Search Results (28)

The Lewis acidic framework Ti sites in Ti-Beta and Si-Beta catalysts were compared by FT-IR and NMR characterization methods before they were applied to the conversion of four butenes. The results showed that Si-Beta has fewer Lewis acid sites and abundant weak Brønsted acidic silanol nests, which play an important role in conversions between n-butene, cis-2-butene, and trans-2-butene. The conversions for these butenes over Si-Beta were always higher than those over a series of Ti-Beta catalysts with gradient-varied Lewis acidic framework Ti sites and silanols. This is because isobutene can only oligomerize, which requires stronger acidity, so its conversion over Si-Beta was lower than those over Ti-Beta zeolites. For a series of Ti-Beta catalysts with different abundances of Lewis acidic Ti sites, the more Lewis acid sites it had, the higher the conversions for the four butenes. Full article

Imidazole molecules entrapped in porous materials can exhibit high and stable proton conductivity suitable for elevated temperature (>373 K) fuel cell applications. In this study, new anhydrous proton conductors based on imidazole and mesoporous KIT-6 were prepared. To explore the impact of the acidic nature of the porous matrix on proton conduction, a series of KIT-6 materials with varying Si/Al ratios and pure silica materials were synthesized. These materials were additionally modified with cerium atoms to enhance their Brønsted acidity. TPD-NH₃ and esterification model reaction confirmed that incorporating aluminum into the silica framework and subsequent modification with cerium atoms generated additional acidic sites. UV-Vis and XPS identified the presence of Ce³⁺ and Ce⁴⁺ in the KIT-6 materials, indicating that high-temperature treatment after cerium introduction may lead to partial cerium incorporation into the framework. EIS studies demonstrated that dispersing imidazole within the KIT-6 matrices resulted in composites showing high proton conductivity over a wide temperature range (300–393 K). The presence of weak acidic centers, particularly Brønsted sites, was found to be beneficial for achieving high conductivity. Cerium-modified composites exhibited conductivity surpassing that of molten imidazole, with the highest conductivity (1.13 × 10⁻³ S/cm at 393 K) recorded under anhydrous conditions for Ce-KIT-6. Furthermore, all tested composites maintained high stability over multiple heating and cooling cycles. Full article

Electron-rich heteroaromatics, such as furan, thiophene and pyrrole, as well as their benzo-condensed derivatives, are of great interest as components of natural products and as starting substances for various products including high-tech materials. Although their reactions with Brønsted and Lewis acids play important roles, in particular as the primary step of various transformations, they are often disregarded and mechanistically not understood. The present publication gives a first overview about this chemistry focusing on the parent compounds. It comprises reactions with strong Brønsted acids forming adducts that can undergo intramolecular proton and/or substituent transfer reactions, ring openings or ring transformations into other heterocycles, depending on their structure. Interactions with weak Brønsted acids usually initiate oligomerizations/polymerizations. A similar behaviour is observed in reactions of these heteroaromatics with Lewis acids. Special effects are achieved when the Lewis acids are activated through primary protonation. Deuterated Brønsted acids allow straight forward deuteration of electron-rich heteroaromatics. Mercury salts as extremely weak Lewis acids cause direct metalation in a straight forward way replacing ring H-atoms yielding organomercury heterocycles. This review will provide comprehensive information about the chemistry of adducts of such heterocycles with Brønsted and Lewis acids enabling chemists to understand the mechanisms and the potential of this field and to apply the findings in future syntheses. Full article

The electrophilic activation of various substrates via double or even triple protonation in superacidic media enables reactions with extremely weak nucleophiles. Despite the significant progress in this area, the utility of organophosphorus compounds as superelectrophiles still remains limited. Additionally, the most common superacids require a special care due to their high toxicity, exceptional corrosiveness and moisture sensitivity. Herein, we report the first successful application of the “Brønsted acid assisted Brønsted acid” concept for the superelectrophilic activation of 2-hydroxybenzo[e][1,2]oxaphosphinine 2-oxides (phosphacoumarins). The pivotal role is attributed to the tendency of the phosphoryl moiety to form hydrogen-bonded complexes, which enables the formation of dicationic species and increases the electrophilicity of the phosphacoumarin. This unmasks the reactivity of phosphacoumarins towards non-activated aromatics, while requiring only relatively non-benign trifluoroacetic acid as the reaction medium. Full article

The reaction of N-phenyl iminoborane with benzaldehyde yielding a fused aromatic compound, recently reported by Liu et al., has been studied within the Molecular Electron Density Theory (MEDT). Formation of the fused aromatic compound is a domino process that comprises three consecutive reactions: (i) formation of a weak molecular complex between the reagents; (ii) an intramolecular electrophilic attack of the activated carbonyl carbon of benzaldehyde on the ortho position of the N-phenyl substituent of iminoborane; and (iii) a formal 1,3-hydrogen shift yielding the final fused aromatic compound. The two last steps correspond to a Friedel–Crafts acylation reaction, the product of the second reaction being the tetrahedral intermediate of an electrophilic aromatic substitution reaction. However, the presence of the imino group adjacent to the aromatic ring strongly stabilizes the corresponding intermediate, being the reaction product when the ortho positions are occupied by t-butyl substituents. This domino reaction shows a great similitude with the Brønsted acid catalyzed Povarov reaction. Although N-phenyl iminoborane can experience a formal [2+2] cycloaddition reaction with benzaldehyde, its higher activation Gibbs free energy compared to the intramolecular electrophilic attack of the activated carbonyl carbon of benzaldehyde on the ortho position of the N-phenyl substituent, 6.6 kcal·mol⁻¹, prevents the formation of the formal [2+2] cycloadduct. The present MEDT study provides a different vision of the molecular mechanism of these reactions based on the electron density. Full article

The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active sites and inter-site distances. A comparative analysis of the literature data allows to formulate the main principles of catalytic particles formation active in FTS and acid-catalyzed transformations of hydrocarbons: (1) the presence of weak Bronsted acid sites to control the cracking depth, (2) an availability of Bronsted acid sites for re-adsorption hydrocarbons and (3) weak Co-zeolite interaction to reduce methane formation. Full article

In the present research, we report on an innovative and quick procedure for the synthesis of metal oxides: a sol-gel procedure which is followed by two steps that are assisted by microwaves (MW) heating. First, MW heating promotes gel drying and successively permits the calcination of the xerogel in a few minutes, using a susceptor that rapidly reaches high temperatures. The procedure was employed for the synthesis of zirconium dioxide (ZrO₂), and MW-assisted calcination enables the collection of tetragonal ZrO₂, as confirmed by different experimental techniques (PXRD, HR-TEM and Raman spectroscopy). Using this MW-assisted sol-gel procedure, a promoted sulphated zirconia (SZ) has been obtained. Both the nature and strength of SZ surface acidity have been investigated with FTIR spectroscopy using CO and 2,6-dimethylpyridine (2,6-DMP) as probe molecules. The obtained materials were tested as catalysts in acid hydrolysis of glucose to give 5-(hydroxymethyl)furfural (5-HMF). One of the obtained catalysts exhibited a better selectivity towards 5-HMF with respect to SZ material prepared by a classical precipitation route, suggesting that this procedure could be employed to obtain a well-known catalyst with a less energy-consuming procedure. Catalytic results also suggest that good selectivity to 5-HMF can be achieved in aqueous media in the presence of weak Lewis and Brønsted sites. Full article

The interaction between (PNP)PdH (1); PNP = bis(2-diisopropylphosphino-4-methylphenyl)amide and different acids (CF₃SO₃H, HBF₄∙Et₂O, fluorinated alcohols and formic acid) was studied in benzene or toluene as well as in neat alcohols by IR and NMR spectroscopies. The structures of hydrogen-bonded complexes were also optimized at the DFT/ωB97-XD/def2-TZVP level. The nitrogen atom of the amidophosphine pincer ligand readily accepts proton not only from strong Brønsted acids but from relatively weak fluorinated alcohols_. That suggests that binding to palladium(II) increases the diarylamine basicity, making it a strong base. Nevertheless, H⁺ can be taken from [(PN(H)P)PdH]⁺ (2) by pyridine or hexamethylphosphoramide (HMPA). These observations confirm the need for a shuttle base to form [(PN(H)P)PdH]⁺ (2) as the result of the heterolytic splitting of H₂ by [(PNP)Pd]⁺. At that, a stoichiometric amount of formic acid protonates a hydride ligand yielding an unstable η²-H₂ complex that rapidly converts into formate (PNP)Pd(OCHO), which loses CO₂ to restore (PNP)PdH, whereas the relatively high acid excess hampers this reaction through competitive protonation at nitrogen atom. Full article

Liquid-phase dehydration of glycerol to acrolein was investigated with solid acid catalysts, including H-ZSM-5, H₃PO₄-modified H-ZSM-5, H₃PW₁₂O₄₀·14H₂O and Cs_2.5H_0.5PW₁₂O₄₀, in the presence of sulfolane ((CH₂)₄SO₂) as a dispersing agent under atmospheric pressure N₂ in a batch reactor. High weak-acidity H-ZSM-5, high temperatures and high-boiling-point sulfolane improved the activity and selectivity for the production of acrolein through suppressing the formation of polymers and coke and promoting the diffusion of glycerol and products. Brønsted acid sites were soundly demonstrated to be responsible for dehydration of glycerol to acrolein by infrared spectroscopy of pyridine adsorption. Brønsted weak acid sites favored the selectivity to acrolein. Combined catalytic and temperature-programmed desorption of ammonia studies revealed that the selectivity to acrolein increased as the weak-acidity increased over the ZSM-5-based catalysts. The ZSM-5-based catalysts produced a higher selectivity to acrolein, while the heteropolyacids resulted in a higher selectivity to polymers and coke. Full article

Developing highly selective and efficient bifunctional catalysts is an important issue for the hydroisomerization of long-chain n-alkanes. It is vital to tailor the balance of isomerization and cracking reactions in hydroisomerization. Herein, a bifunctional Pt/hierarchical SSZ-32 catalyst was fabricated with a sequential desilication–dealumination treatment to boost the selective hydroisomerization of n-hexadecane (C₁₆). The pore structure and acid sites of SSZ-32 zeolite were tailored. More mesopore and Brønsted acid sites were generated, and the ratio of weak to strong Brønsted acidity (B_w/B_s) was increased by the sequential desilication–dealumination. The generated hierarchical structure had little effect on the selectivity of the reaction pathways of hydroisomerization versus cracking. The ratio of isomers/cracking products increased almost linearly with the increase in the B_w/B_s ratios. Meanwhile, the synergetic effect of the hierarchical structure and acidity regulation promoted the selectivity of monobranched i-C16 products. Therefore, the resulting Pt/SSZ-0.6AS exhibited the highest activity with a total isomer yield of 71.5% at 255 °C and the enhanced formation mechanism of monobranched isomers occurred via the pore mouth. Full article

Baeyer–Villiger oxidation can synthesize a series of esters or lactones that have essential application value but are difficult to be synthesized by other methods. Cycloketones can be oxidized to lactones using molecular oxygen, peroxy acids, or hydrogen peroxide as an oxidant. Hydrogen peroxide is one of the environmental oxidants. Because of the weak oxidation ability of hydrogen peroxide, Bronsted acids and Lewis acids are used as catalysts to activate hydrogen peroxide or the carbonyl of ketones to increase the nucleophilic performance of hydrogen peroxide. The catalytic mechanisms of Bronsted acids and Lewis acids differ in the Baeyer–Villiger oxidation of cyclohexanone with an aqueous solution of hydrogen peroxide as an oxidant. Full article

This study primarily addresses the development of dynamic, selective and economical metal–acid (bifunctional) catalysts for one-pot menthol production by citral hydrogenation. Specifically, various metals such as Pd, Pt, Ni, Cs and Sn were doped over alumina support. Additionally, bifunctional composite catalysts were also prepared with the impregnation of heteropoly acids and Pd precursors over alumina support. Analytical techniques (e.g., BET, PXRD, FT-IR, pyridine adsorption and amine titration methods) were applied for characterization of the most efficient and selective catalysts (e.g., Al₂O₃ and PTA-Cat-I). Similarly, most of the essential operational variables (e.g., loading rate of metal precursor, type of heteropoly acid, temperature, gas pressure and reaction time) were examined during this study. The experimental data shows that the bifunctional catalyst (PTA-Cat-I) produced 45% menthol at full citral substrate conversion (r = 0.038 mmoles.min⁻¹) in liquid-phase citral hydrogenation (at optimized operating conditions: 70 °C, 0.5 MPa and 8 h). However, the heteropoly acid-supported bifunctional catalysts (e.g., PTA-Cat-I, PMA-Cat-I, SMA-Cat-I and STA-Cat-I) resulted in cracking and the dehydration of isopulegol/menthol by the generation of side products (e.g., 4-isopropyl-1-methyl, cyclohex-1-ane/ene); therefore, menthol yield was extensively diminished. On the other hand, non-acidic catalysts (e.g., Cat-I, Cat-II, Cat-III, Cat-IV and Cat-V) readily promoted hydrogenation reactions. The optimum menthol yield occurred due to the presence of strong Lewis and weak Bronsted acid sites. Mass transfer and reaction rate were substantially diminished due to acidity strength, heteropoly acid type and blockage of pores by the applied bifunctional catalysts. Full article

NO is a major environmental pollutant. MnO₂ is often used as a denitrification catalyst with poor N₂ selectivity and weak SO₂ resistance. Kiwi twig biochar was chosen to modify MnO₂ samples by using the hydrothermal method. The NO conversion rates of the biochar-modified samples were >90% at 125–225 °C. Kiwi twig biochar made the C2MnO₂ sample with a larger specific surface area, a higher number of acidic sites and O_β/O_α molar ratio, leading to more favorable activity at high temperatures and better SO₂ resistance. Moreover, the inhibition of the NH₃ oxidation reaction and the Mn³⁺ → Mn⁴⁺ process played a crucial role in the redox cycle. What was more, Brønsted acidic sites present on the C1MnO₂ sample participate in the reaction more rapidly. This study identified the role of biochar in the reaction process and provides a reference for the wide application of biochar. Full article

The influence of processing intumescent bio-based poly(lactic acid) (PLA) composites by injection and fused filament fabrication (FFF) was evaluated. A raw (ANa) and two acidic-activated (AH2 and AH5) montmorillonites were added to the intumescent formulation, composed by lignin and ammonium polyphosphate, in order to evaluate the influence of the strength and the nature (Brønsted or Lewis) of their acidic sites on the fire behavior of the composites. The thermal stability and the volatile thermal degradation products of the composites were assessed. The injected and 3D-printed composites were submitted to cone calorimeter (CC), limit oxygen index (LOI), and UL-94 flammability tests. A similar tendency was observed for the injected and 3D-printed samples. The high density of strong Lewis sites in AH2 showed to be detrimental to the fire-retarding properties. For the CC test, the addition of the intumescent composite reduced the peak of heat released (pHRR) in approximately 49% when compared to neat PLA, while the composites containing ANa and AH5 presented a reduction of at least 54%. However, the addition of AH2 caused a pHRR reduction of around 47%, close to the one of the composite without clay (49%). In the LOI tests, the composites containing ANa and AH5 achieved the best results: 39% and 35%, respectively, for the injected samples, and 35 and 38% for the 3D-printed samples. For the composite containing AH2 the LOI values were 34% and 32% for injected and 3D-printed samples, respectively. Overall, the best performance in the flammability tests was achieved by the composites containing clays with only weak and moderate strength acidic sites (ANa and AH5). Full article

Natural zeolite clinoptilolite CLIN with a framework ratio of Si/Al ≥ 4 containing mainly potassium and calcium ions in its internal channel system was used as a starting material. The acidic HCLIN catalysts were prepared under soft conditions avoiding the use of environmental less-benign mineral acids. The starting material was ion exchanged using a 0.2 M aqueous ammonium nitrate solution at a temperature 80 °C for 2 h. The obtained NH₄CLIN was converted into the acid HCLIN catalyst by calcination at 300–600 °C. The obtained samples were characterized by XRD, FTIR, SEM/TEM, AAS, and EDX element mapping. The state of aluminium and silicon was studied by ²⁷Al- and ²⁹SiMAS NMR spectroscopy. The textural properties of the catalysts were investigated by nitrogen adsorption and desorption measurements. The Brønsted acidity of the HCLIN catalysts was studied by temperature-programmed decomposition of the exchanged ammonium ions releasing ammonia as well as ¹H MAS NMR, {¹H–²⁷Al} Trapdor, and {¹H–²⁷Al} Redor experiments. The strongly agglomerated samples were crystalline and thermally stable up to >500 °C. Although a part of the clinoptilolite framework is maintained up to 600 °C, a loss of crystallinity is already observed starting from 450 °C. The specific surface areas of the starting CLIN and ammonium exchanged NH₄CLIN are low with ca. 26 m²/g. The pores are nearly blocked by the exchangeable cations located in the zeolite pores. The thermal decomposition of the ammonium ions by calcination at 400 °C causes an opening of the pore entrances and a markable increase in the specific micropore area and micropore volume to ca. 163 m²/g and 0.07 cm³/g, respectively. It decreases with further rising calcination temperature indicating some structural loss. The catalysts show a broad distribution of Brønsted acid sites (BS) ranging from weak to strong sites as indicated the thermal decomposition of exchanged ammonium ions (TPDA). The ammonium ion decomposition leaving BS, i.e., H⁺ located at Al–O–Si framework bridges, starts at ≥250 °C. A part of the Brønsted sites is lost after calcination specifically at 500 °C. It is related to the formation of penta-coordinated aluminium at the expense of tetrahedral framework aluminium. The Brønsted sites are partially recreated after repeated ammonium ion exchange. The catalytic performance of the acidic HCLIN catalysts was tested in the etherification of glycerol as a green renewable resource with different C₁-C₄ alcohols. The catalysts are highly active in the etherification of glycerol, especially with alcohols containing the branched, tertiary alkyl groups. Highest activity is observed with the soft activated catalyst HCLIN300 (300 °C, temperature holding time: 1 min). A total of 78% conversion of glycerol to mono and di ether were achieved with tert-butanol at 140 °C after 4 h of reaction. The mono- and di-ether selectivity were 75% and 25%, respectively. The catalyst can be reused. Full article