Catalytic Activity For CO Oxidation Research Articles

Effect of cobalt on CeO2 nanorod supported Pt catalyst: Structure, performance, kinetics and reaction mechanism in CO oxidation

Catalytic oxidation represents a highly efficient and extensively employed approach for the elimination of CO in exhaust gas. Rationally designing and preparing catalysts with exceptional activity and stability in the presence of H2O and SO2 at low temperatures represent crucial avenues for future advancements. In this work, a series of Pt catalysts supported on CeO2 nanorods incorporated with varying amounts of Cobalt (Co/CeO2 ratio ranging from 0 to10) were prepared and evaluated for their catalytic activity in CO oxidation under both dry and wet conditions. The ultrahigh dispersion of Pt, outstanding redox properties, and abundant oxygen vacancies on the surface of Co-doped CeO2 nanorod supported Pt catalysts were revealed by XRD, HAADF-STEM, Raman spectroscopy and H2-TPR techniques. The catalytic activity for CO oxidation strongly depends on the Co content and reaction conditions. Among them, Pt/Co-CeO2-5 % exhibits the highest CO oxidation performance with a T90 (the temperature to achieve 90 % conversion of CO) of 170 °C under dry conditions, which is significantly lower by 140 °C compared to T90 of Pt/CeO2. Pt/Co-CeO2-1 % demonstrates superior CO oxidation performance with a T90 of 195 °C under wet conditions, exhibiting a reduction in temperature by 65 °C compared to the T90 of Pt/CeO2. Moreover, Pt/Co-CeO2 exhibits excellent resistance to SO2 compared to Pt/CeO2. Kinetic studies, in situ DRIFT analysis and isotopic experiments demonstrated direct participation of H2O in the reaction. On the catalysts with a low Co/Ce ratio (Co/Ce < 0.03), CO readily reacts with hydroxyl groups dissociated from H2O to form carboxyl intermediates, which subsequently undergo rapid decomposition into CO2, resulting in an enhanced reaction rate of CO oxidation at low temperature.

In situ exsolution of Pt nanoparticles on low Pt-substituted A-site deficient perovskite for efficient CO oxidation

Platinum nanoparticles often lose their efficacy in challenging working environments. In this study, we developed a novel approach for the preparation of highly dispersed precious metal catalysts. The method involves the utilization of composite materials consisting of PtOx/(LC)0.9MP, achieved through the exsolution of a low Pt substituted A-site deficient perovskite (La0.97Ce0.03)0.9Mn0.99Pt0.01O3 ((LC)0.9MP). This procedure facilitates the in situ exsolution of Pt nanoparticles from (LC)0.9MP through heat treatment under 10 vol% H2/Ar environment. During this process, PtOx undergoes transformation to Pt0, exhibiting a high CO catalytic oxidation activity, with the T100(CO) decreasing from 213 to 141 °C. This capability primarily stems from the substantial number of oxygen vacancies and alterations in Pt species induced by the catalyst during the redox process. The active Pt nanoparticles are strongly integrated on the surface of (LC)0.9MP, demonstrate excellent CO oxidation activity and stability. This performance is attributed to the specific structure of perovskite. Upon reoxidation, these particles do not undergo direct reincorporation into the lattice structure. Instead, NPs result in the formation of stable, anchored oxide nanoparticles. This strategy can be extended to other metals oxides catalysts, thus may help the rational design of highly efficient transition metal oxide-based catalysts and beyond.

Effects of Synthesis Method on Catalytic Activities of Ag/TiO2 Catalyst in CO Oxidation Reaction

Supported silver catalysts on titanium dioxide have been synthesized by three different methods to compare catalytic activity in CO oxidation. The catalysts were prepared by the wet impregnation method with 10 mole% of silver. In the first method, the silver catalysts were impregnated on the titanium dioxide nanoparticles (Ag/TNP), while in the second method, the silver catalysts were impregnated on the titanium dioxide nanotubes (Ag/TNT). The third method, the silver catalysts were impregnated on the titanium dioxide nanoparticles before the nanotube process (Ag/TNP-TNT). The Ag/TNP and Ag/TNT catalysts showed highly dispersed silver nanoparticles with an average particle size of less than 5 nm on the surface of titanium dioxide, whereas the Ag/TNP-TNT catalyst exhibited much lower dispersion of silver nanoparticles. The highly dispersed silver on the titanium dioxide resulted in a large number of surface active sites (Ag0). The catalytic activity test found that the Ag/TNT catalysts with the highest number of active sites (2.20 × 1020 atom/g-catalyst) exhibited higher CO oxidation activity than the Ag/TNP and Ag/TNT catalysts with 100% CO conversion at 125°C.

A Ce/hopcalite catalyst for low-temperature oxidation of CO:Preparation, performance and mechanism

The utilization of atomic-scale doping in catalysts has been recognized as an effective strategy for enhancing CO oxidation catalytic activity. This work adjusted the lattice structure of hopcalite (CuMnOx) catalysts via Ce-doping. Ce species was uniformly dispersed on the surface of amorphous porous catalysts, which built abundant interfaces along with many active sites. The lattice distortion degree can be regulated by changing Ce dosage. The modified catalysts with 7.5 wt%Ce-doping exhibited the optimal intrinsic activity for CO oxidation. Compared with the original sample, the CO conversion increased by 50 % at room temperature, and the reaction rate was eight-fold faster, superior to most reported hopcalite catalysts. Integrating with the various characterizations, the enhancing of low-temperature activity mainly originates from the weakened binding of oxygen atoms by lattice distortions. Moreover, the experiments and characterization results revealed that the reactivity of both adsorbed and lattice oxygen is enhanced on Ce-modified samples at low temperature. This work provides new insights into the rational modulation of reactive oxygen species and reinforces the utility of hopcalite catalysts for oxidizing CO at low temperature.

Comparative Study of Exsolved and Impregnated Ni Nanoparticles Supported on Nanoporous Perovskites for Low-Temperature CO Oxidation.

This study investigated the redox exsolution of Ni nanoparticles from a nanoporous La0.52Sr0.28Ti0.94Ni0.06O3 perovskite. The characteristics of exsolved Ni nanoparticles including their size, population, and surface concentration were deeply analyzed by environmental scanning electron microscopy (ESEM), transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) mapping, and hydrogen temperature-programmed reduction (H2-TPR). Ni exsolution was triggered in hydrogen as early as 400 °C, with the highest catalytic activity for low-temperature CO oxidation achieved after a reduction step at 500 °C, despite only a 10% fraction of Ni exsolved. The activity and stability of exsolved nanoparticles were compared with their impregnated counterparts on a perovskite material with a similar chemical composition (La0.65Sr0.35TiO3) and a comparable specific surface area and Ni loading. After an aging step at 800 °C, the catalytic activity of exsolved Ni nanoparticles at 300 °C was found to be 10 times higher than that of impregnated ones, emphasizing the thermal stability of Ni nanoparticles prepared by redox exsolution.

Decoration of Gold and Platinum Nanoparticle Catalysts by 1 nm Thick Metal Oxide Overlayer and Its Effect on the CO Oxidation Activity.

Exfoliated M-Al layered double hydroxide (M-Al LDH; M = Mg, Co, Ni, and Zn) nanosheets were adsorbed on Au/SiO2 and calcined to transform LDH into mixed metal oxides (MMOs) and yield Au/SiO2 coated with a thin MMO overlayer. These catalysts showed a higher catalytic activity than pristine Au/SiO2. In particular, the 50% CO conversion temperature decreased by more than 250 °C for Co-Al MMO-coated Au/SiO2. In contrast, the deposition of CoAlOx on Au/SiO2 by impregnation or the deposition of Au on Co-Al MMO-coated SiO2 resulted in a worse catalytic activity. Moreover, the presence of a thick MMO overlayer decreased the catalytic activity, suggesting that the control of the overlayer thickness to less than 1 nm is a requisite for obtaining a high catalytic activity. Moreover, the thin Co-Al MMO overlayer on Au/SiO2 possessed abundant oxygen vacancies, which would play an important role in O2 activation, resulting in a highly active interface between Au and the defect-rich MMO on the Au NP surface. Finally, this can be applied to Pt/SiO2, and the obtained Co-Al MMO-coated Pt/SiO2 also exhibited a much improved catalytic activity for CO oxidation.

Functionalisation of alkali-resistant nanoporous glass via Au nanoparticle decoration using alkaline impregnation: catalytic activity for CO removal.

The concerted use of nano-metal particles with catalytic functions and nanoporous materials holds promise for effective air purification and gas sensing; however, only a few studies have used porous glasses as supports for Au nanoparticles. Furthermore, Au/nanoporous glasses with activities comparable to that of Au/TiO2, which is a typical Au catalyst, have not been reported to date. This study demonstrates that a nanoporous glass, which is highly acid- and alkali-resistant and chemically stable, can be decorated with Au nanoparticles using an alkali impregnation method. The resulting composite exhibits high catalytic activity in CO oxidation. The catalysts reported herein are as active as Au/TiO2 catalysts per active site. Further optimisation of the pore properties of the glass and sizes of the Au nanoparticles is expected to result in excellent catalytic systems for CO removal and sensing.

Microalgae-derived Co3O4 nanomaterials for catalytic CO oxidation.

Efficient carbon monoxide oxidation is important to reduce its impacts on both human health and the environment. Following a sustainable synthesis route toward new catalysts, nanosized Co3O4 was synthesized based on extracts of microalgae: Spirulina platensis, Chlorella vulgaris, and Haematococcus pluvialis. Using the metabolites in the extract and applying different calcination temperatures (450, 650, 800 °C) led to Co3O4 catalysts with distinctly different properties. The obtained Co3O4 nanomaterials exhibited octahedral, nanosheet, and spherical morphologies with structural defects and surface segregation of phosphorous and potassium, originating from the extracts. The presence of P and K in the oxide nanostructures significantly improved their catalytic CO oxidation activity. When normalized by the specific surface area, the microalgae-derived catalysts exceeded a commercial benchmark catalyst. In situ studies revealed differences in oxygen mobility and carbonate formation during the reaction. The obtained insights may facilitate the development of new synthesis strategies for manufacturing highly active Co3O4 nanocatalysts.

Hydroxyls on CeO2 Support Promoting CuO/CeO2 Catalyst for Efficient CO Oxidation and NO Reduction by CO.

Transition metal catalysts, such as copper oxide, are more attractive alternatives to noble metal catalysts for emission control due to their higher abundance, lower cost, and excellent catalytic activity. In this study, we report the preparation and application of a novel CuO/CeO2 catalyst using a hydroxyl-rich Ce(OH)x support for CO oxidation and NO reduction by CO. Compared to the catalyst prepared from a regular CeO2 support, the new CuO/CeO2 catalyst prepared from the OH-rich Ce(OH)x (CuO/CeO2-OH) showed significantly higher catalytic activity under different testing conditions. The effect of OH species in the CeO2 support on the catalytic performance and physicochemical properties of the CuO/CeO2 catalyst was characterized in detail. It is demonstrated that the abundant OH species enhanced the CuOx dispersion on CeO2, increased the CuOx-CeO2 interfaces and surface defects, promoted the oxygen activation and mobility, and boosted the NO adsorption and dissociation on CuO/CeO2-OH, thus contributing to its superior catalytic activity for both CO oxidation and NO reduction by CO. These results suggest that the OH-rich Ce(OH)x is a superior support for the preparation of highly efficient metal catalysts for different applications.

Hydrogen Spillover Induced PtCo/CoOx Interfaces with Enhanced Catalytic Activity for CO Oxidation at Low Temperatures in Humid Conditions.

The development of catalysts with abundant active interfaces for superior low-temperature catalytic CO oxidation is critical to meet increasingly rigorous emission requirements, yet still challenging. Herein, this work reports a PtCo/CoOx/Al2O3 catalyst with PtCo clusters and enriched Pt─O─Co interfaces induced by hydrogen spillover from the Pt sites and self-oxidation process in air, exhibiting excellent performance for CO oxidation at low temperatures and humid conditions. The combination of structural characterizations and in situ Fourier transform infrared spectroscopy reveals that the PtCo cluster effectively prevents CO saturation/poisoning on the Pt surface. Additionally, the presence of Pt─O─Co interfaces in the PtCo/CoOx/Al2O3 catalyst provides a significant number of active sites for oxygen activation and ─OH formation. This facilitates efficient generation of CO2 at ambient temperature by coupling with nearby adsorbed CO molecules, resulting in superior low-temperature activity and long-term stability for CO oxidation under humid conditions. This work provides a facile route toward rationalizing the design of catalysts with more active interfaces for superior low-temperature CO oxidation under humid conditions for practical applications.

In situ noble metal-ion modified TiO2 rutile nanobars with highly exposed {110} facets: Synthesis, structure, and catalytic properties

The in situ anchoring of metal elements on the surface of nanomaterials is a state-of-the-art technology that can significantly enhance the performance of materials. We have successfully fabricated noble metal-ion modified rutile TiO2 nanobars, which exhibit exceptional catalytic activity in both H2 generation and CO oxidation. Firstly, we synthesized Ti3+ self-doped rutile TiO2-x nanobars by a simple solvothermal method using Zn as a reductant, resulting in highly crystalline structures with a significant proportion of (110) surfaces. The reduced nanobars chemically absorb the noble metal cations with the addition of a solution of a noble metal salt in the absence of light to form in situ noble metal-ion modified catalysts. TiO2 nanobars with 1 wt% Pt2+ and Pd2+ exhibited excellent performance in photocatalytic H2 generation from water and low temperature CO oxidation. Moreover, the samples modified with low noble metal ions (0.1 wt%) also show effective activity in H2 generation.

A theoretical study into the performance of DACs loaded on MgO utilized in CO oxidation

Single-atom catalysts (SACs) have garnered significant attention due to their unique combination of advantages from both heterogeneous and homogeneous catalysts. However, SACs composed of just one metal cannot adequately meet the various catalytic requirements. Thus, this study focused on the addition of a second metal atom to M1/MgO systems (M = Au, Ag and Cu) to create dual-atom catalysts (DACs) supported on different di-vacancy types on MgO(100) surfaces. Homogeneous (Au2, Ag2, Cu2) and multiphase (Au1Ag2, Au1Cu2 and Ag1Cu2) were analyzed for their selectivity in CO oxidation by Langmuir-Hinshaw (LH) and Eley-Rideal (ER) mechanisms using density functional theory (DFT) method. The results indicated that the tri-molecules ER pathway had the highest selectivity, and the multiphase DACs had better CO catalytic oxidation activity compared to homogeneous DACs. Among all multiphase DACs in the tri-molecules ER pathway, alloy DACs of Au1Ag2/MgO(Fc-Fc) and Au1Cu2/MgO(Fc-Vc) had the lowest energy barrier for CO oxidation, and the addition of a second metal atom improved stability compared to SAC of Au1/MgO(Fc). DFT calculations combined with microkinetic simulations revealed that under reaction conditions, Au1Cu2/MgO(Fc-Vc) had a remarkably high TOF of CO2, making it a promising DAC for practical applications. This study provides valuable insights into the development of efficient and low-cost atomic-scale catalysts.

Evaluation of Pr2Zr2−xCexO7±δ pyrochlores as a potential Cu support catalysts for CO oxidation in simulated GDI conditions

This study evaluates the catalytic activity, both as bulk catalysts and as supports for copper catalysts for CO oxidation in a simulated Gasoline Direct Injection Engine (GDI) of two pyrochlores: Pr2Zr2O7 (PZ) and Pr2Zr1.9Ce0.1O7±δ (PZC). These pyrochlores were synthesized by the solvothermal method. XRD, FE-SEM, HR-TEM, XPS, H2-TPR, and O2-TPD characterization techniques were employed to determine the structural, microstructural, and redox properties of the samples. All materials exhibited high catalytic activity for CO oxidation, with Cu-PZC showing the best performance, which is comparable to that of a 1% Pt/Al2O3 commercial catalyst used as a reference. Thus, the synthesized solids could be a promising and cost-effective alternative to noble metal-based catalysts used to control GDI exhaust gas composition.

Investigating the impact of dynamic structural changes of Au/rutile catalysts on the catalytic activity of CO oxidation

AbstractThe surface properties of oxidic supports and their interaction with the supported metals play critical roles in governing the catalytic activities of oxide‐supported metal catalysts. When metals are supported on reducible oxides, dynamic surface reconstruction phenomena, including strong metal–support interaction (SMSI) and oxygen vacancy formation, complicate the determination of the structural–functional relationship at the active sites. Here, we performed a systematic investigation of the dynamic behavior of Au nanocatalysts supported on flame‐synthesized TiO2, which takes predominantly a rutile phase, using CO oxidation above room temperature as a probe reaction. Our analysis conclusively elucidated a negative correlation between the catalytic activity of Au/TiO2 and the oxygen vacancy at the Au/TiO2 interface. Although the reversible formation and retracting of SMSI overlayers have been ubiquitously observed on Au/TiO2 samples, the catalytic consequence of SMSI remains inconclusive. Density functional theory suggests that the electron transfer from TiO2 to Au is correlated to the presence of the interfacial oxygen vacancies, retarding the catalytic activation of CO oxidation.

A comparison of bifunctional MnOx catalysts prepared via different precipitants for simultaneous removal NO and CO

In this work, ammonium carbonate, sodium hydroxide, and ammonium hydroxide were selected as the precipitants to prepare bifunctional MnOx catalysts via the PEG-assisted co-precipitation method. SEM analysis revealed that MnOx catalysts prepared with ammonium carbonate (AC) displayed a spherical morphology with relatively large size, whereas the catalysts synthesized with sodium hydroxide (SH) and ammonium hydroxide (AH) exhibited polyhedron shapes with smaller size. The results demonstrated that Mn-AC catalyst presented superior catalytic activity for both NO reduction and CO oxidation, achieving 89% NO conversion at 100 ºC and over 80% CO conversion at 200 ºC, outperforming Mn-SH and Mn-AH catalysts. Mn-AC catalyst possessed more abundant Mn4+ species and surface chemisorbed oxygen than Mn-AH and Mn-SH catalysts, which served as a significant motivation for the difference in catalytic activity. Additionally, Mn-AC catalyst exhibited stronger surface acidity, which facilitated the adsorption and activation of ammonia species in the NH3-SCR reaction. Furthermore, in situ DRIFTS experiment suggested that the pre-desorption of CO promoted the adsorption and activation of NO. On this basis, the possible mechanism model of three precipitants on bifunctional MnOx catalysts was proposed.

Insights into the underpinning effect of graphene in Cu1Mn10 on enhancing the low-temperature catalytic activity for CO oxidation

CO emission is a critical issue of industrial processes such as steel-smelting, cement manufacturing, and waste incineration. Catalytic oxidation based on Cu–Mn binary catalysts shows great potential for efficient removal of CO, whereas their practical applicability is limited by the inferior low-temperature catalytic activity and the high catalyst cost owing to a substantial quantity of Cu. In this study, doping graphene is designed to adjust the electron transfer capability to improve the low-temperature catalytic activity as well as reduce the amount of Cu, and thereby Cu1Mn10 catalysts doped with slight amounts of graphene (x%G-Cu1Mn10, x is 1∼5) were fabricated. It was found that the introduction of graphene could form effective electron transport channels to enhance the intermetallic interaction and oxygen vacancy generation, thus improving the low-temperature catalytic performance of the Cu1Mn10 catalyst. Among all the catalysts, 4%G-Cu1Mn10 exhibited the highest activity, achieving CO conversion of 92% at 110 °C at a weight hourly space velocity of 120,000 mL/(g∙h). The introduction of graphene also enabled the catalyst with excellent catalytic activity and stability at a relative humidity of 70%. Attractively, 4%G-Cu1Mn10 can be further loaded into the polyester fabric, presenting great application potentials in the effective elimination of CO during the dust removal process since the flue gas temperature in the dust collector is just around the T90% and the catalyst that is inside of fabric fiber rather than on the fabric surface can be rarely influenced by the dust. In general, doping graphene provides a facile method to enhance the low-temperature activities of the Cu–Mn binary catalysts and cut down the use of valuable Cu, showing great application potential.

Enhanced methane combustion and CO oxidation with Pd and Pt substitution LaSrCuO4 perovskites

The LaSrCuO4 as parent perovskite purely lattice was synthesized by new presented solid states technique and Pd and Pt substitution in LaSrCuO4 catalysts instead of Cu were prepared in this method at low temperature. All the perovskites were investigated by X-ray Diffraction, HRTEM, O2-TPD, H2-TPR, BET and XPS analyses. The CO oxidation and methane combustion catalytic activity of prepared perovskites were investigated which the LaSrCuO4 catalytic performance noticeably enhanced via Pd and Pt substitution instead of Cu. Both Langmuir and intra-facial mechanisms were intensified with increasing of surface area and mobility of lattice oxygen due to Pd and Pt doping in CO oxidation and methane combustion reactions. Pd 3d3/2 and 3d5/2 XPS spectra in LaSrCu0.9Pd0.1O4 confirmed Pd incorporation in perovskite structure due to presence of high oxidation state of Pd3+ or Pd4+. Pt 4 f5/2 and 4 f7/2 peaks approved Pt4+ oxidation state in LaSrCu1−xPtxO4 (x = 0.1,0.2) catalysts. The H2-TPR profiles of the Pt and Pd doped LSC perovskites revealed that the reduction peaks of the Cu were shifted to lower temperatures by increasing in Pd and Pt partial substitution due to H2-spillover effect of palladium and platinum.

Insights into SnO2 Nanoparticles Supported on Fibrous Mesoporous Silica for CO Catalytic Oxidation

A large surface area dendritic mesoporous silica material (KCC-1) was successfully synthesized and used as a support to confine SnO2 nanoparticles (NPs). Owing to the large specific surface area and abundant mesoporous structure of dendritic KCC-1, the SnO2 NPs were highly dispersed, resulting in significantly improved CO catalytic oxidation activity. The obtained Snx/KCC-1 catalysts (x represents the mass fraction of SnO2 loading) exhibited excellent CO catalytic activity, with the Sn7@KCC-1 catalyst achieving 90% CO conversion at about 175 °C. The SnO2 NPs on the KCC-1 surface in a highly dispersed amorphous form, as well as the excellent interaction between SnO2 NPs and KCC-1, positively contributed to the catalytic removal process of CO on the catalyst surface. The CO catalytic removal pathway was established through a combination of in situ diffuse reflectance infrared transform spectroscopy and density-functional theory calculations, revealing the sequential steps: ① CO → CO32−ads, ② CO32−ads → CO2free+SnOx−1, ③ SnOx−1+O2 → SnOx+1. This study provides valuable insights into the design of high-efficiency non-precious metal catalysts for CO catalytic oxidation catalysts with high efficiency.

Exploring the key components of Au catalyst during CO oxidation using TG-MS and operando DRIFTS-MS

Nano-Au has a good catalytic activity for CO oxidation, but its catalytic mechanism is still not clear. Here, CO oxidation on Au2O3 and its thermal decomposition products were studied using thermogravimetric-mass spectrometry (TG-MS) and operando diffuse reflectance infrared Fourier transform spectroscopy-mass spectrometry (DRIFTS-MS) to explore the key active components of Au catalyst for CO oxidation. The TG-MS results showed that Au2O3 decomposed to AuO at 210 °C and Au at 375 °C and was oxidized to form Au oxide above 375 °C. When Au2O3 decomposed into AuxOy (x>y) above 210 °C, the CO oxidation activity obviously increased. Au atoms in the Au-Au system serve as electron donor and CO adsorption sites. Au atom is oxidized to AuO by the O atom from O2 decomposition following the Epling-Xu decomposition mechanism. A schematic diagram of the key components of Au2O3 catalysts during CO oxidation was proposed based on TG-MS and operando DRIFTS-MS analysis results.

In situ DRIFTS and TPD studies on surface properties affecting SO2-resistance of Pt/TiO2 catalyst in low-temperature CO oxidation

By pre-calcining two TiO2 (P25 and anatase) supports at various temperatures, Pt/TiO2 of different Pt valence states, surface hydroxyls (OH), and peroxide contents were prepared. Pt/Anatase 450 and Pt/P25 450, whose supports were pre-calcined at 450 °C, performed excellently in the CO oxidation catalytic activity test using flue gas without water and SO2. Their low T50 (165 and 175 °C, respectively) and high TOF at 125 °C (0.204 and 0.247 s−1, respectively) of CO oxidation are attributed to the low stability of the adsorbed CO on Pt sites. Furtherly, in the catalytic test using water and SO2-containing flue gas, the catalysts using anatase supports achieved higher performance than P25 supports, showing T50 of 182−186 °C and TOF of 0.202−0.207 s−1 at 165 °C. The in situ DRIFTS study and TPD analysis indicate that OH participates in the sulfate formation. The limited hydroxylation on the anatase surface provides a small amount of OH, thereby mitigating the stable sulfate accumulation. Less stable sulfate on anatase than P25 gives rise to the high activity of anatase-supported catalysts.