Fundamental insights and recent advances in catalytic oxidation processes using ozone for the control of volatile organic compounds.

The development of technologies for highly efficient treatment of emissions containing low concentrations of volatile organic compounds (VOCs) remains an important challenge. Catalytic oxidation with ozone (catalytic ozonation) is useful for the oxidative decomposition of VOCs, particularly aromatic compounds, under ambient temperature conditions. Only inexpensive transition metal oxides are required as catalysts, and Mn-based catalysts are widely used for catalytic ozonation. This review describes the oxidation reaction mechanisms, reaction pathways of aromatic hydrocarbons, and dependence of the catalytic ozonation activity on the reaction conditions. The reasons why Mn oxides are effective in catalytic ozonation are also explained. The structure of the catalytic active sites and the types of supporting materials contributing to the reaction are also discussed in detail, with the aim of establishing a VOC control technology. In addition, recent progress in catalytic oxidation processes using ozone as an oxidant has been outlined, focusing on catalyst materials and reaction conditions.

Lattice-Plane-Dependent Distribution of Ce3+ at Pt and CeO2 Interfaces for Pt/CeO2 Catalysts.

The interaction between a metal and a support, which is known as the metal-support interaction, often plays a determining role in the catalytic properties of supported metal catalysts. Herein, we have developed model Pt/CeO2 catalysts, which enabled us to investigate the interface atomic and electronic structures between Pt and the {001}, {011}, and {111} planes of CeO2 using scanning transmission electron microscopy and electron energy-loss spectroscopy. We found that the number of Ce3+ ions around the Pt nanoparticles followed the order {001} > {011} > {111}, which was the opposite order of the generally accepted stability of low index surfaces of CeO2. Systematic first-principles calculations revealed that the presence of Pt nanoparticles facilitated the formation of oxygen vacancies and that the appearance of the Ptδ+ state was preferred when Pt nanoparticles were in contact with CeO2 {001} planes due to direct charge transfer from Pt to CeO2. These results provide important insights into the nature of the metal-support interaction for a comprehensive understanding of the properties of supported metal catalysts.

Catalytic degradation of benzene over non-thermal plasma coupled Co-Ni binary metal oxide nanosheet catalysts.

Non-thermal plasma (NTP) has been demonstrated as one of the promising technologies that can degrade volatile organic compounds (VOCs) under ambient condition. However, one of the key challenges of VOCs degradation in NTP is its relatively low mineralization rate, which needs to be addressed by introducing catalysts. Therefore, the design and optimization of catalysts have become the focus of NTP coupling catalysis research. In this work, a series of two-dimensional nanosheet Co-Ni metal oxides were synthesized by microwave method and investigated for the catalytic oxidation of benzene in an NTP-catalysis coupling system. Among them, Co2Ni1Ox achieves 60% carbon dioxide (CO2) selectivity (SCO2) when the benzene removal efficiency (REbenzene) reaches more than 99%, which is a significant enhancement compared with the CO2 selectivity obtained without any catalysts (38%) under the same input power. More intriguingly, this SCO2 is also significantly higher than that of single metal oxides, NiO or Co3O4, which is only around 40%. Such improved performance of this binary metal oxide catalyst is uniquely attributed to the synergistic effects of Co and Ni in Co2Ni1Ox catalyst. The introduction of Co2Ni1Ox was found to promote the generation of acrolein significantly, one of the key intermediates found in NTP alone system reported previously, suggest the benzene ring open reaction is promoted. Compared with monometallic oxides NiO and Co3O4, Co2Ni1Ox also shows higher active oxygen proportion, better oxygen mobility, and stronger low-temperature redox capability. The above factors result in the improved catalytic performance of Co2Ni1Ox in the NTP coupling removal of benzene.

Direct identification of the charge state in a single platinum nanoparticle on titanium oxide.

A goal in the characterization of supported metal catalysts is to achieve particle-by-particle analysis of the charge state strongly correlated with the catalytic activity. Here, we demonstrate the direct identification of the charge state of individual platinum nanoparticles (NPs) supported on titanium dioxide using ultrahigh sensitivity and precision electron holography. Sophisticated phase-shift analysis for the part of the NPs protruding into the vacuum visualized slight potential changes around individual platinum NPs. The analysis revealed the number (only one to six electrons) and sense (positive or negative) of the charge per platinum NP. The underlying mechanism of platinum charging is explained by the work function differences between platinum and titanium dioxide (depending on the orientation relationship and lattice distortion) and by first-principles calculations in terms of the charge transfer processes.

Improved and Reduced Performance of Cu- and Ni-Substituted Co3O4 Catalysts with Varying CoOh/CoTd and Co3+/Co2+ Ratios for the Complete Catalytic Oxidation of VOCs.

The Co3O4 spinel is one of the most promising transition metal oxide (TMO) catalysts for volatile organic compound (VOC) treatment. Substituting effects have usually been utilized to improve the catalytic performance of the Co3O4 spinel. In this study, Cu- and Ni-substituted Co3O4 catalysts derived from mixed metal-organic frameworks (MMOFs) retained similar spinel structures but exhibited improved and reduced performance for o-xylene oxidation, respectively. Physicochemical characterization and DFT calculations revealed that Cu and Ni substitution into the Co3O4 spinel varied the valence (Co3+/Co2+) and geometry (CoOh/CoTd) distributions of Co cations through different partial electron transfer and substitution sites. The higher Co3+/Co2+ and CoOh/CoTd ratios of the CuCo2O4 catalyst contributed to the superior reducibility and oxygen mobility, which facilitated the oxidation of intermediates at lower temperatures in the catalytic oxidation of o-xylene. Meanwhile, the NiCo2O4 catalyst with lower Co3+/Co2+ and CoOh/CoTd ratios could not completely oxidize intermediates under the same conditions due to inferior redox properties. Therefore, the CuCo2O4 catalyst showed superior catalytic activity and stability to the NiCo2O4 catalyst for the catalytic oxidation of o-xylene. This work provides insights into the synthesis of substituted Co3O4 catalysts from MMOFs and mechanism of substituting effects, which might guide the design of efficient TMO catalysts for VOC treatment.

Atomic and Electronic Structure of Pt/TiO2 Catalysts and Their Relationship to Catalytic Activity.

Understanding the nature of the interaction between a metal and support, which is known as the metal-support interaction, in supported metal catalysts is crucial to design catalysts with desired properties. Here, we have developed model Pt/TiO2 catalysts based on the deposition of colloidal Pt nanoparticles and studied their atomic and electronic structures before and after a postdeposition treatment that induces catalytic activity using aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and first-principles calculations. Direct contact between Pt nanoparticles and TiO2 is realized after the postdeposition treatment, which is accompanied by the formation of a Ti3+ state on the TiO2 surface close to the Pt nanoparticles and a Ptδ+ state on the Pt nanoparticles. The origin of these two states and their effect on the catalytic properties are discussed. These findings pave the way for a comprehensive understanding of metal-support interactions in supported metal catalysts.

Enhanced catalytic performance of spinel-type Cu-Mn oxides for benzene oxidation under microwave irradiation.

Microwave-assisted heterogeneous catalytic oxidation of benzene was investigated over Cu-Mn spinel oxides. The spinel oxides were synthesized by a coprecipitation method from metal nitrate hydrolysis in a solution using tetramethylammonium hydroxide (TMAH) as a precipitation reagent. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption fine structure, scanning electron microscopy, transmission electron microscope and H2-temperature-programmed reduction studies. Microwave absorption by the Cu-Mn spinel oxide is mainly driven by dielectric losses (dielectric heating). Cu-Mn spinel oxide with a Cu/Mn ratio of 1 exhibited superior activity to single oxides under microwave heating, demonstrating lower apparent activation energy than that obtained under conventional heating. Microwave irradiation lowered the reaction temperature required for benzene oxidation compared with conventional heating. Transient tests were used to investigate the reactivity of oxygen species in the catalytic reaction, and the high reactivity of Cu-Mn spinel oxides was related to the high reactivity of lattice oxygen on the catalyst surface. The reactivity of the oxygen species was enhanced under microwave heating, leading to an enhanced benzene oxidation reaction. The combination of adsorption and catalytic oxidation processes using Cu-Mn spinel oxides and zeolites efficiently decomposed benzene at low concentrations.

Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis.

Various manganese oxides (MnOx) prepared via citric acid solution combustion synthesis were applied for catalytic oxidation of benzene. The results showed the ratios of citric acid/manganese nitrate in synthesizing process positively affected the physicochemical properties of MnOx, e.g., BET (Brunauer-Emmett-Teller) surface area, porous structure, reducibility and so on, which were in close relationship with their catalytic performance. Of all the catalysts, the sample prepared at a citric acid/manganese nitrate ratio of 2:1 (C2M1) displayed the best catalytic activity with T90 (the temperature when 90% of benzene was catalytically oxidized) of 212℃. Further investigation showed that C2M1 was Mn2O3 with abundant nano-pores, the largest surface area and the proper ratio of surface Mn4+/Mn3+, resulting in preferable low-temperature reducibility and abundant surface active adsorbed oxygen species. The analysis results of the in-situ Fourier transform infrared spectroscopy (in-situ FTIR) revealed that the benzene was successively oxidized to phenolate, o-benzoquinone, small molecules (such as maleates, acetates, and vinyl), and finally transformed to CO2 and H2O.

Removal of benzene by non-thermal plasma catalysis over manganese oxides through a facile synthesis method.

Three manganese oxide catalysts (MnOx) were synthesized via a simple method, and then they were introduced into the non-thermal plasma (NTP) system for benzene removal. The XRD and EXAFS results showed the MnOx were mainly in the Mn3O4 phase, and from the analysis of N2 adsorption/desorption isotherms, we knew the MnOx calcined at 250 °C (Mn250) had the largest surface area of 274.5 m2 g-1. Besides, Mn250 also exerted higher benzene adsorption capacity (0.430 mmol g-1) according to C6H6-TPD. O2-TPD indicated that Mn250 showed better oxygen mobility than Mn300. Moreover, by analyzing XPS results, it revealed that Mn250 exhibited rich abundant of surface adsorbed oxygen species (Oads) and moderate ratio of Mn4+/Mn3+, and the reducibility temperature was also the lowest among all the MnOx catalysts drawn by H2-TPR profiles. As a result, Mn250 combined with NTP could remove 96.9% of benzene at a low input power of 3 W (benzene concentration 200 ppm, and GHSV 60,000 mL gcat.-1 h-1), performing the best catalytic activity among the three catalysts and plasma only. Furthermore, the "NTP + Mn250" system also produced the highest CO2 concentration and lowest CO concentration in downstream, and the residual O3 after catalytic reaction was also the lowest, that is to say, the synergistic effect between NTP and Mn250 was more effective than other catalysts in benzene removal. Graphical abstract.

SOx Tolerant Pt/TiO2 Catalysts for CO Oxidation and the Effect of TiO2 Supports on Catalytic Activity.

We developed a new technique for mitigating catalyst deactivation caused by SO2 in exhaust gases. A series of 0.1 wt %-Pt/TiO2 catalysts with different surface, crystal, and pore structures were prepared and tested for CO oxidation activity in the presence of SO2 and H2O. The order of the CO oxidation activity under the influence of SO2 was much different from that in the absence of SO2. Catalysts with a high ratio of larger pores exhibited higher catalytic activity under the influence of SO2 and H2O in the temperature range of 250-300 °C, whereas other parameters, such as BET surface area and crystal structure of the TiO2 support, had minor effects on the CO oxidation activity. The oxidation state of Pt differed significantly depending on the kind of TiO2 support. Some catalysts were less active without H2 reduction pretreatment due to the presence of oxidized Pt species.

Relationship between cation arrangement and photocatalytic activity for Sr-Al-Nb-O double perovskite.

The relationship between the photocatalytic activity and the arrangement of metal cations was investigated with Sr-Al-Nb-O double perovskite (SAN) synthesized at 1400 °C for various calcination times using a solid state reaction. Transmission electron microscopic observation revealed that SAN particles had a domain structure of completely B-site ordered (Sr(2)AlNbO(6)) and disordered (SrAl(0.5)Nb(0.5)O(3)) phases. The ordered phase fraction was determined using a newly proposed mixed-phase model for the Rietveld refinement and a method using the relative intensity of the superlattice line of powder X-ray diffraction. It turned out that the mass fraction of the ordered phase in SAN calcined at 1400 °C could be controlled by the calcination time as 33% (10 h), 37% (20 h), 44% (30 h), and 48% (50 h). Photocatalytic activities of SAN for the evolution of H(2) and O(2) respectively from aqueous solutions of methanol and AgF decreased with increasing the calcination time, that is, with increasing the fraction of the ordered phase. These results suggested that the photocatalytic activity of ordered Sr(2)AlNbO(6) should be lower than that of disordered SrAl(0.5)Nb(0.5)O(3). This is practically the first report to reveal the photocatalytic activity of SAN as well as the effect of cation ordering in oxides on the photocatalytic activity.

Catalytic oxidation of benzene in the gas phase over alumina-supported silver catalysts.

Catalytic properties of Ag/Al(2)O(3) for complete oxidation of benzene with ozone at 295-373 K were studied and compared with those of Mn/Al(2)O(3). At the reaction temperature of 295 K, the Ag/Al(2)O(3) catalysts showed selectivity to CO(x) (ca. 80%) higher than that of the oxide of metals in the first transition series (Fe, Mn, Co, Ni, Cu) supported on Al(2)O(3), which had selectivities of 28-62%. The catalyst showed gradual deactivation from accumulation of byproduct compounds on the catalyst surface. FTIR studies revealed that the byproduct compounds consisted of easily decomposable species and hardly decomposable species. The rate for benzene oxidation linearly increased with Ag loadings (approximately 15 wt %) and was not improved at higher loading levels. The ratios of ozone decomposition to benzene oxidation and ozone decomposition to CO(x) selectivity were evaluated to be 7.5 and 80%, respectively, and they were independent of benzene conversion. The Ag/Al(2)O(3) catalyst showed steady-state activities at a reaction temperature of 313-373 K, and the conversion increased with the increase in the reaction temperature. The presence of water vapor in the reaction gas inhibited the catalyst deactivation, and steady-state activity was obtained at a reaction temperature of 295 K, while it did not affect the activities for benzene oxidation but improved the CO(2) selectivity.

Benzene oxidation with ozone over supported manganese oxide catalysts: effect of catalyst support and reaction conditions.

Catalytic oxidation of gaseous benzene with ozone was carried out over supported manganese oxides to investigate the factors controlling the catalytic activities. The rate for benzene oxidation linearly increased with the surface area of catalyst, regardless of the kinds of catalyst support, whereas the ratio of ozone decomposition rate to benzene oxidation rate was larger for SiO(2)-supported catalyst than Al(2)O(3)-, TiO(2)-, and ZrO(2)-supported catalysts. The rate for benzene oxidation and CO(x) selectivity increased with the reaction temperature (22-100 degrees C) and were improved by the addition of water vapor to reaction gases. Benzene conversion and carbon balance increased with ozone concentration.

In situ XAFS studies of Au particle formation by photoreduction in polymer solutions.

Formation mechanisms of metal particles (gold (Au) particles) in an aqueous ethanol solution of HAuCl4 with poly(N-vinyl-2-pyrrolidone) (PVP) by the photoreduction method were investigated by UV-vis, transmission electron microscopy (TEM), and in situ and ex situ X-ray absorption fine structure (XAFS) analysis. The average diameters of the dilute and concentrated Au particles in PVP solution are estimated from TEM to be 106 A and 925 A, respectively. XAFS analysis was carried out to elucidate the reduction process of AuCl4- ionic species to metallic Au particles for the Au-L3 edge of the colloidal dispersions of the concentrated Au solutions. In the photoreduction process, the reduction of AuCl2- species to Au0 atoms is a slower process than that of AuCl4- to AuCl2-, and the reduction of AuCl2- to Au0 atoms and the association of Au0 atoms to form seed Au particles (particle diameter between 5.5 and 30 A) concurrently proceeds in the short-duration photoirradiation. In addition, in the long-duration photoirradiation, the slow progression of Au particle growth occurs with the association of Au0-Au0 metallic bonds, resulting in the formation of larger Au particles (particle diameter larger than 500 A).

Preparation of Pt/Rh bimetallic colloidal particles in polymer solutions using borohydride-reduction.

Colloidal dispersions of Pt/Rh bimetallic particles have been synthesized by the reduction of Pt(IV)/Rh(III) ionic solutions by using borohydride-reduction in the presence of poly(N-vinyl-2-pyrrolidone). The size and the structure of the synthesized particles have been examined by transmission electron micrograph (TEM) and extended X-ray absorption fine structure (EXAFS). We have succeeded in producing the bimetallic Pt/Rh particles with an average diameter of 2.8 nm in polymer solutions by the stepwise addition of sodium borohydride aqueous solution. The distribution of different metallic species in a particle tended to be "cluster-in-cluster" structure, in contrast to the bimetallic particle with an average diameter of 1.4 nm synthesized by alcohol-reduction which have a core-shell structure.

Formation mechanism of Pt particles by photoreduction of Pt ions in polymer solutions.

The formation mechanisms of metal particles (platinum (Pt) particles) in an aqueous ethanol solution of poly(N-vinyl-2-pyrrolidone) (PVP) by the photoreduction method have been studied by transmission electron microscopy (TEM) and in situ and ex situ X-ray absorption fine structure (XAFS) analysis. The average diameter of the dilute and concentrated Pt particles in the PVP solution is estimated from TEM to be 2.0 and 2.5 nm, respectively. XAFS analysis was performed for the reduction process of Pt4+ ions to metallic Pt particles for the Pt L3 edge of the colloidal dispersions of the concentrated Pt solutions. The photoreduction process proceeds by the following steps: (1) reduction of PtCl6(2-) to PtCl4(2-), (2) dissociation of Cl from PtCl4(2-), followed by reduction of Pt2+ ionic species to Pt0, (3) formation of a Pt0-Pt0 bond and particle growth by the association of Pt0-Pt0. The reduction of PtCl4(2-) to Pt0 is a slower process, compared with the reduction of PtCl6(2-) to PtCl4(2-). There is a delay between the disappearance of PtCl4(2-) and the formation of Pt0-Pt0 clusters.

Photochemical preparation of poly(N-vinyl-2-pyrrolidone)-stabilized platinum colloids and their deposition on titanium dioxide.

Preparation processes for Pt-deposited TiO(2) (Pt/TiO(2)) by the synthesis of Pt nanoparticles and their deposition were pursued by transmission electron microscopy, extended X-ray absorption fine structure, UV-vis spectroscopy, and Fourier transform infrared spectroscopic studies. Colloidal dispersions of Pt particles stabilized by poly(N-vinyl-2-pyrrolidone) (PVP) were photochemically synthesized in aqueous ethanol solution. The average diameter of Pt particles was estimated to be 2.0 +/- 0.5 nm, which was almost unchanged by changing the reducing agent from ethanol to methanol and 2-propanol. The PVP-stabilized Pt particles were distributed over a TiO(2) surface only by mixing the Pt colloidal dispersions and TiO(2). CO was chemically coordinated on the Pt particles on a TiO(2) surface after heat treatment was carried out in an O(2) flow at 673 K to completely remove the residual PVP on Pt/TiO(2). Hydrogen reduction at 473 K did not increase the amount of CO adsorbed on Pt sites. The Pt/TiO(2) catalyst after the oxidation treatment showed higher activity for CO photooxidation than that obtained for pure TiO(2) catalyst. The CO photooxidation rate was not unchanged by the H(2) reduction.

Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches.

The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV-visible light irradiation, by H202 with UV-visible light irradiation, and by a tungstic heteropolyacid photocatalyst was examined to develop a technique to counteract stationary sources of PFOA. Direct photolysis proceeded slowly to produce CO2, F-, and short-chain perfluorocarboxylic acids. Compared to the direct photolysis, H2O2 was less effective in PFOA decomposition. On the other hand, the heteropolyacid photocatalyst led to efficient PFOA decomposition and the production of F- ions and CO2. The photocatalyst also suppressed the accumulation of short-chain perfluorocarboxylic acids in the reaction solution. PFOA in the concentrations of 0.34-3.35 mM, typical of those in wastewaters after an emulsifying process in fluoropolymer manufacture, was completely decomposed by the catalyst within 24 h of irradiation from a 200-W xenon-mercury lamp, with no accompanying catalyst degradation, permitting the catalyst to be reused in consecutive runs. Gas chromatography/mass spectrometry (GC/MS) measurements showed no trace of environmentally undesirable species such as CF4, which has a very high global-warming potential. When the (initial PFOA)/(initial catalyst) molar ratio was 10: 1, the turnover number for PFOA decomposition reached 4.33 over 24 h of irradiation.

Improvement of catalyst durability by deposition of Rh on TiO2 in photooxidation of aromatic compounds.

Gas-solid heterogeneous photocatalytic oxidation of aromatic compounds in air was carried out at room temperature with a fixed bed flow reactor. The deposition of Rh on TiO2 catalyst improved the catalyst durability in benzene photooxidation. The Rh deposition reduced the amounts of carbonaceous materials on the catalyst surface that were the cause of catalyst deactivation. The highest reaction rate was obtained at the Rh loading of 0.5-1.0 wt %. The Rh/TiO2 catalyst was gradually deactivated in prolonged benzene photooxidation, due to the increasing amount of carbonaceous materials on the catalyst surface. XPS studies showed that the gradual deactivation was related to the changes in the oxidation state of the surface Rh metals. The catalysts were regenerated by the treatment of hydrogen reduction after the photoirradiation in humidified air, indicating that Rh(0) was essential for the improvement of the catalyst durability. The catalyst was also regenerated by the heat treatment in N2 flow instead of the hydrogen reduction. Rh deposition was also effective for the improvement of catalyst durability in toluene photooxidation.

Decomposition of environmentally persistent trifluoroacetic acid to fluoride ions by a homogeneous photocatalyst in water.

Decomposition of trifluoroacetic acid (TFA) was achieved with a tungstic heteropolyacid photocatalyst H3PW12O40*6H2O in order to develop a technique for measures against TFA stationary sources. This is the first example of C-F bond cleavage in an environmentally harmful perfluoromethyl-group-containing compound using a homogeneous photocatalyst. The catalytic reaction proceeds in water at room temperature under UV-visible light irradiation in the presence of oxygen. The system produces only F- ions and CO2; the (mole of formed F-)/(mole of decomposed TFA) and (mole of formed CO2)/(mole of decomposed TFA) ratios were 2.91 and 2.09, respectively. GC/MS measurements showed no trace of other species such as environmentally undesirable CF4, which is the most stable perfluorocarbon and has a very high global warming potential. When the (initial TFA)/(initial catalyst) molar ratio was 20:1, the turnover number of TFA decomposition reached 5.58 by 72 h of irradiation, accompanying with no catalyst degradation. The catalytic reaction mechanism can be explained by a redox reaction between the catalyst and TFA, involving a photo-Kolbe process.