Surface Acid-base Properties Research Articles

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO2 and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO2 and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO2, the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

(Ga1-xAlx)4B2O9: controlled surface acid-base properties and catalytic behavior towards the Strecker reaction.

Solid bases are valuable catalysts for industrial syntheses. However, controlling the basicity of these catalysts remains a challenge. Ga4B2O9, due to μ3-O within its structure, could behave as a special solid base catalyst exhibiting intrinsic Lewis basicity. In this work, a sol-gel method was proposed to obtain continuously adjustable acidity and basicity of the metal borate catalyst (AlxGa1-x)4B2O9. According to the results of NH3-TPD, CO2-TPD, and the systematic experimental design, Lewis basic sites originating from GaO5 groups in (AlxGa1-x)4B2O9 boost the Strecker reaction rather than the Lewis acid sites related to unsaturated Al. This work illustrates the possible application of bulk-type solid solutions with simultaneous Lewis acid and base sites for the first time. A reaction mechanism has also been proposed based on the catalytic reaction results.

The potential of Gd doping as a promising approach for enhancing the adsorption properties of nickel-cobalt ferrites.

The study shows that the addition of gadolinium ions has a significant impact on the structure, morphology, and adsorption properties of Ni-Co spinel ferrite that was synthesized by the sol-gel auto-combustion method. The research also indicates that the higher the Gd content, the greater the increase in the lattice parameter, which suggests that Gd3+ ions uniformly replaced the octahedral Fe3+ ions. The morphology and chemical composition of Gd-doped Ni-Co ferrites have been studied using SEM and EDS. Gd adding to the NiCoFe matrix increases the BET surface area by 50% (from 48 to 72 m2/g) and promotes the formation of mesopores with an average radius from 3.9 to 4.9nm. The pHPZC values of Gd-doped ferrites are in the range of 7.22-7.39, which means that the ferrite surface will acquire a positive charge at natural pH, so this will promote the adsorption of Congo red anionic dye through electrostatic interaction forces. Langmuir, Freundlich, and Dubinin-Radushkevich models were used to explain the mechanism of CR adsorption on the Ni0.5Co0.5GdxFe2-xO4 adsorbent surface. The ionic-covalent parameter has been estimated to describe the surface acid-base properties. Overall, this study highlights the potential of Gd3+ doping as a promising approach for enhancing the adsorption properties of nickel-cobalt ferrites.

Synthesis and application of biochar from agricultural by-products. Effect of pyrolysis temperature on the acid-base properties of biochar

Biochar was synthesized from banana peels using the pyrolysis method in a nitrogen gas environment. The pyrolysis temperature ranged from 100°C to 500°C with a heating rate of 5°C per minute and a pyrolysis time of 1.5 hours. The influence of the pyrolysis temperature on the acid-base properties of the biochar surface was evaluated through characteristic SEM and BET measurements. Boehm titration showed a gradual decrease in the total acid functional groups and an increase in the total base functional groups with the increasing pyrolysis temperature. Methylene Blue (MB) was used as a model substance to investigate the adsorption properties of the synthesized biochar. The Langmuir and Freundlich models were employed to describe the adsorption equilibrium. The kinetics of MB adsorption followed a pseudo-second-order kinetic equation. The adsorption capacity of MB by biological charcoal was influenced by the acid-base properties of the material, indicating the impact of the pyrolysis temperature.

Influence of Fe(II), Fe(III), and Al(III) isomorphic substitutions on acid-base properties of edge surfaces of cis-vacant montmorillonite: Insights from first-principles molecular dynamics simulations and surface complexation modeling

Abstract Knowing the influence of isomorphic substitutions on the acid-base properties of smectite edge surfaces is an important aspect of the detailed understanding of clay minerals’ interfacial properties with implications in the modeling of adsorption processes. We investigated the intrinsic acidity constants of Fe(II)/Fe(III) and Al(III) substituted edge surface sites of montmorillonite with a cis-vacant structure, which includes four crystallographic orientations perpendicular to [010], [010], [110], and [110], using the first-principles molecular dynamics (FPMD) based vertical energy gap method. Fe(II) and Fe(III) substitutions resulted, respectively, in a significant increase and decrease in pKa values of amphoteric groups directly associated with Fe octahedra. In addition, Fe(II) substitution increased the pKa values of the neighboring silanol sites, while Fe(III) substitution had a weak influence on these sites. The Al-substituted tetrahedra had amphoteric sites with higher pKa values than the non-substituted Si tetrahedra, and they increased significantly the pKa values of the sites bridging the tetrahedral and octahedral sheets on surfaces perpendicular to [010] and [110]. The acid-base properties of substituted and non-substituted surface sites of cis-vacant montmorillonite were used to build a state-of-the-art surface complexation model, which successfully reproduced the best available experimental acid-base titration data. This model was further used to predict acid-base properties of dioctahedral smectites (montmorillonite, beidellite, and nontronite) according to their cis- or trans-vacant structures and their layer chemistry. According to these predictions, these smectites exhibit very similar overall pH buffering properties despite significant differences in structure and chemistry. A detailed analysis of the acid-base properties as a function of crystallographic directions demonstrated, however, that these differences should have a large influence on the adsorption of ionic species.

Self-heating photothermal synergistic catalytic decomposition of carcinogenic formaldehyde by α-MnO2 at ambient temperature: Functional roles of surface acidic-basic sites

Formaldehyde is a major pollutant in indoor atmosphere, and the realization of complete mineralization of formaldehyde at room temperature is of great significance and practical demand for improving indoor air quality. Surface acidic-basic sites, as one of the important surface properties that have significant influence on catalytic oxidation of formaldehyde, revealing their functions is beneficial for the development of efficient formaldehyde decomposition materials. Herein, the α-MnO2 acidic-basic sites were regulated and its effects on self-heating photothermal catalytic oxidation of formaldehyde were further contrastive investigated. The acidic-basic sites showed distinct functions: the basic sites exhibited a significant promotion on formaldehyde oxidation; While the acidic sites greatly inhibited the reactivity. Particularly, the basicity enhanced α-MnO2 could reach the 100% conversion of formaldehyde at ambient temperature. Furthermore, the self-heating photothermal mechanism was consonant with the thermal-assisted photocatalysis mechanism, rather than traditional photo-drive thermal catalysis mechanism. The strength of basic sites significantly increased the content of surface hydroxyl groups, and the electron-rich basic sites were favorable for the activation of oxygen, thereby generating more reactive oxygen species for the decomposition of formaldehyde. Moreover, in-situ DRIFTS reveals that the enhancement of basic sites can accelerate the rate oxidation of HCHO to generate formates and carbonates. This work clarified the influence of surface acid-base properties on formaldehyde photothermal decomposition.

Effect of Tacticity on London Dispersive Surface Energy, Polar Free Energy and Lewis Acid-Base Surface Energies of Poly Methyl Methacrylate by Inverse Gas Chromatography

This research was devoted to study the effect of the tacticity on the surface physicochemical properties of PMMA. (1) Background: The determination of the surface free energy of polymers is generally carried out by inverse gas chromatography (IGC) at infinite dilution. The dispersive, polar and surface acid-base properties of PMMA at different tacticities were obtained via IGC technique with the help of the net retention time and volume of adsorbed. (2) Methods: The London dispersion equation was used to quantify the polar free energy of adsorption, while the London dispersive surface energy γsd(T) of PMMAs was determined using the thermal model. (3) Results: The results showed non-linear variations of γsd(T) of atactic, isotactic, and syndiotactic PMMAs with three maxima characterizing the three transition temperatures of PMMAs. The obtained values of the enthalpic and entropic Lewis’s acid-base parameters showed that the basicity of the atactic PMMA was about four times larger than its acidity. (4) Conclusions: A large difference in the behavior of the various PMMAs was proven in the different values of the polar acid and base surface energies of the three PMMAs with an important effect of the tacticity of PMMA on its acid-base surface energies.

Surface Thermodynamic Properties of Poly Lactic Acid by Inverse Gas Chromatography.

Poly lactic acid (PLA) is one of the most commonly used bio-derived thermoplastic polymers in 3D and 4D printing applications. The determination of PLA surface properties is of capital importance in 3D/4D printing technology. The surface thermodynamic properties of PLA polymers were determined using the inverse gas chromatography (IGC) technique at infinite dilution. The determination of the retention volume of polar and non-polar molecules adsorbed on the PLA particles filling the column allowed us to obtain the dispersive, polar, and Lewis's acid-base surface properties at different temperatures from 40 °C to 100 °C. The applied surface method was based on our recent model that used the London dispersion equation, the new chromatographic parameter function of the deformation polarizability, and the harmonic mean of the ionization energies of the PLA polymer and organic molecules. The application of this new method led to the determination of the dispersive and polar free surface energy of the adsorption of molecules on the polymeric material, as well as the glass transition and the Lewis acid-base constants. Four interval temperatures were distinguished, showing four zones of variations in the surface properties of PLA as a function of the temperature before and after the glass transition. The acid-base parameters of PLA strongly depend on the temperature. The accurate determination of the dispersive and polar surface physicochemical properties of PLA led to the work of adhesion of the polar organic solvents adsorbed on PLA. These results can be very useful for achieving reliable and functional 3D and 4D printed components.

Investigating the activity of modified TiO2 photocatalysts used for the photoreforming of biomass derivatives

Different TiO2 modified (with Pt, Cu2O, Nb) photocatalysts have been compared for the photo-reforming of glucose and fructose at ambient conditions with the aim of linking the photoactivity to some structural and surface characteristics. A different degree of conversion, distribution of intermediates and H2 production were observed with the various photocatalysts. Moreover, the results obtained with the same catalysts were slightly different with the two substrates, highlighting the importance of the interaction between the catalyst surface and the organic compound. Bare TiO2 was inactive towards H2 production, Cu2O was effective in replacing Pt for hydrogen generation, and the presence of Pt/Nb was beneficial for both H2 production and selective oxidation. Moreover, Pt not only works as a sink for the photoproduced electrons, as it is well known in the literature, but also modifies the surface acid-base properties of catalysts as revealed by DRIFT and TPD measurements.

New Progress on London Dispersive Energy, Polar Surface Interactions, and Lewis's Acid-Base Properties of Solid Surfaces.

The determination of the polar surface free energy, polar properties, and Lewis's acid base of solid materials is of capital importance in many industrial processes, such as adhesion, coatings, two-dimensional films, and adsorption phenomena. (1) Background: The physicochemical properties of many solid particles were characterized during the last forty years by using the retention time of injected well-known molecules into chromatographic columns containing the solid substrates to be characterized. The obtained net retention time of the solvents adsorbed on the solid, allowing the determination of the net retention volume directly correlated to the specific surface variables, dispersive, polar, and acid-base properties. (2) Methods: Many chromatographic methods were used to quantify the values of the different specific surface variables of the solids. However, one found a large deviation between the different results. In this paper, one proposed a new method based on the London dispersion equation that allowed the quantification of the polar free energy of adsorption, as well as the Lewis's acid-base constants of many solid surfaces. (3) Results: The newly applied method allowed us to obtain the polar enthalpy and entropy of adsorption of polar model organic molecules on several solid substrates, such as silica, alumina, MgO, ZnO, Zn, TiO2, and carbon fibers. (4) Conclusions: our new method based on the separation between the dispersive and polar free surface energy allowed us to better characterize the solid materials.

Catalytic aerobic oxidation of lignin-based vanillyl alcohol over LaFeO3 perovskite towards vanillin production: Relationships between the activity and acid-base property as well as oxygen vacancy

Developing high-performance acid-base catalysis over perovskite for alcohol aerobic oxidation has received increasing attention, but the fundamental understanding of its surface acid-base property and performance relationship remains largely unknown. Accordingly, a series of LaFeO3 perovskites were fabricated via modified Pechini approach with the addition of different chelating agents to modulate their respective acid-base amount and oxygen vacancy concentration, which subsequently were employed in the aerobic oxidation of vanillyl alcohol (a lignin model), to generate vanillin for elucidating the relationships between the catalytic activity of LaFeO3 perovskite and its acid-base property as well as oxygen vacancy. The results demonstrated that existence of non-linear relationships between the vanillin yield and the acid-base amount as well as oxygen vacancy concentration of LaFeO3 catalyst. Moreover, neither acid-base sites nor oxygen vacancies were the solely factors affecting the activity of LaFeO3 perovskite towards vanillyl alcohol oxidation for vanillin production. Mechanism studies proclaimed that the reactive oxygen species derived from the adsorption of molecule oxygen on oxygen vacancies generated by anion defects combing with Lewis acid sites (Fe3+/Fe2+) to yield FeOx active pairs, which jointly dominated the pathway for vanillyl alcohol oxidation to produce vanillin. Overall, this work offers guidance for designing effective perovskite-based catalysts for lignin conversion to produce value-added chemicals by selectively modulating its acid-base property and oxygen vacancy.

Controlling Magnesium Silicates Coprecipitation Conditions: A Tool to Tune Their Surface Acid–Base Reactivity

Magnesium silicates combining acidic and basic surface properties are known to be interesting as heterogeneous catalysts. Nevertheless, their catalytic performances are highly dependent on the synthesis method used. In this study, a series of magnesium silicates was synthesized for the first time using a coprecipitation method with a micromixer. It is first shown that changes in synthesis/precipitation pH led to magnesium silicates with different Mg/Si ratios: the higher the synthesis pH, the higher the Mg/Si ratio. Moreover, prepared silicates with a final Mg/Si ratio greater than 0.7, thus prepared at high pH, exhibit negligible specific surface area, whereas relatively high values (>180 m2/g) have been obtained for lower Mg/Si ratios. A set of experimental characterization data obtained by N2 physisorption, SEM, XRD, TGA-DTA as well as Raman and 29Si NMR spectroscopies are presented and discussed. They show the existence of two distinct families with a similar Magnesium Silicate Hydrate (MSH) phase, but they reveal different aggregation states and textural properties. Finally, the surface acid–base reactivity of the co-precipitated magnesium silicates was determined using the model reaction of 2-methylbut-3-yn-2-ol (MBOH) conversion. The results obtained suggest that it is possible to prepare silicates with a wide range of surface acid–base properties, from purely basic solids to those with both acidic and basic properties, by adjusting the final Mg/Si ratio via the control of the synthesis parameters.

Potentiometric (pH-Metric) Methods of Studying Acid-Base Properties on the Surface of Dispersed Materials

The article presents potentiometric (pH-metric) methods that are used to study the acid-base properties of the surface of dispersed materials of different chemical nature. It is shown that the surface of any solid body has a surface hydroxyl-hydrate layer with a set of active adsorption centers (ACA) of different chemical structure and a wide range of acid-base properties. It has been proven that potentiometric (pH-metric) methods of studying dispersed materials in suspensions allow obtaining the most complete information about surface acid-base properties.

Anti-Alzheimer Drug Delivery via Pickering Emulsions Stabilized by Plate-like Cellulose Nanocrystals.

In this work, we studied for the first time the formation of olive oil emulsions in water stabilized by plate-like nanocrystals with the supramolecular structure of cellulose II (pCNC). Effects of storage, pCNC concentration, and NaCl on the stability and properties of Pickering emulsions, including the creaming index, droplet size, zeta potential, acid-base surface properties, and rheology, were studied. A significant influence of the shape of nanoparticles (compared to the classical rod-like shape) on the stability parameters and rheological characteristics of emulsions is shown. Plate-like cellulose nanocrystals at a concentration of 16 g/L are able to form delamination-resistant emulsions without added electrolytes. The viscosity of pCNC-stabilized emulsions tends to decrease with increasing electrolyte concentration in the system, which is not characteristic of rod-like CNC-stabilized emulsions. This effect in pCNC-stabilized emulsions assumedly can be associated both with weak mechanical engagement between drops due to the shape of stabilizer particles and with an insignificant participation of background electrolyte cations in the formation of interdroplet interactions. Therefore, the resulting aggregates are unstable and easily destroyed, even under weak mechanical stress. As a consequence, the acid-base properties of the pCNC surface are practically independent of the emulsion preparation method (with or without electrolyte) as well as the concentration of the background electrolyte. The reduced viscosity of pCNC-stabilized emulsions in the presence of an electrolyte, coupled with the absence of acute toxicity, allows us to recommend them as a convenient oral delivery system for fat-soluble, biologically active substances. Our emulsions carrying donepezil (an anti-Alzheimer drug) showed better performance than a solution of donepezil hydrochloride in preventing memory impairment tested on laboratory mice.

Exploring the acid–base surface properties of vivianite crystals in aqueous solution

The acid–base surface properties of vivianite crystals highly affect the adsorption capacity of vivianite for heavy metals and organic matters in aqueous solution. Therefore, the aim of the study was to innovatively explore and quantify the acid–base surface characterization of vivianite crystals in aqueous solution. It was found that the two surface active adsorption sites (≡POH and ≡FeOH) and five surface species thereof (i.e., ≡PO, ≡POH, ≡FeOH, ≡FeO−, and ≡FeOH2+) underwent surface reaction on vivianite crystals. Moreover, the active surface site and point of zero charge of vivianite crystals were 18 sites/nm2 and pH 5.9. Importantly, constant capacitance model was successfully employed to model the titration data, from which the distribution of surface species as function of pH and surface reaction constants were also accurately derived. The finding herein can be applied for plausible modeling molecular‐scale adsorption of the impurities on vivianite surface.

Mechanism study on direct synthesis of glycerol carbonate from CO2 and glycerol over shaped CeO2 model catalysts

Direct synthesis of glycerol carbonate (GC) from CO2 and glycerol (a byproduct of biodiesel production) is a route to obtain a high-value chemical from waste and low-cost byproducts but has not yet industrialized due to the lack of efficient catalysts. Ceria (CeO2) exhibits the highest catalytic activity and GC selectivity among the heterogeneous catalysts studied so far. However, the mechanism of this reaction over CeO2 catalysts has not been studied in detail. Herein, we synthesized CeO2 nanocrystals with different morphologies as model catalysts that can predominantly expose {111}, {110}, and {100} facets, and their surface acid-base properties were characterized using high-sensitivity temperature-programmed desorption of NH3 and CO2 with quadrupole mass spectrometry as detector (NH3-TPD-QMS and CO2-TPD-QMS). We found that the catalytic performance (GC formation rate) is strictly linearly dependent on the density of basic sites, which is relevant to the adsorption and activation of CO2. In addition, to illustrate a more microscopic reaction mechanisms underlying the formation of GC from CO2 and glycerol on all three low-index surfaces (111), (110) and (100), we also performed comprehensive first principles calculations. A three-step Langmuir–Hinshelwood (LH) mechanism was identified in which the annulation reaction is the rate-limiting step. The CeO2 (111) surface exhibits the lowest overall activation energy, which agrees well with the catalytic performance that the CeO2 nano-octahedra, predominantly exposing {111} facets, have the highest GC formation rate. This work is the first to combine experiments on shaped CeO2 model catalysts with first-principles calculations to gain insight into the mechanism of direct synthesis of GC from CO2 and glycerol, and will aid in the development of catalysts with improved performance.

Surface Hydroxyl Chemistry of Titania- and Alumina-Based Supports: Quantitative Titration and Temperature Dependence of Surface Brønsted Acid-Base Parameters.

Surface hydroxyl groups on metal oxides play significant roles in catalyst synthesis and catalytic reactions. Despite the importance of surface hydroxyls in broader material applications, quantitative measurements of surface acid-base properties are not regularly reported. Here, we describe direct methods to quantify fundamental properties of surface hydroxyls on several titania- and alumina-based supports. Comparing commercially available anatase, rutile, P25, and P90 titania, thermogravimetric analysis (TGA) indicated that the total surface hydroxyl density varied by a factor of 2, and each surface hydroxyl is associated with approximately one weakly adsorbed water molecule. Proton-exchange site densities, determined at 25 °C with slurry acid-base titrations, led to several conclusions: (i) the intrinsic acidity/basicity of surface hydroxyls were similar regardless of the titania source; (ii) differences in the surface isoelectric point (IEP) were primarily attributable to differences in the surface concentration of acid and base sites; (iii) rutile has a higher surface concentration of basic hydroxyls, leading to a higher IEP; and (iv) P25 and P90 titania have slightly higher surface concentrationsof acidic hydroxyls relative to anatase or rutile. Temperature effects on surface acid-base properties are rarely reported yet are significant: from 5 to 65 °C, IEP values change by roughly one pH unit. The IEP changes were associated with large changes to the intrinsic acid-base equilibrium constants over this temperature range, rather than changes in the composition or concentration of the surface sites.

Significant promotion of MgOy in bifunctional Pt-WOx-MgOy catalysts for the chemoselective conversion of glucose to lower polyols

A novel catalyst prepared by a facile ‘one-pot’ solvothermal method was developed for the efficient production of lower polyols from glucose solution. Under the optimal reaction conditions, the yield of diols was up to 50.7%, outperforming the recent works reported in the literature (<48%). Deeper investigation results revealed that the modification of MgOy on Pt-WOx could tune the surface acid-base properties, thereby promoting the yield of lower polyols. Combining the experimental and characterization results, a possible reaction mechanism during the conversion of glucose to lower polyols over Pt-WOx-MgOy was proposed.

Acid-Base Properties of Cis-Vacant Montmorillonite Edge Surfaces: A Combined First-Principles Molecular Dynamics and Surface Complexation Modeling Approach.

Montmorillonite layer edge surfaces have pH-dependent properties, which arises from the acid-base reactivity of their surface functional groups. Edge surface acidity (with intrinsic reaction equilibrium constant, pKa) is a chemical property that is affected by crystal structure. While a cis-vacant structure predominates in natural montmorillonites, prior molecular-level studies assume a centrosymmetric trans-vacant configuration, which potentially leads to an incorrect prediction of montmorillonite acid-base surface properties. We computed intrinsic acidity constants of the surface sites of a montmorillonite layer with a cis-vacant structure using the first-principles molecular dynamics-based vertical energy gap method. We evaluated pKa values for both non-substituted and Mg-substituted layers on common edge surfaces (i.e., surfaces perpendicular to [010], [01̅0], [110], and [1̅1̅0] crystallographic directions). The functional groups ≡Si(OH), ≡Al(OH2)2/≡Al(OH)(OH2), and ≡SiO(OH)Al sites on surfaces perpendicular to [010] and [01̅0] and ≡Si(OH)U, ≡Si(OH)L, ≡Al(OH2), and ≡Al(OH2)2 on surfaces perpendicular to [110] and [1̅1̅0] determine the proton reactivity of non-substituted cis-vacant edge surfaces. Moreover, the structural OH sites on edge surfaces had extremely high pKa values, which do not show reactivity at a common pH. Meanwhile, Mg2+ substitution results in an increase in pKa values at local or adjacent sites, in which the effect is limited by the distance between the sites. A surface complexation model was built with predicted pKa values, which enabled us to predict surface properties as a function of pH and ionic strength. Edge surface charge of both trans- and cis-vacant models has little dependence on Mg2+ substitutions, but the dependence on the crystal plane orientation is strong. In particular, at pH below 7, edge surfaces are positively or negatively charged depending on their orientation. Implications of these findings on contaminant adsorption by smectites are discussed.

Efficient and Stable O-Methylation of Catechol with Dimethyl Carbonate over Aluminophosphate Catalysts

The O-methylation of catechol is an effective method for the industrial production of guaiacol used as an important chemical. However, the low catechol conversion and poor catalyst stability are the most critical issues that need to be addressed. Herein, the O-methylation of catechol with dimethyl carbonate was investigated over aluminophosphate (APO) catalysts, using a continuous-flow system to produce guaiacol. APO catalysts were synthesized with varying P/Al molar ratios and calcination temperatures to study their effects on catalytic performance for the reaction. The physico-chemical properties of the APO catalysts were thoroughly investigated using XRD, NH3-TPD, CO2-TPD, FTIR, and Py-FTIR. The P/Al molar ratio and catalyst calcination temperature significantly influenced the structure and texture, as well as the surface acid-base properties of APO. Both the medium acid and medium base sites were observed over APO catalysts, and the Lewis acid sites acted as the main active sites. The APO (P/Al = 0.7) exhibited the highest catalytic activity and excellent stability, due to the suitable medium acid-base pairs.