Intrinsic Acidity Research Articles

Characterization of 1,1- and 1,2-ethenedithiol, elusive compounds of potential astrochemical interest.

1,1- and 1,2-ethenedithiol are elusive systems that could potentially exist in interstellar space, similar to analogous diols. In this paper, we investigate the structure, stability, and bonding characteristics of these compounds as well as the ions produced by protonation, deprotonation, or simple ionization processes. 1,2-ethenedithiol has two isomers, Z and E, with the most stable conformer being syn-anti for the Z isomer and anti-anti for the E isomer. However, the energy gaps between the different conformers are never larger than 6kJ·mol-1. For 1,1-ethenedithiol, the global minimum is the syn-anti conformer. The vertical and adiabatic ionization processes as well as the intrinsic basicities and acidities of these families of compounds were analyzed and compared with those of the corresponding diols previously reported in the literature. This comparison revealed not only the numerical differences in these thermodynamic properties but also distinct trends between the two families of compounds. State-of-the-art G4 ab initio calculations were employed to calculate the structures and total energies of the systems under investigation. The QTAIM, ELF, and NBO approaches were used to analyze the electron density of all the neutral and charged systems included in our study. Van der Waals contributions, when relevant, were analyzed by locating regions of low reduced density gradient(s) using the NCIPLOT approach.

Constructing Hierarchical Zeolites with Highly Complete Framework via Controlled Desilication.

Desilication in alkaline medium has been widely used in construction of hierarchical zeolites for industrially relevant catalytic processes. The built of hierarchy in zeolites, especially with low aluminum stability or high Si/Al ratio, often suffers from uncontrolled destruction of zeolitic framework, accompanied by a significant loss of microporous domains and intrinsic acidity after desilication. Here, we report a novel and simple methodology for preparation of hierarchical zeolites with highly complete framework and minimum sacrifice of microporosity and acidity. The pre-impregnated amines in zeolite micropores act as inner pore-directing agents (iPDAs), largely protecting the zeolitic framework and moderating the silicon extraction during the alkaline treatment. The resulting hierarchical zeolites exhibit high crystallinity, tunable hierarchy, stable framework, and well-preserved acidity, endowing them with significantly improved mass transport properties and enhanced activities in catalytic conversion of methanol or furfural.

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.

Discovering trends in the Lewis acidity of beryllium and magnesium hydrides and fluorides with increasing clusters size.

We have reported in the last years the strong effect that Be- and Mg-containing Lewis acids have on the intrinsic properties of typical bases, which become acids upon complexation. In an effort to investigate these changes when the Be and Mg derivatives form clusters of increasing size, we have examined the behavior of the (MX2)n (M = Be, Mg; X = H, F; n = 1, 2, 3) clusters when they interact with ammonia, methanimine, hydrogen cyanide and pyridine, and with their corresponding deprotonated forms. The complexes obtained at the M06-2X/aug-cc-pVTZ level were analyzed using the MBIE energy decomposition formalism, in parallel with QTAIM, ELF, NCIPLOT and AdNDP analyses of their electron density. For n = 1 the interaction enthalpy for the different families of monomers, Be (Mg) hydrides and Be (Mg) fluorides, follows the same trend as the intrinsic basicity of the base that interacts with them. This interaction is greatly reinforced after the deprotonation of the base, resulting in a significant enhancement of the intrinsic acidity of the corresponding MX2-Base complex. For (MX2)2 clusters a further reinforcement of the interaction with the base is observed, this reinforcement being again larger for the deprotonated complexes. However, the concomitant increase of their intrinsic acidity is one order of magnitude larger for hydrides than for fluorides. Unexpectedly, the cyclic conformers (MX2)3, which are more unstable than the linear ones, become the global minima after association with the base and the same is true for the deprotonated complex. Accordingly, a further increase of the intrinsic acidity of the (MX2)3-Base complexes with respect to the (MX2)2-Base ones is observed. This effect is maximum for (MgF2)3 clusters, to the point that the (MgF2)3-Base complexes become more acidic than nitric acid, the extreme case being the cluster (MgF2)3-NCH, whose acidity is higher than that of perchloric acid.

Hydrothermally Ce modified HZSM-5 zeolite enhancing its strong acidity and Brønsted/Lewis acid ratio: Stably boosting ethylene/propylene ratio for cracking n-heptane

Modulating zeolite acidity by conventional metal impregnation is a challenge in preparing hydrocarbon cracking catalyst, which often eliminates its intrinsic strong acidity, resulting in reduced the hydrocarbon conversion capacity and low light olefins (C2=-C4=) yield. Here, the Ce/HZ5-HM and CeO2/HZ5-HM catalysts were readily prepared by hydrothermally modifying HZSM-5 zeolite (HZ5) with cerium salts (Ce3+) and cerium oxide (CeO2), respectively. Comparatively, Ce/HZ5-IW catalyst was obtained by modifying HZ5 with Ce3+ using the incipient wetness impregnation. It is revealed that, compared to HZ5, Ce/HZ5-HM and CeO2/HZ5-HM catalysts have an increased ratio of strong/weak (S/W) acid and Brønsted/Lewis (B/L) acid, while Ce/HZ5-IW sample has reduced strong acidity. Further, the Ce/HZ5-HM exhibits higher acid strength, acid density, and B/L value than that of CeO2/HZ5-HM sample. When applied to cracking n-heptane reaction, compared with HZ5 and Ce/HZ5-IW, heptane conversion and ethylene yield on Ce/HZ5-HM and CeO2/HZ5-HM catalysts increase by 6–11 % and 7–9 %, yielding the ratio of ethylene/propylene (E/P) more than 1. Moreover, Ce/HZ5-HM and CeO2/HZ5-HM catalysts perform a lifetime of 117 h and 150 h, with four-to-five times longer than that of HZ5 zeolite (∼29 h) and Ce/HZ5-IW catalyst (∼39 h). The characterization results demonstrate that, adopting hydrothermal method ensures more Ce3+ interacting with the silanol groups in Ce/HZ5-HM, generating the new Brønsted acid sites and makes CeOx species incorporating into the hydroxyl nest of zeolite, which can heal the defective sites and improve stabilization of acidity and framework structure of zeolite. Therefore, the above two catalysts can highlight the monomolecular cracking reaction, low coke deposit rate, long catalytic stability.

Pairing Ga/Al-Zeolites with tailored acidity as tandem catalysts for the conversion of alcohols to olefins

Zeolites are versatile catalysts owing to their tunable acidity where the active site(s) can be placed within the crystal framework or as extra-framework species in confined pores. A common approach to tailor Brønsted acidity is heteroatom exchange involving the replacement of framework aluminum with alternative elements. Introduction of heteroatoms often results in less acidic catalysts that can be used in tandem reactions for targeted reactive intermediates. In this study, we prepare a series of three different zeolites with MWW, CHA, and MFI frameworks as aluminosilicates and gallosilicates to demonstrate their performance in alcohol dehydration reactions. The two reactions examined in this study are methanol conversion to dimethyl ether and ethanol conversion to ethylene. Our findings reveal that Ga-zeolites exhibit superior performance with Ga-MCM-22 (MWW) achieving nearly 100 % alcohol conversion and selectivity to desired products at contact times that are significantly less than most dehydration catalysts reported in literature. The unique properties of Ga-zeolites are attributed to their reduced acid site strength via a direct (one-pot) synthesis that avoids conventional time-intensive, multi-step post-synthesis modifications of Al-zeolites. Here we demonstrate the use of Ga-zeolites as tandem catalysts when paired with a downstream Al-zeolite in a dual-bed reactor configuration to convert cheaper reagents (alcohols) upstream to more desired intermediates as feeds for downstream catalysts to produce light olefins. We demonstrate that dual beds using Ga-zeolite – Al-ZSM-5 (upstream–downstream) pairings outperform single bed configurations with Al-ZSM-5 or a physical mixture (Ga-/Al-zeolite) for methanol to hydrocarbons reactions, with notable improvements in catalyst lifetime and increased light olefins selectivity. Similarly, dual beds using Ga-zeolite – Al-SSZ-13 (upstream–downstream) pairings result in improved performance for ethanol to propylene reactions with significant increases in propylene selectivity (>20 %) compared to a conventional single bed configuration of Al-SSZ-13. Overall, this study offers a new perspective on the use of heteroatom-exchanged zeolite catalysts in tandem reactions as a means of capitalizing on their reduced acid site strength and suggests differences in the intrinsic acidity of zeolite crystal structures.

Bimetallic UiO‐66(Zr/Ti)‐Ionic Liquid Grafted Fillers with Intensified Lewis Acidity for High‐Performance Composite Solid Electrolytes

AbstractEnhancing the incorporation of highly accessible Lewis acid sites on fillers is crucial for achieving exceptional electrochemical performances in composite solid electrolytes (CSEs). Typically, they can provide a vital role in improving CSEs performance by interacting with lithium salt anions and the polymer matrix through Lewis acid–base interactions. To address this technological need, in this work, a novel filler of bimetallic UiO‐66(Zr/Ti)‐ionic liquid grafted composite (BUIL) is developed to enhance its inherent electrochemical properties. The bimetallic structure, which introduces structural defects, along with the grafted ionic liquid, abundantly creates accessible Lewis acid sites. This modification of the intrinsic Lewis acidity results in a remarkable enhancement of CSEs performances. The incorporation of BUIL in CSEs leads to a significant increase in ionic conductivity (0.458 mS cm−1) and lithium‐ion transference number (0.668) at 30 °C. Furthermore, LiFePO4/CSEs/Li cells demonstrate a high specific capacity of 148.5 mAh g−1 at a current density of 1 C, which is stably maintained over 880 cycles. Overall, the innovative synthetic approach in producing multifunctional fillers for CSEs shows strong potential for enhancing the performance of advanced lithium metal batteries.

DFT study on zeolites’ intrinsic Brønsted acidity: The case of BEA

Since Brønsted acidity is a crucial aspect for the applications of zeolitic materials in heterogeneous catalysis, great effort was devolved to characterize the number, strength and location of the potentially active acidic sites. Quantum chemical calculations can turn out essential in estimating the intrinsic acidity by computing deprotonation energy (DPE) values, although each method comes with its own difficulties. In this context, three approaches within density functional theory were employed to study the intrinsic acidity of 30 topologically distinct Brønsted sites in the β-zeolite framework. Advantages and disadvantages of the three methods were outlined and the acidity order between the sites was assessed, being the DPE range 59 kJ mol−1 wide, with the proposed best approach. By dividing the range into three portions, the sites were classified as having high, medium and low acidity. Hydrogen bonds formation was found to be a contributing factor in determining a low Brønsted acidity.

Correlation between pitting susceptibility and surface acidity, point of zero charge of passive film on aluminum: Influence of alloying elements

The pitting potential, intrinsic surface acidity, point of zero charge of passive film on Al are studied using first-principles calculations to establish their relationships. Influences of alloying elements Zn, Cr, Nb, Si, Mo and Sc on adsorption of NH3 and NaCl, pHpzc of Al2O3 and pitting susceptibility of Al are investigated. The efficiency for enhancing pitting resistance of Al is evaluated, yielding the ratios Si: Zn: Cr: Mo: Nb: Sc = 1.8: − 0.3: 1: 1.9: 1.4: 0.2. A model for the dependence of pitting potential on the concentration of alloying elements in Al alloy matrix is developed, based on effects of alloying elements on the surface charge of passive film. The effects of Sc on pitting potential and pHpzc of Al oxide are predicted based on the calculated results, which are supported by electrochemical measurement, XPS analysis and contact angle titration.

Controllable synthesis of gallium-containing MFI zeolite for bifunctionally catalyzing methanol aromatization

Ga-MFI zeolites with controllable crystal sizes were hydrothermally synthesized by using colloidal silicalite-1 as seed crystals and their catalytic performances for methanol-to-aromatics (MTA) were evaluated. It was found that the crystal size of as-made Ga-MFI zeolite became small with the adding amounts of seed crystals. Small-sized Ga-MFI zeolite with short channels shows much better coking-resistance and thus longer catalytic lifetime owning to its more favorable outward diffusion of aromatic products. In addition, the stability could be further improved by impregnating gallium species into Ga-MFI zeolite, but which slightly sacrificed its aromatic selectivity. The Ga species with different locations in zeolite play distinct roles in MTA. The weak intrinsic protonic acidity from tetrahedral framework Ga3+ could suppress hydrogen transfer reactions for light alkane formation while non-framework gallium species especially Ga2O3 nanoparticles promoted the dehydrocyclization process. The synergy between the strong Brønsted and weak Lewis acid sites contributes to the excellent aromatic yield.

Ionization, intrinsic basicity, and intrinsic acidity of unsaturated diols of astrochemical interest: 1,1- and 1,2-ethenediol: A theoretical survey.

The structure, stability, and bonding characteristics of 1,1- and 1,2-ethenediol, their radical cations, and their protonated and deprotonated species were investigated using high-level ab initio G4 calculations. The electron density of all the neutral and charged systems investigated was analyzed using the QTAIM, ELF, and NBO approaches. The vertical ionization potential (IP) of the five stable tautomers of 1,2-ethenediol and the two stable tautomers of 1,1-ethenediol go from 11.81 to 12.27 eV, whereas the adiabatic ones go from 11.00 to 11.72 eV. The adiabatic ionization leads to a significant charge delocalization along the O-C-C-O skeleton. The most stable protonated form of (Z)-1,2-ethenediol can be reached by the protonation of both the anti-anti and the syn-anti conformers, whereas the most stable deprotonated form arises only from the syn-anti one. Both charged species are extra-stabilized by the formation of an O-H···O intramolecular hydrogen bond (IHB) which is not found in the neutral system. (Z)-1,2-ethenediol is predicted to be less stable, less basic, and more acidic than its cis-glycolaldehyde isomer. The most stable protonated species of (E)-1,2-ethenediol comes from its syn-syn conformer, although the anti-anti conformer is the most basic one. Contrarily, the three conformers yield a common deprotonated species, so their acidity follows exactly their relative stability. Again, the (E)-1,2-ethenediol is predicted to be less stable, less basic, and more acidic than its trans-glycolaldehyde isomer. Neither the neutral nor the protonated or the deprotonated forms of 1,1-ethenediol show the formation of any O-H···O IHB. The most stable protonated species is formed by the protonation of any of the two tautomers, but the most stable deprotonated form arises exclusively from the syn-anti neutral conformer. The conformers of 1,1-ethenediol are much less stable and significantly less basic than their isomer, acetic acid, and only slightly more acidic.

Investigation of Brønsted acidity in zeolites through adsorbates with diverse proton affinities

Understanding the adsorption behavior of base probes in aluminosilicates and its relationship to the intrinsic acidity of Brønsted acid sites (BAS) is essential for the catalytic applications of these materials. In this study, we investigated the adsorption properties of base probe molecules with varying proton affinities (acetonitrile, acetone, formamide, and ammonia) within six different aluminosilicate frameworks (FAU, CHA, IFR, MOR, FER, and TON). An important objective was to propose a robust criterion for evaluating the intrinsic BAS acidity (i.e., state of BAS deprotonation). Based on the bond order conservation principle, the changes in the covalent bond between the aluminum and oxygen carrying the proton provide a good description of the BAS deprotonation state. The ammonia and formamide adsorption cause BAS deprotonation and cannot be used to assess intrinsic BAS acidity. The transition from ion-pair formation, specifically conjugated acid/base interaction, in formamide to strong hydrogen bonding in acetone occurs within a narrow range of base proton affinities (812–822 kJ mol−1). The adsorption of acetonitrile results in the formation of hydrogen-bonded complexes, which exhibit a deprotonation state that follows a similar trend to the deprotonation induced by acetone. This allows for a semi-quantitative comparison of the acidity strengths of BAS within and between the different aluminosilicate frameworks.

The Surface acidity of freshly synthesized microplastics particles in simple electrolyte

The surface chemistry of sub-micron microplastics (MP) particles, specifically, the pH-dependent surface charge (or surface acidity), plays a role on the transport, transformation, and effect of contaminants in the aquatic environment. Little is known on the origin of surface charge and the quantification of surface acidity of MP. In this study, the surface charge of submicron particles of six major polymers, including low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET), was characterized in inert electrolytes, namely, NaClO4, NaCl, and NaNO3 for the elucidation of surface acidity. IR absorbance revealed that oxygen-rich functional groups were introduced during the resynthesis of MP particles, whose surface chemical structure consists of three main functional groups, i.e., carboxylic/ester, ether/alcohol, and aliphatic. Results show clearly that the zeta potential of MP particles was negatively charged in simple electrolytes at pH greater than ca. 2.0. Hydroxide ions adsorption on the non-polar aliphatic sites, and deprotonation of surface hydroxy group on the polar carboxylic/ester and ether/alcohol sites, contributed to the negative charges on MP surface. The surface acidity of selected MP particles was established in terms of acid strength (intrinsic acidity constants) and capacity (total surface site concentration) for the three distinct surface sites. Results also show the surface acid site density increases with hydration/hydrolysis time with rate constants of the polar surface sites, i.e., carboxylic/ester and ether/alcohol being 2.3 times greater than that of the non-polar aliphatic group.

Optimizing hollow ZSM-5 spheres (hZSM5) morphology and its intrinsic acidity for hydrogenation of CO2 to DME with copper–aluminum

Hollow zeolites are normally made by synthesizing parent rigid zeolites form soluble silica-alumina suspension followed by removal of the aluminum-deficient centers, during which the uniformity of hollow zeolites is compromised. Herein, two uniform spherical hollow ZSM-5 (hZSM5) with distinct morphologies, monodispersed (mhZSM5) and networked (nhZSM5), were hydrothermally synthesized using premade Stöber SiO2 spheres along with structure directing agents with and without aluminum. Subsequently, both mhZSM5 and nhZSM5 supports were impregnated with mono- and multimetallic Cu-based catalysts to investigate CO2 hydrogenation with in-depth catalyst characterizations (HRTEM-EDX, Pyridine-FTIR, H2-TPR, XPS, XANES, and DRIFTS). It was evidenced that uniform and decent morphology of mhZSM5 spheres arises from the existence of framework-intrinsic Al3+. Besides, it was revealed that mhZSM5-AlCu containing both framework-intrinsic Al3+ and catalyst-extrinsic Al3+ promoter leads to an optimal DME production (33.5 mgDME·gcat.−1·h−1), which is comparable or even higher to the ones reported in several published works. Not only was mhZSM5-AlCu activity even better, but also it showed a prolonged stability compared to comZSM5-AlCu and nsZSM5-AlCu samples that were derived using commercial ZSM-5 supports with better physiochemical properties. Based on our in-situ DRIFTS, a step-wise mechanistic pathway of DME formation over mhZSM5-AlCu was proposed, assuming that the hollow ZSM-5 shell framework dehydrates methanol that is formed in-situ via CO2 hydrogenation.

Inhibitory activity of catecholic phosphonic and phosphinic acids against Helicobacter pylori ureolysis

Catechols have been reported to be potent covalent inhibitors of ureases, and they exhibit activity by modifying cysteine residues at the entrance to enzymatic active sites. Following these principles, we designed and synthesized novel catecholic derivatives that contained carboxylate and phosphonic/phosphinic functionalities and assumed expanded specific interactions. When studying the chemical stability of the molecules, we found that their intrinsic acidity catalyzes spontaneous esterification/hydrolysis reactions in methanol or water solutions, respectively. Regarding biological activity, the most promising compound, 2-(3,4-dihydroxyphenyl)-3-phosphonopropionic acid (15), exhibited significant anti-urease potential (Ki = 2.36 μM, Sporosarcinia pasteurii urease), which was reflected in the antiureolytic effect in live Helicobacter pylori cells at a submicromolar concentration (IC50 = 0.75 μM). As illustrated by molecular modeling, this compound was bound in the active site of urease through a set of concerted electrostatic and hydrogen bond interactions. The antiureolytic activity of catecholic phosphonic acids could be specific because these compounds were chemically inert and not cytotoxic to eukaryotic cells.

A Strategy of Fenton Reaction Cycloacceleration for High-Performance Ferroptosis Therapy Initiated by Tumor Microenvironment Remodeling.

The emerging tumor ferroptosis therapy confronts impediments of the tumor microenvironment (TME) with weak intrinsic acidity, inadequate endogenous H2 O2 , and a powerful intracellular redox balance system that eliminates toxic reactive oxygen species (ROS). Herein, a strategy of Fenton reaction cycloacceleration initiated by remodeling the TME for magnetic resonance imaging (MRI)-guided high-performance ferroptosis therapy of tumors is proposed. The synthesized nanocomplex exhibits enhanced accumulation at carbonic anhydrase IX (CAIX)-positive tumors based on the CAIX-mediated active targeting, and increased acidification via the inhibition of CAIX by 4-(2-aminoethyl) benzene sulfonamide (ABS) (remodeling TME). This accumulated H+ and abundant glutathione in TME synergistically trigger biodegradation of the nanocomplex to release the loaded cuprous oxide nanodots (CON), β-lapachon (LAP), Fe3+ , and gallic acid-ferric ions coordination networks (GF). The Fenton and Fenton-like reactions are cycloaccelerated via the catalytic loop of Fe-Cu, and the LAP-triggered and nicotinamide adenine dinucleotide phosphate quinone oxidoreductase1-mediated redox cycle, generating robust ROS and plenitudinous lipid peroxides accumulation for ferroptosis of tumor cells. The detached GF network has improved relaxivities in response to the TME. Therefore, the strategy of Fenton reaction cycloacceleration initiated by remodeling the TME is promising for MRI-guided high-performance ferroptosis therapy of tumors.

Dramatic effect of the nature of R on the intrinsic acidity and basicity of potential astrochemical R–C≡COH and R–C≡CSH compounds

The effect of changing the nature of the R substituent from the first row (H, Li, BeH, BH2, CH3, NH2, OH and F) to second row (Na, MgH, AlH2, SiH3, PH2, SH and Cl) on the intrinsic acidity and basicity of R–C≡COH and R–C≡CSH compounds was investigated through the use of G4 high-level ab initio calculation. The variation of the acidity and basicity of the R–C≡CSH derivatives as a function of R is practically parallel to that found for the corresponding R–C≡COH analogs; though the basicities of the former are 9–14% higher than those of the latter, the acidity gap being very small (~ 2%). When this analysis is extended to the derivatives in which the triple CC bond is replaced by a double or single bond, it is found that the acidity gap increases systematically as the CC bond goes from triple to single; whereas, as expected for the basicity, the trend is the opposite. Quite surprisingly, however, the variation of the basicity of R–C≡CX (X = OH, SH) compounds with the nature of the first-row substituents, R, is remarkably different from that produced by the second-row analogs. The same is observed as far as intrinsic acidities are concerned. These dissimilarities reflect the rather different changes in the strength of the CC and the CX (X = OH, SH) bonds when a first-row substituent is replaced by the second-row analog, as reflected in the atoms in molecules (AIM), natural bond orbital (NBO) and the electron localization function (ELF) analyses of the corresponding species.

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.

Improved catalytic performance in gas-phase dimethyl ether carbonylation over facile NH4F etched ferrierite.

Gas-phase dimethyl ether (DME) carbonylation to methyl acetate (MA) initiates a promising route for producing ethanol from syngas. Ferrierite (FER, ZSM-35) has received considerable attention as it displays excellent stability in the carbonylation reaction and its modification strategy is to improve its catalytic activity on the premise of maintaining its stability as much as possible. However, conventional post-treatment methods such as dealumination and desilication usually selectively remove framework Al or Si atoms, ultimately altering the intrinsic composition, crystallinity, and acidity of zeolites inevitably. In this study, we successfully prepared a series of hierarchical ZSM-35 materials through post-treatment with NH4F etching, which dissolved framework Al and Si at similar rates and preferentially attacked the defective sites. Interestingly, the produced pore systems effectively penetrated the [100] plane, offering elevated access to both the 8-membered ring (8-MR) and 10-membered ring (10-MR) channels. The physicochemical and acid properties of the pristine and NH4F etched ZSM-35 samples were comprehensively characterized using various techniques, including XRD, XRF, FESEM, HRTEM, Nitrogen adsorption-desorption, NH3-TPD, Py-IR, 27Al MAS NMR, and 29Si MAS NMR. Under moderate treatment conditions, the intrinsic microporous structure, acid properties, and crystallinity of zeolite were retained, leading to superior catalytic activity and stability with respect to the pristine sample. Nonetheless, severe NH4F etching disrupted the crystalline framework and created additional defective sites, bringing about faster deposition of coke precursors on the interior Brønsted acid sites (BAS) and decreased catalytic performance. This technique provides a novel and efficient method to slightly enhance the micropore and mesopore volume of industrially pertinent zeolites through a straightforward post-treatment, thus elevating the catalytic performance of these zeolites.

Computational Insights on Periodicity in Bonding and Lewis Acidity and Basicity of the p‐Block Trispyrazolylborate Complexes

AbstractHydrotris(pyrazolyl)borate ligands are a popular class of ligands to stabilize both Lewis acidic and Lewis basic main group compounds. In this work we analyze the low‐valent group 13–15 compounds of hydrotris(3,5‐dimethyl‐pyrazolyl)borate ligand, [Tp*E]x, 1–15 (E=group 13 element, x=0; E=group 14 element, x=1+ ; E=group 15 element, x=2+) based on density functional theory. A periodic increment in intrinsic Lewis acidity is observed down the group due to increased E−N bond polarization towards nitrogen, resulting in lower energy secondary binding sites. However, global Lewis acidity measures in terms of FIA and IIA indicate the dependency on the choice of the nucleophile. In general, this study underscores the potential of the Tp* ligand in stabilizing the reactive low‐valent p‐block elements.