Oxidation Of Volatile Organic Compounds Research Articles

Contrasting molecular characteristics and formation mechanisms of biogenic and anthropogenic secondary organic aerosols at the summit and foot of Mt. Huang, East China

Secondary organic aerosol (SOA) exerts a considerable influence on atmospheric chemistry. However, little information about the vertical distribution of SOA in the alpine setting is available, which limited the simulation of SOA using chemical transport models. Here, a total of 15 biogenic and anthropogenic SOA tracers were measured in PM2.5 aerosols at both the summit (1840 m a.s.l.) and foot (480 m a.s.l.) of Mt. Huang during the winter of 2020 to explore their vertical distribution and formation mechanism. Most of the determined chemical species (e.g., BSOA and ASOA tracers, carbonaceous components, major inorganic ions) and gaseous pollutants at the foot of Mt. Huang were 1.7–3.2 times higher concentrations than those at the summit, suggesting the relatively more significant effect of anthropogenic emissions at the ground level. The ISORROPIA-II model showed that aerosol acidity increases as altitude decreases. Air mass trajectories, potential source contribution function (PSCF), and correlation analysis of BSOA tracers with temperature revealed that SOA at the foot of Mt. Huang was mostly derived from the local oxidation of volatile organic compounds (VOCs), while SOA at the summit was mainly influenced by long-distance transport. The robust correlations of BSOA tracers with anthropogenic pollutants (e.g., NH3, NO2, and SO2) (r = 0.54–0.91, p < 0.05) indicated that anthropogenic emissions could promote BSOA productions in the mountainous background atmosphere. Moreover, most of SOA tracers (r = 0.63–0.96, p < 0.01) and carbonaceous species (r = 0.58–0.81, p < 0.01) were correlated well with levoglucosan in all samples, suggesting that biomass burning played an important role in the mountain troposphere. This work demonstrated that daytime SOA at the summit of Mt. Huang was significantly influenced by the valley breeze in winter. Our results provide new insights into the vertical distributions and provenance of SOA in the free troposphere over East China.

Unravelling the pathway determining the CO2 selectivity in photocatalytic toluene oxidation on TiO2 with different particle size

The rapid intermediate species accumulation on TiO2 induces the deactivation and is a long-standing unsolved issue in the photocatalytic oxidation of volatile organic compounds (VOCs). Exploring efficient pathway to achieve deep oxidation is of crucial significance. In this study, we observed that TiO2 with small particle size (S-TiO2) had high toluene conversion but low CO2 mineralization, while TiO2 with large particle size (L-TiO2) had low toluene conversion but high CO2 mineralization. The characterization results showed that S-TiO2 had a larger specific surface area and more surface hydroxyl groups than L-TiO2, which accounted for its higher toluene conversion. Additionally, low toluene adsorption but a larger quantity of reactive oxygen species (ROS) was observed on L-TiO2. Our findings further revealed that toluene on S-TiO2 was initially oxidized to benzene-ring-containing intermediate species by ROS. However, the accumulation of these species suppressed the ROS production and blocked the ring-opening reaction, resulting in low CO2 selectivity. In contrast, nearly no intermediate species was accumulated on L-TiO2 due to the low toluene adsorption and abundant ROS production, which allowed the photocatalytic oxidation of toluene on L-TiO2 to follow the direct ring-opening pathway and achieve higher CO2 selectivity. This study provides new insight into the mechanism of the photocatalytic oxidation of VOCs.

Room temperature removal of high-space-velocity formaldehyde boosted by fixing Pt nanoparticles into Beta zeolite framework

Catalytic oxidation of volatile organic compounds like formaldehyde (HCHO) over the noble metals catalysts at room temperature is among the most promising strategies to control indoor pollution but remains one challenge to maximize the efficiency of noble metal species. Herein, we demonstrated the straightforward encapsulation of highly dispersive Pt nanoparticles (NPs) within BEA zeolite and adjacent with the surface hydroxyl groups to reach the synergistic HCHO oxidation at 25 °C. High efficiency and long-term stability was reached under large space velocity (∼100% conversion at 180,000 mL (gcat × h)−1 and >95% at 360,000 mL (gcat × h)−1), affording rapid elimination rate of 129.4 μmol (gPt × s)−1 and large turnover frequency of 2.5 × 10−2 s−1. This is the first synergy example derived from the hydroxyl groups and confined noble metals within zeolites that accelerated the rate-determining step, the formate transformation, in the HCHO elimination.

Weak Metal-Support Interaction over CuO/TiO2 Catalyst Governed Low-Temperature Toluene Oxidation.

Regulating the metal-support interaction is essential for obtaining highly efficient catalysts for the catalytic oxidation of volatile organic compounds (VOCs). In this work, CuO-TiO2(coll) and CuO/TiO2(imp) with different metal-support interactions were prepared via colloidal and impregnation methods, respectively. The results demonstrated that CuO/TiO2(imp) has higher low-temperature catalytic activity, with a 50% removal of toluene at 170 °C compared to CuO-TiO2(coll). Additionally, the normalized reaction rate (6.4 × 10-6 mol·g-1·s-1) at 160 °C over CuO/TiO2(imp) was almost four-fold higher than that over CuO-TiO2(coll) (1.5 × 10-6 mol·g-1·s-1), and the apparent activation energy value (27.9 ± 2.9 kJ·mol-1) was lower. Systematic structure and surface analysis results disclosed that abundant Cu2+ active species and numerous small CuO particles were presented over CuO/TiO2(imp). Owing to the weak interaction of CuO and TiO2 in this optimized catalyst, the concentration of reducible oxygen species associated with the superior redox property could be enhanced, thus significantly contributing to its low-temperature catalytic activity for toluene oxidation. This work is helpful in exploring the influence of metal-support interaction on the catalytic oxidation of VOCs and developing low-temperature catalysts for VOCs catalytic oxidation.

Recent Advances of VOCs Catalytic Oxidation over Spinel Oxides: Catalyst Design and Reaction Mechanism.

Volatile organic compounds (VOCs) harm the environment and human health and have been of wide concern and purified efficiently by catalytic oxidation. Spinel oxides, mainly composed of transition metal elements with low price and extensive sources, have been widely investigated as efficient and stable catalysts for VOCs oxidation due to their adjustable element composition, flexible structure, and high thermal/chemical stability. However, it is necessary to dissect the design of the spinel in a targeted way to satisfy the removal of different types of VOCs. This article systematically summarizes the recent advances regarding the application of spinel oxides for VOCs catalytic oxidation. Specifically, the design strategies of spinel oxides were first introduced to clarify their effect on the structure and properties of the catalyst. Then the reaction mechanism and degradation pathway of different kinds of VOCs on the spinel oxides were in detail summarized, and the characteristic requirements of the spinel oxides for various VOCs purification were analyzed. Furthermore, the practice applications were also discussed. Finally, the prospects were proposed to guide the rational design of spinel-based catalysts for VOCs purification and intensify the understanding of reaction mechanisms.

Redox-Induced In Situ Growth of MnO2 with Rich Oxygen Vacancies over Monolithic Copper Foam for Boosting Toluene Combustion.

Catalytic combustion has been known to be an effective technique in volatile organic compound (VOC) abatement. Developing monolithic catalysts with high activity at low temperatures is vital yet challenging in industrial applications. Herein, monolithic MnO2-Ov/CF catalysts were fabricated via the in situ growth of K2CuFe(CN)6 (CuFePBA, a family of metal-organic frames) over copper foam (CF) followed by a redox-etching route. The as-synthesized monolith MnO2-Ov-0.04/CF catalyst displays a superior low-temperature activity (T90% = 215 °C) and robust durability for toluene elimination even in the presence of 5 vol % water. Experimental results reveal that the CuFePBA template not only guides the in situ growth of δ-MnO2 with high loading over CF but also acts as a source of dopant to create more oxygen vacancies and weaken the strength of the Mn-O bond, which considerably improves the oxygen activation ability of δ-MnO2 and consequently boosts the low-temperature catalytic activity of the monolith MnO2-Ov-0.04/CF toward toluene oxidation. In addition, the reaction intermediate and proposed mechanism in the MnO2-Ov-0.04/CF mediated catalytic oxidation process were investigated. This study provides new insights into the development of highly active monolithic catalysts for the low-temperature oxidation of VOCs.

Direct evaluation of the ozone production regime in smog chamber experiments

Understanding the atmospheric ozone (O3) production regime is necessary for development of strategies to effectively control the amount of atmospheric O3. We have developed an instrument to directly evaluate the O3 production regime by measuring incremental changes of O3 production rate after injection of nitric oxide and propene into sample air. In this study, we conduct smog-chamber experiments on the oxidation of nitrogen oxides (NOx) and volatile organic compounds (VOC) and use the above instrument to measure O3 production during air mass oxidation. We also perform box model simulations with two chemical mechanisms (one near-explicit and one lumped) to cross validate the measured and simulated O3 production regimes. Oxidation experiments are conducted under VOC-rich and NOx-rich conditions; and the simulation generally reproduced O3 concentrations, OH reactivity (OHR), and contribution of NOx to total OHR. The measured O3 production regime changed from VOC-limited to NOx-limited after 1–3 h of irradiation by xenon arc lamps under the VOC-rich condition, whereas the regime remains VOC-limited throughout our experiment under the NOx-rich condition. The simulated timing of the regime transition under the VOC-rich condition is slower than that of the measured data, which could be attributed to overestimation of the NOx concentration. Both the measured and simulated timing of the regime transition estimated from the sensitivity to injection of O3 precursors NOx and VOC agree well with that estimated from the radical budget. The O3 production regimes estimated by the new instrument and by simulations are consistent with each other, suggesting that both methods are useful for estimating O3 production regime.

Harnessing Solar Energy Towards Synergistic Photothermal Catalytic Oxidation of Volatile Organic Compounds

Volatile organic compounds (VOCs) are prominent air pollutants, hazardous to human health and the environment. Sunlight is a sustainable energy source capable of meeting the demands for heterogeneous catalysis. Photothermal catalysis has emerged as an energy‐efficient technology for VOCs oxidation by merging the advantages of thermochemistry and photocatalysis. This review examines the advantages of the photothermal catalytic system, such as the absorption and conversion of solar light, accelerated reaction rates, and improved product selectivity. The photothermal catalytic system is clearly categorized according to the significant contributions of light and thermal energy to the reaction. As a result of the direct conversion of photons into thermal energy to surpass the light‐off temperature and drive the catalytic reaction, an ample discussion of light‐induced thermal catalytic processes is presented. Furthermore, the participation of the localized surface plasmon resonance effect and oxygen vacancies in the surface reaction under irradiation and thermal energy are spotlighted. A comprehensive discussion is provided for the various photothermal active nanostructures. The underlying superior resistance mechanism to water vapour and coke formation as well as high oxygen concentrations in photothermal catalytic system are emphatically highlighted. Finally, current research trends and prospects are discussed.

Improving oxidation removal of toluene in plasma coupling perovskite catalysts system by constructing Au sites on a La0.5Ce0.5CoO3-δ

Plasma-catalysis technique is a promising approach to control air pollution caused by volatile organic compounds (VOCs). Perovskite-type oxides have excited much interest in constructing plasma-catalytic system for the oxidation removal of VOCs owing to their flexible electronic structure, alterable geometry, unique catalytic properties and high stability. However, the perovskites commonly suffer from low surface area and small amounts of active surface sites because of their high synthesis temperature, which limits the synergism between the perovskites and plasma and thus decreases the performance of plasma-catalytic oxidation of VOCs. Here we show that the oxidation removal of toluene (typical refractory VOCs) in the plasma-catalytic system is improved by constructing Au sites on a perovskite of La0.5Ce0.5CoO3-δ (Au/La0.5Ce0.5CoO3-δ). Compared with plasma-catalytic systems integrated by LaCoO3 or La0.5Ce0.5CoO3-δ, coupling the Au/La0.5Ce0.5CoO3-δ with plasma enables the boost of toluene conversion and CO2 selectivity, but suppresses the generation of secondary pollutants (O3 and NOx). The calculation of apparent activation energy (Ea) demonstrates that the plasma-catalytic system integrated by Au/La0.5Ce0.5CoO3-δ obtains lower Ea of 6.9 kJ/mol than those integrated by LaCoO3 (9.5 kJ/mol) and La0.5Ce0.5CoO3-δ (8.1 kJ/mol) as well as plasma alone (15.0 kJ/mol), confirming a favorable toluene oxidation process in the plasma coupling Au/La0.5Ce0.5CoO3-δ system. Catalyst characterizations, discharge diagnosis and density functional theory calculations suggest that depositing Au on the La0.5Ce0.5CoO3-δ render the favorable gas and surface reactions for toluene oxidation in the plasma-catalytic system and thus a strong synergism between the perovskites and plasma, by modulating the discharge mode and creating large numbers of highly active Auδ+-Oδ--Ce interfacial sites on the surface of La0.5Ce0.5CoO3-δ.

Winning Combination of Cu and Fe Oxide Clusters with an Alumina Support for Low-Temperature Catalytic Oxidation of Volatile Organic Compounds.

A γ-alumina support functionalized with transition metals is one of the most widely used industrial catalysts for the total oxidation of volatile organic compounds (VOCs) as air pollutants at higher temperatures (280-450 °C). By rational design of a bimetal CuFe-γ-alumina catalyst, synthesized from a dawsonite alumina precursor, the activity in total oxidation of toluene as a model VOC at a lower temperature (200-380 °C) is achieved. A fundamental understanding of the catalyst and the reaction mechanism is elucidated by advanced microscopic and spectroscopic characterizations as well as by temperature-programmed surface techniques. The nature of the metal-support bonding and the optimal abundance between Cu-O-Al and Fe-O-Al species in the catalysts leads to synergistic catalytic activity promoted by small amounts of iron (Fe/Al = 0.005). The change in the metal oxide-cluster alumina interface is related to the nature of the surfaces to which the Cu atoms attach. In the most active catalyst, the CuO6 octahedra are attached to 4 Al atoms, while in the less active catalyst, they are attached to only 3 Al atoms. The oxidation of toluene occurs via the Langmuir-Hinshelwood mechanism. The presented material introduces a prospective family of low-cost and scalable oxidation catalysts with superior efficiency at lower temperatures.

Contributions of Surface Oxygen Species and Photoinduced Holes on Photothermocatalytic Toluene Oxidation over CeO2–MgO

To reveal the activity enhancement mechanism of volatile organic compounds (VOC) oxidation reaction, is vital for developing high-efficiency and cost-effective photothermocatalytic materials. Herein, porous and low-cost CeO2–MgO composite oxides were simply constructed via the solution combustion method and applied for toluene photothermocatalytic oxidation. The conversion rate for 1500 ppm of toluene over the optimized sample could reach 90% under the photothermocatalytic process at 330 °C and a gas hourly space velocity of 60,000 mL·g–1·h–1. Both gas phase oxygen and reactive oxygen species (ROS) played the dominant role in the photothermocatalytic activity while the total contribution rate of photoinduced holes and surface lattice oxygen was 25% to the activity. In situ Fourier transform infrared and electron paramagnetic resonance results revealed that the synergistic photothermo activation of molecular oxygen accelerated the low-temperature ROS formation. Under irradiation, photoinduced electrons could benefit the efficient transfer from superoxide radicals to peroxide radicals on material. Hence, it provides not only a comprehensive understanding on the activity enhancement mechanism at the molecular level but also a theoretical reference for designing objective catalysts for VOC abatement.

Characterization of products formed from the oxidation of toluene and m-xylene with varying NOx and OH exposure

Aromatic volatile organic compounds (VOCs) are an important precursor of secondary organic aerosol (SOA) in the urban environment. SOA formed from the oxidation of anthropogenic VOCs can be substantially more abundant than biogenic SOA and has been shown to account for a significant fraction of fine particulate matter in urban areas. A potential aerosol mass (PAM) chamber was used to investigate the oxidised products from the photo-oxidation of m-xylene and toluene. The experiments were carried out with OH radical as oxidant in both high- and low-NOx conditions and the resultant aerosol samples were collected using quartz filters and analysed by GC × GC-TOFMS. Results show the oxidation products derived from both precursors included ring-retaining and -opening compounds (unsaturated aldehydes, unsaturated ketones and organic acids) with a high number of ring-opening compounds observed from toluene oxidation. Glyoxal and methyl glyoxal were the major ring-cleavage products from both oxidation systems, indicating that a bicyclic route plays an important role in their formation. SOA yields were higher for both precursors under high-NOx (toluene: 0.111; m-xylene: 0.124) than at low-NOx (toluene: 0.089; m-xylene: 0.052), likely linked to higher OH concentrations during low-NOx experiments which may lead to higher degree of fragmentation. DHOPA (2,3-dihydroxy-4-oxo-pentanoic acid), a known tracer of toluene oxidation, was observed in both oxidation systems. The mass fraction of DHOPA in SOA from toluene oxidation was about double the value reported previously, but it should not be regarded as a tracer solely for oxidation of toluene as m-xylene oxidation gave a similar relative yield.

Characteristics of catalytic destruction of dichloromethane and ethyl acetate mixture over HxPO4-RuOx/CeO2 catalyst

Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds (VOCs) originating from solvent-based industrial processes. The varied composition tends to influence each VOC's catalytic behavior in the reaction mixture. We investigated the catalytic destruction of multi-component VOCs including dichloromethane (DCM) and ethyl acetate (EA), as representatives from pharmaceutical waste gases, over co-supported HxPO4-RuOx/CeO2 catalyst. A mutual inhibitory effect relating to concentrations because of competitive adsorption was verified in the binary VOCs oxidation and EA posed a more negative effect on DCM oxidation owing to EA's superior adsorption capacity. Preferential adsorption of EA on acidic sites (HxPO4/CeO2) promoted DCM activation on basic sites (O2−) and the dominating EA oxidation blocked DCM's access to oxidation centers (RuOx/CeO2), resulting in boosted monochloromethane yield and increased chlorine deposition for DCM oxidation. The impaired redox ability of Ru species owing to chlorine deposition in turn jeopardized deep oxidation of EA and its by-products, leading to increased gaseous by-products such as acetic acid originating from EA pyrolysis. Notably, DCM at low concentration slightly promoted EA conversion at low temperatures with or without water, consistent with the enhanced EA adsorption in co-adsorption analyses. This was mainly due to that DCM impeded the shielding effect of hydrolysate deposition from rapid EA hydrolysis depending on the decreased acidity. Moreover, water benefited EA hydrolysis but decreased CO2 selectivity while the generated water derived from EA was likely to affect DCM transformation. This work may provide theoretical guidance for the promotion of applied catalysts toward industrial applications.

Homogeneous CoCeOx nanocomposites with rich oxygen vacancies for effective catalytic oxidation of toluene

A CoCeOx nanocomposite catalyst was obtained by a template sacrificing method, with hydrothermally prepared carbon spheres as the template. The existence of plenty of functional groups on the surface of carbon spheres led to the uniform dispersion of the Co and Ce metal oxides, with an average crystal size of 6.1 nm. Compared with the conventional coprecipitation method, the catalyst prepared by template sacrificing exhibits better catalytic activity and stability, lower activation energy, and higher turnover frequency in the catalytic oxidation of toluene. The small crystal size, larger pore size, enhanced low-temperature reducibility and abundant oxygen vacancies are responsible for the superior activity. Using in situ FTIR, the oxidation intermediates and reaction pathways were proposed over the Co-Ce oxide nanocomposite catalyst. This work provides an effective method for the synthesis of uniform bimetallic nanocomposites with ultrasmall crystal size, which opens an avenue for new catalyst design methods for the oxidation of volatile organic compounds.

Novel Control System Strategy for the Catalytic Oxidation of VOCs with Heat Recovery

A theoretical study of the dynamic closed-loop behaviour of a reactor/feed-effluent heat exchanger (FEHE)/furnace system for the catalytic combustion of volatile organic compounds (VOCs) is presented. A 1D pseudohomogeneous plug-flow model is proposed to simulate the non-steady-state operation of the monolith reactor and the FEHE, while the furnace behaviour is described by means of a heterogeneous model of lumped parameters. Positive energy feedback is a source of instability that leads to strong thermal oscillations (limit cycles) and may cause damage to the equipment and sintering of the catalyst. The design of a robust and flexible control system and an efficient control strategy are, therefore, required to ensure safe and stable operation. The response of the system under three different control strategies to the most frequent disturbance variables—the feed flowrate (FV0) and feed concentration of VOCs (C0Et)—was evaluated. One of the control strategies consisted of a single-loop feedback system with servomechanism changes in the reactor inlet temperature (T0) that manipulated the bypass valve and, sequentially, the natural gas flowrate in the furnace (FNG). This approach made it possible to meet the control objective (reducing VOCs) without losing controllability and while minimizing the use of external fuel.

Molecular Characterization of Oxygenated Organic Molecules and Their Dominating Roles in Particle Growth in Hong Kong.

Oxygenated organic molecules (OOMs) are critical intermediates linking volatile organic compound oxidation and secondary organic aerosol (SOA) formation. Yet, the understanding of OOM components, formation mechanism, and impacts are still limited, especially for urbanized regions with a cocktail of anthropogenic emissions. Herein, ambient measurements of OOMs were conducted at a regional background site in South China in 2018. The molecular characteristics of OOMs revealed dominant nitrogen-containing products, and the influences of different factors on OOM composition and oxidation state were elucidated. Positive matrix factorization analysis resolved the complex OOM species to factors featured with fingerprint species from different oxidation pathways. A new method was developed to identify the key functional groups of OOMs, which successfully classified the majority species into carbonyls (8%), hydroperoxides (7%), nitrates (17%), peroxyl nitrates (10%), dinitrates (13%), aromatic ring-retaining species (6%), and terpenes (7%). The volatility estimation of OOMs was improved based on their identified functional groups and was used to simulate the aerosol growth process contributed by the condensation of those low-volatile OOMs. The results demonstrate the predominant role of OOMs in contributing sub-100 nm particle growth and SOA formation and highlight the importance of dinitrates and anthropogenic products from multistep oxidation.

Revealing the equilibrium relationship between lattice oxygen mobility and styrene removal: Sources of adsorption and activation by in situ experiments

Copper-manganese composite oxides have been extensively researched for the catalytic oxidation of volatile organic compounds (VOCs), but there is little understanding of the adsorption and activation of VOCs over these compounds. In this work, a series of amorphous Cu-Mn binary oxides with varying Cu/Mn ratios were prepared to explore their catalytic performance and the species involved in the adsorption and activation of styrene (C8H8). It was found that Cu1Mn5Ox demonstrated better catalytic activity among the four samples, better stability and water resistance due to the presence of more structural flaws, weaker Mn-O bonds and more surface lattice oxygen species. In situ designed experiments showed that the adsorbed oxygen species, O2, lattice oxygen, and copper species all played roles in the adsorption and activation of C8H8 at low temperatures. The degradation route for C8H8 was revealed by in situ DRIFTS, and benzoic acid decomposition was identified as the rate-limiting step of C8H8 degradation. This work provides a novel technique for regulating the synergistic adsorption and catalytic ability of amorphous bimetallic oxides to remove VOCs.

Photocatalytic oxidation of volatile organic compounds (VOCs) in air using ultraviolet light-emitting diodes (UV-LEDs)

The aim of this study was to experimentally investigate the application of ultraviolet light-emitting diodes (UV-LEDs) for removing volatile organic compounds (VOCs) from air. For this purpose, a 365 nm UV-LED and a photocatalyst were used in a batch reactor to study the photocatalysis of toluene as the representative pollutant. It was demonstrated that combining reduced graphene oxide (rGO) with titanium dioxide (TiO2) and immobilizing the catalyst on the porous substrate could significantly improve the photocatalytic activity compared with the pristine TiO2 catalyst on a solid substrate. Photocatalyst deactivation was also studied by running cyclical tests. The photocatalytic crystal structure remained intact, but catalytic activity declined more than 80% after five consecutive photocatalytic tests for treating relatively high toluene concentrations. The adsorbed intermediates of toluene photocatalysis, such as benzoic acid, benzaldehyde, and benzyl alcohol, were identified, and the deactivation mechanism was proposed. It was shown that the deactivated photocatalyst can be effectively regenerated by UV-LED irradiation of 38.5 mW/cm2 irradiance within two hours. Overall, it was concluded that the UV-LED with a TiO2 on porous support provides an effective method for practical air purification applications.

Sr-doped calcium and barium manganites as catalysts in heterogeneous oxidation of volatile organic compounds

Sr-doped calcium and barium manganites as catalysts in heterogeneous oxidation of volatile organic compounds

Tailoring Oxygen Vacancies and Active Surface Oxygen Species in Copper-Doped MnO2 Catalysts for Total Catalytic Oxidation of VOCs

Catalytic oxidation has been considered an essential route to tackle volatile organic compounds (VOCs)-driven pollution. To this point, surface engineering has emerged as a robust pathway to promote the efficiency of MnO2-based materials toward VOC oxidation. However, regulating such surface properties has been a critical challenge. This investigation attempts to tailor surface oxygen vacancies and active surface oxygen for the total catalytic oxidation of various VOCs (e.g., formaldehyde, isopropanol, and toluene) via doping copper into cryptomelane and birnessite-type MnO2 catalysts. The catalysts are synthesized by a novel facile successive redox precipitation method between KMnO4 and an ethanol solution containing copper nitrate precursors, followed by annealing. It turns out that the low amount of Cu dopants, corresponding to the copper-to-manganese ratio of 0.17 (RCu/Mn = 0.17), generates a tunnel-structured cryptomelane-type MnO2 with strong bulk oxygen mobility. Such a crystalline structure exhibits the best catalytic performance for the total catalytic oxidation of toluene. The higher copper loading (RCu/Mn = 0.27–0.34) drives the formation of Cu-doped layered birnessite-type MnO2 materials containing rich oxygen vacancies and high active surface oxygen species. Those catalysts promote the oxidation of isopropanol and formaldehyde, respectively. To this end, oxygen vacancies and surface oxygen species crucially steer the molecular oxygen activation and interactions toward adsorbed oxygen species, significantly promoting the total oxidation of isopropanol and formaldehyde, respectively. The explored finding could disclose an outstanding platform toward highly selective and efficient oxidation of VOCs.