Liquid-phase Reaction Research Articles

Kinetic Modeling of Brilliant Blue Discoloration by Ozonation

This paper presents the results of investigations on the kinetic modeling of Brilliant Blue FCF (BB) discoloration reactions in aqueous solutions with different ozone concentrations and pH conditions. Kinetic studies involve knowledge of the structure and properties of dye and ozone, as well as of the experimental conditions. In general, scientists admit that the predominant oxidation pathway is direct (by free oxygen atoms) or indirect (by free hydroxyl radicals); this will depend on influencing factors such as the physicochemical properties of the dye, the pH of the aqueous solution, ozone concentration, reaction time, and the contact mode with/without stirring. In this experimental research, two pathways were chosen following CBB = f(t)—1. a constant dye concentration and different ozone concentrations, in the concentration range of 100–250 mg/L, in three pH media (acidic, neutral, and basic), with and without stirring; 2. a constant concentration of ozone and different dyes in the concentration range of 2.5–10 mg/L, under the conditions of point 1. With the obtained experimental data, the curves CBB = f(t) were drawn and processed according to the integral method of classical kinetics, based on first- and second-order equations. Unfortunately, this simple procedure did not give any results for the pH values studied. The rate constants were negative, and/or the reaction order depended on the initial conditions. Due to its structure, the BB dye has several chromophore groups, and thus multiple attack centers, resulting in several oxidation by-products, which is why the 1H-NMR spectrum was recorded for the discoloration of BB with ozone. Since the stoichiometry of the overall oxidation reaction, as well as the relationship between the rate constant and the reaction conditions mentioned above, is not known, a kinetic model based on mass transfer coupled with a chain reaction in the bulk liquid phase was proposed and successfully tested at pH = 7. This research approach also involves the consolidation of the theoretical bases of the ozonation process through the kinetic study carried out, as well as the proposal of a kinetic model. These systematics lead to results that are applicable to other aqueous systems that are impure with dyes, allowing for generalizations and the development of the field, ensuring the sustainability of the research.

The coupling model of random forest and interpretable method quantifies the response relationship between PM2.5 and influencing factors

Ambient fine particulate matter (PM2.5) is affected by many factors, such as source emissions, meteorological conditions, and chemical reactions. Revealing the effects of these factors on PM2.5 is essential to understand the causes of PM2.5 pollution. The machine learning method can establish the non-linear relationship between influencing factors and PM2.5. Here, a coupling model of machine learning and interpretation method was constructed to comprehensively quantify the importance of influencing factors to PM2.5 from multiple dimensions and analyze the sensitivity of influencing factors. Among the primary indicators of influencing factors, the importance of emission, meteorological conditions, and atmospheric chemical reaction to PM2.5 is 49%, 29%, and 22%, respectively. In the secondary indicator of influencing factors, the transmission effect is the most important meteorological condition, with an important degree of 15%. The liquid phase reaction is the most important atmospheric chemical reaction, with an importance of 7%. Among the three levels of influencing factors, emission, transport distance, liquid phase reaction coefficient, aerosol acidity, and accumulation promotion coefficient are important factors. The sensitivity of a single factor is complex and changeable, and the interaction between emission and other important factors is the strongest among the two factors. Of which the interaction between transmission distance and emission during the observation period is the strongest, and the interaction coefficient is 1.82. Our study focuses on the effect of influencing factors on PM2.5, provides a basis for the analysis of the causes of PM2.5 pollution, and technical support for the treatment of PM2.5.

Hollow silicalite-1 encapsulated nickel nanoparticles as highly stable catalysts in maleic anhydride hydrogenation

Anchoring active metal particles in zeolite cages can significantly improve catalytic stability. In this study, hollow silicalite-1 (HoS-1) encapsulated Ni nanoparticles catalyst (Ni@HoS-1) was prepared using the impregnation method and applied in MA hydrogenation. The encapsulation mechanism was explained as the zeolite wall restricting the evaporation of water in HoS-1, hence Ni particles would be spontaneously enriched within the zeolite cage after drying and calcination. Experiments revealed the specially designed structure effectively protected Ni particles from leaching, and after 5 cycles in liquid-phase batch reactions, the final MA conversion of Ni@HoS-1 is 40.8 % higher than that of Ni/S-1 (85.5 % vs 44.7 %). Moreover, the low acidity of Ni@HoS-1 also delayed the accumulation of carbon deposits, extending the continuous reaction lifespan from 128 h of Ni/S-1 to 188 h. These findings provided a new perspective for the controllable locating of active metal sites against the supports.

A general flame aerosol route to kinetically stabilized metal-organic frameworks

Metal-organic frameworks (MOFs) are highly attractive porous materials with applications spanning the fields of chemistry, physics, biology, and engineering. Their exceptional porosity and structural flexibility have led to widespread use in catalysis, separation, biomedicine, and electrochemistry. Currently, most MOFs are synthesized under equilibrium liquid-phase reaction conditions. Here we show a general and versatile non-equilibrium flame aerosol synthesis of MOFs, in which rapid kinetics of MOF formation yields two distinct classes of MOFs, nano-crystalline MOFs and amorphous MOFs. A key advantage of this far-from-equilibrium synthesis is integration of different metal cations within a single MOF phase, even when this is thermodynamically unfavorable. This can, for example, produce single-atom catalysts and bimetallic MOFs of arbitrary metal pairs. Moreover, we demonstrate that dopant metals (e.g., Pt, Pd) can be exsolved from the MOF framework by reduction, forming nanoclusters anchored on the MOF. A prototypical example of such a material exhibited outstanding performance as a CO oxidation catalyst. This general synthesis route opens new opportunities in MOF design and applications across diverse fields and is inherently scalable for continuous production at industrial scales.

Reaction kinetics for catalytic hydrogenation of quinoline to decahydroquinoline as liquid organic hydrogen carrier

The catalytic hydrogenation of quinoline to decahydroquinoline (DHQ) formation is studied for various parameters such as temperature, hydrogen pressure, reaction time, solvents, reactant-to-solvent ratio, and catalyst loading over 5%Pd loaded on alumina (Pd/Al2O3) to obtain optimal reaction conditions. The hydrogen uptake of quinoline in the liquid phase reaction using isopropylalcohol (IPA) is studied in an autoclave reactor. The optimum reaction parameters of 50 bar H2 pressure and 175oC with reactant to solvent ratio of 1:9 for reaction time of 5 h are observed. The effect of IPA solvent showed that hydrogen uptake of 6.91 wt% with complete hydrogenation of quinoline and DHQ yield of more than 99% is observed. The reaction kinetic model is developed for a simplified reaction mechanism and is simulated using the Markov Chain Monte Carlo (MCMC) simulation tool to predict the rate constants and the experimental observations are validated with the model predictions. The activation energy for quinoline hydrogenation to py-THQ formation is estimated to be 136.57 kJ/mol. It is envisaged that quinoline hydrogenation to pz-THQ is the rate-limiting step in the DHQ formation.

Assessing the effect of deep eutectic solvents on α-chymotrypsin thermal stability and activity.

Optimizing the liquid reaction phase holds significant potential for enhancing the efficiency of biocatalytic pro- cesses since it determines reaction equilibrium and kinetics. This study investigates the influence of the addition of deep eutectic solvents on the stability and activity of α-chymotrypsin, a proteolytic enzyme with industrial rele- vance. Deep eutectic solvents, composed of choline chloride or betaine mixed with glycerol or sorbitol, were added in the reaction phase at various concentrations. Experimental techniques, including kinetic and fluorometry, were employed to assess the α-chymotrypsin activity, thermal stability, and unfolding reversibility. Atomistic molecular dynamics simulations were also conducted to assess the interactions and provide molecular-level insights between α-chymotrypsin and the solvent. The results showed that among all studied mixtures, adding choline chloride + sorbitol improved thermal stability up to 18 °C and reaction kinetic efficiency up to two-fold upon adding choline chloride + glycerol. Notably, the choline chloride + sorbitol system exhibited the most substantial stabilization effect, attributed to the surface preferential accumulation of sorbitol, as corroborated by the computational anal- yses. This work highlights the potential of tailoring liquid reaction phase of α-chymotrypsin catalyzed reaction using neoteric solventsto enhance α-chymotrypsin performance and stability in industrial applications.

Design and optimization of reaction-separation-recycle systems using a pseudo-transient continuation model

The reaction-separation-recycle (RSR) systems are an important part of chemical processes. Due to the interaction between reaction and separation sections, the behavior of RSR processes becomes highly complex and non-linear, posing different challenges for their design and optimization. The purpose of this study is to design and optimize RSR processes for irreversible liquid phase reaction systems using the pseudo-transient continuation (PTC) approach within an equation-oriented programing environment. This approach was applied to investigate one binary system and four ternary systems. The differential-algebraic models of the proposed process flowsheets were solved until the steady-state conditions were reached. The tray bypass efficiency method was incorporated into the PTC to circumvent the need for discrete optimization. The results demonstrated that in those cases where the product was heavier than the reactants, employing a stripping column was more economical than using a conventional distillation column for both the binary and ternary systems. In the ternary systems with two recycle streams, when the product was the intermediate component in terms of boiling point, the utilization of a divided-wall distillation column (DWC) resulted in a total annual cost saving of 35 % and 41 % compared to direct and indirect separation methods, respectively.

Structural control of ceramics through multi-step processes with liquid phase reactions

Structural control of ceramics through multi-step processes with liquid phase reactions

A lumped kinetic model and experimental investigation of poly(ethylene terephthalate) condensed-phase pyrolysis

In a circular economy perspective, plastic waste (PW) is a valuable source of chemicals and energy vectors. Understanding the effect of poly(ethylene terephthalate) (PET) in thermochemical valorisation of complex and contaminated PW mixtures requires definition of suitable kinetic models. This work proposes a condensed-phase semi-detailed kinetic model for PET pyrolysis based on a consolidated functional group approach already validated for other polymers. The reaction network is built considering studies on thermal degradation of PET, model compounds, and small gas-phase esters. Reaction pathways proposed in the scientific literature are critically assessed through analogy with high accuracy gas-phase calculation and are complemented by new proposed pathways. The resulting model couples molecular and radical mechanism and consists of 85 gas and liquid species with 700 liquid-phase reactions, being suitable for CFD simulations of PW pyrolysis upon further reduction. This work also presents new experimental data including TG analysis coupled with GC × GC speciation measurements and elemental characterization of the solid residue. The model is validated by comparison with the new experimental data and a comprehensive set of literature data in terms of characteristic degradation times and detailed product yields. The present work expands the relevant data available for chemistry models development and extends the CRECK kinetic framework for thermochemical recycling of PW mixtures. The proposed kinetic model is attached as Supplementary material and freely available as an open GitHub repository.

Molecular dynamics investigation of IEPOX chemical behavior at the interface and in the bulk phase of acidic aerosols

Isoprene epoxydiol (IEPOX) is an important reactive gas-phase intermediate produced by the photooxidation of isoprene under low NOx conditions, playing a key role in the formation of secondary organic aerosols (SOA). Previous studies have mostly focused on the liquid-phase reactions of IEPOX within aerosols; however, interfacial heterogeneous chemical reactions are equally important in SOA formation. This study systematically explores the reaction mechanisms of IEPOX at the acidic aerosol interface and in the bulk phase using classical molecular dynamics (MD) and ab initio molecular dynamics simulations (AIMD). The study found that the free energy of IEPOX at the aerosol interface significantly decreases, indicating that interfacial heterogeneous chemical reactions are indispensable for the formation of IEPOX-derived SOA. The research reveals the formation pathways of 2-methyltetrols (2-MTO) and 1,3,4-trihydroxy-3-methylbutan-2-yl sulfates (2-MTOOS), finding that the protonation of the epoxy O atom and the cleavage of the C–O bond are the rate-controlling steps, while the nucleophilic addition is a spontaneous process. Through multiple sets of simulations, it was observed that the formation frequency of 2-MTO at the acidic aerosol interface and in the bulk phase reached 53.8%, significantly higher than the 30.8% of 2-MTOOS, which is consistent with field observation data. Additionally, through metadynamics (MTD) simulations, it was suggested that IEPOX could undergoes acid-catalyzed ring-opening reactions at the interface, potentially followed by the transfer of H atoms from primary alcohols into the aerosol, leading to the possible formation of the intermediate product 3-methylbut-3-ene-1,2,4-triol (one of the proposed structures of C5-alkene triols). These findings provide new insights into the formation mechanism of IEPOX-derived SOA and offer a scientific basis for future studies on their physicochemical properties and atmospheric fate.

The interplay of shape and catalyst distribution in the yield of compressible flow microreactors.

We develop a semi-analytical model for transport in structured catalytic microreactors, where both reactant and product are compressible fluids. Using lubrication and Fick-Jacobs approximations, we reduce the three-dimensional governing equations to an effective one-dimensional set of equations. Our model captures the effect of compressibility, corrugations in the shape of the reactor, and an inhomogeneous catalytic coating of the reactor walls. We show that in the weakly compressible limit (e.g., liquid-phase reactors), the distribution of catalyst does not influence the reactor yield, which we verify experimentally. Beyond this limit, we show that introducing inhomogeneities in the catalytic coating and corrugations to the reactor walls can improve the yield.

Measurement report: Occurrence of aminiums in PM2.5 during winter in China – aminium outbreak during polluted episodes and potential constraints

Abstract. Amines and aminiums play an important role in particle formation, liquid-phase reactions, and climate change and have attracted considerable attention over the years. Here, we investigated the concentrations and compositions of aminiums in PM2.5 in 11 Chinese cities during the winter, focusing on the characteristics of aminiums during the polluted days and the key factors influencing aminium outbreak. Monomethylaminium was the dominant aminium species in most cities, except Taiyuan and Guangzhou, followed by dimethylaminium. Diethylaminium dominated the total aminiums in Taiyuan and Guangzhou. Thus, the main amine sources in Taiyuan and Guangzhou were significantly different from those in other cities. The concentrations of the total aminiums (TAs) in most cities increased significantly during the polluted days, while relatively weak aminium outbreaks during the polluted days occurred in Xi'an and Beijing. Additionally, the concentrations of TAs in Xi'an and Beijing were insignificantly correlated with those of PM2.5 and the major acidic aerosol components, while the opposite pattern was observed in nine other cities. Thus, acid–base chemistry was significantly associated with the formation of aminiums in PM2.5 in all cities, except Xi'an and Beijing. Based on the sensitivity analysis of the aminiums : ammonium ratio to ammonium changes, as well as excluding the effects of relative humidity and atmospheric oxidation, we proposed the possibility of the competitive uptake of ammonia versus amines on acidic aerosols or the displacement of aminiums by ammonia in Xi'an and Beijing (constraining aminium outbreaks). Overall, this study deepens the understanding of the spatiotemporal differences in aminium characteristic and formation in China. However, the uptake of amines on particles to form aminiums and the relevant influencing factors require further mechanistic research.

Efficient structural and compositional modulation of vanadium oxides for high-areal-capacity zinc-ion batteries

Although rechargeable aqueous zinc-ion batteries (RAZIBs) have been revitalized as competitive candidates for large-scale energy storage, the development of this technology is stalled by the underutilization of cathode materials due to sluggish reaction kinetics, resulting in low areal capacities that cannot meet the practical requirements. Herein, this study reveals a simple, efficient, and low-energy synthetic route to effectively convert relatively inactive α-V2O5 (131 mAh g−1 at 0.1 A g−1) into highly active MxV8O20·nH2O (MVO, M = Li, Na, and K) by liquid-phase dissolution-recrystallization reaction and chemical preintercalation under low-temperature conditions. Particularly, NaVO presents the most expansive diffusion channel, the highest specific surface area, and the smallest band gap, allowing faster electron/ion transport kinetics and better material utilization. With these features, NaVO accommodates electrolyte Zn2+ and H+ with good reversibility, showing high capacity (383 mAh g−1 at 0.1 A g−1) and rate-performance (207 mAh g−1 at 8 A g−1). More importantly, high-areal-capacity of 3.2 mAh cm−2 and remarkable cycle stability over 1500 cycles can be achieved from free-standing high-mass-loading electrode (∼14 mg cm−2) made of NaVO and multi-walled carbon nanotubes (MWCNTs). This work enriches the synthetic methods for obtaining high-performance vanadium-based host materials with practical areal capacity and cycle stability.

Photoinduced C(sp3)-H Bicyclopentylation Enabled by an Electron Donor-Acceptor Complex-Mediated Chemoselective Three-Component Radical Relay.

The photoredox electron donor-acceptor (EDA) complex-mediated radical coupling reaction has gained prominence in the field of organic synthesis, finding widespread application in two-component coupling reactions. However, EDA complex-promoted multi-component reactions are not well developed with only a limited number of examples have been reported. Herein, we report a photoinduced and EDA complex-promoted highly chemoselective three-component radical arylalkylation of [1.1.1]propellane, which allows the direct functionalization of C(sp3)-H with bicyclo[1.1.1]pentanes (BCP)-aryl groups under mild conditions. A variety of unnatural α-amino acids, featuring structurally diversified 1,3-disubstituted BCP moieties, were synthesized in a single-step process. Notably, leveraging the high tension release of [1.1.1]propellane, the highly unstable transient aryl radical undergoes rapid conversion into a relatively stable tertiary alkyl transient radical, and consequently, the competing side-reaction of two-component coupling was entirely suppressed. The strategic use of this transient radical conversion approach would be useful for the design of diverse EDA complex-mediated multi-component reactions. It is noteworthy that the highly chemoselective late-stage incorporation of the 1,3-disubstituted BCP pharmacophores into peptides was achieved both in liquid-phase and solid-phase reactions. This advancement is anticipated to have significant application potential in the future development of peptide drugs.

Elaborating the Atmospheric Transformation of Combined and Free Amino Acids From the Perspective of Observational Studies

AbstractProteinaceous matter (PrM) is a substantial component of bioaerosols. Although numerous studies have examined the characteristics and sources of PrM in the atmosphere, its interactions with atmospheric oxidants remain uncertain. A 1‐year observation of PrM characteristics in PM2.5 was performed in both urban Nanchang (eastern China) and suburban Guiyang (southwestern China), respectively. Glycine was the dominant free amino acid (FAA) species in urban Nanchang. In contrast, proline dominated both total free amino acids (FAAs) and total combined amino acids (CAAs) in suburban Guiyang. We found that oxidative degradation can significantly promote the release of FAAs, especially glycine, from CAAs in Nanchang. The controlled experiment on protein oxidation by hydroxyl radical suggested that the contribution of free glycine to the total FAA fraction tended to increase during the oxidative degradation of CAAs, supporting the predominance of glycine in FAAs in Nanchang and most previous observations. The composition of FAAs was mainly influenced by primary sources in suburban Guiyang with weak atmospheric degradation of PrM. These results suggest that the degradation of aerosol PrM by atmospheric oxidants can be responsible for the difference in FAA composition between the biosphere and the atmosphere, and also imply that the oxidative degradation of aerosol PrM may be a potential source of secondary organic nitrogen compounds in aerosols. Thus, this study can improve the current understanding of the composition characteristics of PrM in the biosphere and the atmosphere, as well as the liquid phase reactions of proteinaceous compounds with atmospheric oxidants.

Understanding and Controlling Reactivity Patterns of Pd1@C3N4-Catalyzed Suzuki-Miyaura Couplings.

Using heterogeneous single-atom catalysts (SACs) in the Suzuki-Miyaura coupling (SMC) has promising economic and environmental benefits over traditionally applied palladium complexes. However, limited mechanistic understanding hinders progress in their design and implementation. Our study provides critical insights into the working principles of Pd1@C3N4, a promising SAC for the SMC. We demonstrate that the base, ligand, and solvent play pivotal roles in facilitating interface formation with reaction media, activating Pd centers, and modulating competing reaction pathways. Controlling the previously overlooked interplay between base strength, reagent solubility, and surface wetting is essential for mitigating mass transfer limitations in the triphasic reaction system and promoting catalyst reusability. Optimum conditions for Pd1@C3N4 require polar solvents, intermediate base strength, and increased water content. Our investigations reveal that high selectivity requires minimizing competitive coordination of bases and phosphine ligands to the Pd centers, to avoid homocoupling and alternative reductive elimination mechanisms giving rise to phosphonium side-products. Furthermore, in situ XAS investigations probing electronic structures and coordination environments of Pd sites further rationalize the base and ligand coordination, confirming and expanding upon previous computational hypotheses for Pd1@C3N4. This understanding allows for designing a more selective ligand-free reaction pathway using the solvent and base to modulate the chemical environment of the active sites. We highlight the importance of environment-compatible surface tension, the creation of coordinatively available active sites, and the stabilization of partially reduced Pd centers, emphasizing the importance of mechanistic studies to advance the design of SACs in organic liquid phase reactions.

Melt growth of crystalline α-SrSi2 by the vertical Bridgman method and its thermoelectric characteristics

As a candidate thermoelectric material operating in the low-temperature regime (room temperature to 473 K), we have examined α-SrSi2: a narrow bandgap semiconductor material, which is composed of environmentally benign elements. We are able to report the successful production of single-crystalline-like α-SrSi2 with clear semiconducting properties by melting synthesis, a thermodynamically stable and thermally equilibrium process that reduces unexpected process contamination and improves crystallinity.The crystals up to 20 × 20 × 5 mm3 have been obtained for a solid–liquid phase reaction temperature of 1308 K for 10 h with a growth rate averaging at 0.617 K/h in the temperature range from 1403 K to 1373 K. The band gap of this material was measured at 48 meV, which is higher than the values previously reported. The power factor was measured at 2.9 mW/mK2 at 300 K, which is the highest value ever reported for undoped α-SrSi2.Based on the experimental bandgap values, the hybrid functional was used to correct the first-principles calculation method, and the Seebeck coefficient obtained from the first-principles calculation was compared with experimental values. Which values showed good agreement with experimental values.

Discovery of Molecular Intermediates and Nonclassical Nanoparticle Formation Mechanisms by Liquid Phase Electron Microscopy and Reaction Throughput Analysis

Formation kinetics of metal nanoparticles are generally described via mass transport and thermodynamics‐based models, such as diffusion‐limited growth and classical nucleation theory (CNT). However, metal monomers are commonly assumed as precursors, leaving the identity of molecular intermediates and their contribution to nanoparticle formation unclear. Herein, liquid phase transmission electron microscopy (LPTEM) and reaction kinetic modeling are utilized to establish the nucleation and growth mechanisms and discover molecular intermediates during silver nanoparticle formation. Quantitative LPTEM measurements show that their nucleation rate decreases while growth rate is nearly invariant with electron dose rate. Reaction kinetic simulations show that Ag4 and Ag− follow a statistically similar dose rate dependence as the experimentally determined growth rate. We show that experimental growth rates are consistent with diffusion‐limited growth via the attachment of these species to nanoparticles. The dose rate dependence of nucleation rate is inconsistent with CNT. A reaction‐limited nucleation mechanism is proposed and it is demonstrated that experimental nucleation kinetics are consistent with Ag42+ aggregation rates at millisecond time scales. Reaction throughput analysis of the kinetic simulations uncovered formation and decay pathways mediating intermediate concentrations. We demonstrate the power of quantitative LPTEM combined with kinetic modeling for establishing nanoparticle formation mechanisms and principal intermediates.

Discovering Nanoparticle Formation Mechanisms and Molecular Intermediates with Liquid Phase Electron Microscopy and Reaction Networks

Discovering Nanoparticle Formation Mechanisms and Molecular Intermediates with Liquid Phase Electron Microscopy and Reaction Networks

Consequences of Pore Polarity and Solvent Structure on Epoxide Ring-Opening in Lewis and Brønsted Acid Zeolites.

The structure of solvent molecules within zeolite pores influences the rates and selectivities of catalytic reactions by altering the free energies of reactive species. Here, we examine the consequences of these effects on the kinetics and thermodynamics of 1,2-epoxybutane (C4H8O) ring-opening with methanol (CH3OH) in acetonitrile (CH3CN) cosolvent over Lewis acidic (Zr-BEA) and Brønsted acidic (Al-BEA) zeolites of varying (SiOH) x density. Despite ostensibly identical reaction mechanisms across materials, turnover rates depend differently on (SiOH) x density between acid types. (SiOH) x -rich Zr-BEA (Zr-BEA-OH) provides ∼10 times greater rates than a (SiOH) x -poor material (Zr-BEA-F), while Al-BEA-OH and Al-BEA-F give turnover rates within a factor of 2. Zr-BEA-OH shows more positive activation enthalpies and entropies than Zr-BEA-F across the range of [CH3OH], which reflect the displacement of solvent molecules and lead to greater rates in Zr-BEA-OH due to the dominant role of entropic gains. Measurements of the density and composition of solvent within the pores show that the (SiOH) x nests within Zr-BEA-OH promote hydrogen-bonded solvent structures distinct from Zr-BEA-F, while the Brønsted acid sites confer interactions similar to (SiOH) x nests and give solvent structures within Al-BEA-F that resemble those within Al-BEA-OH. Correlations between apparent activation enthalpies and C4H8O adsorption enthalpies show that interactions with solvent molecules give proportional changes to both C4H8O adsorption and ring-opening transition state formation. The differences in intrapore environment carry consequences for both rates and regioselectivities of epoxide ring-opening, as demonstrated by product regioselectivities that increase by a factor of 3 in response to changes in solvent composition and the type of acid site in the *BEA structure (i.e., Lewis or Brønsted). These results demonstrate the ability to control rates, regioselectivities, and adsorption thermodynamics relevant for industrially relevant liquid-phase reactions through the design of noncovalent interactions among solvating molecules, reactive species, and (SiOH) x functions.