

Analysis of temperature rise of low temperature adiabatic oxidation of sulfur-containing “coal-like substances”

ABSTRACT Spontaneous combustion of coal is one of the main natural disasters in the process of coal mining, and spontaneous combustion of sulfur-containing coal is an urgent problem to be solved. In order to understand the influence of different sulfur structures and sulfur content on spontaneous combustion tendency of coal, the self-developed synchronous temperature compensation adiabatic oxidation experiment system was used to study the oxidation self-heating performance of a series of sulfur-containing “coal-like materials.” Through the analysis of the heating rate of coal containing specific sulfur structure, it is considered that the time of adiabatic oxidation temperature of different organic sulfur “coal” to rise to 70°C is dimethyl sulfoxide > phenylene sulfide > dibenzothiophene. By analyzing the oxidation temperature rise characteristics of organic sulfur models with different sulfur contents, it is believed that the higher sulfur content, the faster the low temperature oxidation reaction of “coal-like substance,” the faster the temperature rise rate, and the shorter the time to reach the uncontrollable self-heating temperature, so the shorter the spontaneous combustion period. In general, in the stage of low temperature oxidation, active sulfur containing small molecules (dimethyl sulfoxide) promote the oxidation temperature rise, stable structure, larger molecular weight of dibenzothiophene slow down the “coal-like” oxidation temperature rise.

Density functional theory-based screening of Ti4C3O2-loaded single atoms for efficient selective catalytic oxidation of formaldehyde

Indoor formaldehyde (HCHO) pollution poses a major risk to human health. Low-temperature catalytic oxidation is an effective method for HCHO removal. The high activity and selectivity of single atomic catalysts provide a possibility for the development of efficient non-precious metal catalysts. In this study, the most stable single-atom catalyst Ti–Ti4C3O2 was screened by density functional theory among many single atomic catalysts with two-dimensional (2D) monolayer Ti4C3O2 as the support. The computational results show that Ti–Ti4C3O2 is highly selective to HCHO and O2 in complex environments. The HCHO oxidation reaction pathways are proposed based on the Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanisms. According to the reaction energy and energy span models, the E-R mechanism has a lower maximum energy barrier and higher catalytic efficiency than the L-H mechanism. In addition, the stability of the Ti–Ti4C3O2 structure and active center was verified by diffusion energy barrier and ab initio molecular dynamics simulations. The above results indicate that Ti–Ti4C3O2 is a promising non-precious metal catalyst. The present study provides detailed theoretical insights into the catalytic oxidation of HCHO by Ti–Ti4C3O2, as well as an idea for the development of efficient non-precious metal catalysts based on 2D materials.

Pinpointing the catalytic role of water in low-temperature CO oxidation on gold catalysts at a molecular level

Water substantially promotes the low-temperature redox reactions catalyzed by gold. However, clarifying the catalytic role of water is challenging due to co-existing OH and H2O species on Au catalysts under working conditions. Here, via controlled preparation of OH and adsorbed H2O species on a NiO/Au(111) inverse model surface combined with isotope-labelling reactants, we provide unambiguous spectroscopic experimental evidence to identify adsorbed H2O species, instead of OH groups, to promote O2 activation for low-temperature CO oxidation at the NiO-Au interface. In combination with theoretical calculations, adsorbed H2O-stabilized O2 species was found to be facilely activated into reactive OOH species but OH stabilized-O2 species could not. These results successfully discriminate the role of adsorbed H2O species and OH group in O2 activation in gold catalysis, which significantly advances our fundamental understanding of both Au catalysis and catalytic role of H2O.

Enhancing Low-Temperature HCHO Oxidation: Investigation selectivity and Catalytic Activity of Ag, Co, Mo, and Cr Catalysts Supported on γ-Al2O3

Enhancing Low-Temperature HCHO Oxidation: Investigation selectivity and Catalytic Activity of Ag, Co, Mo, and Cr Catalysts Supported on γ-Al2O3

Research on the mechanism of coal adsorption of CO2 hindering oxygen

This paper investigates the inhibitory effect of CO2 on oxygen adsorption during the low-temperature oxidation of coal. Taking the example of Tingnan coal, the physical adsorption barriers of CO2 during coal oxidation at different temperatures were analyzed in terms of competitive adsorption curves, adsorption capacity, adsorption selectivity and diffusion coefficients using a combination of indoor experiments and molecular simulations. It is proposed that the competitive adsorption advantage of CO2 is significantly greater than that of O2, and it is negatively correlated with temperature. Additionally, the variations of aliphatic gas-phase products are evident during the pre-oxidation temperature stages. When the pre-oxidation temperature exceeds 70 °C, the amounts of CH4 and C2H4 released increase with the pre-oxidation temperature, and the inhibitory effect of injected CO2 deteriorates. The simulation results validate the experimental conclusions and are in line with the actual situation, providing auxiliary optimization and guidance for coal mine fire prevention work.

Synthesis and characterization of Co3O4 spinel nanowall: understanding the growth mechanism and properties

Formation of spinel tricobalt tetraoxide (Co3O4) nanostructures through a controlled thermal oxidation process is discussed here. Thin films of high purity cobalt (Co) were deposited on glass/quartz substrates using an electron beam (E-beam) evaporation technique. Thermal oxidation of the as-deposited Co thin films was carried out at various oxidation temperatures (400 °C to 600 °C) for different durations (5 h to 15 h) to grow various oxide nanostructures. Different surface characterizations techniques were used to investigate the structure, chemistry and electronic properties of the as-grown cobalt oxide nanostructures. x-ray diffraction analysis revealed the presence of the CoO phase along with the Co3O4 phases at relatively lower oxidation temperature. However, the Co3O4 phase becomes more predominant for longer oxidation durations at higher oxidation temperatures. Field emission scanning electron microscopy analysis showed a surface morphological transition from nanowalls to nanograins with an increase in the oxidation temperature. The surface electrical conductivity of the oxidized Co films is also increased for higher oxidation temperature and/or duration mainly due to the oxide phase purity and larger particle sizes. Ultraviolet–visible spectroscopy indicated two distinct optical energy bandgaps, which effectively decreased with an increase in the oxidation temperature and duration. Raman spectroscopy identified five different Raman-active modes corresponding to the Co3O4 phase, with the F2g mode dominating at higher temperatures. All these findings provide clear insights into the structural, electrical, chemical and optical properties of cobalt oxide thin films. Moreover, it provides a mechanism on how to grow 2D nanowalls morphology of Co3O4 films which can further be used in energy, sensor or catalytic applications.

Enhancement Effect Induced by the Second Metal to Promote Ozone Catalytic Oxidation of VOCs.

It is a promising research direction to develop catalysts with high stability and ozone utilization for low-temperature ozone catalytic oxidation of VOCs. While bimetallic catalysts exhibit excellent catalytic activity compared with conventional single noble metal catalysts, limited success has been achieved in the influence of the bimetallic effect on the stability and ozone utilization of metal catalysts. Herein, it is necessary to systematically study the enhancement effect in the ozone catalytic reaction induced by the second metal. With a simple continuous impregnation method, a platinum-cerium bimetallic catalyst is prepared. Also highlighted are studies from several aspects of the contribution of the second metal (Ce) to the stability and ozone utilization of the catalysts, including the "electronic effect" and "geometric effect". The synergistic removal rate of toluene and ozone is nearly 100% at 30 °C, and it still shows positive stability after high humidity and a long reaction time. More importantly, the instructive significance, which is the in-depth knowledge of enhanced catalytic mechanism of bimetallic catalysts resulting from a second metal, is provided by this work.

Experimental Study on Low-Temperature-Oxidation Parameters and Simulations of Exothermic Process during Air Injection in Light Oil Reservoirs

Summary The thermal development process for light oil reservoirs using air injection technology is to release heat through low-temperature oxidation (LTO) between the injected air and crude oil and gradually increase the reaction zone’s temperature to displace crude oil. However, existing LTO experimental methods for air injection do not adequately capture the characteristics of LTO and struggle to directly obtain LTO kinetic parameters at low temperatures. In this paper, we used light oil samples from the Huabei Oilfield, China, as the studied objects and proposed innovative methods for obtaining and calculating LTO kinetic parameters. Further, we validated the feasibility of the proposed methods through experimental and numerical simulations. The results indicate that the lower limit temperature at which oxidation parameters can be directly measured through the accelerating rate calorimeter (ARC) experiments is 124°C. We matched the calculations from the ARC experiment curve-extension method for kinetic parameters with the results from both the high-pressure thermogravimetric analyzers (HP-TGA) experiment and the ramped thermal oxidizer (RTO) experiment. The fit between these results indicates that three methods are suitable for obtaining LTO parameters and can be used to derive chemical equations for LTO reactions in numerical simulation models. The simulation results from the reservoir scale indicate that, following air injection into the light oil reservoir, the peak temperature at the leading edge of the high-temperature zone reaches 370.9°C. The interaction between crude oil and air remains in the LTO phase, facilitating a sustained thermal accumulation within the reservoir. This study can provide a reference for reservoir development under similar conditions.

Combined experimental and kinetic modeling study on the low-temperature oxidation of OME3/n-heptane blends

Experimental and kinetic studies on the blending of ethers or diesters with larger alkanes at low temperatures are enormously scarce. In this paper, the low-temperature oxidation (LTO) kinetics model of polyoxymethylene dimethyl ether 3 (OME3)/n-heptane (500 K∼950 K) was established by using the jet-stirred reactor (JSR) to conduct the LTO experiments of OME3/n-heptane with different blending ratios. GC/MS was used to detect and quantify 17 kinds of stable products in the LTO process of OME3/n-heptane. The detailed OME3/n-heptane kinetic model was fully verified experimentally. The interaction mechanism of OME3/n-heptane was discussed based on the experiments and corresponding chemical kinetic analysis. Results show that the oxidative decomposition processes of OME3 and n-heptane were significantly different, the LTO and NTC process of OME3 were significantly weaker than those of n-heptane, but the high-temperature reactivity of OME3 was much stronger. In addition, n-heptane significantly promoted the intermediate species CH3OCHO and COCOC*O of OME3, mainly because n-heptane significantly prolonged the LTO of OME3 in the fuel blends. And the NTC process of the fuel blends was mainly dominated by OME3, while the LTO process was more influenced by n-heptane, which resulted in the weakened NTC of n-heptane and the significantly enhanced LTO process of OME3.

SnO2-modified CuMnOx catalysts for humid CO oxidation at low temperature

Low-temperature CO oxidation has been widely applied in environmental pollution control, but challenges remain in CO purification in high-humidity environments. In this study, the CuMnSn8 catalyst exhibited excellent low-temperature CO oxidation performance, achieving complete CO oxidation at temperatures below 55 °C in 85 % relative humidity. A series of characterizations indicated that an appropriate amount of SnO2 doping could promote the formation of more amorphous oxides, increase the oxygen species content, and facilitate the dispersion of Cu and Mn elements. The catalytic active sites for CO oxidation and the influence of SnO2 doping on the CO oxidation mechanism were investigated through in-situ DRIFTS experiments. The results indicated that Sn enhanced the synergistic effect between Cu and Mn, altered the pathway of CO oxidation reaction, generated more easily decomposable bidentate carbonate intermediates. This work provides insight into the design of CO oxidation catalysts with high activity in high humidity.

Low-Temperature Oxidation of Methane on Rutile TiO2(110): Identifying the Role of Surface Oxygen Species.

Understanding the microkinetic mechanism underlying photocatalytic oxidative methane (CH4) conversion is of significant importance for the successful design of efficient catalysts. Herein, CH4 photooxidation has been systematically investigated on oxidized rutile(R)-TiO2(110) at 60 K. Under 355 nm irradiation, the C-H bond activation of CH4 is accomplished by the hole-trapped dangling OTi- center rather than the hole-trapped Ob- center via the Eley-Rideal reaction pathway, producing movable CH3• radicals. Subsequently, movable CH3• radicals encounter an O/OH species to form CH3O/CH3OH species, which could further dissociate into CH2O under irradiation. However, the majority of the CH3• radical intermediate is ejected into a vacuum, which may induce radical-mediated reactions under ambient conditions. The result not only advances our knowledge about inert C-H bond activation but also provides a deep insight into the mechanism of photocatalytic CH4 conversion, which will be helpful for the successful design of efficient catalysts.