Highly Dispersed SiOx/Al2O3 Catalysts Illuminate the Reactivity of Isolated Silanol Sites

The reaction of γ‐alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiO_x species on the alumina surface. These isolated (‐AlO)₃Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH₃, CO, and pyridine, and ²⁹Si and ²⁷Al DNP‐enhanced solid‐state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ‐Al₂O₃ surface, functionalizing the surface with “mild” Brønsted acid sites. For liquid‐phase catalytic cyclohexanol dehydration, these SiO_x sites exhibit up to 3.5‐fold higher specific activity than the parent alumina with identical selectivity.     

A FTIR assessment of surface acidity and dispersion of surface species in titania and alumina-supported molybdena

Adsorption of pyridine on the MoO₃/TiO₂ and MoO₃/Al₂O₃ systems has been studied by FTIR spectroscopy, in order to identify surface acid sites existing in samples with different molybdena loadings. The results show that both Lewis and Brönsted surface acid sites exist, whatever the molybdena loading. The percentage of Brönsted sites is larger for loadings below the theoretical monolayer, and should correspond to bidimensional molybdenum oxides species, while for loadings above the monolayer these sites are associated with bulk MoO₃.     

Nano‐MoO3‐modified MCM‐22 for methane dehydroaromatization

The work reported was aimed at a simple method to improve the catalytic activity of Mo/HMCM‐22 in methane aromatization. The catalysts were characterized using X‐ray diffraction, scanning electron microscopy, N₂ adsorption–desorption, NH₃ temperature‐programmed desorption, infrared spectra of pyridine adsorption, X‐ray photoelectron spectroscopy and thermogravimetric analysis. Physicochemical measurements indicated that Mo species with smaller size in HMCM‐22 would sublimate more easily and form Mo species at the atomic/molecular level and then interact well with the internal Brønsted acid sites to form Mo–O–Al active species. Catalytic results confirmed that nano‐MoO₃‐modified HMCM‐22 showed higher methane conversion and aromatics yield (13.1 versus 8.9%) than commercial MoO₃‐modified HMCM‐22 (11.0 versus 7.5%). In addition, nano‐MoO₃‐modified HMCM‐22 showed better durability compared with commercial MoO₃‐modified MCM‐22. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhanced Stability of Mo-Promoted Zn/HZSM-5 Catalyst for Methanol to Aromatics

A Mo-promoted Zn/HZSM-5 catalyst was prepared by isometric impregnation method (IM). The physicochemical properties of catalysts were characterized by X-ray diffraction, registration of N₂ adsorption-desorption isotherms, transmission electron microscopy, NH₃ temperature-programmed desorption and IR spectroscopic study of pyridine adsorption. The results show that by doping zeolite with Mo species it is possible to tune the microstructures, acidity and crystallinity of the catalyst. Additionally, it was found that the 1%Mo(IM)–5%Zn(IE)/HZSM-5 catalyst had a high catalytic activity and stability for methanol to aromatics (MTA) reaction. The yield of aromatics reached 77.3% at 450°C and TOS = 3 h. When the TOS = 98 h, the yield of total aromatics remains at a 60.4% level. The lifetime of catalysts was influenced by the synergetic effect of Brønsted and Lewis acid sites, so the modification with Mo may bring an opportunity to prolong the lifetime of Zn/HZSM-5 catalyst in the MTA reaction. The metal components are sintered and lost in continuous reaction-regeneration cycles. Accordingly, the activity of deactivated catalyst cannot be completely restored to the initial level.     

Bifunctional catalysis of Mo/HZSM-5 in the dehydroaromatization of methane with CO/CO2 to benzene and naphthalene

The catalytic dehydrocondensation of methane to aromatics such as benzene and naphthalene was studied on the Mo carbide catalysts supported on micro- and mesoporous materials such as HZSM-5 (0.6 nm) and FSM-16 (2.7 nm). The Mo catalysts supported on H-ZSM-5 having appropriate micropores (0.6 nm size) and Si/Al ratios (20-70) exhibit higher yields (90-150 nmol/g-cat/s) and selectivities (higher than 74% on the carbon basis) in methane conversion to aromatic products such as benzene and naphthalene at 973 K and 1 atm, although they are drastically deactivated because of substantial coke formation. It was demonstrated that the CO/CO₂ addition to methane effectively improves the catalyst performance by keeping a higher methane conversion and selectivities of benzene formation in the prolonged time-on-stream. The oxygen derived from CO and CO₂ dissociation suppresses polycondensation of aromatic products and coke formation in the course of methane conversion. XAFS and TG/DTA/mass-spectrometric studies reveal that the zeolite-supported Mo oxide is endothermally converted under the action of methane around 955 K to nanosized particles of molybdenum carbide (Mo₂C) (Mo-C, coordination number = 1,R- 2.09 å; Mo-Mo, coordination number = 2.3–3.5;R = 2.98 å). The SEM pictures showed that the nanostructured Mo carbide particles are highly dispersed on and inside the HZSM-5 crystals. On the other hand, it was demonstrated by IR measurements of pyridine adsorption that the Mo/HZSM-5 catalysts having the optimum SiO₂/Al₂O₃ ratios around 40 show the maximum Brönsted acidity among the catalysts with the SiO₂/Al₂O₃ ratios of 20–1900. There is a close correlation between the activity of benzene formation in the methane aromatization and the Brönsted acidity of HZSM-5 due to the bifunctional catalysis.     

Acidity of Alginate Aerogels Studied by FTIR Spectroscopy of Probe Molecules

Supercritical drying of alginate gels is an efficient way to prepare aerogels with high surface area (>300 m² · g⁻¹). FTIR spectroscopy allows to monitor the adsorption of NH₃ from the gas phase onto the acid sites of the alginate. Free carboxylic groups are effective Brønsted sites, whereas the divalent cations used in the ionotropic gelation present the properties of Lewis sites. The ratio between Brønsted and Lewis sites provides infomation on the role of pH in alginate gelation and suggests that non-buffered gelation by transition-metal cations is a mixed ionotropic-acid process.     

Impacts of Composition and Post‐Treatment on the Brønsted Acidity of Steam‐Treated Faujasite: Insights from FTIR Spectroscopy

A detailed FTIR study of the effects of steaming and acid leaching on protonated Y faujasite (FAU) and EMT zeolites is provided and the results are thoroughly analysed. In particular, emphasis is placed on the Brønsted acidic evolution and acidic strength measurements for a large series of as‐modified zeolites using CO as a sensitive probe to distinguish various protonic sites. While an increase of acidity for framework OH groups is observed during the strengthening of dealumination for both FAU and EMT series, the steaming process also generates a large variety of additional Brønsted acidic groups. Regarding acidic strength, these heterogeneous OH groups are sensitive to post‐treatments and their existence strongly depends on the initial composition of the zeolites. The presence of residual Na⁺ cations in the starting materials induces dramatic Brønsted acidic changes after steaming. As a result, steamed zeolites that initially contain traces of sodium possess unusual acidic Brønsted groups with low acidity. This result contradicts the trend generally observed with framework OH groups, for which steaming results in an increase of Brønsted acidic strength. The study reveals that the situation is indeed more complex, as some compositions and post‐treatments strongly influence the Brønsted acidity of as‐steamed zeolites both in their nature and their corresponding acidic strength. By linking these IR‐compiled features to the as‐exposed modifications, a large acidity scale better suited to characterizing catalysts having Brønsted acidity expanding from lowest to highest strength is proposed.     

Caractérisation part FT-IR des propriétés supercicielles et acido-basiques de la zircone phosphatée

FT-IR Characterization of superficial and acidic properties of phosphated zirconia. The nature of phosphate species formed by impregnation of zirconia by (NH₄)₂HPO₄ followed by decomposition at 400°C was studied by IR spectroscopy. These species present hydroxyl groups characterized by a ν(OH) band at 3666 cm⁻¹ due to the P-OH stretching vibration. The structure of phosphate species was examined using H₂¹⁸O isotopic exchange. Acid-base properties of phosphated zirconia was investigated by CO₂, pyridine and acetonitrile adsorption followed by FT-IR spectroscopy. The introduction of phosphated species, creates Brønsted acid sites on zirconia. A slight increase in Lewis acidity and a strong decrease in basicity is also detected.     

Preparation of ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> mixed oxide by combination of sol–gel and alcohol-aqueous heating method and its application in tetrahydrofuran polymerization

Without using any acid or base catalyst, complexing agent or zirconium alkoxides, ZrO₂–SiO₂ mixed oxide with the ZrO₂ content of 50 mol% was prepared by combination of sol–gel and alcohol-aqueous heating method using zirconyl nitrate and tetraethoxysilane as starting materials. The structural and surface acidic properties were characterized by FT-IR, XRD, NH₃-TPD and pyridine adsorption FTIR. Compared with another mixed oxide with the same ZrO₂ content prepared by mechanical grinding, the obtained ZrO₂–SiO₂ mixed oxide was homogeneously mixed in molecular level. The existed Zr–O–Si hetero-linkages strongly retarded the ZrO₂ particle growth. The obtained mixed oxide maintained amorphous phase until it was calcined at 1,173 K for 3 h when crystallization of tetragonal zirconia took place. NH₃-TPD and pyridine adsorption FTIR showed that both Brønsted and Lewis acidity were largely developed in the mixed oxide and most of the acidic sites belonged to the medium acidity. Because of the existence of abundant medium acidity, the mixed oxide showed catalytic activity for tetrahydrofuran polymerization. Furthermore, the produced poly tetramethylene ether glycol had moderate average molecular weight around 2,000. Neither the pure oxides nor the mixed oxide prepared by the mechanical grinding presented catalytic activity for this reaction.     

Acidic and basic sites in NaX and NaY faujasites investigated by NH3, CO2 and CO molecular probes

The acid-base properties of samples of NaY and NaX faujasites have been investigated by adsorbing different probe molecules and measuring IR spectra. In the case of the NaY sample, only Na⁺ ions were found to be involved in the adsorption of CO₂ and CO, confirming the overwhelming Lewis acid character of this material. In contrast, carbonate-like species were formed by adsorbing carbon dioxide on the NaX sample, due to the reaction of basic framework oxygen atoms with CO₂ molecules polarised on neighbour Na⁺ ions. The spectroscopic analysis of NaX also showed evidence of Brønsted acid hydroxyls and OH groups bonded to extra-framework Al atoms. Ammonia adsorption revealed that the amount of Brønsted acid hydroxyls is significantly lower than the Lewis acid Na⁺ countercations. Moreover, small oxide particles, carrying carbonate-like species on their surface, are present in the zeolitic cavities. These particles could be responsible for the basic reactivity towards CO observed after outgassing the NaX sample at high temperature.     

Synthesis and FT–IR study of the acido–basic properties of the V2O5 catalysts supported on zirconia

In this paper we describe the synthesis and characterization of the acido–basic properties of catalysts containing varied amounts of vanadium supported on ZrO₂. The preparation of the zirconia was carried out using a hydrolysis method and the vanadium was introduced by impregnation with a porous volume in several stages, followed by calcinations under air at a temperature of 723 K. The obtained samples are characterized by adsorption–desorption of nitrogen and infrared spectral analysis of different species formed by acidic and basic probes. This adsorption on the surface of these compounds has been studied in order, in the hand to investigate information on their surface acidity and in the other hand to know particularly the nature and strength of acidic and basic sites. Among the molecular probes, we used carbon monoxide, carbon dioxide, pyridine and 2,6-dimethylpyridine. The adsorption of CO has shown that contrary to pure zirconia and oxidized V₂O₅/ ZrO₂, the reduced V₂O₅/ ZrO₂ samples favour the formation of CO co-ordinated on Lewis acidic sites of reduced V₂O₅ species (CO on V⁴⁺ or V³⁺). We also observe the creation of Brønsted acidic sites by means of the incorporation of vanadium.     

FTIR study of the effects of water pretreatment on the acid sites and the dispersion of metal particles in Y zeolites and mordenites

FTIR results on zeolite-supported Pt and Pd show that the presence of water during metal reduction modifies both the acid and the metal functions of these catalysts. The water treatment eliminates Lewis acid sites and lowers the concentration of Brønsted acid sites by partial dealumination. At low temperature CO is adsorbed on Brønsted sites; the position of the corresponding FRIR band indicates that for Pt/HMOR, (MOR = mordenite) unlike Pt/HY, the intrinsic acid strength of these sites is increased by the wet reduction procedure. FTIR spectra after CO adsorption at room temperature show that wet reduction markedly improves the dispersion of Pt in HMOR; this effect is weaker for HY and absent for the Na forms of the zeolites. Bands of gem-Pt(CO)₂, which are indicative of very small, possibly electron-deficient Pt clusters, are detected in Pt/HMOR.     

Effect of Brønsted/Lewis Acid Ratio on Conversion of Sugars to 5‐Hydroxymethylfurfural over Mesoporous Nb and Nb‐W Oxides

A series of mesoporous Nb and Nb‐W oxides were employed as highly active solid acid catalysts for the conversion of glucose to 5‐hydroxymethylfurfural (HMF ). The results of solid state ³¹P MAS NMR spectroscopy with adsorbed trimethylphosphine as probe molecule show that the addition of W in niobium oxide increases the number of Brønsted acid sites and decreases the number of Lewis acid sites. The catalytic performance for Nb‐W oxides varied with the ratio of Brønsted to Lewis acid sites and high glucose conversion was observed over Nb₅W₅ and Nb₇W₃ oxides with high ratios of Brønsted to Lewis acid sites. All Nb‐W oxides show a relatively high selectivity of HMF , whereas no HMF forms over sulfuric acid due to its pure Brønsted acidity. The results indicate fast isomerization of glucose to fructose over Lewis acid sites followed by dehydration of fructose to HMF over Brønsted acid sites. Moreover, comparing to the reaction occurred in aqueous media, the 2‐butanol/H₂O system enhances the HMF selectivity and stabilizes the activity of the catalysts which gives the highest HMF selectivity of 52% over Nb₇W₃ oxide. The 2‐butanol/H₂O catalytic system can also be employed in conversion of sucrose, achieving HMF selectivity of 46% over Nb₅W₅ oxide.     

Chemoselective Catalysis with Organosoluble Lewis Acidic Polyoxotungstates

The preparation of new organosoluble Lewis acidic polyoxometalates (POMs) is reported. These complexes were prepared by the incorporation of Zr, Sc, and Y atoms into the corresponding monolacunary Dawson [P₂W₁₇O₆₁]^10? and Keggin [PW₁₁O₃₉]^7? polyoxotungstates. The catalytic activity of these compounds was evaluated for C? C bond formation in the Diels–Alder, Mannich, and Mukaiyama‐type reactions. Comparisons with previously described Lewis acidic POMs are reported. Competitive reactions between imines and aldehydes or between various imines demonstrated that fine tuning of the reactivity could be reached by varying the metal atom incorporated into the polyanionic framework. A series of experiments that employed pyridine derivatives allowed us to distinguish between the Lewis and induced Brønsted acidity of the POMs. These catalysts activate imines in a Lewis acidic way, whereas aldehydes are activated by indirect Brønsted catalysis.     

Infrared study of surface species arising from ammonia adsorption on oxide surfaces

Infrared spectra of ammonia adsorbed on CoO, NiO, SiO₂, CaO, MgO, ZrO₂, ZnO, TiO₂, BeO and Al₂O₃, have been studied in the NH stretching and bending vibration regions at various stages of sample dehydroxylation. Several types of adsorption were found: hydrogen bonding to surface oxygen atoms or hydroxyl groups, coordination to Lewis acid sites and coordination plus hydrogen bonding; on some oxides ammonia molecules dissociate to produce surface NH₂ and OH groups. Frequencies characteristic of the distinct adsorbed species were determined. Except for Al₂O₃, no evidence was found for Brönsted acid sites on the surface of the above oxides.     

Investigation of catalytic property in the t-butylation of 1,2-dihydroxybenzene using FT-IR and XPS study

Catalytic properties of HZSM-5s with three different Na⁺ ion-exchange levels and SiO₂ /Al₂O₃ ratios used in tert-butylation of DHB (1,2-dihydroxybenzene) are interpreted through pyridine adsorbed FT-IR and XPS study. The DHB conversion decreases as increment of degree of Na⁺ ion-exchange level and of Si content in HZSM-5. Catalytic properties with respect to Na amount in ZSM-5 are more sensitive than those of HZSM-5s with different SiO₂/Al₂O₃ ratios. But selectivity for 4-TBC (4-t-butylcatechol) is not changed significantly. Acidic properties, i.e. acid strength and acid density are characterized by pyridine adsorbed FT-IR and XPS study. Based on FTIR and XPS analyses, DHB conversion and selectivities for DTBC (3,5-di-t-butylcatechol) and 3-TBC (3-t-butylcatechol) depend on type and strength of acid sites, with the result that strong Brønsted acid rather than weak Brønsted or Lewis acid sites are more closely related to the conversion. Furthermore, t-butyl alcohol is selectively adsorbed on the Brønsted acid site of FT-IR band at 3612 cm^-1, which signifies that the Brønsted acid site is the active site. The mechanism for t-butylation of DHB is suggested based on the FT-IR results of adsorption/desorption of reactants.     

Organometallic titanocene complex as highly efficient bifunctional catalyst for intramolecular Mannich reaction

Bifunctional catalysts bearing two catalytic sites, Lewis acidic organometallic titanocene and Brønsted acidic COOH, have been assembled in situ from Cp₂TiCl₂ with carboxylic acid ligands, showing high catalytic activity over an intramolecular Mannich reaction towards synthesis of 2‐aryl‐2,3‐dihydroquinolin‐4(1H)‐ones. The determination of the bifunctional catalyst Cp₂Ti(C₈H₄NO₆)₂ was elucidated by single X‐ray HR‐MS and investigation of catalytic behavior. In particular, masking the Brønsted acidic COOH catalytic site with dormant COOMe lowered the reaction yield greatly, indicating that two catalytic sites work together to maintain high catalytic efficiency.     

Insight into Three‐Coordinate Aluminum Species on Ethanol‐to‐Olefin Conversion over ZSM‐5 Zeolites

Commercial bioethanol can be readily converted into ethylene by a dehydration process using solid acids, such as Brønsted acidic H‐ZSM‐5 zeolites, and thus, it is an ideal candidate to replace petroleum and coal for the sustainable production of ethylene. Now, strong Lewis acidic extra‐framework three‐coordinate Al³⁺ species were introduced into H‐ZSM‐5 zeolites to improve their catalytic activity. Remarkably, Al³⁺ species working with Brønsted acid sites can accelerate ethanol dehydration at a much lower reaction temperature and shorten the unsteady‐state period within 1–2 h, compared to >9 h for those without Al³⁺ species, which can significantly enhance the ethanol dehydration efficiency and reduce the cost. The reaction mechanism, studied by solid‐state NMR, shows that strong Lewis acidic EFAl‐Al³⁺ species can collaborate with Brønsted acid sites and promote ethanol dehydration either directly or indirectly via an aromatics‐based cycle to produce ethylene.     

Synthesis and characterization of a novel organic–inorganic hybrid salt and its application as a highly effectual Brønsted–Lewis acidic catalyst for the production of N,N′‐alkylidene bisamides

In this research, a novel organic–inorganic hybrid salt, namely, N¹,N¹,N²,N²‐tetramethyl‐N¹,N²‐bis(sulfo)ethane‐1,2‐diaminium tetrachloroferrate ([TMBSED][FeCl₄]₂) was prepared and characterized by Fourier‐transform infrared spectroscopy (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), elemental mapping, field emission scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), thermal gravimetric (TG), differential thermal gravimetric (DTG), and vibrating‐sample magnetometry (VSM) analyses. Catalytic activity of the hybrid salt was tested for the synthesis of N,N′‐alkylidene bisamides through the reaction of benzamide (2 eq.) and aromatic aldehydes (1 eq.) under solvent‐free conditions in which the products were obtained in high yields and short reaction times. The catalyst was superior to many of the reported catalysts in terms of two or more of these factors: the reaction medium and temperature, yield, time, and turnover frequency (TOF). [TMBSED][FeCl₄]₂ is a Brønsted–Lewis acidic catalyst; there are two SO₃H groups (as Brønsted acidic sites) and two tetrachloroferrate anions (as Lewis acidic sites) in its structure. Highly effectiveness of the catalyst for the synthesis of N,N′‐alkylidene bisamides can be attributed to synergy of the Brønsted and Lewis acids and also possessing two sites of each acid.     

Nature of the Ftir Band in Acidic Zeolites

The nature of a FTIR band (1490 cm ^-1 ) in the spectrum of zeolite HZSM-5 after pyridine adsorption was investigated. It is shown that the source of this band is not a combined contribution from Brönsted and Lewis acidic sites as widely believed.