Catalytic Oxidation Of Methane Research Articles

Anchoring PdOx clusters on defective alumina for improved catalytic methane oxidation

Evolution of the Pd active centers in size and spatial distribution leads to an irreversible deactivation in many high-temperature catalytic processes. This research demonstrates the use of a defective alumina (Al2O3-x) as catalyst support to anchor Pd atoms and suppress the growth of Pd clusters in catalytic methane oxidation. A combination of operando spectroscopy and density functional theory (DFT) calculations provide insights into the evolution of Pd species and reveals distinct catalytic methane oxidation mechanisms on Pd single atoms, clusters, and nanoparticles (NPs). Among these Pd species, the cluster active centers are found to be the most favorable participants in methane oxidation due to their high dispersion, high content of Pd2+ oxidation state, and resistance to deactivation by carbonates, bicarbonates, and water. The Pd/Al2O3-x catalyst shows increased stability with respect to a Pd/Al2O3 counterpart during simulated aging in alternating reducing and oxidizing conditions due to stronger interactions with the support. This study demonstrates that defect engineering of non-reducible supports can constrain the evolution of active centers, which holds promising potential for widespread utilization across diverse industrial catalytic processes, including various hydrogenation and oxidation reactions.

Advancing catalytic oxidation of lean methane over cobalt-manganese oxide via a phase-engineered amorphous/crystalline interface.

CoMnOx catalysts were prepared using a microwave (MW)/ultrasonic (US)-assisted method. Amorphous/crystalline regions in CoMnOx (MW = 250 W US = 300 W) increased the oxygen vacancy content and CoMnOx exhibited excellent activity for methane oxidation (T90 = 330 °C). A new approach is provided here to improve the activity of transition metal catalysts.

Synthesis of surface-engineered SrFe2O4 for efficient catalytic partial oxidation of methane

In this study, a series of platinum (Pt)-doped strontium iron oxide (SrFe2O4) catalysts with varying particle sizes were synthesized through the four different catalysis synthesis methods such as solution combustion synthesis (SCS), co-precipitation (Co-PPT), oxalic acid assisted sol-gel (OXA) and, hydrothermal (HT). The objective was to investigate the impact of particle size on the catalytic activity and long-term stability of these four catalysts. The XRD and Raman results confirmed the formation of the SrFe2O4 perovskite structure. HRTEM, SEM, and other characterizations revealed a clear correlation between the synthesis conditions and the resulting particle sizes. The highest%CH4 conversion was around 95 % for the catalyst prepared through Solution combustion synthesis and the catalyst was found to be thermally stable up to. 100 h at 800 °C with a negligible variation of conversion while maintaining the H2/CO ratio at 2.0. To gain insight into catalytic activity, stability, and selectivity of catalysts we have performed Temperature-programmed surface reaction (TPSR) at a controlled temperature ramping program. This study also includes the study of coke deposition on the spent catalysts through different characterization techniques. Furthermore, we have performed a kinetic study to find the initial rate of the reaction and the activation energy of the Pt-doped SrFe2O4 catalyst and it has been found that activation energy was 35 KJ/mol for the catalyst Pt/SrFe2O4 synthesis through the solution combustion method.

The role of ceria in promoting Ni catalysts supported on phosphate‐modified zirconia for the partial oxidation of methane

AbstractThe catalytic partial oxidation of methane (POM) is aimed at the mitigation of CH4 (a highly potent greenhouse gas) from the environment and the synthesis of syngas with a high H2/CO ratio. Herein, to enhance the POM reaction, Ni‐supported phosphate‐modified‐zirconia were synthesized with promotor “Ce” to achieve high H2/CO ratio (2.4–3.2). The catalysts were characterized by surface area and porosity, X‐ray diffraction, RAMAN, temperature‐programmed experiments (TPR, CO2‐TPD, and TPO), and TEM. Increasing the ceria addition over 10Ni/PO4 + ZrO2 resulted in lower crystallinity, higher dispersion of active sites, and enhanced the surface area of catalyst. The unique and prominent reducibility and basicity of NiO‐species and surface oxide ions, respectively, are particularly notable at 4 wt.% ceria loading. At a reaction temperature of 600°C, the highest concentration of active sites and a unique concentration of moderate strength basic sites can be achieved with 4 wt.% ceria loading over 10Ni/PO4 + ZrO2. This leads to 44% conversion of CH4, 36% yield of H2, 35% yield of CO2, and H2/CO ratio of 3.16 for the POM reaction. The cyclic H2TPR‐O2TPO‐H2TPR experiment confirms the reorganization of the active site towards high temperature under oxidizing gas O2 and reducing gas H2 gas stream during the POM reaction.

High-Throughput Screening Strategy for Electrocatalysts for Selective Catalytic Oxidation of Formaldehyde to Formic Acid.

Electrocatalytic oxidation of formaldehyde (FOR) is an effective way to prevent the damage caused by formaldehyde and produce high-value products. A screening strategy of a single-layer MnO2-supported transition metal catalyst for the selective oxidation of formaldehyde to formic acid was designed by high-throughput density functional calculation. N-MnO2@Cu and MnO2@Cu are predicted to be potential FOR electrocatalysts with potential-limiting steps (PDS) of 0.008 and -0.009 eV, respectively. Electronic structure analysis of single-atom catalysts (SACs) shows that single-layer MnO2 can regulate the spin density of loaded transition metal and thus regulate the adsorption of HCHO (Ead), and Ead is volcanically distributed with the magnetic moment descriptor -|mM - mH|. In addition, the formula quantifies Ead and |mM - mH| to construct a volcano-type descriptor α describing the PDS [ΔG(*CHO)]. Other electronic and structural properties of SACs and α are used as input features for the GBR method to construct machine learning models predicting the PDS (R2 = 0.97). This study hopes to provide some insights into FOR electrocatalysts.

Self-heating photothermal synergistic catalytic decomposition of carcinogenic formaldehyde by α-MnO2 at ambient temperature: Functional roles of surface acidic-basic sites

Formaldehyde is a major pollutant in indoor atmosphere, and the realization of complete mineralization of formaldehyde at room temperature is of great significance and practical demand for improving indoor air quality. Surface acidic-basic sites, as one of the important surface properties that have significant influence on catalytic oxidation of formaldehyde, revealing their functions is beneficial for the development of efficient formaldehyde decomposition materials. Herein, the α-MnO2 acidic-basic sites were regulated and its effects on self-heating photothermal catalytic oxidation of formaldehyde were further contrastive investigated. The acidic-basic sites showed distinct functions: the basic sites exhibited a significant promotion on formaldehyde oxidation; While the acidic sites greatly inhibited the reactivity. Particularly, the basicity enhanced α-MnO2 could reach the 100% conversion of formaldehyde at ambient temperature. Furthermore, the self-heating photothermal mechanism was consonant with the thermal-assisted photocatalysis mechanism, rather than traditional photo-drive thermal catalysis mechanism. The strength of basic sites significantly increased the content of surface hydroxyl groups, and the electron-rich basic sites were favorable for the activation of oxygen, thereby generating more reactive oxygen species for the decomposition of formaldehyde. Moreover, in-situ DRIFTS reveals that the enhancement of basic sites can accelerate the rate oxidation of HCHO to generate formates and carbonates. This work clarified the influence of surface acid-base properties on formaldehyde photothermal decomposition.

Lattice-confined Ag over MnCoLDH accelerated catalytic oxidation of formaldehyde at ambient temperature: The novel pathway with different oxygen species

Catalytic oxidation of formaldehyde (HCHO) at ambient temperature represents a cost-effective and efficient strategy for indoor HCHO removal. Although precious metal-based catalysts have been considered practical for oxidizing gaseous HCHO indoors, the limited activity of Ag-based catalysts can be attributed to their typical +1 and 0 valence states, as well as their single electron transport pathway. This characteristic impedes the reestablishment of the low state during oxygen activation, thereby resulting in catalyst deactivation. The present study successfully incorporated Ag atoms into manganese-cobalt layered double hydroxide (MnCoLDH) through doping, resulting in the development of a catalyst that exhibited complete formaldehyde oxidation activity at 30 °C. Lattice-confined Ag enables continuous activation of oxygen, while LDH facilitates the sustained provision of surface hydroxyl groups. The roles and mechanisms of surface hydroxyl groups, adsorbed oxygen, and lattice oxygen in the oxidation of formaldehyde were investigated using in-situ DRIFTS. By comparing Ag with the impregnation method, the confinement of Ag within the lattice enables continuous activation of oxygen. This study presents a viable strategy for designing efficient catalysts for volatile organic compounds (VOCs) removal by utilizing active lattice oxygen species.

Efficient catalytic oxidation of formaldehyde by defective g–C3N4–anchored single-atom Pt: A DFT study

Indoor volatile formaldehyde is a serious health hazard. The development of low-temperature and efficient nonhomogeneous oxidation catalysts is crucial for protecting human health and the environment but is also quite challenging. Single-atom catalysts (SACs) with active centers and coordination environments that are precisely tunable at the atomic level exhibit excellent catalytic activity in many catalytic fields. Among two-dimensional materials, the nonmagnetic monolayer material g-C3N4 may be a good platform for loading single atoms. In this study, the effect of nitrogen defect formation on the charge distribution of g-C3N4 is discussed in detail using density functional theory (DFT) calculations. The effect of nitrogen defects on the activated molecular oxygen of Pt/C3N4 was systematically revealed by DFT calculations in combination with molecular orbital theory. Two typical reaction mechanisms for the catalytic oxidation of formaldehyde were proposed based on the Eley-Rideal (E-R) mechanism. Pt/C3N4–V3N was more advantageous for path 1, as determined by the activation energy barrier of the rate-determining step and product desorption. Finally, the active centers and chemical structures of Pt/C3N4 and Pt/C3N4–V3N were verified to have good stability at 375 K by determination of the migration energy barriers and ab initio molecular dynamics simulations. Therefore, the formation of N defects can effectively anchor single-atom Pt and provide additional active sites, which in turn activate molecular oxygen to efficiently catalyze the oxidation of formaldehyde. This study provides a better understanding of the mechanism of formaldehyde oxidation by single-atom Pt catalysts and a new idea for the development of Pt as well as other metal-based single-atom oxidation catalysts.

Atomically dispersed MoNi alloy catalyst for partial oxidation of methane

The catalytic partial oxidation of methane (POM) presents a promising technology for synthesizing syngas. However, it faces severe over-oxidation over catalyst surface. Attempts to modify metal surfaces by incorporating a secondary metal towards C–H bond activation of CH4 with moderate O* adsorption have remained the subject of intense research yet challenging. Herein, we report that high catalytic performance for POM can be achieved by the regulation of O* occupation in the atomically dispersed (AD) MoNi alloy, with over 95% CH4 conversion and 97% syngas selectivity at 800 °C. The combination of ex-situ/in-situ characterizations, kinetic analysis and DFT (density functional theory) calculations reveal that Mo-Ni dual sites in AD MoNi alloy afford the declined O2 poisoning on Ni sites with rarely weaken CH4 activation for partial oxidation pathway following the combustion reforming reaction (CRR) mechanism. These results underscore the effectiveness of CH4 turnovers by the design of atomically dispersed alloys with tunable O* adsorption.

Three-dimensional Ni foam supported Pt/NiFe LDH catalyst with enhanced oxygen activation for room-temperature formaldehyde oxidation

Room-temperature catalytic oxidation of formaldehyde (HCHO) has been extensively investigated due to its high efficiency, convenience, and environmental friendliness. Herein, nickel-iron layered double hydroxide (NiFe LDH) nanosheets were synthesized in-situ on a nickel foil (NF) using a facile one-step hydrothermal method, followed by the deposition of ultra-low content (0.069 wt%) of Pt nanoparticles through NaBH4 reduction. The resulting three-dimensional (3D) hierarchical Pt/NiFe-NF catalyst exhibited exceptional activity for the complete decomposition of formaldehyde to carbon dioxide (CO2) at room temperature (∼95 % conversion within 1 h), as well as remarkable cycling stability. The 3D porous structure of Pt/NiFe-NF provides fast transport channels for the diffusion of gas molecules, making the active catalyst surfaces more accessible. Moreover, abundant hydroxyl groups in NiFe LDH serve as adsorption centers for HCHO molecules to form dioxymethylene (DOM) and formate intermediates. Furthermore, electronic interactions between NiFe LDH and Pt enhance the adsorption and activation of O2 on Pt surfaces, leading to the complete decomposition of intermediates into non-toxic products. This work presents new insights into the design and preparation of Pt-based 3D hierarchical catalysts with surface-rich hydroxyl groups for the efficient removal of indoor HCHO.

Noble metal modified copper-exchanged mordenite zeolite (Cu-ex-MOR) catalysts for catalyzing the methane efficient gas-phase synthesis methanol

Copper mordenite catalysts are key for methane oxidation to methanol, yet lack sufficient activity. In this paper, noble metal (Au, Ru, Pt and Pd) modified copper ion-exchanged mordenite catalysts were prepared by the ion-exchange method for further improving the methanol yield in the gas-phase continuous catalytic direct partial oxidation of methane to methanol reaction, and the role of noble metal doping on Cu-ex-MOR catalysts was investigated. Experimental results showed that the doping of Ru resulted in a significant increase in the methanol yield of Ru/Cu-ex-MOR catalyst to 157.36 μmol/gcat/h compared to that of Cu-ex-MOR catalyst (12.89 μmol/gcat/h). SEM, XRD, FT-IR, N2 adsorption-desorption, XPS, NH3-TPD and H2-TPR results showed that Ru/Cu-ex-MOR had uniformly dispersed Ru elements and the largest number of surface acidic and oxidation sites, which facilitated the adsorption and activation of methane. Additionally, it was found by TEM, in situ FT-IR and DFT characterization that Ru played a role in stabilizing the Cu active sites, the adsorptive activation of water on the Ru site and the H-transfer process reduced the energy required for breaking C–H bond of CH4 at the Cu active site, which significantly improved the methane activation capacity of the Ru/Cu-ex-MOR catalysts, resulting in higher methanol yields.

Alkali-modified copper manganite spinel for room temperature catalytic oxidation of formaldehyde in air

Formaldehyde (FA) is present ubiquitously in indoor environment as a hazardous pollutant with carcinogenic risks. For the efficient mitigation of FA, catalytic oxidation is a recommendable option to simultaneously satisfy both material cost (e.g., avoiding noble metals) and low-energy requirement (under dark and at room temperature (RT)). From this perspective, a cost-effective alkali modified copper manganite spinel (CuMn2O4) catalyst has firstly been prepared and employed for FA oxidation. Specifically, alkali (1 mol L−1 potassium hydroxide)-modified CuMn2O4 (1-CuMn2O4) achieves 100% FA (50 ppm (gas hourly space velocity of 4777 h−1)) conversion (XFA) at RT. The steady-state reaction rate of 1-CuMn2O4 at 10% XFA is 8.18 × 10−2 mmol g−1 h−1. According to in situ diffuse reflectance infrared Fourier transform spectroscopy, FA molecules are oxidized into water and carbon dioxide through dioxymethylene and formate intermediates. Based on density functional theory simulation, the higher catalytic performance of 1-CuMn2O4 for FA oxidation is attributed to the combined effects of firmer attachment of FA molecules to 1-CuMn2O4 surface, lower energy cost of FA adsorption, and lower desorption energy for the final products from the substrate surface. The present work is expected to provide insights into high-performing non-noble metal catalysts for RT oxidative removal of FA from indoor air.

Catalytic performance of Pd catalyst supported on CeO2 or ZrO2 modified beta zeolite for methane oxidation

Two kinds of oxide-zeolite composite support, Ce-beta and Zr-beta were prepared by a simple wet impregnation method and adopted for the preparation of palladium-based catalysts for catalytic oxidation of methane. The Pd/6.8Zr-beta catalyst showed superior methane oxidation performance, achieving T50 and T90 of 417 °C and 451 °C, respectively, together with robust hydrothermal stability. Kinetic analysis has shown that incorporating Zr into the catalyst significantly enhanced its efficiency, nearly tripling the turnover frequency (TOF) for methane combustion compared to the Pd/beta catalyst. This enhanced performance was attributed to the dispersion of Zr on the zeolite surface, which not only promoted the formation of active PdO sites but also helped maintain the high Pd2+ content via facilitating the oxygen migration during the reaction, thus improving both the catalyst's activity and stability. In the Pd/8.6Ce-beta catalyst, doped CeO2 tended to aggregate in the zeolite's pores, adversely affecting the catalyst's efficiency. This aggregation promoted the formation of inactive Pd4+ species, a result of the enhanced metal-support interaction. This finding is critical for understanding the implications of dopant selection in the design of high-activity methane oxidation catalysts.

Deep understanding the formation of MnCoOx in-situ grown on foam nickel towards efficient lean methane catalytic oxidation

Methane is the second largest greenhouse gas in the world, with a stronger greenhouse effect than carbon dioxide. The efficient elimination of methane in the atmosphere has important engineering significance in slowing down global temperature rise, energy resource utilization, collaborative control of pollutants, and promoting technological innovation. In this work, a general hydrothermal synthesis method was introduced to in-situ construct four different morphologies of MnCoOx (including rod-, spherical-, filamentous- and bulk-shape) on foam nickel (NF). The synthesis of MnCoOx/NF with different morphologies was due to changes in NF pretreatment conditions and precipitants, which affected the nucleation and growth rates of MnCoOx, ultimately resulting in different morphologies. When the four different morphologies of MnCoOx/NF were used as catalysts for lean methane catalytic oxidation, MnCoOx/NF-r exhibited the best excellent catalytic activity, and the T90 occurred at 428 °C in space velocity of 48,000 mL g−1 h−1. Such an outstanding performance was attributed to the unique properties of the MnCoOx/NF-r including the larger surface area and more oxygen vacancies for providing more active sites and a higher oxygen migration rate, which was very beneficial for improving the catalytic oxidation performance of methane.

Investigation of catalytic methane oxidation over Ag/Co2MOx (M = Co, Ni, Cu) catalysts with varying interfacial electron transfer

Atom-doped Co3O4 catalysts loaded with Ag were examined as cost-effective catalysts for methane oxidation. The synthesized Ag/Co2NiOx catalysts exhibited distinctive surface characteristics in contrast with Ag/Co3O4 and Ag/Co2CuOx catalysts prepared using a similar method. Characterization results unveiled that Ag/Co2NiOx featured a higher presence of active surface oxygen species, lattice defects, a larger surface area, and enhanced reducibility. A methane oxidation catalytic performance followed the sequence: Ag/Co2NiOx > Ag/Co3O4 > Ag/Co2CuOx. The investigation delved into methane degradation pathways on the surfaces of three catalysts, examining their behavior under both aerobic and anaerobic atmospheres through in-situ DRIFTS analysis. Furthermore, introducing Ag showed a marked positive effect on Co-Ni mixed oxide, inducing electron transfer and a more active electron system, whereas it exhibited an inverse impact within the surface of Co-Cu mixed oxide. This work provides innovative perspectives on the development of forthcoming environmental catalysts.

Preparation of MnO2@MPIA catalysts with a controlled oxygen vacancy for the efficient catalytic oxidation of formaldehyde at room temperature

δ-MnO2 catalysts have attracted much attention because of the abundance of oxygen vacancies (OVs) on the surface to achieve efficient catalytic oxidation of volatile organic compounds (VOCs) such as formaldehyde (HCHO). However, the recycling and regeneration of powdered δ-MnO2 nano-catalysts still limits the practical application of the catalysts. Here, the surface of aramid fiber (MPIA) was treated by corona activation to introduce reactive groups, such as -OH, and -COOH. These reactive groups can promote the exposure of more Mn3+ on the surface of loaded δ-MnO2 to produce OVs. Meanwhile, the strong interactions between the activated MPAI and δ-MnO2 was formed, which helped to improve the stability and cyclic regeneration of the fiber-based δ-MnO2 catalysts. The effects of Mn3+ and OVs on the catalytic performance of δ-MnO2 were targeted and characterized by SEM, XPS and BET. The pathways of HCHO removal by OVs on the δ-MnO2 surface and the relative free energies of the corresponding intermediates were also explored. The results revealed that optimizing the morphology of MPIA surface-loaded δ-MnO2 can obtain a higher concentration of oxygen vacancies, with excellent HCHO removal efficiency at room temperature and high catalytic activity even after multiple cycle regeneration.

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.

The practical utility of ternary nickel-cobalt-manganese oxide-supported platinum catalysts for room-temperature oxidative removal of formaldehyde from the air

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel–cobalt-manganese oxide–supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h−1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir–Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO–, and CO32–. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

The effects of metal-oxide content in MnO2-activated carbon composites on reactive adsorption and catalytic oxidation of formaldehyde and toluene in air

The deterioration in air quality caused by volatile organic compounds (VOCs) has become an important environmental issue. Here, activated carbon (AC) composites with manganese oxide (MnO2: 1 % to 50 %) are synthesized as MAC for the removal of formaldehyde (FA) and toluene in air through a combination of reactive adsorption and catalytic oxidation (RACO) at room temperature (RT). The best-performing composite (MAC-20: 20 % of MnO2) exhibits a 10 % breakthrough volume (BTV10%) of FA and toluene at 41.2 and 377 L g−1, respectively while realizing complete oxidation of FA and toluene into carbon dioxide (CO2) at 100 °C and 275 °C, respectively. The reaction kinetic rates (r) for 10 % removal efficiency of FA and toluene (XFA or T) at RT are estimated as 9.82E-02 and 3.20E-02 mmol g−1 h−1, respectively. The high performance of MAC-20 can be attributed to its enriched adsorption capacity of oxygen vacancy (OV) and the presence of adsorbed oxygen (OA), as shown by an Mn3+/Mn4+ ratio of 0.729 and an OA/lattice‑oxygen (OL) ratio of 1.50. The results of this study highlight the interactive roles of oxygen abundance and temperature in the generation of distinctive oxidation patterns for FA in reference to toluene. This study is expected to offer practical guidance for the implementation of RACO against diverse VOCs for efficient management of air quality.

Catalytic oxidation of formaldehyde by MnOx-decorated anatase TiO2{001}: Investigation of the effect of calcination temperature on catalytic activity and reaction mechanism

The removal of indoor formaldehyde (HCHO) is crucial for human health. The design of highly catalytically active nonprecious metal catalysts has major challenges, and the use of transition metal element modification to improve the catalytic performance is an effective strategy. In this study, the active component Mn was loaded on highly active crystalline anatase TiO2{001}, and the effect of the calcination temperature on the catalytic activity was investigated. The important influence of temperature on the catalyst valence distribution, surface active oxygen species, and content was thoroughly determined by characterization techniques, such as XPS, H2-TPR, and O2-TPD. The catalytic reaction process was further analyzed by in situ infrared technology to determine the reaction intermediates and to clarify the catalyst reaction poisoning mechanism; additionally, a reasonable HCHO catalytic reaction pathway was proposed with the combination of density function theory calculations. In addition, oxygen defects on the catalyst surface were determined by EPR, and based on theoretical calculations, the oxygen defects could further reduce the reaction energy barrier through the Langmuir-Hinshelwood mechanism. By exposing specific crystal surfaces and increasing the number of oxygen defects, the catalytic activity could be effectively improved; based on these results, our study provides a concept for the subsequent development of nonprecious metal catalysts.