Reverse oxygen spillover triggered by CO adsorption on Sn-doped Pt/TiO2 for low-temperature CO oxidation.

The spillover of oxygen species is fundamentally important in redox reactions, but the spillover mechanism has been less understood compared to that of hydrogen spillover. Herein Sn is doped into TiO2 to activate low-temperature (<100 °C) reverse oxygen spillover in Pt/TiO2 catalyst, leading to CO oxidation activity much higher than that of most oxide-supported Pt catalysts. A combination of near-ambient-pressure X-ray photoelectron spectroscopy, in situ Raman/Infrared spectroscopies, and ab initio molecular dynamics simulations reveal that the reverse oxygen spillover is triggered by CO adsorption at Pt2+ sites, followed by bond cleavage of Ti-O-Sn moieties nearby and the appearance of Pt4+ species. The O in the catalytically indispensable Pt-O species is energetically more favourable to be originated from Ti-O-Sn. This work clearly depicts the interfacial chemistry of reverse oxygen spillover that is triggered by CO adsorption, and the understanding is helpful for the design of platinum/titania catalysts suitable for reactions of various reactants.

Advances in the treatment of multi-pollutant flue gas in China's building materials industry.

In most of the world's building material industries, the control of flue gas pollutants mainly focuses on a single pollutant. However, given the large capacity and high contribution of China's building materials industry to global air pollution, the need to develop multi-pollutant emission reduction technology is urgent. Recently, China has focused on reducing the emissions of flue gas pollutants in the building materials industry, established many key research and development projects, and gradually implemented more stringent pollutant emission limits. This project focuses on the most recent advances in flue gas emission control technology in China's building materials industry, including denitration, dust removal, desulfurization, synergistic multi-pollutant emission reduction, and the construction of pilot research and demonstration projects for pollutant removal in several building material industries. On this basis, revised pollutant limits in flue gas emitted in China's building material industry are proposed.

Structure-Directing Role of Support on Hg0 Oxidation over V2O5/TiO2 Catalyst Revealed for NOx and Hg0 Simultaneous Control in an SCR Reactor.

The crystal structure of TiO2 strongly influences the physiochemical properties of supported active sites and thus the catalytic performance of the as-synthesized catalyst. Herein, we synthesized TiO2 with different crystal forms (R = rutile, A = anatase, and B = brookite), which were used as supports to prepare vanadium-based catalysts for Hg0 oxidation. The Hg0 oxidation efficiency over V2O5/TiO2-B was the best, followed by V2O5/TiO2-A and V2O5/TiO2-R. Further experimental and theoretical results indicate that gaseous Hg0 reacts with surface-active chlorine species produced by the adsorbed HCl and the reaction orders of Hg0 oxidation over V2O5/TiO2 catalyst with respect to HCl and Hg0 concentration were approximately 0 and 1, respectively. The excellent Hg0 oxidation efficiency over V2O5/TiO2-B can be attributed to lower redox temperature, larger HCl adsorption capacity, and more oxygen vacancies. This work suggests that to achieve the best simultaneous removal of NOx and Hg0 on state-of-the-art V2O5/TiO2 catalyst, a combination of anatase and brookite TiO2-supported vanadyl tandem catalysts is supposed to be employed in the SCR reactor, and the brookite-type catalyst should be on the downstream of the anatase-based catalyst due to the inhibition of NH3 on Hg0 oxidation.

Like Cures like: Detoxification Effect between Alkali Metals and Sulfur over the V2O5/TiO2 deNOx Catalyst.

The V2O5/TiO2 (VTi) catalyst has been widely employed for the NH3 selective catalytic reduction (NH3-SCR) reaction, and sulfur (S) and alkali metals (K) were usually considered as poisons during this reaction. In this work, the synergistic effect of S and K over the VTi catalyst for the NH3-SCR reaction was analyzed and discussed. It is surprisingly observed that the synergistic effects of S and K exhibited a detoxification effect on the NH3-SCR reaction. That is, although the VTi catalyst exhibited moderate resistance to S poisoning and unsatisfactory resistance to K deactivation, the SCR activity was restored to close to fresh VTi when K and S coexisted. This detoxification effect also could occur between other alkali metals (e.g., Ca and Na) and sulfur. X-ray photoelectron spectroscopy and charge density difference studies both indicate that the introduction of K could significantly affect the electronic structure of V, but this toxic effect was recovered by the further addition of S because of the strong interaction between S and K. Therefore, this detoxification effect can occur in the practical reaction atmosphere, which alleviates the alkali metal poisoning of commercial catalysts.

Dual Active Centers Bridged by Oxygen Vacancies of Ruthenium Single-Atom Hybrids Supported on Molybdenum Oxide for Photocatalytic Ammonia Synthesis.

Photocatalytic synthesis of ammonia (NH3 ) holds significant potential compared with the Haber-Bosch process. However, the reported photocatalysts suffer from low efficiency owing to localized electron deficiency. Herein, Ru-SA (single atoms)/Hx MoO3-y hybrids with abundant of Mon+ (4

In Situ Modulation of A-Site Vacancies in LaMnO3.15 Perovskite for Surface Lattice Oxygen Activation and Boosted Redox Reactions.

Modulation of A-site defects is crucial to the redox reactions on ABO3 perovskites for both clean air application and electrochemical energy storage. Herein we report a scalable one-pot strategy for in situ regulation of La vacancies (VLa ) in LaMnO3.15 by simply introducing urea in the traditional citrate process, and further reveal the fundamental relationship between VLa creation and surface lattice oxygen (Olatt ) activation. The underlying mechanism is shortened Mn-O bonds, decreased orbital ordering, promoted MnO6 bending vibration and weakened Jahn-Teller distortion, ultimately realizing enhanced Mn-3d and O-2p orbital hybridization. The LaMnO3.15 with optimized VLa exhibits order of magnitude increase in toluene oxidation and ca. 0.05 V versus RHE (reversible hydrogen electrode) increase of half-wave potential in oxygen reduction reaction (ORR). The reported strategy can benefit the development of novel defect-meditated perovskites in both heterocatalysis and electrocatalysis.

Boosting the Catalytic Performance of CeO2 in Toluene Combustion via the Ce-Ce Homogeneous Interface.

Catalytic combustion is an advanced technology to eliminate industrial volatile organic compounds such as toluene. In order to replace the expensive noble metal catalysts and avoid the aggregation phenomenon occurring in traditional heterogeneous interfaces, designing homogeneous interfaces can become an emerging methodology to enhance the catalytic combustion performance of metal oxide catalysts. A mesocrystalline CeO2 catalyst with abundant Ce-Ce homogeneous interfaces is synthesized via a self-flaming method which exhibits boosted catalytic performance for toluene combustion compared with traditional CeO2, leading to a ∼40 °C lower T90. The abundant Ce-Ce homogeneous interfaces formed by both highly ordered stacking and small grain size endow the CeO2 mesocrystal with superior redox property and oxygen storage capacity via forming various oxygen vacancies. Surface and bulk oxygen vacancies generate and activate crucial oxygen species, while interfacial oxygen vacancies further promote the reaction behavior of oxygen species (i.e., activation, regeneration, and migration), causing the splitting of redox property toward lower temperature. These properties facilitate aromatic ring decomposition, the important rate-determining step, thus contributing to toluene catalytic degradation to CO2. This work may shed insights into the catalytic effects of homogeneous interfaces in pollutant removal and provide a strategy of interfacial defect engineering for catalyst development.

Penetration of Arsenic and Deactivation of a Honeycomb V2O5-WO3/TiO2 Catalyst in a Glass Furnace.

Deactivation of honeycomb V2O5-WO3/TiO2 catalysts by arsenic has been studied widely in coal-fired power plants but rarely in glass furnaces. In this paper, deactivated catalysts that had been used for more than 4000 h were analyzed. We maintained the catalysts in their original monolith shape to retain their adhered substance and used appropriate methods to strip the substance layer by layer. With various characterization techniques, it was determined that the adhered substance was composed almost entirely of Na2SO4 and CaSO4. We also quantified the penetration depth of arsenic visually, which was more than 370 µm. A three-stage penetration and deactivation process induced by arsenic was proposed. It was pointed out that molten and volatile As2O3 played a key role in the deactivation process, while substances in the solid state had little impact on the deep bulk of the catalyst. In this study, we proposed an integrated deactivation process consisting of adhesion, penetration, and deactivation in a honeycomb V2O5-WO3/TiO2 catalyst by arsenic in a glass furnace. Finally, we also provided guidance on alleviating the deactivation caused by arsenic. The key is to convert molten and volatile As2O3 to solid-state substances before it contacts the catalyst.

Balance of activation and ring-breaking for toluene oxidation over CuO-MnOx bimetallic oxides.

CuMn oxides have been studied for many years to catalytic degradation of toluene, but there are still many divergences on the essence of their great catalytic activity and reaction mechanism. A series of CuMn bimetallic oxides were synthesized for the catalytic oxidation of toluene in this study. Cu2Mn1 exhibited the highest toluene oxidation rate per specific surface area, which was approximately 4 times that of monometallic CuO and Mn3O4. Benzoic acid was the only intermediates which could be observed during toluene oxidation. Between monometallic CuO and Mn3O4, toluene was more difficult to be activated by Mn3O4 to generate benzoic acid (toluene activation), whereas benzoic acid was oxidized (ring-breaking) by CuO with more difficulty. As for CuMn, the superior reducibility combined with the balance between ring-breaking of benzoic acid and activation of toluene-to-benzoic acid determined the high toluene oxidation rate. DFT simulations exhibited that in O-Cu-O-Mn-O structure, the Mn-O site was a more effective activation site for toluene-to-benzoic acid oxidation, whereas Cu-O mainly performed as an adsorption site for toluene. This work identifies the different roles of Cu and Mn entities in toluene oxidation and provides the novel design strategy for toluene removal catalysts.

Roles of Oxygen Vacancies in the Bulk and Surface of CeO2 for Toluene Catalytic Combustion.

Catalytic combustion technology is one of the effective methods to remove VOCs such as toluene from industrial emissions. The decomposition of an aromatic ring via catalyst oxygen vacancies is usually the rate-determining step of toluene oxidation into CO2. Series of CeO2 probe models were synthesized with different ratios of surface-to-bulk oxygen vacancies. Besides the devotion of the surface vacancies, a part of the bulk vacancies promotes the redox property of CeO2 in toluene catalytic combustion: surface vacancies tend to adsorb and activate gaseous O2 to form adsorbed oxygen species, whereas bulk vacancies improve the mobility and activity of lattice oxygen species via their transmission effect. Adsorbed oxygen mainly participates in the chemical adsorption and partial oxidation of toluene (mostly to phenolate). With the elevated temperatures, lattice oxygen of the catalysts facilitates the decomposition of aromatic rings and further improves the oxidation of toluene to CO2.

Balance between Reducibility and N2O Adsorption Capacity for the N2O Decomposition: CuxCoy Catalysts as an Example.

CuxCoy (CuO-Co3O4 mixed oxides) catalysts were prepared via co-precipitation for the N2O decomposition reaction. They exhibited a higher N2O decomposition activity than that of pure CuO and Co3O4 because of the balance of the redox property and N2O adsorption capacity. Co3O4 presented a large number of surface oxygen vacancies, increasing the N2O chemical adsorption as "□-Co-ON2" on the catalyst surface, whereas CuO was dispersed around Co3O4 and presented high reducibility on the interface of Co3O4-CuOx for the N-O break of N2O, healing oxygen vacancies by leaving one oxygen atom in the vacancy. Based on kinetic studies, the rate constant of N2O decomposition was related to the number of surface vacancy sites ([Mn+]) and the rate of N-O break (k3), whereas the rate-determining step is the N-O break. Therefore, the N2O decomposition rate is first order to the N2O concentration. Overall, both the density functional theory calculations and kinetic results indicate that the quantities of adsorption and activation sites derived from the interaction between Co and Cu (dual-function mechanism) were accounted for the excellent N2O decomposition performance of CuxCoy catalysts.

Performance of Modified La xSr1- xMnO3 Perovskite Catalysts for NH3 Oxidation: TPD, DFT, and Kinetic Studies.

The modified perovskites (La xSr1- xMnO3) were prepared using the selective dissolution method for the selective catalytic oxidation (SCO) of NH3. We found that more Mn4+ cations and active surface oxygen species formed on the catalyst's surface with increasing the dissolution time (dis). The 1h-dis catalyst exhibited excellent NH3 conversion, and it performed well in the presence of SO2 and H2O. The 10h-dis and 72h-dis catalysts produced considerable N2O and NO at high temperatures, while they were not detected from the fresh catalyst. Both temperature-programmed experiments and density functional theory calculations proved that NH3 strongly and mostly bonded to the B-site cations of the perovskite framework rather than A-site cations: this framework limited the bonding of SO2 to the surface. The reducibility increased superfluously after more than 10 h of immersion. The adsorptions of NH3 on Mn4+ exposed surface were stronger than that on La3+ or Sr4+ exposed surfaces. The selective catalytic reduction, nonselective catalytic reduction, and catalytic oxidation reactions all contributed to NH3 conversion. The formed NO from catalytic oxidation preferred to react with -NH2/-NH to form N2/N2O.

H2S-Modified Fe-Ti Spinel: A Recyclable Magnetic Sorbent for Recovering Gaseous Elemental Mercury from Flue Gas as a Co-Benefit of Wet Electrostatic Precipitators.

The nonrecyclability of the sorbents used to capture Hg0 from flue gas causes a high operation cost and the potential risk of exposure to Hg. The installation of wet electrostatic precipitators (WESPs) in coal-fired plants makes possible the recovery of spent sorbents for recycling and the centralized control of Hg pollution. In this work, a H2S-modified Fe-Ti spinel was developed as a recyclable magnetic sorbent to recover Hg0 from flue gas as a co-benefit of the WESP. Although the Fe-Ti spinel exhibited poor Hg0 capture activity in the temperature range of flue gas downstream of flue gas desulfurization, the H2S-modified Fe-Ti spinel exhibited excellent Hg0 capture performance with an average adsorption rate of 1.92 µg g-1 min-1 at 60 °C and a capacity of 0.69 mg g-1 (5% of the breakthrough threshold) due to the presence of S22- on its surface. The five cycles of Hg0 capture, Hg0 recovery, and sorbent regeneration demonstrated that the ability of the modified Fe-Ti spinel to capture Hg0 did not degrade remarkably. Meanwhile, the ultralow concentration of Hg0 in flue gas was increased to a high concentration of Hg0, which facilitated the centralized control of Hg pollution.

Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

The design of a high-performance catalyst for Hg0 oxidation and predicting the extent of Hg0 oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg0 oxidation, and the reaction mechanism and the reaction kinetics of Hg0 oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg0 oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg0 concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg0 oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg0 with adsorbed HCl), and the rate of Hg0 oxidation mainly depended on Cl• concentration on the surface. As H2O, SO2, and NO not only inhibited Cl• formation on the surface but also interfered with the interface reaction between gaseous Hg0 and Cl• on the surface, Hg0 oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H2O, SO2, and NO. Furthermore, the extent of Hg0 oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter kE-R, and the predicted result was consistent with the experimental result.

Recyclable Naturally Derived Magnetic Pyrrhotite for Elemental Mercury Recovery from Flue Gas.

Magnetic pyrrhotite, derived from the thermal treatment of natural pyrite, was developed as a recyclable sorbent to recover elemental mercury (Hg0) from the flue gas as a cobenefit of wet electrostatic precipitators (WESP). The performance of naturally derived pyrrhotite for Hg0 capture from the flue gas was much better than those of other reported magnetic sorbents, for example Mn-Fe spinel and Mn-Fe-Ti spinel. The rate of pyrrhotite for gaseous Hg0 capture at 60 °C was 0.28 µg g min-1 and its capacity was 0.22 mg g-1 with the breakthrough threshold of 4%. After the magnetic separation from the mixture collected by the WESP, the spent pyrrhotite can be thermally regenerated for recycle. The experiment of 5 cycles of Hg0 capture and regeneration demonstrated that both the adsorption efficiency and the magnetization were not notably degraded. Meanwhile, the ultralow concentration of gaseous Hg0 in the flue gas was concentrated to high concentrations of gaseous Hg0 and Hg2+ during the regeneration process, which facilitated the centralized control of mercury pollution. Therefore, the control of Hg0 emission from coal-fired plants by the recyclable pyrrhotite was cost-effective and did not have secondary pollution.

The centralized control of elemental mercury emission from the flue gas by a magnetic rengenerable Fe-Ti-Mn spinel.

A magnetic Fe-Ti-Mn spinel was developed to adsorb gaseous Hg(0) in our previous study. However, it is currently extremely restricted in the control of Hg(0) emission from the flue gas for at least three reasons: sorbent recovery, sorbent regeneration and the interference of the chemical composition in the flue gas. Therefore, the effect of SO2 and H2O on the adsorption of gaseous Hg(0) on the Fe-Ti-Mn spinel and the regeneration of spent Fe-Ti-Mn spinel were investigated in this study. Meanwhile, the procedure of the centralized control of Hg(0) emission from the flue gas by the magnetic Fe-Ti-Mn spinel has been analyzed for industrial application. The spent Fe-Ti-Mn spinel can be regenerated by water washing followed by the thermal treatment at 450 °C with no obvious decrease of its ability for Hg(0) capture. Meanwhile, gaseous Hg(0) in the flue gas can be remarkably concentrated during the regeneration, facilitating its safe disposal. Initial pilot test demonstrated that gaseous Hg(0) in the real flue gas can be concentrated at least 100 times by the Fe-Ti-Mn spinel. Therefore, Fe-Ti-Mn spinel was a novel magnetic regenerable sorbent, which can be used for the centralized control of Hg(0) emission from the flue gas.

Mechanism of N2O formation during the low-temperature selective catalytic reduction of NO with NH3 over Mn-Fe spinel.

The mechanism of N2O formation during the low-temperature selective catalytic reduction reaction (SCR) over Mn-Fe spinel was studied. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and transient reaction studies demonstrated that the Eley-Rideal mechanism (i.e., the reaction of adsorbed NH3 species with gaseous NO) and the Langmuir-Hinshelwood mechanism (i.e., the reaction of adsorbed NH3 species with adsorbed NOx species) both contributed to N2O formation. However, N2O selectivity of NO reduction over Mn-Fe spinel through the Langmuir-Hinshelwood mechanism was much less than that through the Eley-Rideal mechanism. The ratio of NO reduction over Mn-Fe spinel through the Langmuir-Hinshelwood mechanism remarkably increased; therefore, N2O selectivity of NO reduction over Mn-Fe spinel decreased with the decrease of the gas hourly space velocity (GHSV). As the gaseous NH3 concentration increased, N2O selectivity of NO reduction over Mn-Fe spinel increased because of the promotion of NO reduction through the Eley-Rideal mechanism. Meanwhile, N2O selectivity of NO reduction over Mn-Fe spinel decreased with the increase of the gaseous NO concentration because the formation of NH on Mn-Fe spinel was restrained. Therefore, N2O selectivity of NO reduction over Mn-Fe spinel was related to the GHSV and concentrations of reactants.