Apparent Activation Enthalpy Research Articles

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.

Fast relaxation in metallic glasses studied by measurements of the internal friction at high frequencies

We performed high-frequency (0.4–1.7 MHz) measurements of the internal friction (IF) on 14 bulk metallic glasses (MGs). It is found that 12 of these MGs display relaxation IF peaks at temperatures ≈ 400–500 K, which are weakly affected by heat treatment within the amorphous state. The corresponding relaxation time is about 0.3 μs. This fast relaxation is reported for the first time in the literature. The apparent activation enthalpy for 4 MGs is determined. It is shown that if measured at a low frequency of 1 Hz, these IF peaks would appear near room temperature or by 30–50 K below it. Thus, the IF peaks found in the present investigation are direct analogues of low-temperature/low-frequency β′- and/or γ-relaxations described in the literature. It is argued that the origin of these IF peaks is related to the relaxation of structural defects similar to dumbbell interstitials, which are frozen in solid glass from the liquid state upon melt quenching. These defects can be considered as elastic dipoles and their re-orientation in the applied stress provides anelastic deformation and corresponding IF peak. After correction for temperature dependence of the shear modulus, the true activation enthalpy (0.62–1.08 eV) and activation entropy (4 ≤ΔS∕kB≤15) for defect re-orientation are determined.

The Dominance of Pretransitional Effects in Liquid Crystal-Based Nanocolloids: Nematogenic 4-methoxybenzylidene-4'-butylaniline with Transverse Permanent Dipole Moment and BaTiO3 Nanoparticles.

The report presents static, low-frequency, and dynamic dielectric properties in the isotropic liquid, nematic, and solid phases of MBBA and related nanocolloids with paraelectric BaTiO3 nanoparticles (spherical, d = 50 nm). MBBA (4-methoxybenzylidene-4'-butylaniline) is a liquid crystalline compound with a permanent dipole moment transverse to the long molecular axis. The distortions-sensitive analysis of the dielectric constant revealed its hidden pretransitional anomaly, strongly influenced by the addition of nanoparticles. The evolution of the dielectric constant in the nematic phase shows the split into two regions, with the crossover coinciding with the standard melting temperature. The 'universal' exponential-type behavior of the low-frequency contribution to the real part of the dielectric permittivity is found. The critical-like pretransitional behavior in the solid phase is also evidenced. This is explained by linking the Lipovsky model to the Mossotti catastrophe concept under quasi-negative pressure conditions. The explicit preference for the 'critical-like' evolution of the apparent activation enthalpy is worth stressing for dynamics. Finally, the long-range, 'critical-like' behavior of the dissipation factor (D = tgδ), covering the isotropic liquid and nematic phases, is shown.

Sintering kinetics and microstructure development of synthetic lunar highlands and mare regolith

Kinetics and microstructure development during pressureless sintering of two Lunar regolith simulants are reported and discussed. Dry-pressed cylindrical specimens of either a Highlands simulant or a Mare simulant were heated at 80 K min−1 to a prescribed sintering temperature and held for ten hours while dimensional changes were tracked in situ by optical dilatometry. The axial and volumetric strains and densification rates were calculated as a function of time and temperature. Possible phase transformations were evaluated by quantitative X-ray powder diffraction. The relative density increased with the logarithm of time at any temperature, and densification rates decreased continuously and sharply with increasing density. Sintered microstructures and compositional characteristics were observed by scanning electron microscopy and X-ray microprobe analysis of polished surfaces. The microstructures of both materials show evidence of heterogeneous densification, with large but isolated high-density domains surrounded by lower-density regions with interconnected porosity. No significant compositional differences were detected between the higher- and lower-density regions, meaning that the heterogeneous local densities are caused by gradients in particle size or packing that induce locally varying thermodynamic driving forces for densification. The apparent activation enthalpy for densification was measured as 445 kJ mol−1 and 440 kJ mol−1 for the Highlands and Mare simulants, respectively, values that were observed to be independent of temperature and sintered density to within the measurement uncertainty.

Modifying reaction rates and stimulus-responsive behavior of polymer-coated catalysts using aprotic solvents

The impact of solvent composition on the reaction rates and apparent activation barriers for the reduction of nitrobenzene on Pd has been investigated by changing the solvent from pure water to mixtures with increasing concentrations of 1-methyl-2-pyrrolidone (NMP). When using pure NMP as the solvent, the activity was negligible and a high activation energy barrier was observed. Surprisingly, switching to water led to faster reaction rates and lower apparent barriers. Considering that previous research has demonstrated that water molecules near the catalyst surface facilitate the hydrogen insertion on R-NO* and R-HNO* surface species via proton-electron transfer, it is possible to link the herein observed trends in activity for the nitrobenzene hydrogenation to the ability of the reaction media to shuttle protons during the reaction. Furthermore, the polymer-induced solvation effects were investigated using thermo-responsive Pd/SiO2-p-NIPAM catalyst. Here, we observed that the utilization of NMP inhibits the thermo-responsive behaviour of poly N-isopropylacrylamide (p-NIPAM). This explains the constant particle size of Pd/SiO2-p-NIPAM catalyst observed at different temperatures during dynamic light scatting characterization (DLS). We speculate that this non-responsive behaviour of the p-NIPAM in the presence of NMP is the cause of the constant activation energy barrier at temperatures above and below the lower critical solution temperature (LCST) of the polymer (32 °C). When the reaction was conducted in pure water, the polymer-coated catalyst showed significant changes in both the apparent enthalpy and entropy of activation for temperatures below and above the LCST. This suggests that the microenvironment induced by the polymer can significantly influence the reaction rate.

Solvent Mediated Interactions on Alkene Epoxidations in Ti-MFI: Effects of Solvent Identity and Silanol Density

Selective alkene oxidation rates within zeolite pores reflect differences in contributions from thermodynamic nonidealities introduced by noncovalent interactions at solid–liquid interfaces and spatial constraints enforced by the zeolite topology. Epoxidation turnover rates for 1-hexene in Ti-MFI zeolite differ by 1000-fold across 10 combinations of solvents, including alcohols and acetonitrile, over Ti-MFI with distinct silanol defect densities. Solvent mediated noncovalent interactions persist across an extended binding environment that influences the stability of epoxidation transition states. Apparent activation enthalpies (ΔHApp⧧) and entropies (ΔSApp⧧) span 80 kJ mol–1 and 200 J mol–1 K–1, respectively, with the most positive values for both appearing in methanol. Hydrophilic (i.e., (SiOH)x defect rich) Ti-MFI-OH catalysts in methanol give the greatest turnover rates because entropic gains associated with the disruption of hydrogen-bonded networks of intrapore methanol and water dominate activation free energies. In situ infrared spectra show that the adsorption of 1,2-epoxyhexane to Ti sites disturbs the equilibrium solvent structure within pores in ways that reflect the density of the hydrogen bond donor and acceptors near active sites. This interpretation agrees with measured enthalpies for adsorption of 1,2-epoxyhexane to Ti active sites within solvent filled pores that correlate with ΔHApp⧧ across solvent and catalyst combinations. The displacement of solvent molecules and the associated rupture and formation of hydrogen bonds among solvents, pore walls, and nearby reactive molecules during catalysis and adsorption events incur substantial excess contributions that govern the reaction rates and barriers. These realizations explain the particular success of alkene epoxidations in mixtures of H2O2 and methanol over hydrophilic forms of Ti-MFI in industrial processes (e.g., the hydrogen peroxide–propylene oxide process). These findings demonstrate the gains achieved by appropriately pairing organic solvents with microporous catalysts to manipulate the intrinsic kinetics of reactions and the thermodynamics of adsorption at solid–liquid interfaces.

The effect of N2/CO2 blend ratios on the pyrolysis and combustion behaviors of coal particles: Kinetic and thermodynamic analyses

The aim of this work is to investigate the impact of various CO2/N2 ratios on coal pyrolysis and combustion properties and to provide theoretical guidance for better preventing and controlling coal spontaneous combustion in the goaf. The dynamic pyrolysis and combustion characteristics of DX coal were analyzed by using a thermal gravimetric analyzer (TGA) in a constant oxygen atmosphere with different CO2/N2 blend ratios. The Málek method combining Coats-Redfern and Achar methods was used to determine the most probable mechanism functions. CO2 containing atmospheres increased characteristic temperatures, burnout rate, maximum mass loss rate and comprehensive combustion performance index compared to O2/N2 atmospheres. In stages I-III, a lower apparent activation energy was observed in O2/CO2 atmospheres. Apparent activation energy and enthalpy changes showed upward trends in the reaction stage (I→III→IV), whereas Gibbs free energy change and entropy change decreased. The dynamic pyrolysis and combustion of DX coal necessitated increased energy in environment with a CO2/N2 ratio of 4:6, revealing the optimal inhibitory effect on DX coal with this particular ratio.

Rapid Kinetics of Pistol Ribozyme: Insights into Limits to RNA Catalysis.

Pistol ribozyme (Psr) is a distinct class of small endonucleolytic ribozymes, which are important experimental systems for defining fundamental principles of RNA catalysis and designing valuable tools in biotechnology. High-resolution structures of Psr, extensive structure-function studies, and computation support a mechanism involving one or more catalytic guanosine nucleobases acting as a general base and divalent metal ion-bound water acting as an acid to catalyze RNA 2'-O-transphosphorylation. Yet, for a wide range of pH and metal ion concentrations, the rate of Psr catalysis is too fast to measure manually and the reaction steps that limit catalysis are not well understood. Here, we use stopped-flow fluorescence spectroscopy to evaluate Psr temperature dependence, solvent H/D isotope effects, and divalent metal ion affinity and specificity unconstrained by limitations due to fast kinetics. The results show that Psr catalysis is characterized by small apparent activation enthalpy and entropy changes and minimal transition state H/D fractionation, suggesting that one or more pre-equilibrium steps rather than chemistry is rate limiting. Quantitative analyses of divalent ion dependence confirm that metal aquo ion pKa correlates with higher rates of catalysis independent of differences in ion binding affinity. However, ambiguity regarding the rate-limiting step and similar correlation with related attributes such as ionic radius and hydration free energy complicate a definitive mechanistic interpretation. These new data provide a framework for further interrogation of Psr transition state stabilization and show how thermal instability, metal ion insolubility at optimal pH, and pre-equilibrium steps such as ion binding and folding limit the catalytic power of Psr suggesting potential strategies for further optimization.

Some Brassicaceae Extracts as Potential Antioxidants and Green Corrosion Inhibitors.

Glucosinolates-rich extracts of some Brassicaceae sources, such as broccoli, cabbage, black radish, rapeseed, and cauliflower, were obtained using an eco-friendly extraction method, in a microwave field, with 70% ethanol, and evaluated in order to establish their in vitro antioxidant activities and anticorrosion effects on steel material. The DPPH method and Folin-Ciocâlteu assay proved good antioxidant activity (remaining DPPH, 9.54-22.03%) and the content of total phenolics between 1008-1713 mg GAE/L for all tested extracts. The electrochemical measurements in 0.5 M H2SO4 showed that the extracts act as mixed-type inhibitors proving their ability to inhibit corrosion in a concentration-dependent manner, with a remarkable inhibition efficiency (92.05-98.33%) achieved for concentrated extracts of broccoli, cauliflower, and black radish. The weight loss experiments revealed that the inhibition efficiency decreased with an increase in temperature and time of exposure. The apparent activation energies, enthalpies, and entropies of the dissolution process were determined and discussed, and an inhibition mechanism was proposed. An SEM/EDX surface examination shows that the compounds from extracts may attach to the steel surface and produce a barrier layer. Meanwhile, the FT-IR spectra confirm bond formation between functional groups and the steel substrate.

Effect of Interactions between Alkyl Chains and Solvent Structures on Lewis Acid Catalyzed Epoxidations

Solvent molecules within zeolite pores provide interactions that influence the stability of reactive intermediates and impact rates and selectivities for catalytic reactions. We show the kinetic and thermodynamic consequences of these interactions and reveal their origins using alkene epoxidations in titanium-substituted *BEA (Ti-BEA) zeolites. Epoxidation turnover rates vary widely among primary n-alkenes (C6–C18) in hydrophilic (Ti-BEA-OH) and hydrophobic (Ti-BEA-F) catalysts in aqueous acetonitrile (CH3CN). Apparent activation enthalpies (ΔHapp‡) and entropies (ΔSapp‡) increase with alkene carbon number in both catalysts; however, the span of ΔHapp‡ values in Ti-BEA-OH (68 kJ mol–1) greatly exceeds that in Ti-BEA-F (18 kJ mol–1). These trends, and commensurate gains in ΔSapp‡, reflect the displacement and reorganization of solvent molecules that scale with the size of transition states and the numbers of solvent molecules stabilized by silanol defects near active sites. Experimental and computational assessments of intrapore solvent composition from 1H NMR, infrared spectroscopy, and grand canonical molecular dynamics (GCMD) simulations show that Ti-BEA-OH uptakes larger quantities of both CH3CN and H2O than Ti-BEA-F. The Born–Haber decomposition of simulated enthalpies of adsorption (ΔHads,epox) for C6–C18 epoxides attributes ΔHads,epox that become more endothermic for larger adsorbates to the displacement of greater numbers of solvent molecules bound to silanol defects into the bulk solvent. A strong correlation between ΔHapp‡ and ΔHads,epox (from GCMD and isothermal titration calorimetry) gives evidence that the disruption of solvent structures provides excess thermodynamic contributions (e.g., Gε) that depend on the solvent composition in the pores, the excluded volume of reactive species, and the density of silanol groups near active sites. Altering Gε values offers opportunities to control selectivities and rates of reactions through the design of extended active site environments.

Pathways for Reactions of Esters with H2 over Supported Pd Catalysts: Elementary Steps, Site Requirements, and Particle Size Effects

The direct reduction of esters to ethers offers an efficient pathway to ethers from renewable intermediates. This chemistry previously required homogeneous catalysts and utilized costly and unstable hydride reagents. Here, we elucidate pathways for reactions of propyl acetate (C5H10O2) in the presence of hydrogen (H2) over Pd nanoparticles supported on high-surface-area Nb2O5. Over Pd-Nb2O5, C5H10O2 reacts by three competing primary pathways: hydrogenation to form ethyl propyl ether (C5H12O) by apparent C═O bond rupture, hydrogenolysis to form acetaldehyde and propanol (Cacyl–O bond rupture), and hydrolysis to form acetic acid and propanol. Secondary reactions yield other alcohols, esters, ethers, and hydrocarbons. Hydrogenation and hydrogenolysis rates do not change with the pressure of C5H10O2 and increase with a sublinear dependence on H2 pressure. Furthermore, these dependencies and apparent activation enthalpies remain similar for Pd nanoparticles with different mean diameters (4–22 nm), which shows that the extent of undercoordination of Pd does not significantly affect the mechanism or kinetics for C–O bond rupture steps. Ether formation rates remain constant when D2 replaces H2 as the reductant, which together with the rate dependence on H2 suggests that ethers form by kinetically relevant C–O bond cleavage in a partially hydrogenated intermediate (e.g., hemiacetal). Ex situ titration of Brønsted acid sites by exchange with K+ ions suppresses mass-averaged rates of C5H12O formation by sevenfold, and physical mixtures of Pd-SiO2 and Nb2O5 give rates more than 10 times lower than Pd-Nb2O5. These results demonstrate that C5H12O formation requires Brønsted acid sites that reside in close proximity to Pd nanoparticles. Collectively, these observations suggest a reaction mechanism for the reduction of esters that hydrogenates the carbonyl by stepwise addition of H* atoms to form a hemiacetal that dehydrates at proximal Brønsted acid sites or cleaves the Cacyl–O bond to form lower carbon number products. These findings reveal a pathway to convert renewable oxygenates, such as carboxylic acid derivatives, into value-added chemicals useful as surfactants and solvents.

Identity of the metal oxide support controls outer sphere interactions that change rates and barriers for alkene epoxidations at isolated Ti atoms

Atomically disperse Ti sites on metal oxides (MOx, including SiO2, γ-Al2O3, ZnO, GeO2) activate H2O2 to create intermediates active for alkene epoxidations. Turnover rates for 1-hexene epoxidation in acetonitrile vary 1000-fold at identical conditions due to differences in apparent activation enthalpies (ΔH‡epox) and entropies (ΔS‡epox). Ligand-to-metal charge transfer energies and vibrational frequencies of reactive species assessed by in situ UV–Vis and Raman spectroscopy, respectively, indicate supports do not detectably change electronic properties of H2O2-derived intermediates. However, isoelectric points and solution-phase water uptakes for these metal oxides correlate with ΔH‡epox and suggest that non-covalent interactions at the solid-liquid interface influence the stability of epoxidation transition states. Supports with lower pKa values concentrate water near the solid-liquid interface and enthalpically stabilize the transition state. These findings illustrate that outer sphere interactions impact epoxidation reactions upon metal oxide catalysts including titanium silicates.

Influence of faceting-roughening on triple-junction migration in zinc

Abstract The faceting and migration of individual triple junctions in Zn tricrystals under a constant driving force was investigated. The triple junction (TJ) was formed by three [101̅0] tilt grain boundaries (GBs) with misorientation angles θ of 43°, 37° and 6°. The stationary shape of the migrating triple junction was studied, and the migration rate was measured in-situ between 670 and 688 K using polarized light. In some experimental runs, a facet was formed on the θ = 37° [101̅0] tilt GB. This facet was parallel to the close-packed plane in the constrained coincidence site lattice (CCSL). The length of this facet decreases with increasing temperature and becomes zero at 688 K. The temperature dependence of the facet length is better described by the mean-field Andreev approximation than by the solid-on-solid model. The step energy estimated in the framework of the Bonzel approximation is about 0.1 eV/atom. In other experimental runs, the θ = 37° [101̅0] tilt GB did not facet and remained rough in the same temperature interval. This fact allowed us to compare the stationary migration of the same TJ with faceted and rough GBs. ATJ formed by faceted GBs migrates one to two orders of magnitude more slowly in comparison with a rough TJ. An unrealistically high value of the apparent migration activation enthalpy of faceted TJs can appear due to the changing geometry of faceted GBs, similar to the case of migration of faceted twin tips.

Determination of ignition temperature and kinetics and thermodynamics analysis of high-volatile coal based on differential derivative thermogravimetry

In order to accurately determine the ignition temperature (Ti) of coal, Coal spontaneous combustion (CSC) process was tested by a simultaneous thermal analyzer. Next, the abrupt change point of the differential derivative thermogravimetric curve (DDTG) of coal after the high adsorption temperature was taken as the Ti of CSC. Besides, variations of kinetics and thermodynamics during the CSC before and after the Ti were calculated. It was found that the mass loss, heat releases and gaseous products of coal changed slowly before the Ti and surged sharply after the Ti. The coal at ignition temperature was in thermodynamic equilibrium with low activity. However, when the temperature was greater than Ti, the aromatic hydrocarbons in coal begin to decompose, resulting in the increased of active sites and the release of volatiles, and the coal enters an irreversible combustion stage. At this time, upward trends were obtained for the apparent activation energy, pre-exponential factor, enthalpy change, and entropy change, while a gradual decrease was observed for the Gibbs free energy change. Moreover, reaction intensity between oxygen and coal would be increased due to increased of active sites in the coal and enhanced of volatiles release under a slower heating rate.

Amphoteric surfactant of octadecyl dimethyl betaine as an efficient corrosion inhibitor for cold rolled steel in phosphoric acid solution

The inhibition effect of amphoteric surfactant of octadecyl dimethyl betaine (BS-18) on cold rolled steel (CRS) in H3PO4 solution was studied by weight loss, electrochemical technique, surface analysis and quantum chemical calculations. The results show that BS-18 acts as an efficient inhibitor on CRS in 1.0 M H3PO4 medium at 20–50 °C, and the maximum inhibition efficiency is 87.1% with 50 mg L−1 at 20 °C. Its adsorption on steel surface obeys Langmuir adsorption isotherm, which is endothermic process accompanying with the increase of entropy. Compared with uninhibited solution, apparent activation energy, pre-exponential factor, activation enthalpy and activation entropy become higher in inhibited solution, while both reaction constant and rate constant decrease after adding BS-18. Inhibition performance remains more stable from 3 to 48 h, and fluctuates slightly with the acid concentration from 0.5 to 5.0 M. BS-18 is a mixed-type inhibitor through “geometric blocking effect”. EIS is a time constant with one depressed capacitive loop in Nyquist plot and one phase angle in Bode phase plot, and the charge transfer resistance turns to become more larger in the presence of BS-18. SEM and AFM micrographs of inhibited CRS surface appear little corrosion, and its contact angle is increased. There are functional groups of C–N and C–N+ in the adsorptive film of BS-18 on CRS surface using XPS analysis. Critical micelle concentration (CMC) of BS-18 is about 20 mg L−1 from surface tension measurements. Quantum chemical calculations confirm that the active adsorption site of BS-18 is the hydrophilic group of N+ and –CH2COO−.

H2O-assisted O2 reduction by H2 on Pt and PtAu bimetallic nanoparticles: Influences of composition and reactant coverages on kinetic regimes, rates, and selectivities

Hydrogen peroxide (H2O2) can replace hazardous oxidants in industrial processes but is currently too expensive for many such applications. While direct synthesis of H2O2 (H2 + O2 → H2O2) may reduce costs in comparison to incumbent technology, current catalysts lack the requisite stability and selectivity. Here, we examine the direct synthesis of H2O2 on bimetallic Pt1Aux (0 ≤ x ≤ 230) and Pt catalysts at steady-state in pure water and relate kinetic parameters for H2O2 and H2O formation to possible active site structures informed by complementary characterization methods. X-ray photoelectron spectra show significant Pt surface enrichment compared to the bulk composition. Analysis of infrared spectra of mixed monolayers of 12CO* and 13CO* indicate that Pt and Au form substitutional surface alloys. The Pt1Aux nanoparticles with the greatest mole fractions of Au predominantly expose Pt monomers (i.e., isolated Pt atoms), yet Pt atoms exposed upon all these nanoparticles possess electronic structures distinct from bulk Pt. Despite these differences, rate measurements are consistent with product formation through proton-electron transfer pathways for all Pt1Aux catalysts. In situ XAS indicate that Pt remains metallic during H2O2 synthesis. Under the most oxidizing conditions, selectivities toward H2O2 increase strongly with the Au to Pt ratio from 2% for monometallic Pt to 85% for Pt1Au170. However, selectivities are similar among all catalysts within reducing conditions. Comparisons of apparent activation enthalpies for the formation of H2O2 and H2O across these catalysts and the range of conditions suggest that Pt monomers within Au provide the greatest selectivities for H2O2 formation, because these active sites present high barriers for O-O bond rupture. Selectivities decrease with increasing ratios of H2 to O2 pressures, because Pt atoms aggregate and form oligomers that readily dissociate dioxygen intermediates. The combined use of spectroscopy, kinetics, and concepts employed in reaching these conclusions take inspiration from the legacy of Prof. Michel Boudart, and specifically his elegant methods for interrogating bimetallic catalysts.

Closing in on the heat‐activation mechanisms of TRPV channels

The sensation of heat is mediated by cation-permeable ion channels of the thermoTRP kind. Among these, some of the principal heat-activated ion channels are formed by the TRPV1–4 members of the TRPV subfamily (Latorre et al. 2009). The mechanism by which these membrane proteins convert thermal energy to a channel-opening conformational change is still being intensely investigated and for the most part is not well understood. The availability of high-resolution structures provided by the cryo-EM revolution has made it easier to propose structure–function hypotheses to study heat activation. However, high quality functional studies based in electrophysiology are still the benchmark to prove mechanisms for ion channels. Quantifying the contribution of a channel region to the heat-absorbing step is a difficult task. So far, a good experimental approximation is the estimation of the activation enthalpy associated with the opening of the channel, measured from the steepness of the channel open probability as a function of temperature. In previous seminal work (Yao et al. 2011), the laboratory of Feng Qin identified a so-called membrane proximal domain (MPD), located between the first transmembrane domain and the N-terminal ankyrin repeat domains in all TRPV channels. The authors produced evidence which suggests that the MPD is a main determinant of the activation enthalpy in TRPV1–4 thermoTRP channels. Importantly, the suggestion that this region is involved in a heat-absorbing conformational change was supported by careful measurement of the apparent enthalpy. In the present work, Liu and Qin (2021) further dissect the contribution of the components of the MPD and of individual amino acid residues within the MPD to the apparent enthalpy of activation in TRPV1 and TRPV2 channels. These important new results begin to paint a detailed picture of the fine-tuning involved in channel activation by temperature. TRPV2 channels are the thermoTRP channels with the highest enthalpy of activation –more than double the activation enthalpy of TRPV1 – and are also activated by very high temperatures (>50°C compared to >40°C for TRPV1). Interestingly, the activation of TRPV2 is also different from TRPV1 in that it shows marked hysteresis. TRPV2 channels activate steeply after initial temperature stimuli that do not activate a large fraction of current. Regardless of these differences, Liu and Qin make use of a unique heat-activation technique that relies on rapid infrared laser activation of currents and of chimeric constructions in which parts of the MPD region are swapped between both types of channels to successfully identify a helix–turn–helix motif comprising 10 residues in TRPV2 and 11 residues in TRPV1 that is part of the MPD. Transplantation of this motif between the two channels is enough to produce chimaeras that activate with the enthalpy of activation of the donor channel. Further mutagenesis experiments identified single residues that are implicated in the high temperature dependence of activation of TRPV2. Of particular interest is a serine present in TRPV1 and absent in TRPV2 and TRPV3, another high temperature-activated channel. Reintroduction of the serine in the 10-residue motif of TRPV2 reduced the apparent enthalpy of activation to values comparable to TRPV1. The fact that a single serine is capable of such a large effect suggests that this serine drastically modulates the local structure of the motif or its local interactions or both. According to cryo-EM structures of TRPV2 (Zubcevic et al. 2016), this helix–turn–helix motif is poised to interact with the S2–S3 intracellular loop and the functionally important TRP domain helix. What is the function of the helix–turn–helix in the complete gating cycle of thermoTRP channels? One possibility is that it is part of a protein domain involved in heat absorption, a heat sensor of sorts. As discussed by the authors, this possibility is unlikely due to its small size and the fact that it is generally thought that a large number of interactions are needed to produce high temperature sensitivity. Another possible function for this motif is as a coupling region, capable of transmitting a heat-induced conformational change initiated in other regions of the channel to the activation gate formed by the S6 transmembrane segments. Careful functional experiments such as the ones reported in the present work as well as detailed structural determination of activated and deactivated states will be needed in the future in order to fully understand heat activation in TRPV channels. Meanwhile, these experiments remind us of the immense usefulness of careful electrophysiology. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. None declared. Sole author. Funded by grant DGAPA-PAPIIT-UNAM No. IN215621.

Effects of bromide adsorption on the direct synthesis of H2O2 on Pd nanoparticles: Formation rates, selectivities, and apparent barriers at steady-state

The direct synthesis reaction (H2 + O2 → H2O2) may provide a low-cost method to form H2O2 if catalytic systems with sufficient selectivities and stabilities are developed. Here, we examine how sodium bromide, a ubiquitous promoter for direct synthesis, impacts steady-state rates and apparent barriers for H2O2 and H2O formation in water and relate changes to the effect of NaBr on surface and bulk properties of Pd nanoparticle catalysts. Comparisons of turnover rates and selectivities measured over an extended period (>80 h) demonstrate that these systems require more than 10 h to reach steady-state, whereupon, H2O2 selectivities depend strongly upon [NaBr] and increase from 17% in pure water to ~65% at 10−4 M NaBr (55 kPa H2, 200 kPa O2). Contact with these NaBr solutions irreversibly modifies Pd nanoparticles, such that H2O2 selectivities remain at 40% in pure water, due to irreversible uptake of Br*-atoms. Bromide adsorption isotherms measured show that reduced Pd nanoparticles adsorb several monolayers of Br*-atoms, which suggests Br saturates surfaces but also resides within the near-surface region of Pd nanoparticles. Ex situ X-ray photoelectron spectroscopy indicates that Br*-atoms withdraw charge from Pd atoms and yield greater fractions of Pd2+. Comparisons among infrared spectra of adsorbed CO imply that persistent Br atoms preferentially bind to undercoordinated sites. H2O2 and H2O formation rates, both in the presence and absence of Br*-atoms, change with H2 and O2 pressures in ways consistent with elementary steps that involve H2O-mediated proton-electron transfer (PET). Therefore, increased selectivities on Br*-modified surfaces reflect differences in apparent activation enthalpies for H2O2 (ΔH‡H2O2)and H2O (ΔH‡H2O) formation. ΔH‡H2O2and ΔH‡H2O increase systematically with [NaBr], although with different sensitivities. Comparisons of activation enthalpies alongside ex situ characterization provide compelling evidence that Br atoms adsorb onto and intercalate beneath the surfaces of Pd nanoparticles and increase steady-state H2O2 selectivities, which persist without further addition of liquid-phase bromide for at least 15 h. These findings indicate H2O2 selectivities for a continuous catalytic process may be increased by a one-time (or infrequent) addition of halide promoters, which can reduce the complexity of subsequent product purification for many applications of H2O2.

Effect of Pd Coordination and Isolation on the Catalytic Reduction of O2 to H2O2 over PdAu Bimetallic Nanoparticles.

The direct synthesis of hydrogen peroxide (H2 + O2 → H2O2) may enable low-cost H2O2 production and reduce environmental impacts of chemical oxidations. Here, we synthesize a series of Pd1Aux nanoparticles (where 0 ≤ x ≤ 220, ∼10 nm) and show that, in pure water solvent, H2O2 selectivity increases with the Au to Pd ratio and approaches 100% for Pd1Au220. Analysis of in situ XAS and ex situ FTIR of adsorbed 12CO and 13CO show that materials with Au to Pd ratios of ∼40 and greater expose only monomeric Pd species during catalysis and that the average distance between Pd monomers increases with further dilution. Ab initio quantum chemical simulations and experimental rate measurements indicate that both H2O2 and H2O form by reduction of a common OOH* intermediate by proton-electron transfer steps mediated by water molecules over Pd and Pd1Aux nanoparticles. Measured apparent activation enthalpies and calculated activation barriers for H2O2 and H2O formation both increase as Pd is diluted by Au, even beyond the complete loss of Pd-Pd coordination. These effects impact H2O formation more significantly, indicating preferential destabilization of transition states that cleave O-O bonds reflected by increasing H2O2 selectivities (19% on Pd; 95% on PdAu220) but with only a 3-fold reduction in H2O2 formation rates. The data imply that the transition states for H2O2 and H2O formation pathways differ in their coordination to the metal surface, and such differences in site requirements require that we consider second coordination shells during the design of bimetallic catalysts.

Mechanism and Kinetics of Light Alkane Dehydrogenation and Cracking over Isolated Ga Species in Ga/H-MFI

Author(s): Phadke, NM; Mansoor, E; Head-Gordon, M; Bell, AT | Abstract: The objective of this study is to examine the mechanisms and kinetics of C2H6 dehydrogenation and n-C4H10 dehydrogenation and cracking over isolated Ga species in Ga/HMFI and to compare these results to those reported previously for C3H8 dehydrogenation and cracking. C2H6 dehydrogenation is found to be catalyzed by both [GaH]2+ and [GaH2]+ cations at similar turnover frequencies. Rate measurements over Ga/H-MFI containing predominantly [GaH2]+ cations reveal that C2H6 dehydrogenation rates exhibit a Langmuir.Hinshelwood dependence on C2H6 partial pressure at elevated temperatures (g730 K), consistent with the involvement of chemisorbed [C2H5.GaH]+ species. The reaction kinetics suggest that C2H6 dehydrogenation proceeds via heterolytic C-H cleavage of adsorbed C2H6 by [GaH2]+ cations to form H2 and [C2H5-GaH]+ species, which further decompose via β-hydride elimination to form C2H4. By contrast, C4H10 dehydrogenation and both terminal and central cracking are catalyzed exclusively by [GaH]2+ cations. All three reactions exhibit a Langmuir-Hinshelwood dependence on C4H10 partial pressure and are inhibited by H2. Ratios of dehydrogenation to cracking (total) and terminal to central cracking are approximately independent of C4H10 partial pressure consistent with the involvement of a common C4H10-derived surface intermediate. The observed reaction kinetics are consistent with an alkyl-mediated mechanism occurring over [GaH]2+, analogous to that reported previously for C3H8 dehydrogenation/cracking over Ga/H-MFI (Phadke, N. M.; et al. J. Am. Chem. Soc. 2019, 141, 1614-1627). The mechanism proceeds via facile, heterolytic dissociation of adsorbed C4H10 to form [C4H9-GaH]+-H+ cation pairs via methyl C-H-activated pathways. Dehydrogenation then proceeds via β-hydride elimination, respectively, forming butene, while terminal and central cracking proceed via C-H-activated H+ attack. Methylene activation was also considered but found to occur at a significantly lower rate. Theoretical analysis of the proposed reaction pathways leads to apparent activation enthalpies in good agreement with values extracted from the measured kinetics, thereby supporting the proposed pathways and the roles of [GaH]2+ and [GaH2]+ cations in the dehydrogenation and cracking of light alkanes on Ga/H-MFI.