Graphite-N reinforced sludge biochar electrode: A experimental and DFT theoretical analysis of efficient evolution and in-situ utilization of H2O2.

Rational reuse of municipal sludge to produce electro-Fenton electrode can not only save resources, but also produce superior peroxide and degradation pollutants simultaneously. Herein, a novel electro-Fenton electrode derived from sludge biochar loaded on Ni foam (SBC@Ni) was constructed via high temperature pyrolysis and chemical coating for efficient H2O2 evolution and pollutant degradation. Systematic experiments and density functional theory calculations (DFT calculation) explained that the production of graphite C and graphite N during high-temperature pyrolysis of municipal sludge can greatly enhance the oxygen reduction reaction of SBC@Ni electrode and promote the evolution of H2O2. And the hybrid heterojunctions, such as FeP, also played a key role in electrocatalytic processes. Notably, the electrode still exhibited excellent performance after 1000 linear scans and 12 h of continuous current stimulation, which demonstrated the excellent stability of the electrode. Moreover, SBC@Ni electrode can not only effectively oxidize 4-chlorophenol through the electro-Fenton effect, but also fully mineralize organic matter, indicating promising environmental application. The free radical quenching experiment also revealed that the ·OH is the main active species for 4-CP degradation in SBC@Ni electro-Fenton system.

Spatial distribution pattern and correlation of dominant species in the arbor layer at a 25 hm2 forest plot in Lushan Mountain, China.

To explore the spatial pattern of zonal tree species in the subtropical subalpine mountain area on Lushan Mountain, a 25 hm2 forest plot was established in Yangtianping area of Lushan Mountain following the technical specification of CTFS in 2021. We classified these species into evergreen conifer species, deciduous broad-leaved species and evergreen broad-leaved species based on their leaf shape and deciduous or not to analyze the spatial pattern of dominant species of different types by spatial point pattern method. The results showed that Pinus taiwanensis, Cornus kousa subsp. chinensis, Platycarya strobilacea, Castanea henryi, Quercus serrata, Cornus controversa, Eurya muricata, Litsea elongata, and Eurya hebeclados were dominant species. Among these species, P. taiwanensis was the constructive one. The spatial pattern of dominant species was clustered at a certain scale, and gradually became to randomly distribution with the increases of scales. Evergreen conifer species was independent with deci-duous broad-leaved species and evergreen broad-leaved species at small scales, but was negatively correlated with them at large scales. Deciduous broad-leaved species and evergreen broad-leaved species were obviously negatively correlated with each other. Deciduous broad-leaved species were positively correlated or independent with each other at small scales, but were negatively correlated with each other at large scales. Evergreen broad-leaved species were positively correlated at small scales, independent at medium scales, and negatively correlated with each other at large scales.

Enhanced etching terminal wastewater treatment and H2 production by in-situ deposited heavy metals on carbon dots/g-C3N4 photocathode microbial electrolysis cells.

Sustainable and cost-effective semiconducting photocathodes of microbial electrolysis cells (MECs) are attractively promising for efficient treatment of actual industrial wastewaters containing complex recalcitrant organics and multiple heavy metals. Herein carbon dots/graphitic carbon nitride (CDs/g-C3N4) photocathodes were employed to achieve efficient treatment of actual etching terminal wastewater (ETW) with simultaneous H2 production in MECs, allowing the effluent meeting national discharge standards (GB39731-2020). The progressively in-situ deposited heavy metals on the CDs/g-C3N4 photocathodes, formed as metal oxides/CDs/g-C3N4 after simple calcinations, further enhanced the ETW treatment (recalcitrant organics mineralization: 42.2 mg/L/h vs. 35.5 mg/L/h; heavy metal removal: Cu(II): 9.9 mg/L/h vs. 7.4 mg/L/h, Ni(II): 4.7 mg/L/h vs. 3.5 mg/L/h, Zn(II): 0.7 mg/L/h vs. 0.5 mg/L/h) and H2 production (0.1138 m3/m3/d vs. 0.0662 m3/m3/d). The importation of heavy metals, formed as metal oxides/CDs/g-C3N4 altered the proportion of reactive oxidative species and thus promoted mineralization of recalcitrant organics, besides offering additional electrochemical removal of heavy metals with simultaneous more H2 production. This study demonstrates a new feasible protocol for achieving efficient ETW treatment, and gives a comprehensive appreciation of the effect of in-situ deposited heavy metals on the CDs/g-C3N4 photocathodes, which has a profound effect on subsequent ETW treatment with simultaneous H2 production.

The key role of persistent free radicals on the surface of hydrochar and pyrocarbon in the removal of heavy metal-organic combined pollutants.

We show that persistent free radicals (PFRs) on the surface of biochar can produce hydroxyl radicals (•OH) by catalyzing H2O2 to facilitate the removal of the combined pollutant BPA-Cr(VI). Microstructure characterization showed that the structures of pyrocarbon and hydrochar were significantly different when prepared at different temperatures. As the preparation temperature and preparation time for biochar increased, the concentration of PFRs first increased and then decreased. When biochar, PFRs, and H2O2 were present in the same solution, the single pollutants BPA and Cr(VI) as well as the combined pollutant BPA-Cr(VI) could be removed effectively, with removal rates greater than 90%. However, when PFRs, BPA, H2O2, and Cr(VI) were present in the same solution, Cr(VI) competed with H2O2 for electrons and promoted the removal of BPA. The results of this study could be applied to sludge recycling and be used to develop approaches to catalytically degrade combined pollutants.

Regioselective conversions of H4pdta (1,2-propanediaminetetraacetic acid) and H4eed3a to their triacetates on peroxotitanates.

1,2-Propanediaminetetraacetic acid (H4pdta = C11H18O8N2) is degraded selectively to 1-methyl-1,2-propanediaminetriacetic acid (H3pd3a = C9H16O6N2) with a yield of 75% at room temperature, while N-(2-hydroxyethyl) ethylenediaminetriacetic acid (H4eed3a = C10H18O7N2) is converted with difficulty to ethylenediaminetriacetic acid (H3ed3a = C8H14O6N2) on peroxotitanates(iv), showing the influence of the uncoordinated leaving group. Various species in the reaction sequence are isolated and fully characterized, including (NH4)[Ti(O2)(Hpdta)]·H2O (1), (NH4)3[Ti(O2)(pdta)H(pdta)(O2)Ti]·7H2O (2), (NH4)[Ti(O2)(pd3a)]·H2O (3) and (NH4)[Ti(O2)(Heed3a)]·H2O (5). Peroxo dimer 2 forms a strong intramolecular hydrogen bond [2.451(3) Å] as an intermediate in the peroxo Ti-pdta system, which results in the absence of a fully deprotonated species of peroxo pdta titanate. A catalytic reaction of the peroxo titanate (NH4)3[Ti(O2)(pdta)H(pdta)(O2)Ti]·7H2O (2) for the conversion of pyridine to pyridine N-oxide shows 94% conversion at 80 °C.

The feasibility of UF-RO integrated membrane system combined with coagulation/flocculation for hairwork dyeing effluent reclamation.

This paper aims to validate the feasibility of hairwork dyeing effluent (HDE) reclamation using an ultrafiltration (UF)-reverse osmosis (RO) integrated membrane system combined with coagulation-flocculation and sedimentation acquiring the highest possible product water recovery rate along with both satisfactory separation performance and well controlled membrane fouling. Under the circumstance of only physical cleaning involved, the laboratory-scale test yielded a higher and satisfactory reuse ratio of 76% for HDE, and the corresponding RO product as reclaimed water contained only 223 mg·L-1 of TDS, 3.87 mg·mL-1 of DOC and 10.3 mg·mL-1 of total hardness, which was obviously better than the quality of existing feedwater in hairwork dyeing process. After each processing unit, the distributions of fulvic (region III) and humic (region V) organics decreased continuously, while an overall rising trend in distribution of protein-like organics (regions I and II) was observed. Contact angle for the fouled UF and RO membranes significantly increased by 19.5° and decreased by 19.7°, respectively, which suggested that different polarity of organic or inorganic adsorption rather than membrane roughness was the main factors affecting wetting properties of the fouled employed membranes. Both ATR-FTIR and XPS spectra indicated that organic fouling on UF membrane surface under harsh condition (RUF = 90%) was mild and tolerable, whereas a surprising amount of hydrophilic micromolecular organics riched in carboxyl and hydroxyl functional groups were absorbed on RO membrane surface after permeation.

Biosorption of anionic and cationic dyes via raw and chitosan oligosaccharide-modified Huai Flos Chrysanthemum at different temperatures.

Raw Huai Flos Chrysanthemum (HFC) and modified HFC (HFC@CO) were used for the first time as a biosorbent material to remove cationic dyes Malachite green (MG) and Crystal violet (CV), and anionic dyes Sunset yellow (SY), Lemon yellow (LY), and Carmine (CM), at different temperatures (5-50 °C). The highest removal rates (R) for dye adsorption were observed at low temperature (5 °C) and room temperature (20 °C). At high (500 mg L-1) dye concentration, adsorption was completed within one minute, but the time required to reach adsorption equilibrium was longer than at the low (20 mg L-1) concentration. The experimental data fitted very well to the Langmuir model and the values of the maximum adsorption capacity for SY, LY, CM, CV, and MG, were 481.41, 507.23, 141.78 mg g-1, 526.32, and 769.23 mg L-1, respectively. The adsorption data fit well to a pseudo-second-order kinetic model.

New Insights into the Role of Al2 O3 in the Promotion of CuZnAl Catalysts: A Model Study.

The Cu/Al2 O3 /ZnO(0001)-Zn ternary model catalysts and their binary analogues were prepared and characterized. It was found that Al2 O3 grew on the ZnO(0001)-Zn surface by a layer-by-layer model, whereas Cu grew on the ZnO(0001)-Zn surface as two-dimensional clusters up to 0.2 monolayers (ML), and thereafter formed three-dimensional clusters. Because of the layer-by-layer growth of Al2 O3 on the ZnO(0001)-Zn, Cu/Al2 O3 can be considered without the effect of ZnO. Ternary model catalyst Cu/Al2 O3 /ZnO(0001)-Zn, which has all three parts on the surface, was prepared by deposition of Cu on the surface of Al2 O3 /ZnO(0001)-Zn. Low-energy ion scattering spectra showed that Cu preferred to locate at the Al2 O3 /ZnO interfaces. Compared with Cu/ZnO, the addition of Al2 O3 obviously suppressed the reduction of copper oxides and led to a higher concentration of Cu+ . The Cu clusters were found to be covered by thin ZnOx overlayers after reduction of Cu/Al2 O3 /ZnO(0001)-Zn by using H2 . Therefore, the high activity of industrial Cu/ZnO/Al2 O3 catalysts may origin from Cu+ -rich clusters at the Al2 O3 /ZnO interface that are covered by thin ZnOx overlayers.

Photoinduced Formation of Peroxide Ions on La2O3 and Nd2O3 under O2: Effects of Excitation Wavelength and Crystal Structure.

Photoinduced formation of peroxide ions on La2O3 and Nd2O3 under O2 was studied by in-situ microprobe Raman spectroscopy with attention focused on the effect of excitation wavelength and crystal structure on the O2(2-) formation. It was found that photoexcitations at 633, 532, 514, and 325 nm can induce O2(2-) formation over La2O3 at 450 °C. By contrast, photoexcitation at 785 nm does not cause formation of O2(2-) up to 500 °C. Photoexcitation at 325 nm can induce O2(2-) formation on cubic Nd2O3 at 25 °C, but cannot induce O2(2-) formation on hexagonal Nd2O3 up to 200 °C. The significant difference in the behavior of O2(2-) formation over the Nd2O3 samples of the two structures can be related to the difference in the capacity to adsorb O2. Since the number of oxygen vacancies in cubic Nd2O3 is larger than that in the hexagonal one, the former has a higher capacity than the latter to adsorb O2. As a result, cubic Nd2O3 is more favorable to the reaction of O2 with O(2-) to generate O2(2-). The structural similarity between cubic Nd2O3 and Nd2O2(O2) may be another factor in favor of peroxide formation.

Dimeric 1,3-propanediaminetetraacetato lanthanides as the precursors of catalysts for the oxidative coupling of methane.

From neutral solutions, dimeric 1,3-propanediaminetetraacetato lanthanides (NH4)2[Ln2(1,3-pdta)2(H2O)4]·8H2O [Ln = La, 1; Ce, 2] and K2[Ln2(1,3-pdta)2(H2O)4]·11H2O [Ln = La, 3; Ce, 4] (1,3-H4pdta = 1,3-propanediaminetetraacetic acid, C11H18N2O8) were isolated in high yields. The reaction of excess strontium nitrate with 1 resulted in the formation of a two dimensional coordination polymer [La2(1,3-pdta)2(H2O)4]n·[Sr2(H2O)6]n·[La2(1,3-pdta)2(H2O)2]n·18nH2O (5) at 70 °C. Complexes 1-4 show a similar central molecular structure. The lanthanide ions are coordinated by two nitrogen atoms, four carboxy oxygen atoms from one 1,3-pdta ligand, two from the neighboring 1,3-pdta ligand forming a four-membered ring and two water molecules. Complex 5 has two kinds of dimeric lanthanum unit and extends into a 2D coordination polymer through strontium ions and bridged oxygen atoms, and forms a fourteen membered ring linked by oxygen atoms from carboxy groups of pdta. Complexes 1-4 are soluble in water. The (13)C{(1)H} NMR experiments for complex 1 were tested in solution. Thermal products from 1 and 5 show good catalytic activities towards the oxidative coupling reaction of methane (OCM). The conversion of methane and selectivity to C2 reached 29.7% and 51.7% at 750 °C for the product of 5. From TGA, XRD and SEM analyses, the thermal products from 1 and 5 are rod- and poly-shaped, which are assigned as lanthanum oxocarbonate and a mixture of La2O3, SrCO3 and La2O2CO3 for 1 and 5, respectively. The precursor method is favorable for the formation of regular shaped mixed oxides.

Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water.

The direct transformation of cellulose, which is the main component of lignocellulosic biomass, into building-block chemicals is the key to establishing biomass-based sustainable chemical processes. Only limited successes have been achieved for such transformations under mild conditions. Here we report the simple and efficient chemocatalytic conversion of cellulose in water in the presence of dilute lead(II) ions, into lactic acid, which is a high-value chemical used for the production of fine chemicals and biodegradable plastics. The lactic acid yield from microcrystalline cellulose and several lignocellulose-based raw biomasses is >60% at 463 K. Both theoretical and experimental studies suggest that lead(II) in combination with water catalyses a series of cascading steps for lactic acid formation, including the isomerization of glucose formed via the hydrolysis of cellulose into fructose, the selective cleavage of the C3-C4 bond of fructose to trioses and the selective conversion of trioses into lactic acid.

Synergistic effects of VO(x)-Pt probed by the oxidation of propane on VO(x)/Pt(111).

VO(x)/Pt(111), which was grown layer-by-layer and exhibited a well-defined structure, was used as a model catalytic surface to study the intrinsic catalytic activity of Pt, as well as the effect of VO(x) additive, for the oxidation of propane. A special sample system was designed to ensure a reliable analysis of the trace amount of model catalytic reaction products. The results show that the catalytic activities for the oxidation of C3H8 on the Pt(111) surface as adding VO(x) are suppressed apparently at temperatures below 400 K, but enhanced significantly at temperatures above 400 K. Maximum reaction rates are achieved at a VO(x) coverage of about 0.3 ML at the test temperatures of 423 and 473 K. The infrared reflection-absorption spectroscopy (IRAS) results show that the redox property of the VO(x)-Pt is much better than that of the bulklike VO(x). This is confirmed by CO poisoning tests, in that the oxidation of VO(x)/Pt(111) is significantly suppressed by the coadsorbed CO. The kinetic data demonstrate that there are at least two catalytically active sites, metallic Pt and VO(x)-Pt interface, for the activation and oxidation of C3H8. The promotion effects of VO(x) on Pt for the oxidation of C3H8 can be attributed to the synergy between VO(x) and Pt.

Effects of O2 pressure on the oxidation of VO(x)/Pt(111).

Vanadium oxide (VO(x)) has been extensively used in many oxidation and selective oxidation reactions. In this study, VO(x) thin films were prepared in an ultra-high vacuum (UHV) chamber by evaporating V onto a Pt(111) surface followed by subsequent oxidation at 623 K in 1 × 10(-7) Torr O2, and further oxidized in the 'high-pressure' reaction cell with 1 Torr O2. The film quality and structure were investigated by high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), low energy ion scattering spectroscopy (LEIS), Auger electron spectroscopy (AES), and in situ infrared reflection absorption spectroscopy (IRAS). On the Pt(111) surface, VO(x) forms isolated O=VO(x) (x = 0-3) species, surface two-dimensional (2D) (2 × 2)-V2O3 domains, a bi-layer structure with a (3√3 × 6) arrangement, and a complicated tri-layer structure as the coverage increases from submonolayer to multilayer. Under the UHV conditions, the oxidation state of V is mainly +3 and the stability was found to be surface V2O3 > bi-layer V2O3 > tri-layer one. After exposing to 0.3-1 Torr O2, VO(x) can be oxidized to higher oxidation states, mainly V2O5, as evidenced by the shifts of the core-level binding energies and presence of V=O. These results indicate that thorough oxidation of VO(x) requires sufficiently high O2 pressure, and that vanadium-based catalysts may possess higher oxidation states under most reaction conditions in the presence of O2.

A novel visible-light-response plasmonic photocatalyst CNT/Ag/AgBr and its photocatalytic properties.

A facile, one-step synthesis of carbon nanotube (CNT)-loaded Ag/AgBr is reported. The as-prepared samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), UV/Vis absorption spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, photoluminescence (PL) spectroscopy and electrochemical impedance spectroscopy (EIS). The CNT/Ag/AgBr composite exhibited much higher photocatalytic activity than pure Ag/AgBr in degrading methyl orange (MO) dye solution. The loading amount of CNT had a significant influence on the photoactivity of the CNT/Ag/AgBr composite. When the CNT loading amount was 1.4 at%, the hybrid material showed the highest photocatalytic ability. The result showed that a small amount of CNT was beneficial for photo-generated electron transfer, which could enhance the photoactivity of CNT/Ag/AgBr. The degradation dye solution was tested by liquid chromatography/mass spectrometry (LC/MS) and total organic carbon (TOC) analysis. Based on the results, the structure of the synthesized CNT/Ag/AgBr hybrid material was verified and the possible degradation path of the MO dye was proposed. A possible visible-light photocatalytic degradation mechanism was also discussed.

Effect of calcination temperature and pretreatment with reaction gas on properties of Co/γ-Al2O3 catalysts for partial oxidation of methane.

The effects of calcination temperature and feedstock pretreatment on the catalytic performance of Co/γ-Al(2)O(3) catalysts were studied for partial oxidation of methane (POM) to synthesis gas, with emphasis on the role of feedstock pretreatment. The physicochemical properties of the catalysts were characterized by N(2) adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), H(2) temperature-programmed reduction (H(2) -TPR), and Raman spectroscopy. The results showed that the pretreatment of the catalyst by reaction gas significantly improved the catalytic activity and stability for the POM reaction. On the other hand, the effect of calcination temperature was less significant. Although the initial activity was increased by an increased calcination temperature, the catalyst without the feedstock pretreatment suffered a rapid deactivation. The reaction-atmosphere pretreatment was revealed as a process that mainly modified the surface structure of the catalyst. In that process, the formation of a CoAl(2)O(4) -like compound led to high Co metal dispersion after reduction, and the transformation of the carrier into α-Al(2)O(3) occurred over the catalyst surface. Both the high dispersion of cobalt and the presence of α-Al(2)O(3) surface phase were assumed as the important factors resulting in an excellent catalytic performance in terms of high activity and high stability.

Mechanistic aspects of photo-induced formation of peroxide ions on the surface of cubic Ln2O3 (Ln = Nd, Sm, Gd) under oxygen.

The photo-induced formation of peroxide ions on the surface of cubic Ln2O3 (Ln = Nd, Sm, Gd) was studied by in situ microprobe Raman spectroscopy using a 325 nm laser as excitation source. It was found that the Raman bands of peroxide ions at 833-843 cm(-1) began to grow at the expense of the Ln(3+)-O(2-) bands at 333-359 cm(-1) when the Ln2O3 samples under O2 were continuously irradiated with a focused 325 nm laser beam at temperatures between 25-150 °C. The intensity of the peroxide Raman band was found to increase with increasing O2 partial pressure, whereas no peroxide band was detected on the Ln2O3 under N2 as well as on the samples first irradiated with laser under Ar or N2 followed by exposure to O2 in the dark. The experiments using (18)O as a tracer further confirmed that the peroxide ions are generated by a photo-induced reaction between O2 and the lattice oxygen (O(2-)) species in Ln2O3. Under the excitation of 325 nm UV light, the transformation of O2 to peroxide ions on the surface of the above lanthanide sesquioxides can even take place at room temperature. Basicity of the lattice oxygen species on Ln2O3 also has an impact on the peroxide formation. Higher temperature or laser irradiation power is required to initiate the reaction between O2 and O(2-) species of weaker basicity.

Synthesis, characterization and photocatalytic property of AgBr/BiPO4 heterojunction photocatalyst.

A novel heterojunction AgBr/BiPO(4) photocatalyst was synthesized with the hydrothermal method. The photocatalyst was characterized by X-Ray powder Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectrscopy (XPS) and Diffuse Reflectance Spectroscopy (DRS). The XRD, SEM-EDS, TEM and XPS analyses indicated that the heterojunction structure formed during the process of hydrothermal treatment. The photocatalytic activity of the photocatalysts was evaluated by degradation of methylene blue dye (MB). The results indicated that the AgBr/BiPO(4) heterojunction exhibited a much higher photocatalytic activity than the pure BiPO(4). The mechanism of the enhancing AgBr/BiPO(4) heterojunction's photocatalytic activity was discussed. It was also found that the photocatalytic degradation of MB over AgBr/BiPO(4) heterojunction photocatalysts followed the pseudo-first-order reaction model.

In situ Raman and pulse reaction study on the partial oxidation of methane to synthesis gas over a Pt/Al2O3 catalyst.

Catalytic partial oxidation of methane (POM) to synthesis gas (syngas) over Pt/Al(2)O(3) was investigated by in situ microprobe Raman and pulse reaction methods with attention focused on the mechanism of syngas formation in the oxidation zone (i.e., the catalyst zone in which O(2) was still available in the reaction feed). It was found that the amount of platinum oxide in the catalyst under POM conditions was below the detection level of Raman spectroscopy. Raman bands of carbon species that originated from methane dissociation were detected at the entrance of the catalyst bed under working conditions. The results of the pulse reaction study on POM as well as steam and CO(2) reforming of methane at 700 °C with a contact time of less than 1 ms over the catalyst suggest that pyrolysis of methane on reduced platinum sites followed by coupling of two surface hydrogen atoms to H(2) and partial oxidation of surface carbon species to CO are the major reactions responsible for syngas formation in the oxidation zone. Under the experimental conditions, steam and CO(2) reforming of methane play only a minor role in syngas formation in the same reaction zone. The contribution of the last two reactions increases with increasing contact time.

Brønsted-NH(4)(+) mechanism versus nitrite mechanism: new insight into the selective catalytic reduction of NO by NH(3).

The selective catalytic reduction (SCR) of NO by NH(3) over V(2)O(5)-based catalysts is used worldwide to control NO(x) emission. Understanding the mechanisms involved is vital for the rational design of more effective catalysts. Here, we have performed a systematic density functional theory (DFT) study of a SCR reaction by using cluster models. Three possible mechanisms have been considered, namely (i) a Lewis acid mechanism, (ii) a Brønsted acid mechanism and (iii) a nitrite mechanism. Our calculations down-play the significance of mechanism (i) due to its high barrier as well as the incorrect reaction order. On the other hand, our calculations demonstrate that both mechanisms (ii) and (iii) can lead to a first order reaction with respect to NO with the predicted barriers being consistent with the experimental observations. Thus, we conclude: there exists two competitive pathways for SCR. Mechanism (ii) is dominant when the Brønsted acidity of the catalysts is relatively strong, while mechanism (iii) becomes important when Brønsted acidity is weak or absent. Importantly, we demonstrate that the latter two mechanisms share a common feature where N-N bond formation is ahead of N-H bond cleavage, in contrast to that in mechanism (i). Such a sequence provides an effective way to reduce the side reaction of ammonia combustion since the relatively strong N-N bond has already been formed.

Active surfaces for CO oxidation on palladium in the hyperactive state.

Hyperactivity was previously observed for CO oxidation over palladium, rhodium, and platinum surfaces under oxygen-rich conditions, characterized by reaction rates 2-3 orders higher than those observed under stoichiometric reaction conditions [Chen et al. Surf. Sci. 2007, 601, 5326]. In the present study, the formation of large amounts of CO(2) and the depletion of CO at the hyperactive state on both Pd(100) and polycrystalline Pd foil were evidenced by the infrared intensities of the gas phase CO(2) and CO, respectively. The active surfaces at the hyperactive state for palladium were characterized using infrared reflection absorption spectroscopy (IRAS, 450-4000 cm(-1)) under the realistic catalytic reaction condition. Palladium oxide on a Pd(100) surface was reduced eventually by CO at 450 K, and also under CO oxidation conditions at 450 K. In situ IRAS combined with isotopic (18)O(2) revealed that the active surfaces for CO oxidation on Pd(100) and Pd foil are not a palladium oxide at the hyperactive state and under oxygen-rich reaction conditions. The results demonstrate that a chemisorbed oxygen-rich surface of Pd is the active surface corresponding to the hyperactivity for CO oxidation on Pd. In the hyperactive region, the CO(2) formation rate is limited by the mass transfer of CO to the surface.