NO Oxidation Kinetics on Iron Zeolites: Influence of Framework Type and Iron Speciation

Zeolites having MFI, FER and *BEA topology were loaded with iron using solid state cation exchange method. The Fe:Al atomic ratio was 1:4. The zeolites were characterized using nitrogen adsorption, FTIR and DR UV–Vis–NIR spectroscopy. The catalytic activity in NO oxidation and the occurrence of NO _x adsorption was determined in a fixed-bed mini reactor using gas mixtures containing oxygen and water in addition to NO and NO₂ and temperatures of 200–350 °C. Under these reaction conditions, the NO _x adsorption capacity of these iron zeolites was negligible. The kinetic data could be fitted with a LHHW rate expression assuming a surface reaction between adsorbed NO and adsorbed O₂. The kinetic analysis revealed the occurrence of strong reaction inhibition by adsorbed NO₂. FER and MFI zeolites were more active than *BEA type zeolite. MFI zeolite is most active but suffers most from NO₂ inhibition of the reaction rate. FTIR and UV–Vis spectra suggest that isolated Fe³⁺ cations and binuclear Fe³⁺ complexes are active NO oxidation sites. Compared to the isolated Fe³⁺ species, the binuclear complexes abundantly present in the MFI zeolite seem to be most sensitive to poisoning by NO₂.     

Do Cu(II) ions need Al atoms in their environment to make CuSiBEA active in the SCR of NO by ethanol or propane? A spectroscopy and catalysis study

The two-step postsynthesis method (creation of vacant T-sites and associated SiOH groups by dealumination of BEA zeolite with nitric acid followed by incorporation of copper in the resulting SiBEA by impregnation with an aqueous solution of copper nitrate) allows to obtain a CuSiBEA zeolite which contains 0.8 Cu wt%. The incorporation of Cu(II) into the lattice of SiBEA is evidenced by XRD while the concomitant consumption of SiOH groups is monitored by FTIR. The presence of mainly isolated mononuclear Cu(II) in D_2d-distorted tetrahedral symmetry is evidenced by diffuse reflectance UV–vis-NIR, EXAFS and XANES. The CuSiBEA zeolite is active in the selective catalytic reduction (SCR) of NO with ethanol or propane with maximum NO conversion of 40 and 20% and selectivity toward N₂ close to 80–90 and 90–100%, respectively. These results suggest that the SCR process occurs on isolated mononuclear Cu(II) in D_2d-distorted tetrahedral symmetry after Al atoms have been removed from the zeolite structure. Thus, Cu(II) ions do not need Al atoms in their environment to be catalytically active. The lack of correlation between the SCR activity in presence of ethanol and the oxidation of NO to NO₂ suggests that the two reactions are more competitive than sequential. The higher activity of CuSiBEA with ethanol than with propane may be due to different activation energies and/or reaction mechanisms.     

Oxidative dehydrogenation of ethane over vanadium-based hexagonal mesoporous silica catalysts

Vanadium-containing hexagonal mesoporous silica catalysts were tested in oxidative dehydrogenation of ethane. V-HMS catalysts (0.3–9.0 wt.% V) were prepared by impregnation with solution of vanadyl acetylacetonate, and by incorporation of vanadium in the synthesis process. The prepared catalysts achieved a different distribution of vanadium species (isolated monomeric units with tetrahedral coordination, oligomeric units connected by VOV bonds up to distorted tetrahedral coordination, two-dimensional polymeric units in octahedral coordination, and bulk vanadium oxides). The contribution deals with the understanding of the relationship between the distribution of vanadium species and their activity in ODH of ethane. It has been found that both monomeric and oligomeric vanadium species play important role in ODH of ethane. The activity correlated with the population of oligomeric tetrahedrally coordinated vanadium species, which were evidenced by the UV–vis band at 315 nm. To analyze this effect, V-HMS catalysts were characterized by means of UV–vis spectroscopy, H₂-TPR and N₂-adsorption.     

Screening of Fe–BEA catalysts for wet hydrogen peroxide oxidation of crude olive mill wastewater under mild conditions

A series of Fe–BEA catalysts, differing in the amount of iron have been characterized by XRD, BET surface area, UV–vis spectroscopy and chemical analysis. The zeolite samples have been tested as heterogeneous catalysts for the wet hydrogen peroxide oxidation of crude olive mill wastewaters (OMW) under very mild conditions (at 28 °C and atmospheric pressure). All experiments were performed on a laboratory scale set-up.BSE-1/3 catalyst with a moderate Fe content (Fe/Al = 1.19) showed the best results in terms of catalytic activity and loss of active species into the aqueous solutions. The stability of Fe species has been shown to be strongly dependent on the Fe environment into the zeolite framework.Over the selected catalyst, application of catalytic procedure on diluted OMW solution permitted high removal efficiencies of pollutants. The process produces a removal capacity of 28% of total organic carbon (TOC), 40% of total phenols, 30% of chemical oxygen demand (COD) and 59% of colour, just after 12 h. 5-Day biochemical oxygen demand (BOD₅), and toxicity towards the bioluminescent bacteria Vibrio fischeri were selected to follow the performance of this process in terms of reducing the ecotoxicity of OMW. Results showed an increase in the biodegradability of the treated sample and a decrease of the microtoxicity from 100% to 70% load towards V. fischeri.Occurrence of small catalyst deactivation by carbonaeous during the oxidation reaction was observed through scanning electron microscopy (SEM) and elemental analysis.     

Impregnation of a triphenylpyrylium cation into zeolite cavities using supercritical CO2

scCO₂ technology was used for the impregnation of microporous zeolites with organic molecules. Specifically, faujasite Y was impregnated with 1,3,5-triphenyl-2-pentene-1,5-dione that after reacting with the acid sites of the zeolite large cavities, formed the 2,4,6-triphenylpyrylium cation. Since the triphenylpyrylium cation has a size higher than the diameter of the zeolite channels, the fabrication method was considered as a ship-in-a-bottle procedure. To optimize the loading, different pressures and temperatures were tested in both the diffusion and cyclisation steps used in the impregnation supercritical process. The obtained impregnated samples were purified either by conventional Soxhlet extraction with dichloromethane or by cleaning with a scCO₂ continuous flow. Loaded amounts of ca. 4–7 wt% were obtained following the supercritical procedure, which resulted more time-effective than the conventional procedure based in the use of organic solvents. Samples obtained were analyzed by thermal analysis, UV–vis and IR spectroscopy and characterization of surface area and micropore volume.     

Direct synthesis of vanadium incorporated three-dimensional KIT-6: A systematic study in the oxidation of cyclohexane

The direct synthesis of three-dimensional (3-D) cubic V-KIT-6 was prepared using a Pluronic P123 triblock copolymer as the structure directing agent and n-butanol as the co-surfactant. The material obtained therein showed a very high specific surface area 1000 m²/g with pore diameters that could be tuned within a narrow size distribution of 5.7–6.0 nm. After calcination, Raman and UV–vis analysis revealed the presence of V⁵⁺ species in a highly dispersed state with much less crystalline V₂O₅ formation. ⁵¹V-NMR analysis showed that the vanadium species interacted directly with the silica framework in an almost symmetrical tetrahedral environment. NH₃-TPD analysis for V-KIT-6 showed a wide distribution of acid sites at temperatures ranging from 200 to 800 °C. The calcined V-KIT-6 materials showed excellent catalytic activity in the direct oxidation of cyclohexane using dilute aqueous H₂O₂ as the oxidant.     

Inclusion Compound of Poly(vinyl alcohol) with Multivalent Molybdenum Coordination Compound

An inclusion compound of Mo(VI,V,IV) complexes and poly(vinyl alcohol) (PVA) that contains some carbonyl groups was prepared by a photoelectron transfer reaction between PVA and 12-molybdophosphoric acid (PMo₁₂). A dark-blue film was obtained when the aqueous solution of PMo₁₂ and PVA was irradiated with UV light. The film exhibited the characteristic electron spin resonance (ESR) signal of Mo(V). The existence of Mo(VI,V,IV) complexes was supported by XPS analysis of the film. Furthermore, the infrared (IR) and ultraviolet–visible (UV–Vis) spectra of the film showed weak absorption bands at 1710 cm^–1 and 300–314 nm that are consistent with carbonyl groups, which presumably are a result of partial oxidation of secondary hydroxyl groups on PVA. Differential scanning calorimetry (DSC) of the dark-blue film exhibited a peak at 220.3°C that is different from PMo₁₂ and PVA. Except for the IR absorption at 1710 cm^–1, the wavelengths and shapes of the other IR bands were similar to those of PVA. The UV–Vis spectrum of the film showed a new absorption band at 742–770 nm. In addition, the XRD spectrum of the film, the diffraction angles, and the crystalline sites were different from that in PMo₁₂ or PVA. However, the peak shape was similar to that of PVA. In summary, the DSC, IR, UV–Vis, and XRD data support a Mo(VI,V,IV) complex that is included into the spiral tube structure of PVA, which contains some carbonyl groups.     

Photocatalytic decomposition of acetone over dc-magnetron sputtering supported vanadia/TiO2 catalysts

Two series of titania-based photocatalysts were prepared by the sputtering method, in pure Ar atmosphere at a pressure of 0.5 Pa using a vanadium target source in a direct dc mode with a discharge of 300 V. The time of deposition was varied between 1 and 10 min in order to obtain different thickness of vanadium films. The first catalysts series (samples V/TiO₂(A)-n) was prepared deposing vanadium on pure TiO₂ anatase, while for the second series (samples V/TiO₂(AR)-n) the deposition was made onto TiO₂ Degussa P25. The samples have been investigated by means of vibrational (DRIFT and Raman) and optical (UV–vis in the DRS mode). Chemical analysis of the samples was made using the ICP-AES technique, while the crystalline structure of the deposed films onto the TiO₂ supports was checked by X-ray diffraction (XRD). The samples morphology was analyzed using the AFM microscopy. The photocatalytic decomposition of acetone was considered as a reaction test. The activity of the investigated catalysts was found to be influenced by both the amount of vanadium and the support nature. Among the investigated catalysts V/TiO₂(AR)-32 nm exhibited the higher activity. The activity of this catalyst was also superior to that of TiO₂ Degussa P25.     

Dispersion and Solid State Ion Exchange of VCl3, CrCl3?6H2O, MnCl2?4H2O and CoCl2?6H2O onto the Surface of NaY Zeolite Using Microwave Irradiation

Transition metal/Y zeolites have been prepared by solid state ion exchange with microwave irradiation of mechanical mixtures of VCl₃, CrCl₃ ⋅ 6H₂O, MnCl₂ ⋅ 4H₂O or CoCl₂ ⋅ 6H₂O with NaY zeolite at 900 W in 10–20 min. The prepared transition metal/Y zeolites were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), simultaneous thermal analysis (STA) and surface area measurement (BET). Concentration of dispersed transition metal on zeolite was measured and results revealed that transition metal was dispersed and ion exchanged onto the surface of NaY zeolite.     

Liquid phase oxidation of dibenzothiophene with alumina-supported vanadium oxide catalysts: An alternative to deep desulfurization of diesel

Alumina-supported vanadium oxide catalysts were prepared by different methods as thermal spreading, incipient wetness impregnation of ammonium metavanadate and sol–gel synthesis of alkoxide precursors, with different vanadium loadings, in order to increase the performance in oxidative desulfurization (ODS) of dibenzothiophene. The catalysts were characterized by several techniques: X-ray diffraction, UV–vis DRS, Raman spectroscopy, FT-IR of adsorbed pivalonitrile, and TPR. As additional experimental techniques, SEM–EDX and N₂ adsorption–desorption were applied, to obtain elemental analyses and textural properties. Results evidenced the presence of different superficial V species, which depend on both vanadium loading and preparation method, while significant differences in ODS activity were observed due to the catalysts preparation method.     

Fabrication and photoactivities of spherical-shaped BiVO4 photocatalysts through solution combustion synthesis method

Spherical-shaped BiVO₄ photocatalysts were prepared by the solution combustion synthesis method. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), nitrogen absorption for the BET specific surface area, field emission scanning electron microscopy (FE-SEM) and ultraviolet–visible diffraction reflection spectroscopy (UV–vis). The BiVO₄ crystallites show a monoclinic structure with diameter of about 400–600 nm. UV–vis diffusion absorption spectra indicate that the band gap absorption edge of pure BiVO₄ crystallites prepared by the SCS method and the SSR method are 523 nm and 540 nm, corresponding to the band gap energies of 2.45 eV and 2.40 eV, respectively. It is also found that the photocatalytic activity of degradation of methylene blue improves when the molar ratio of fuels to oxidizer is 5.     

Molecular Engineering of Supported Vanadium Oxide Catalysts Through Support Modification

Highly dispersed, multilayered surface metal oxide catalysts (V₂O₅/MO _x /SiO₂, M = Ti(IV), Zr(IV) or Al(III)) were successfully synthesized by taking into account various factors that govern the maximum dispersion of metal oxide species on silica. The characterization results revealed that the molecular structures of the surface vanadium oxide species on the modified supports are a strong function of environmental conditions. The surface vanadium oxide species under dehydrated conditions are predominantly isolated VO₄ units, similar to the dehydrated V₂O₅/SiO₂ catalysts. Upon hydration, the surface vanadium oxide species on the modified supports consist of polymerized VO₅/VO₆ units and/or less polymerized (VO₃) _n species, which depend on the vanadia content and the specific second metal oxide loading. The surface V cations are found to preferentially interact with the surface metal (Ti, Zr or Al) oxide species on silica. The V(V) cations in the dehydrated state appear to possess both oxygenated ligands of Si(IV)–O^– and M–O^–. Consequently, the reducibility and catalytic properties of the surface vanadium oxide species are significantly altered. The turnover frequencies of the surface VO₄ species on these modified supports for methanol oxidation to redox products (predominantly formaldehyde) increase by more than an order of magnitude relative to the unmodified V₂O₅/SiO₂ catalysts. These reactivity enhancements are associated with the substitution of Si(IV)–O^– oxygenated ligands by less electronegative M–O^– ligands in the O=V(–O–support)₃ structure, which strongly suggests that the bridging V–O–support bonds play a key role in determining the reactivity of the surface vanadium oxide species on oxide supports.     

Catalytic behavior of hybrid Co/SiO2-(medium-pore) zeolite catalysts during the one-stage conversion of syngas to gasoline

The catalytic properties of 10-MR (membered ring) zeolites (ZSM-5, MCM-22, IM-5, ITQ-2, all with a similar Si/Al ratio of ca. 15) in hybrid Co/SiO₂-zeolite catalysts for the direct conversion of syngas to mainly high-octane gasoline-range hydrocarbons has been studied under typical Fischer-Tropsch (FT) conditions: 250 °C, 2.0 MPa, and H₂/CO = 2. Special emphasis has been given to the deactivation behavior and the characterization of the amount and nature of the carbonaceous deposits formed by a combination of techniques (elemental analysis, TGA (thermogravimetric analyses), GC–MS, and DR (diffuse reflectance) UV–vis spectroscopy). The presence of the medium-pore zeolite increases the gasoline yield by about 20–50%, depending on the particular zeolite, and enhances the formation of branched products with respect to the base Co/SiO₂ catalyst, which is explained by the promotion of isomerization and cracking of long-chain (C₁₃₊) n-paraffins formed on the FT component. The initial zeolite activity is mostly determined by the surface acidity rather than by the total amount of Brønsted acid sites, pointing out to the existence of limitations for the diffusion of the long-chain n-paraffins through the 10-MR channels under FT conditions. Thus, ITQ-2 bearing the largest surface area presents the highest initial yield of branched gasoline-range products, followed by ZSM-5, IM-5, and MCM-22. All zeolites experience a loss of activity with TOS, particularly during the initial reaction stages. This deactivation is governed by the morphological and structural properties of the zeolite, which finally determine the amount and location of the coke species, and not by the acidity.     

In situ ATR-FTIR study of bulk CO oxidation on a polycrystalline Pt electrode

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) measurements were conducted to analyze the electrochemical oxidation of CO dissolved in bulk electrolyte solution on a polycrystalline Pt electrode during linear sweep (cyclic) voltammetry (CV) in 1% and 100% CO-saturated 0.1 M HClO₄. A CO adlayer was first formed on Pt at 0.05 V vs. the reversible hydrogen electrode (RHE) during CO bubbling in each electrolyte, followed by the CV measurement. In 1% CO-saturated 0.1 M HClO₄, a well-developed prepeak was found, showing an onset and a peak at around 0.25–0.3 V and 0.42 V, respectively. A major contribution of bridge-bonded CO, CO(B), to the prepeak is concluded based on a decrease in the corresponding band intensity. In 100% CO-saturated 0.1 M HClO₄, the onset of bulk CO oxidation takes place around 0.25–0.3 V, which is closely associated with a band intensity decrease of CO(B), whereas atop (linear) CO, CO(L), did not exhibit intensity change in this potential region. This suggests that vacant sites made available upon oxidation of CO(B) serve as active sites for bulk CO oxidation. The oxidation of CO(B) at such low potentials is interpreted in terms of an adsorption energy on Pt that is lower than that for CO(L) and also of the specific structure of an adlayer that consists of intermixed CO(L) and CO(B). The bulk CO oxidation becomes diffusion-limited by dissolved CO above ca. 0.72 V, where we observed hardly any infrared spectral features ascribed to reaction intermediates. During a negative-going scan back to 0.05 V from 1.2 V, a steep decrease of the bulk CO oxidation current takes place around 0.66 V, at which preferential adsorption of CO(L) is observed. A rigid CO(L) island formation is strongly suggested from its high CO stretching frequency vs. its very small initial coverage and from its subsequent dependence on potential, with a linear Stark shift characterized by a slope of −29 cm⁻¹/V. Such an island formation is in marked contrast to the adlayer structure with intermixed CO(L) and CO(B) initially formed at 0.05 V during CO bubbling. It is concluded that the Pt surface saturated with the CO adlayer formed initially at 0.05 V exhibits a low overpotential for bulk CO oxidation owing to its adlayer structure with intermixed atop and bridge-bonded CO.     

Stability of protonic zeolites in the catalytic oxidation of chlorinated VOCs (1,2-dichloroethane)

The deactivation of protonic zeolites in the catalytic oxidation of 1,2-dichloroethane (DCA) was evaluated. DCA oxidation reactions were carried out in a conventional fixed-bed reactor at atmospheric pressure under conditions of lean DCA concentration in air (1000 ppm). The outlet composition was analysed by a gas chromatograph, an IR spectroscopy-based analyser and another UV analyser. The effect of the zeolite crystalline structure was examined in order to track the catalytic stability of H-ZSM-5, H-MOR and H-BEA under typical reaction environment and conditions (1000 ppm DCA, 300 °C, 13,500 h⁻¹). With the aim of a better understanding of the deactivation pathway, the influence of the space velocity and temperature on the durability of protonic zeolites was analysed. Since some products formed during reaction could also cause deactivation, H₂O and HCl were introduced in the feed stream along with the DCA itself, so as to evaluate their effect. In general terms, coke formation was concluded to be the main reason for zeolite catalyst deactivation. Coke was formed from the intermediate vinyl chloride (VC), which resulted from a first dehydrochlorination step of DCA.     

The role of surface vanadia species in butane dehydrogenation over VOx/Al2O3

A series of θ-Al₂O₃ supported VO_x catalysts, of different vanadium loadings, have been characterised and employed for the selective dehydrogenation of n-butane. Characterisation of the unreacted catalysts has been carried out by solid-state NMR (⁵¹V MAS NMR, ²⁷Al MAS NMR and ²⁷Al 3Q-MAS NMR), and FT-IR spectroscopies, with reference to previously acquired Raman and UV–vis spectroscopy data. As vanadium loading increases, so does the domain size of the supported vanadate units with significant quantities of V₂O₅ observed at the highest loadings. The influence of calcination, pre-reduction, reaction and regeneration on the structure of the catalysts has been studied by NMR, FT-IR, EPR, microanalysis and TEOM. Calcination disperses crystalline vanadate units, and at high loadings AlVO₄ formation is observed. Pre-reduction reduces the vanadium oxidation state from 5+ to 3+, while regeneration results in the formation of highly crystalline V⁵⁺ species. From these data it is possible to determine structure–activity relationships, with polymeric vanadia clusters favouring the formation of butenes and butadienes, while more isolated species are highly active towards the formation of polynuclear aromatic hydrocarbons retained on the catalyst surface post-reaction. These large polynuclear aromatic hydrocarbons are however not the principle cause of catalyst deactivation in this reaction.     

Catalytic wet air oxidation of dye pollutants by polyoxomolybdate nanotubes under room condition

In order to develop a catalyst with high activity and stability for catalytic wet air oxidation of pollutant dyes at room condition, a new polyoxometalate Zn_1.5PMo₁₂O₄₀ with nanotube structure was prepared using biological template. The structure and morphology were characterized using infrared (IR) spectra, UV–vis diffuse reflectance spectra (DR-UV–vis), elemental analyses, X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). And the degradation of Safranin-T (ST), a hazardous textile dye, under air at room temperature and atmospheric pressure was studied as a model experiment to evaluate the catalytic activity of this polyoxomolybdate catalyst. The results show that the catalyst has an excellent catalytic activity in treatment of wastewater containing 10 mg/L ST, and 98% of color and 95% of chemical oxygen demand (COD) can be removed within 40 min. And the organic pollutant of ST was totally mineralized to simple inorganic species such as HCO₃⁻, Cl⁻ and NO₃⁻ during this time (total organic carbon (TOC) decreased 92%). The structure and morphology of the catalyst under different cycling runs show that the catalyst are stable under such operating conditions and the leaching tests show negligible leaching effect owning to the lesser dissolution. So this polyoxomolybdate nanotube is proved to be a heterogeneous catalyst in catalytic wet air oxidation of organic dye.     

Unusual Forms of Molecular Hydrogen Adsorption by Cu+1 Ions in the Copper-Modified ZSM-5 Zeolite

DRIFT and IR transmittance spectra of H₂ adsorbed at 77 K or at room temperature by the copper-modified ZSM-5 zeolite pre-evacuated or pre-reduced in CO at 873 K indicated several unusual forms of adsorbed hydrogen. H–H stretching frequencies of adsorbed species at 3075–3300 cm^–1 are by about 1000 cm<>^–1<> lower than in the free hydrogen molecules. This indicates unusually strong perturbation of adsorbed hydrogen by reduced Cu<>⁺¹<> ions that has been never before reported neither for hydrogen nor for adsorption of other molecules by any cationic form of zeolites or oxides.     

Sb-V-Ox catalysts—Role of chemical composition of MCM-41 supports in physicochemical properties

SbVO_x binary oxides were loaded on MCM-41 matrices of various chemical compositions: silicate (MCM-41), Nb-silicate (NbMCM-41), and Al-silicate (AlMCM-41). Vanadium and antimony were introduced by the post synthesis wetness impregnation carried out step by step (first V next Sb). The materials were characterised by N₂ adsorption/desorption, XRD, UV–vis, ESR, H₂-TPR, FT-IR combined with pyridine adsorption, and test reaction–hydrosulphurisation of methanol. SbVO_x dispersion was much higher when the support contained transition metal (NbMCM-41). Tetrahedrally coordinated vanadium(IV) species were deduced on all prepared samples from UV–vis spectra and were the only registered species on SbV/NbMCM-41 and SbV/AlMCM-41, whereas octahedrally ones were also present on SbV/MCM-41 and SbV/SiO₂. In bulk SbVO_x octahedral coordination dominated. The chemical composition of mesoporous support determined acidic–basic properties of SbVO_x catalysts and influenced the activity and selectivity in methanol hydrosulphurisation. The presence of Lewis acid–base pairs in the SbV/AlMCM-41 and SbV/NbMCM-41 catalysts strongly activated thiol formation in the reaction between methanol and hydrogen sulphide, whereas bulk binary oxides and SbVO_x loaded on silicate MCM-41 were less active and exhibited different selectivity.     

Luminescent π-conjugated poly(aryleneethynylene)s consisting of plural aromatic units: Preparation and systematic studies on their optical properties

A series of π-conjugated poly(aryleneethynylene)s (PAEs) containing two or three different arylene units in the main chain have been prepared by palladium-catalyzed coupling reactions. The PAEs consist of 2,5-dihexyloxy-1,4-phenylene diethynylene (–CC–C₆H₂(OC₆H₁₃)₂-p-CC–; C₆H₁₃ = hexyl) units with alternating arylene (–Ar–) units. Various kinds of arylenes, including 9,10-dihydrophenanthrene-2,7-diyl (Phen), pyridine-2,5-diyl (Py), thiophene-2,5-diyl (Th), anthracene-9,10-diyl (Ant), and 2,1,3-benzothiadiazole-4,7-diyl (BTdz), are used as the –Ar– units. The obtained PAEs were soluble in organic solvents by virtue of the attached hexyloxy side chains, and were characterized by NMR, IR, GPC, and UV–vis absorption and photoluminescence (PL) spectroscopy. The cooperation of different polymer segments induces variations in the electronic structure of the PAEs that show π–π* absorption peaks in the range of 380–530 nm and PL emission peaks in the range of 430–610 nm with quantum yields of 5–55% in their solutions. The UV–vis and PL peaks of the PAEs shifted to a longer wavelength in films and in colloidal solutions, indicating the occurrence of intermolecular electronic interactions by aggregation. In Ant-containing PAEs, the PL of the polymer chain was entirely replaced with a red-shifted PL emission assignable to the Ant segments due to intramolecular energy transfer.