The influence of the cationic ratio on the incorporation of Ti in the brucite-like sheets of layered double hydroxides

The incorporation of the tetravalent Ti⁴⁺ cations into layered double hydroxide (LDH) type materials was studied as a function of the cationic ratio in the brucite-like sheets. Therefore, Zn–Ti-LDHs with different cationic ratio were prepared by the coprecipitation method at constant pH. The X-ray diffraction patterns revealed that only for the cationic ratio of 3, the characteristic layered structure was formed. The presence and the symmetry of the interlayer carbonate anions were investigated with FTIR–PAS spectroscopy. The UV–DR shows the octahedral environment of the Ti⁴⁺ cations in the brucite-like sheets. Following the same synthesis procedure, a reference sample containing Zn²⁺ and Al³⁺ (cationic ratio of 3) was synthesized. The Zn–Al- and Zn–Ti-LDHs textural features were investigated with N₂ adsorption at 77 K and scanning electron microscopy. Incorporation of Ti⁴⁺ cations in the brucite-like sheets of LDHs lead to a material with much smaller particles, therefore more interparticle porosity and higher volume of N₂ adsorbed at high relative pressures was observed.     

Preparation of novel porous solids from alumina-pillared fluorine micas by acid-treatment

New porous solids from alumina-pillared fluorine micas (APMs), which were obtained from synthetic Na-tetrasilicic fluorine mica [NaMg_2.5Si₄O₁₀F₂], were prepared by sulfuric acid-treatment under mild conditions at 25 °C. The products were investigated by XRD, ICP, SEM, TEM and N₂ adsorption–desorption isotherm at 77 K. XRD measurements indicated that the interlayer pillared structure having a large basal spacing collapsed during the early stages of the acid-treatment. ICP analyses indicated that Al³⁺ and Mg²⁺ ions were leached out from the pillared micas during the acid-treatment. The pore properties of the leached products were found to differ from those of the mother pillared micas: the acid leaching of the pillared micas leads to the formation of mesopores around 3.2 nm in diameter. The correlation between the change in pore properties and cation elution behavior suggests that the mesopore formation results from the leaching of Mg²⁺ ions from the octahedral sheet of the pillared micas. The leached products thus obtained retained the flaky morphology of the mother pillared micas. These results show that the mild acid-treatment using APMs provides a novel route for obtaining unique mesopore solids having the large particle sizes of the mother micas.     

Synthesis of metatungstate pillared layered double hydroxides with variable layer composition. Effect of the Mg:Al ratio on the microporous structure

A series of layered double hydroxides (LDHs) pillared with the Keggin ion H₂W₁₂O₄₀⁶⁻ has been synthesized with final Mg:Al ratios of 1.75:1, 2.31:1 and 3.51:1 by ion exchange reaction of the LDH-hydroxide and LDH-adipate precursors. In each case, the pillared product was characterized by specific BET N₂ surface areas of more than 110 m² g⁻¹ and micropore volumes in excess of 0.026 ml g⁻¹. The micropore size distribution plots obtained from the argon adsorption isotherms indicate that the micropore diameters become smaller as the surface charge density of the LDH increases. A study was also performed on each of the LDH precursors in order to determine any problematic steps in the overall synthesis. Significant differences were noticed in the POXRD patterns of the LDH-adipate precursor; these are believed to be due to differences in the orientation and degree of order of the adipate anions in the gallery space of the LDH. It was found that adipate anions orientated with the long axis perpendicular to the inorganic layers were easier to exchange than those where the long axis was aligned parallel to the inorganic layers.     

Theoretical Evaluation of the Microporosity of Pillared Layered Double Hydroxides

Over the last ten years, the concept of pillaring has frequently been applied on layered double hydroxides (LDHs). Due to the variety of possible anionic pillaring species and the adjustable layer charge density, LDHs offer good perspectives with regard to the creation of porous adsorbents and catalysts. But despite these possibilities, their porosity properties can still not compete with those of industrially applicable materials like zeolites. In this study, theoretical calculations based on geometrical models and performed on both Fe(CN)₆-MgAl-LDHs (A) and [PV₂W¹⁰ O⁴⁰]-ZnAl-LDHs (B) were reported. Properties such as the micropore volume and the interpillar distance were calculated, and compared to experimental data. For a M(II)/M(III) ratio in the layers of 3, the theoretical maximum micropore volumes were 0.3843 cm³/g (A) and 0.1497 cm³/g (B), respectively. By implementing parameters like the stack size, pillars on the outside of the stacks and the possibility of collapse, the model was adjusted in order to create a realistic picture of the microstructure of pillared LDHs. This led to a better understanding of the limiting factors, and gave an explanation for the relatively low micropore volumes of pillared LDHs. For the Fe(CN)₆-MgAl-LDHs, small interpillar distances were responsible for the partial inaccessibility of the interlayer regions by N₂. This effect was the most pronounced for high charge density LDHs. The situation for the [PV₂W¹⁰O⁴⁰]-ZnAl-LDHs is more complex. Probably due to an incomplete pillaring process, the theoretical maximum values are not reached.     

Studies of the effects of synthetic procedure on base catalysis using hydroxide-intercalated layer double hydroxides

Layer double hydroxides (LDHs) based on the hydrotalcite structure (Mg₆Al₂(OH)₁₆CO₃·4H₂O) have been synthesized by coprecipitation, sol–gel and urea hydrolysis methods and with Mg:Al ratios of 2:1 and 5:1. Scanning electron microscopy shows the coprecipitated phases present the smallest individual crystallite sizes (ca. 150 nm) with the largest crystallites (2–4 μm) for urea hydrolysis. Sol–gel samples show crystallites (150–450 nm) fused together into much larger particles. The samples have been calcined at 723 K in flowing air to produce metal oxide phases which have then been rehydrated in the presence of hydroxide ions to produce meixnerite-like LDH phases (Mg₆Al₂(OH)₂₀·4H₂O). The base catalytic activity of these rehydrated samples has been measured by GC for the aldol self-condensation of acetone. Activity data has been correlated with sample characteristics to gain insight into the active sites and mode of action of these catalysts.     

镁铝离子共存硅酸体系的聚合行为

通过对镁铝离子共存硅酸体系中硅酸胶凝时间、单硅酸聚合反应速率以及凝胶热性能的研究,得出：在pH<;4的微酸性条件下,硅酸体系的胶凝时间随镁铝离子共存浓度的增大而减小,且铝离子在对硅酸体系的促凝过程中起主要作用。镁铝离子共存硅酸体系的单硅酸反应速率常数比不含金属离子硅酸体系的有所增大,计算得出MA_0.1+0.1硅酸体系的单硅酸平均速率常数为：k₀=7.28×10^-4,k₁=5.62×10^-4。镁铝离子共存硅酸体系凝胶的晶化转变温度与晶型转变温度,相较于不含金属离子硅酸体系的均有所降低,根据热重曲线计算出MA_0.1+0.1硅酸体系水合二氧化硅的化学式为：SiO₂·0.556 H₂O。     

Study of the acid character of some palladium-modified pillared clay catalysts: Use of isopropanol decomposition as test reaction

Preparation, textural and structural characterizations as well as acid properties of some aluminium, zirconium pillared montmorillonite (from Algerian bentonite) and including alumina or zirconium pillared montmorillonite supported palladium are reported. Heat resistant basal spacings of 1.7 nm, surface areas in the range of 250–300 m²/g and micropore volumes of about 0.1 cm³/g were obtained. The acid activation of montmorillonite prior pillaring conduces to a resulting material with significantly higher pore volume and acidity. The improvement in acidity is mainly of the Brønsted acid type. The modification of zirconium-pillared montmorillonite with sulfate ions affects the structural properties of the pillared sample but gives a material with strong acid properties and both Lewis and Brønsted acid types are enhanced. It is reported also that textural and structural properties are not affected by the impregnation of a metallic function (1 wt.% Pd loading) but the acid properties changed. The pillared montmorillonite supported palladium has more Brønsted acidity than does the pillared montmorillonite. Decomposition of isopropanol was studied on these systems at low reaction temperature.     

Conductivity of molten hydrated salts: Mg(NO3)2. 6H2O + NH4NO3 system

Conductivity of molten Mg(NO₃)₂. 6H₂O + NH₄NO₃ system containing up to 80 mole percent of the latter was measured in the temperature range 320–400 K. Temperature dependence of conductivity exhibited Arrhenian behaviour. Conductivity—composition isotherms were non-linear indicating weak ordering tendencies. Equivalent conductivity data did not obey Markov equation; deviations have been interpreted in terms of the Tobolsky parameter (θ). Constancy of θ indicate that the water of hydration in the system remains with Mg²⁺ ions and is unaffected by the addition of NH⁺₄ ions.     

Gold supported on ceria and ceria–alumina promoted by molybdena for complete benzene oxidation

New gold–molybdena catalysts supported on ceria and ceria–alumina in reaction of complete benzene oxidation were studied. The catalysts were characterized by means of XRD, TPR, XPS and Raman spectroscopy. High and stable catalytic activity was established in the temperature region 200–240 °C. The presence of gold causes a modification in ceria structure leading to an increase of Ce³⁺ and oxygen vacancies formation. The loading of Al³⁺ increases additionally the oxygen vacancies, while a tendency of decrease of Ce³⁺ amount was observed. The presence of alumina results also in a larger share of active oxygen species proved by analysis of O 1s XPS spectra. The differences in the activities within the starting temperature range (150–180 °C) and in the region of 100% conversion (200–240 °C) could be explained by supposing that in the LT region the electron transfer between nanosized gold and ceria particles via oxygen vacancies has a crucial role. In the HT region the oxygen mobility, provoked by the defective structure of ceria due to the presence of Al³⁺, becomes of prevailing importance. It was also concluded that alumina prevents the gold and ceria agglomeration, which is the main factor to avoid deactivation under extreme reaction conditions.     

Decolorization of reactive brilliant red X-3B by heterogeneous photo-Fenton reaction using an Fe–Ce bimetal catalyst

Decolorization of reactive brilliant red X-3B was studied by using an Fe–Ce oxide hydrate as the heterogeneous catalyst in the presence of H₂O₂ and UV. The decolorization rate was in the order of UV–Fe–Ce–H₂O₂ > UV–Fe³⁺–H₂O₂ > UV–H₂O₂ > UV–Fe–Ce ≥ Fe–Ce–H₂O₂ > Fe–Ce. Under the conditions of 34 mg l⁻¹ H₂O₂, 0.500 g l⁻¹ Fe–Ce, 36 W UV and pH 3.0, 100 mg l⁻¹ X-3B could be decolorized at efficiency of more than 99% within 30 min. The maximum dissolved Fe during the reaction was 1 mg l⁻¹. From the fact that the decolorization rate of the UV–Fe–Ce–H₂O₂ system was significantly higher than that of the UV–Fe³⁺–H₂O₂ system at Fe³⁺ = 1 mg l⁻¹, it is clear that the Fe–Ce functioned mainly as an efficient heterogeneous catalyst. UV–vis, its second derivative spectra, and ion chromatography (IC) were employed to investigate the degradation pathway. Fast degradation after adsorption of X-3B is the dominant mechanism in the heterogeneous catalytic oxidation system. The first degradation step is the breaking down of azo and CN bonds, resulting in the formation of the aniline- and phenol-like compounds. Then, the breaking down of the triazine structure occurred together with the transformation of naphthalene rings to multi-substituted benzene, and the cutting off of sulphonic groups from the naphthalene rings. The last step includes further decomposition of the aniline structure and partial mineralization of X-3B.     

Hydroxy-Al pillaring of concentrated suspensions of smectite clays

The addition of solid 5/6 basic aluminum chloride salt (ACH) to a concentrated (50% w/w) acetone suspension of various dioctahedral and trioctahedral smectites, followed by washing with distilled water and centrifugation, leads to the formation of well formed pillared derivatives (PILCs). The samples were characterized by chemical analysis, X-ray diffraction, N₂ adsorption, ²⁹Si and ²⁷Al MAS NMR spectroscopy, and turned out to be highly microporous with micropore volumes in the range 0.10–0.12 cm³/g, and with highly ordered clay sheets (d₀₀₁ = 1.8 nm). The number and strength of the acid sites were estimated by analysing the product distribution of the 1-butene isomerization reaction. A mechanism of the pillaring process is proposed on the basis of MAS NMR, XRD, and N₂ adsorption data.     

Microwave-hydrothermally aged Zn,Al hydrotalcite-like compounds: Influence of the composition and the irradiation conditions

Zn,Al–CO₃ compounds with the hydrotalcite-like (layered double hydroxide, LDH) structure were prepared by a co-precipitation method followed by hydrothermal treatment under microwave irradiation. The influence of the ageing treatment was studied in two series of samples with different Zn²⁺/Al³⁺ ratios, namely, 3/1 and 2/1. Moreover, the effects of the heating temperature and of the irradiation time were studied in order to select the optimum preparation conditions. The solids were fully characterised by powder X-ray diffraction (PXRD), ²⁷Al MAS-NMR, FT-IR spectroscopy, thermal analyses (DTA and TG), N₂ adsorption/desorption at −196 °C and TEM. The results showed that whatever the chemical composition of the starting mixture, HTlcs with Zn²⁺/Al³⁺ ratio equal to 2 were obtained, and it was impossible to overcome the ZnO segregation when the molar ratio was >2. These compounds were stable and their crystallinity could be quickly enhanced when the temperature treatment was 100 °C, whereas at 125 °C the ZnO segregation was not prevented.     

Catalytic oxidation of sulfide ions over nickel hydroxides

The catalytic sulfide ion oxidation by oxygen to elemental sulfur over β-Ni(OH)₂ and LiNiO₂ has been studied. As a result of experimental investigation performed, a reaction mechanism is suggested which involves heterogeneous and homogeneous processes. Dioxygen activation in the heterogeneous process proceeds via a redox Ni²⁺ ↔ Ni³⁺ transition and participation of OH⁻ groups. The active HO⁻₂ species thus formed carries on the reaction in homogeneous phase. Nickel hydroxides are promising catalysts for practical application.     

Photodegradation catalyst screening by combinatorial methodology

In this work, a combinatorial methodology was developed for photodegradation catalyst screening. A fluorescence imaging detection system was designed for high throughput analysis, 1,6-hexamethylenediamine was used as the probe molecule for catalyst testing. The photodegradation activity of catalysts was evaluated by 1,6-hexamethylenediamine consumption during the photodegradation reaction. The methodology could provide reliable results. We found that pure TiO₂, ZrO₂, Nb₂O₅, MoO₃, and WO₃ did not show much activity for 1,6-hexamethylenediamine photodegradation under visible light. TiO₂ catalysts doped with different metal ions were tested. When TiO₂ was doped with Ta₂O₅, Nb₂O₅, V₂O₅, MoO₃, or WO₃, higher activity for photodegradation was observed. The doping of La³⁺, Ba²⁺, and Br⁻ to TiO₂ did not improve the catalytic activities. When doping TiO₂ with Mn²⁺, Cl⁻, Al³⁺, Cu²⁺, Fe³⁺, Na⁺, Mg²⁺, Li⁺, F⁻, Co²⁺, or K⁺, catalytic activity was lower than that of pure TiO₂. After elaborate catalysts screening, we discovered new catalysts, such as 50–70% TiO₂/0–20% WO₃/20–40% VO_2.5 and 20–30% TiO₂/30–50% MoO₃/40–60% VO_2.5 as well as 30% WO₃/20% ZrO₂/50% NbO_2.5 (synthesized from ZrCl₄, NbCl₅, and (NH₄)₅H₅[H₂(WO₄)₆]·H₂O in ethanol solution or suspension) and 60–70% WO₃/Nb₂O₅ (synthesized from WCl₆ and NbCl₅ in ethanol solution). We observed that the catalytic activity is sensitive to preparation methods and catalyst specific surface areas. When P123 (HO(CH₂CH₂O)₂₀(CH₂CH(CH₃)O)₇₀(CH₂CH₂O)₂₀H, designated EO₂₀PO₇₀EO₂₀) was used as template to synthesize mesoporous materials, the mesoporous catalysts showed higher activity than regular catalytic materials.     

Adsorption of 2,4-D on Mg/Al–NO3 layered double hydroxides with varying layer charge density

Layered double hydroxides (LDHs) have high surface area and high anion exchange capacity, so they have been proposed to be an effective scavenger for contaminants. In this study, the adsorption of 2,4-dichlorophenoxyacetate (2,4-D) on Mg/Al–NO₃ LDHs with varying layer charge density was investigated with particular attention on the effect of the orientation of the interlayer nitrate. Three Mg/Al LDHs were synthesized with Al³⁺/(Al³⁺ + Mg²⁺) molar ratios of 3.3 (LDH3), 2.6 (LDH4) and 2.1 (LDH5). The results of adsorption experiments showed that LDH5 exhibited an S-type isotherm with a low 2,4-D adsorption capacity due to the low accessibility of 2,4-D to the interlayer space. The accessibility was restricted by the small basal spacing of LDH5 as a result of the parallel orientation of the interlayer nitrate with respect to the hydroxide sheet. Thus, the 2,4-D adsorption occurred mainly on the external surface of the material. On the contrary, LDH3, which has the highest layer charge density among the samples, contains nitrate with an orientation perpendicular to the hydroxide sheet of LDH3. The interlayer nitrate was readily exchanged by 2,4-D. Thus, in addition to the adsorption on the external surface, the replacement of the interlayer nitrate by 2,4-D contributed to a higher adsorbed amount of 2,4-D; the 2,4-D adsorption of LDH3 exhibited an L-type isotherm. For LDH4 that contained interlayer nitrate with both parallel and perpendicular orientations, the adsorption characteristics were between those of LDH3 and LDH5. This work has demonstrated the dependence of 2,4-D adsorption characteristics on the nitrate orientation in LDHs, as a consequence of changing layer charge density.     

Synthesis and characterization of Zn/Al and Pt/Zn/Al layered double hydroxides obtained by the sol–gel method

The influence of the nature of the Zn, Al and Pt precursors, and of the temperature of precipitation and aging have been studied in connection with the preparation of Zn/Al and Pt/Zn/Al layered double hydroxides (LDH) by the sol–gel method. Whatever the precursors the XRD analysis shows that LDH is formed at the expense of ZnO when the precipitation and aging temperatures decrease from 353 K to 273 K. Moreover, chemical composition and TG analysis suggest the presence of weak amounts of hydrozincite, hydrozincite-like and Al(OH)₃ phases. When the precursors are Zn acetate-2-hydrate or Al acetylacetonate the amount of LDH reaches a maximum of 50 mol% at 273 K. At variance, about 90 mol% of LDH is obtained when using Zn acetylacetonate and Al isopropoxide as precursors, which are precipitated at 273 K. This proportion is slightly improved for the Pt-containing sample prepared under the same conditions. The specific surface areas of the different samples obtained after calcination at 723 K increase with their LDH content, reaching values of 110–120 m² g⁻¹. They make them particularly attractive for catalytic applications.     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Recovery of fluoride values from spent pot-lining: Precipitation of an aluminium hydroxyfluoride hydrate product

Treatment of spent pot-lining (SPL) from aluminium smelting cells by a two-stage leaching scheme comprising a water wash and an Al³⁺ leach and fluoride recovery as an aluminium hydroxyfluoride product has been studied for extraction of fluoride and then recovery as smelter grade AlF₃. The NaF content of a −1.18 mm size fraction was removed by the water wash, while the more refractory Na₃AlF₆ and CaF₂ were removed by treatment with 0.34 M Al³⁺ solution at 25 °C for 24 h, which yielded an overall fluoride extraction of 76–86 mol%. Mathematical modelling using experimental stability constant data was carried out to predict the effect of combining solutions and identify ways to manipulate the solution equilibria to maximise fluoride precipitation yields. The predictions were then tested experimentally. In the 4.5–5.5 pH range, selective precipitation of fluoride as an aluminium hydroxyfluoride hydrate product was achieved by neutralisation of the combined solutions with addition of 2 M NaOH solution. Higher pH values lead to the co-precipitation of hydrolysed sodium fluoroaluminates. Characterisation of precipitates using X-ray diffraction, scanning electron microscopy coupled with energy-dispersive spectroscopy, thermogravimetric analysis, differential thermal analysis, aluminium and fluoride determination have pointed out both the AlF₂(OH)·1.4H₂O stoichiometry and possible thermal decomposition pathways to yield a dehydrated aluminium hydroxyfluoride product, AlF₂(OH), that could be used for smelter grade AlF₃ production. The kinetics of hydrolysis are such that nucleation dominates while particle growth is restricted. Techniques to allow slow hydrolysis are necessary to form smelter grade AlF₃.     

Electrical resistivity of transition metal ion doped Mullite

The electrical resistivity of pure mullite (3Al₂O₃.2SiO₂) varies from 10¹³ ohm-cm at room temperature (r.t.) to 10⁴ ohm-cm at 1400 °C. It was observed that by doping mullite with the 3d-type transition metal ions, e.g. Mn, Fe, Cr and Ti, the resistivity of mullite could be reduced to 10¹¹ ohm-cm, i.e. 1/100 that at r.t. and 1/5 that at 1400 °C. The resistivity of doped and undoped mullite decreased by 6–5 orders at about 500–600 °C but 4–3 orders between this temperature and 1400 °C. The 3d orbital electrons, the oxidation states and the concentration of the transition metal ions as well as the sites of mullite lattice occupied by the ions were found responsible for lowering of resistivity of mullite. Evidence of the presence of Mn²⁺, Mn³⁺, Fe³⁺, Cr³⁺ and Ti⁴⁺ ions in mullite had been obtained which entered the octahedral site. The Ti⁴⁺ ion which substituted Al³⁺ ion in the octahedral site of mullite structure appeared to be the most efficient one to reduce the resistivity. This has been confirmed by the results of activation energy of resistivity/band gap energy, Eg which was the lowest for mullite doped with 1·0 wt% Ti⁴⁺ ion. At 1·0 wt% concentration level, these ions lowered the resistivity of mullite to minimum.     

Copper-impregnated Al–Ce-pillared clay for selective catalytic reduction of NO by C3H6

The selective catalytic reduction (SCR) of NO by hydrocarbon is an efficient way to remove NO emission from lean-burn gasoline and diesel exhaust. In this paper, a thermally and hydrothermally stable Al–Ce-pillared clay (Al–Ce-PILC) was synthesized and then modified by SO₄²⁻, whose surface area and average pore diameter calcined at 773 K were 161 m²/g and 12.15 nm, respectively. Copper-impregnated Al–Ce-pillared clay catalyst (Cu/SO₄²⁻/Al–Ce-PILC) was applied for the SCR of NO by C₃H₆ in the presence of oxygen. The catalyst 2 wt% Cu/SO₄²⁻/Al–Ce-PILC showed good performance over a broad range of temperature, its maximum conversion of NO was 56% at 623 K and remained as high as 22% at 973 K. Furthermore, the presence of 10% water slightly decreased its activity, and this effect was reversible following the removal of water from the feed. Py-IR results showed SO₄²⁻ modification greatly enhanced the number and strength of Brönsted acidity on the surface of Cu/SO₄²⁻/Al–Ce-PILC, which played a vital role in the improvement of NO conversion. TPR and XPS results indicated that both Cu⁺ and isolated Cu²⁺ species existed on the optimal catalyst, mainly Cu⁺, as Cu content increased to 5 wt%, another species CuO aggregates which facilitated the combustion of C₃H₆ were formed.