In acidic HZSM-5 zeolite, the reactivity of a methanol molecule interacting with the zeolite proton is amenable to modification via coadsorbing a stochiometric amount of an electron density donor E to form the [(E)(CH3OH)(HZ)] complex. The rate of the methanol in this complex undergoing dehydration to dimethyl ether was determined for a series of E with proton affinity (PA) ranging from 659 kJ mol-1 for C6F6 to 825 kJ mol-1 for C4H8O and was found to follow the expression: Ln(Rate) - Ln(RateN2) = beta(PA - PAN2)gamma, where E = N2 is the reference and beta and gamma are constants. This trend is probably due to the increased stability of the solvated proton in the [(E)(CH3OH)(HZ)] complex with increasing PA. Importantly, this is also observed in steady-state flow reactions when stoichiometric quantities of E are preadsorbed on the zeolite. As demonstrated with E being D2O, the effect on methanol reactivity diminishes when E is present in excess of the [(E)(CH3OH)(HZ)] complex. It is proposed that the methanol dehydration reaction involves [(E)(CH3OH)(CH3OH)(HZ)] as the transition state, which is supported by the isotopologue distribution of the initial dimethyl ether formed when a flow of CH3OH was passed over ZSM-5 containing one CD3OH per zeolite proton. The implication of this on the mechanism of catalytic methanol dehydration on HZSM-5 is discussed.

In recent years, new methods of generating continuum mid-infrared pulses through filamentation in gases have been developed for ultrafast time-resolved infrared vibrational spectroscopy. The generated infrared pulses can have thousands of wavenumbers of bandwidth, spanning the entire mid-IR region while retaining pulse length below 100 fs. This technology has had a significant impact on problems involving ultrafast structural dynamics in congested spectra with broad features, such as those found in aqueous solutions and molecules with strong intermolecular interactions. This study describes the recent advances in generating and characterizing these pulses and the practical aspects of implementing these sources for broadband detection in transient absorption and 2D IR spectroscopy.

The protonation behavior of zeolite Bronsted acidsites (BAS)in the presence of water is important for the performance of thesewidely used catalysts. Despite extensive study, the number of watermolecules necessary for deprotonation is not well understood, in largepart because experiments have been unable to access this information.In this work, we report experimental evidence for full deprotonationof the BAS in the presence of two or more water molecules, with adeprotonation energy of 1.6 kcal/mol. Linear IR absorption and 2DIR spectra were measured over a wide range of controlled hydrationlevels from 0.5 to 8.0 equivalents of H2O/Al at a constanttemperature. Distinct spectral signatures of the protonated BAS andexcess proton are identified, and their hydration dependence is analyzedquantitatively. Using the experiment as a benchmark, ab initio molecular dynamics simulations are reported that reproduce the experimentaltrends in the protonation state and IR spectra. The proton chargeposition and delocalization are quantified in clusters of 1-8H(2)O molecules using the recently developed rCEC method.This analysis provides insight into the proton structure in confinedwater clusters, showing that the excess charge remains relativelylocalized between two oxygen atoms across the hydration range.

Hydrogen bonding between water molecules and zeolite Bro̷nsted acid sites (BAS) has received much attention due to the significant influence of water on the adsorption and catalytic properties of these widely used porous materials. When a single water molecule is adsorbed at the BAS, the zeolite O-H stretch vibration decreases in frequency and splits into two extraordinarily broad bands peaked near 2500 and 2900 cm-1 in the infrared (IR) spectrum. This broad doublet feature is the predominant IR signature used to identify and interpret water-BAS H-bonding at low hydration levels, but the origin of the band splitting is not well understood. In this study, we used broadband two-dimensional infrared (2D IR) spectroscopy to investigate zeolite HZSM-5 prepared with a single water molecule per BAS. We find that the 2D IR spectrum is not explained by the most common interpretation of Fermi resonance coupling between the stretch and the bend of the BAS OH group, which predicts intense excited-state transitions that are absent from the experimental results. We present an alternative model of a double-well proton stretch potential, where the band splitting is caused by excited-state tunneling through the proton-transfer barrier. This one-dimensional model reproduces the basic experimental pattern of transition frequencies and amplitudes, suggesting that the doublet bands may originate from a highly anharmonic potential in which the excited state proton wave functions are delocalized over the H-bond between zeolite BAS and adsorbed H2O. Additional details about molecular orientation and coordination of the adsorbed water molecule are also resolved in the 2D IR spectroscopy.

We report the generation and characterization of microjoule level, broad bandwidth femtosecond pulses in the mid-infrared (MIR) using optical parametric amplification of continuum MIR seed pulses in GaSe. The signal (3 μm) and idler (6 μm) pulses have energies of 6 μJ and 3 μJ with bandwidths of ∼950 cm-1 and 650 cm-1 FWHM and pulse lengths of 34 fs and 80 fs. Broadband 2D IR spectra of O-H and N-H transitions are acquired with the signal beam demonstrating the capabilities of this source for cross peak and line shape measurements.

The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water—and often the water molecules themselves—to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular- and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and provide an outlook for prioritizing strategic research directions.

A molecular description of the structure and behavior of water confined in aluminosilicate zeolite pores is a crucial component for understanding zeolite acid chemistry under hydrous conditions. In this study, we use a combination of ultrafast two-dimensional infrared (2D IR) spectroscopy and ab initio molecular dynamics (AIMD) to study H2O confined in the pores of highly hydrated zeolite HZSM-5 (∼13 and ∼6 equivalents of H2O per Al atom). The 2D IR spectrum reveals correlations between the vibrations of both terminal and H-bonded O-H groups and the continuum absorption of the excess proton. These data are used to characterize the hydrogen-bonding network within the cluster by quantifying single-, double-, and non-hydrogen-bond donor water molecules. These results are found to be in good agreement with the statistics calculated from an AIMD simulation of an H+(H2O)8 cluster in HZSM-5. Furthermore, IR spectral assignments to local O-H environments are validated with DFT calculations on clusters drawn from AIMD simulations. The simulations reveal that the excess charge is detached from the zeolite and resides near the more highly coordinated water molecules in the cluster. When they are taken together, these results unambiguously assign the complex IR spectrum of highly hydrated HZSM-5, providing quantitative information on the molecular environments and hydrogen-bonding topology of protonated water clusters under extreme confinement.

The aqueous proton is a common and long-studied species in chemistry, yet there is currently intense interest devoted to understanding its hydration structure and transport dynamics. Typically described in terms of two limiting structures observed in gas-phase clusters, the Zundel H5O2 + and Eigen H9O4 + ions, the aqueous structure is less clear due to the heterogeneity of hydrogen bonding environments and room-temperature structural fluctuations in water. The linear infrared (IR) spectrum, which reports on structural configurations, is challenging to interpret because it appears as a continuum of absorption, and the underlying vibrational modes are strongly anharmonically coupled to each other. Recent two-dimensional IR (2D IR) experiments presented strong evidence for asymmetric Zundel-like motifs in solution, but true structure-spectrum correlations are missing and complicated by the anharmonicity of the system. In this study, we employ high-level vibrational self-consistent field/virtual state configuration interaction calculations to demonstrate that the 2D IR spectrum reports on a broad distribution of geometric configurations of the aqueous proton. We find that the diagonal 2D IR spectrum around 1200 cm-1 is dominated by the proton stretch vibrations of Zundel-like and intermediate geometries, broadened by the heterogeneity of aqueous configurations. There is a wide distribution of multidimensional potential shapes for the proton stretching vibration with varying degrees of potential asymmetry and confinement. Finally, we find specific cross peak patterns due to aqueous Zundel-like species. These studies provide clarity on highly debated spectral assignments and stringent spectroscopic benchmarks for future simulations.

Ion pairing is a fundamental consideration in many areas of chemistry and has implications in a wide range of sciences and technologies that include batteries and organic photovoltaics. Ions in solution are known to inhabit multiple possible states, including free ions (FI), contact ion pairs (CIP), and solvent-separated ion pairs (SSIP). However, in solutions of organic radicals and nonmetal electrolytes, it is often difficult to distinguish between these states. In the first part of this work, we report evidence for the formation of SSIPs in low-polarity solvents and distinct measurements of CIP, SSIP, and FI, by using the ν(C≡N) infrared (IR) band of a nitrile-substituted fluorene radical anion. Use of time-resolved IR detection following pulse radiolysis allowed us to unambiguously assign the peak of the FI. In the presence of nonmetal electrolytes, two distinct red-shifted peaks were observed and assigned to the CIP and SSIP. The assignments are interpreted in the framework of the vibrational Stark effect (VSE) and are supported by (1) the solvent dependence of ion-pair populations, (2) the observation of a cryptand-separated sodium ion pair that mimics the formation of SSIPs, and (3) electronic structure calculations. In the second part of this work, we show that a blue-shift of the ν(C≡N) IR band due to the VSE can be induced in a nitrile-substituted fluorene radical anion by covalently tethering it to a metal-chelating ligand that forms an intramolecular ion pair upon reduction and complexation with sodium ion. This adds support to the conclusion that the shift in IR absorptions by ion pairing originates from the VSE. These results combined show that we can identify ion-pair structures by using the VSE, including the existence of SSIPs in a low-polarity solvent.

The hydrogenation rates of C=C and C=O bonds in methyl vinyl ketone and crotonaldehyde were measured over a series of silica-supported Pt-Re catalysts (1:1 atomic ratio of Pt/Re) in liquid water with H-2 (15psig) at 333K. The hydrogenation of methyl vinyl ketone did not produce any unsaturated alcohol because of the rapid hydrogenation of C=C relative to that of C=O. The addition of Re to Pt impacted the rate of C=C hydrogenation negatively in methyl vinyl ketone and crotonaldehyde, but promoted the selectivity of C=O hydrogenation in crotonaldehyde in which the unsaturated alcohol increased from 5% on Pt to 21% on Pt-Re. The addition of Re to Pt also promoted the rate of C=O hydrogenation in 2-butanone, whereas little effect was observed during the hydrogenation of butanal. The results of electron microscopy and H-2 chemisorption on the Pt-Re catalysts showed the increasing interaction between Pt and Re with the increasing metal weight loading, and results from rate measurements suggest that oxophilic Re can be used to promote the Pt-catalyzed hydrogenation of carbonyl groups in multifunctional molecules.

Rhenium substantially promotes the rate of Pt-catalyzed glycerol hydrogenolysis to propanediols and shifts the product selectivity from 1,2-propanediol to a mixture of 1,2 and 1,3-propanediols. This work presents experimental evidence for a tandem dehydration hydrogenation mechanism that occurs over a bifunctional Pt-Re catalyst. Infrared spectroscopy of adsorbed pyridine and the rate of aqueous-phase hydrolysis of propyl acetate were used to identify and quantify Bronsted acid sites associated with the Re component. Near-ambient-pressure XPS revealed a range of Re oxidation states on the Pt-Re catalysts after reduction in H-2 at 393 and 493 K, which accounts for the presence of Bronsted acidity. A mechanism involving acid-catalyzed dehydration followed by Pt-catalyzed hydrogenation was consistent with the negative influence of added base, a primary kinetic isotope effect with deuterated glycerol, an inverse isotope effect with dideuterium gas, and the observed orders of reaction.