Heterolytic C-H Activation Routes in Catalytic Dehydrogenation of Light Alkanes on Lewis Acid-Base Pairs at ZrO2 Surfaces.

Alkane dehydrogenation is an enabling route to make alkenes useful as chemical intermediates. This study demonstrates the high reactivity of Lewis acid-base (LAB) site pairs at ZrO2 powders for dehydrogenation of C2-C4 alkanes and the essential requirement for chemical treatments to remove strongly bound H2O and CO2 titrants to avoid the high temperatures required for their desorption and the concomitant loss of active sites through sintering and annealing of ZrO2 crystallites. The energies and free energies of bound intermediates and transition states from density functional theory (DFT), taken together with kinetic analysis and isotopic methods, demonstrated the kinetic relevance and heterolytic character of the first C-H activation at terminal C-atoms for all alkanes with a modest activation barrier (84 kJ mol-1) at essentially bare Zr-O LAB site pairs. ß-Hydride elimination from the formed alkyl carbanions lead to their desorption as alkene products in steps that are favored over their parallel C-C cleavage reactions (by 100 kJ mol-1), leading to high dehydrogenation selectivities (>98%) at the temperatures required for practical yields in such endothermic dehydrogenation reactions (700-900 K). The facile recombination of bound proton-hydride pairs then completes a dehydrogenation turnover. These findings provide compelling evidence for the remarkable reactivity and selectivity of LAB sites on earth-abundant oxides and for the need to uncover them through chemical treatments, which combine to give gravimetric dehydrogenation rates that exceed those on the toxic (Cr) or costly (Pt) catalysts used in practice.

Single-Atom Alloy Formation via Reaction-Driven Catalyst Restructuring.

We demonstrate that single-atom alloy catalysts can be made by exposing physical mixtures of monometallic supported Cu and Pd catalysts to vinyl acetate (VA) synthesis reaction conditions. This reaction induces the formation of mobile clusters of metal diacetate species that drive extensive metal nanoparticle restructuring, leading to atomic dispersion of the precious metal, smaller nanoparticle sizes than the parent catalysts, and high activity and selectivity for both VA synthesis and ethanol dehydrogenation reactions. This approach is scalable and appears to be generalizable to other alloy catalysts.

Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design.

The identification of thermodynamic descriptors of catalytic performance is essential for the rational design of heterogeneous catalysts. Here, we investigate how spillover energy, a descriptor quantifying whether intermediates are more stable at the dopant or host metal sites, can be used to design single-atom alloys (SAAs) for formic acid dehydrogenation. Using theoretical calculations, we identify NiCu as a SAA with favorable spillover energy and demonstrate that formate intermediates produced after the initial O-H activation are more stable at Ni sites where rate-determining C-H activation occurs. Surface science experiments demonstrated that NiCu(111) SAAs are more reactive than Cu(111) while they still follow the formate reaction pathway. However, reactor studies of silica-supported NiCu SAA nanoparticles showed only a modest improvement over Cu resulting from surface coverage effects. Overall, this study demonstrates the potential of engineering SAAs using spillover energy as a design parameter and highlights the importance of adsorbate-adsorbate interactions under steady-state operation.

A Combination of "Push Effect" Strategy with "Triple-Phase-Boundary Engineering" on Iron Porphyrin-Based MOFs: Enhanced Selectivity and Activity for Oxygen Reduction.

Herein, the "push effect" strategy combined with "triple-phase-boundary" (TPB) engineering was innovatively employed to target the single Fe-N4 sites in an iron porphyrin-based metal-organic framework, with axially coordinated 4-octylpyridine groups on Fe-N4 (named as PCN-224 (Fe)-1). The amphiphilic 4-octylpyridine groups donate sufficient electrons toward Fe-N4 by the Fe-N(pyridine) coordination bond and simultaneously provide effective TBP reactive sites by the hydrophobic octyl terminals, resulting in enhanced ORR activity of the PCN-224 (Fe)-1 in hydrophobic octyl terminals, with an E1/2 of 0.81 V and complete 4-electron selectivity. Furthermore, TPB engineering is utilized to construct the PCN-224 (Fe)-1-based Zn-air battery with a maximum power density of 98 mW cm-2, demonstrating great practical application potential for molecule-based ORR catalysts. Meanwhile, the "push effect" mechanism on ORR is revealed by electron paramagnetic resonance, in situ UV-vis spectroelectrochemical analysis, and density functional theory.

Dynamic Restructuring Induced Oxygen Activation on AgCu Near-Surface Alloys.

Recent studies have shown that the addition of Cu to Ag catalysts improves their epoxidation performance by increasing the overall selectivity of the bimetallic catalyst. We have prepared AgCu near-surface alloys and used scanning tunneling microscopy to gain an atomistic picture of O2 dissociation on the bimetallic system. These data reveal a higher dissociative sticking probability for O2 on AgCu than on Ag(111), and density functional theory (DFT) confirms that the O2 dissociation barrier is 0.17 eV lower on the alloy. Surprisingly, we find that, after a slow initial uptake of O2, the sticking probability increases exponentially. Further DFT calculations indicate that surface oxygen reverses the segregation energy for AgCu, stabilizing Cu atoms in the Ag layer. These single Cu atoms in the Ag surface are found to significantly lower the O2 dissociation barrier. Together, these results explain nonlinear effects in the activation of O2 on this catalytically relevant surface alloy.

Reactivity descriptors in acid catalysis: acid strength, proton affinity and host-guest interactions.

Brønsted acids mediate chemical transformations via proton transfer to bound species and interactions between the conjugate anion and bound cationic intermediates and transition states that are also stabilized by van der Waals forces within voids of molecular dimensions in inorganic hosts. This Feature Article describes the relevant descriptors of reactivity in terms of the properties of acids and molecules that determine their ability to donate and accept protons and to reorganize their respective charges to optimize their interactions at bound states. The deprotonation energy (DPE) of the acids and the protonation energy (Eprot) of the gaseous analogs of bound intermediates and transition states reflect their respective properties as species present at non-interacting distances. These properties accurately describe the reactivity of acids of a given type, such as polyoxometalates (POM) with a given type of addenda atom but different central atoms and heterosilicates, for different families of reactions. They do not fully capture, however, differences among acid types (e.g., Mo and W POM, heterosilicates, mineral acids) for diverse types of chemical transformations (e.g., elimination, isomerization, dimerization, condensation). The incompleteness of such descriptors reflects their inability to describe how protonated molecular species and conjugate anions restructure their respective charges when present as a binding pair at interacting distances. Such interaction energies represent electrostatic forces that depend on charge distributions in the cations and anions and the ability to reorganize the distributions to maximize the interactions. In the case of deprotonation, the electrostatic and charge reorganization components of DPE for various acids solely reflect the ability of the conjugate anion to accept and distribute the negative charge, a characteristic unique of each type of solid acid and specifically of the composition of its extended conjugate anion framework. The energy required to accept and rearrange the positive charge in bound intermediates and transition states reflects, in turn, their respective ability to recover the ionic and covalent components of DPE, the energy required to detach proton from conjugate anions. The DPE components and the recovery fractions together lead to a modified DPE, which captures only the part of DPE that remains unrecovered by the ion-pair interactions at bound intermediates and transition states, as the unifying descriptor for broad families of acids and reactions. The electrostatic and charge reorganization energies involved in these general descriptors are placed in historical context by assessing their connections to the heuristics of hard-soft acid-base displacements. Further development of these concepts requires benchmarking and extension of electrostatic and reorganization components of energies for a more diverse set of reaction types and acid families and advancement of methods for more efficient calculations of electrostatic interactions. Reactivity descriptors must also account for dispersive interactions between host cavities and guest molecules, requiring a framework analogous to the one described here for ion-pair interactions; these dispersive interactions depend on the fit between their shapes and sizes as well as their "structural stiffness" that determines the ability to modify the shapes of molecules and voids to minimize free energy. Entropy considerations and estimates of their dependence on properties of catalysts and molecules are also required for accurately determining Gibbs free energies that ultimately determine reaction rates.

Multifunctional Photostable Nanocomplex of ZnO Quantum Dots and Avobenzone via the Promotion of Enolate Tautomer.

Ideal multifunctional ultraviolet radiation (UVR) absorbents with excellent photostability, high molar absorptivity, broadband UVR screening, and desired skin sensorial properties remain a significant challenge for the sunscreen industry. The potential of the nanocomplex (NCx) formed by microwave synthesis of ZnO quantum dots (QDs) in the presence of Avobenzone (Av) for achieving these goals is reported. The NCx exhibits unique synergy between ZnO QD and Av components, which enhances the photostability and molar absorptivity, extends UVA filtering range, and provides a visible emission that matches the typical human in vivo skin emission color. Density functional theory (DFT) and time-dependent DFT calculations of ZnO-Av hybrid structures and comparison of their spectroscopic features with experiments suggest that ZnO QDs catalyze the formation of highly photostable surface enolate species via aldol condensation reaction. The combination of experiments and computations used in this study can advance the science and technology of photoprotection.

Ionic and covalent stabilization of intermediates and transition states in catalysis by solid acids.

Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Brønsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POM clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE-reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born-Haber thermochemical cycles indicate that these differences reflect more effective charge reorganization upon deprotonation of Mo than W POM clusters and the much weaker reorganization in mineral acids. Such covalency is disrupted upon deprotonation but cannot be recovered fully upon formation of ion pairs at transition states. Predictive descriptors of reactivity for general classes of acids thus require separate assessments of the covalent and ionic DPE components. Here, we describe methods to estimate electrostatic interactions, which, taken together with energies derived from density functional theory, give the covalent and ionic energy components of protons, intermediates, and transition states. In doing so, we provide a framework to predict the reactive properties of protons for chemical reactions mediated by ion-pair transition states.

Influence of dipole-dipole interactions on coverage-dependent adsorption: CO and NO on Pt(111).

Density functional theory (DFT) calculations of energetic, geometric, vibrational, and electrostatic properties of different arrangements of CO and NO at quarter and half monolayer coverage on Pt(111) are presented. Differences in the extents of electron back-donation from the Pt surface to these molecules cause the low-coverage adsorbate dipoles to have opposite signs at atop and more highly coordinated bridge or fcc sites. These dipoles of opposite sign occupy adjacent positions in the experimentally observed atop-bridge or atop-fcc high -coverage arrangements, leading to attractive electrostatic interactions and concomitant changes in dipole moments, bond lengths, and vibrational frequencies. The interaction energies are estimated by charge partitioning to extract individual dipoles from the mixed arrangement and by calculations of field-dipole interactions. These estimated dipole interactions contribute significantly (20-60%) to the DFT-calculated relative stability of mixed arrangements over atop-, bridge-, or fcc-only arrangements and thus play an important role in coverage-dependent adsorption. We further extend these analyses to a range of molecules with varying dipole moments and show that the general nature of these interactions is not limited to CO and NO.

Direct control of electron transfer to the surface-CO bond on a Pt/TiO2 catalytic diode.

We study CO adsorption on a multilayer catalytic diode in which electron transfer at the metal-semiconductor (Pt/TiO(2)) junction is controlled by an applied external voltage. The multilayer diode structure enhances infrared absorption signals from CO molecules adsorbed on the small area Pt surface. We find that the diode behaves like a Schottky junction and that changes in electron transfer at the junction are directly correlated with reversible shifts in the vibrational frequency of adsorbed CO. Infrared polarization and incidence angle dependent studies show that the magnitude of vibrational frequency shift varies with orientation of the molecules being probed and increases with proximity to the Pt/TiO(2) interface. The results demonstrate the ability to control the metal-adsorbate bond through external electronic modifications of a metal-support junction. The catalytic diode can potentially provide control of the surface chemical bond by an external voltage, providing a new approach for investigations in heterogeneous catalysis, sensors, and plasmonic devices.