Achieving Ultra-High Selectivity to Hydrogen Production from Formic Acid on Pd-Ag Alloys.

Palladium-silver-based alloy catalysts have a great potential for CO-free hydrogen production from formic acid for fuel cell applications. However, the structural factors affecting the selectivity of formic acid decomposition are still debated. Herein, the decomposition pathways of formic acid on Pd-Ag alloys with different atomic configurations have been investigated to identify the alloy structures yielding high H2 selectively. Several PdxAg1-x surface alloys with various compositions were generated on a Pd(111) single crystal; their atomic distribution and electronic structure were determined by a combination of infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). It was established that the Ag atoms with Pd neighbors are electronically altered, and the degree of alteration correlates with the number of nearest Pd. Temperature-programmed reaction spectroscopy (TPRS) and DFT demonstrated that the electronically altered Ag domains create a new reaction pathway that selectively dehydrogenates formic acid. In contrast, Pd monomers surrounded by Ag are demonstrated to have a similar reactivity compared to pristine Pd(111), yielding CO and H2O in addition to the dehydrogenation products. However, they bind to the produced CO weaker than pristine Pd, demonstrating an enhancement in resistance to CO poisoning. This work therefore shows that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition of formic acid, while surface Pd atoms are detrimental to selectivity. Hence, the decomposition pathways can be tailored for CO-free H2 production on Pd-Ag alloy systems.

Direct Observation of Solvent-Reaction Intermediate Interactions in Heterogeneously Catalyzed Alcohol Coupling.

The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. Herein, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol self-coupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.

Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti-Cu Catalysts.

The dissociation of H2 is an essential elementary step in many industrial chemical transformations, typically requiring precious metals. Here, we report a hierarchical nanoporous Cu catalyst doped with small amounts of Ti (npTiCu) that increases the rate of H2-D2 exchange by approximately one order of magnitude compared to the undoped nanoporous Cu (npCu) catalyst. The promotional effect of Ti was measured via steady-state H2-D2 exchange reaction experiments under atmospheric pressure flow conditions in the temperature range of 300-573 K. Pretreatment with flowing H2 is required for stable catalytic performance, and two temperatures, 523 and 673 K, were investigated. The experimentally determined H2-D2 exchange rate is 5-7 times greater for npTiCu vs the undoped Cu material under optimized pretreatment and reaction temperatures. The H2 pretreatment leads to full reduction of Cu oxide and partial reduction of surface Ti oxide species present in the as-prepared catalyst as demonstrated using in situ ambient pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The apparent activation energies and pre-exponential factors measured for H2-D2 exchange are substantially different for Ti-doped vs undoped npCu catalysts. Density functional theory calculations suggest that isolated, metallic Ti atoms on the surface of the Cu host can act as the active surface sites for hydrogen recombination. The increase in the rate of exchange above that of pure Cu is caused primarily by a shift in the rate-determining step from dissociative adsorption on Cu to H/D atom recombination on Ti-doped Cu, with the corresponding decrease in activation entropy that it produces.

Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites.

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition, and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts─in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity─are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag, and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. The integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu.

With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces serves as a prototype for comparing experiment and theory. Previously measured pre-exponential factors for CO2 formation from formate on metal surfaces, including Cu(110), are substantially higher than expected from the often used value of k B T/h, or ∼6 × 1012 s-1, suggesting that the entropy of the transition state is higher than that of the adsorbed formate. Herein, the rate constant parameters for formate decomposition on Au(110) and Cu(110) are addressed quantitatively by both experiment and theory and compared. A pre-exponential factor of 2.3 × 1014 s-1 was obtained experimentally on Au(110). DFT calculations revealed the most stable configuration of formate on both surfaces to be bidentate and the transition states to be less rigidly bound to the surface compared to the reactant state, resulting in a higher entropy of activation and a pre-exponential factor exceeding k B T/h. Though reasonable agreement is obtained between experiment and theory for the pre-exponential factors, the activation energies determined experimentally remain consistently higher than those computed by DFT using the GGA-PBE functional. This difference was largely erased when the metaGGA-SCAN functional was applied. This study provides insight into the underlying factors that result in the relatively high pre-exponential factors for unimolecular decomposition on metal surfaces generally, highlights the importance of mobility for the transition state, and offers vital information related to the direct use of DFT to predict rate constants for elementary reaction steps on metal surfaces.

Facilitating hydrogen atom migration via a dense phase on palladium islands to a surrounding silver surface.

The migration of species across interfaces can crucially affect the performance of heterogeneous catalysts. A key concept in using bimetallic catalysts for hydrogenation is that the active metal supplies hydrogen atoms to the host metal, where selective hydrogenation can then occur. Herein, we demonstrate that, following dihydrogen dissociation on palladium islands, hydrogen atoms migrate from palladium to silver, to which they are generally less strongly bound. This migration is driven by the population of weakly bound states on the palladium at high hydrogen atom coverages which are nearly isoenergetic with binding sites on the silver. The rate of hydrogen atom migration depends on the palladium-silver interface length, with smaller palladium islands more efficiently supplying hydrogen atoms to the silver. This study demonstrates that hydrogen atoms can migrate from a more strongly binding metal to a more weakly binding surface under special conditions, such as high dihydrogen pressure.

Evolution of Metastable Structures at Bimetallic Surfaces from Microscopy and Machine-Learning Molecular Dynamics.

The restructuring of interfaces plays a crucial role in materials science and heterogeneous catalysis. Bimetallic systems, in particular, often adopt very different compositions and morphologies at surfaces compared to the bulk. For the first time, we reveal a detailed atomistic picture of long-time scale restructuring of Pd deposited on Ag using microscopy, spectroscopy, and novel simulation methods. By developing and performing accelerated machine-learning molecular dynamics followed by an automated analysis method, we discover and characterize previously unidentified surface restructuring mechanisms in an unbiased fashion, including Pd-Ag place exchange and Ag pop-out as well as step ascent and descent. Remarkably, layer-by-layer dissolution of Pd into Ag is always preceded by an encapsulation of Pd islands by Ag, resulting in a significant migration of Ag out of the surface and a formation of extensive vacancy pits within a period of microseconds. These metastable structures are of vital catalytic importance, as Ag-encapsulated Pd remains much more accessible to reactants than bulk-dissolved Pd. Our approach is broadly applicable to complex multimetallic systems and enables the previously intractable mechanistic investigation of restructuring dynamics at atomic resolution.

Hydrogen migration at restructuring palladium-silver oxide boundaries dramatically enhances reduction rate of silver oxide.

Heterogeneous catalysts are complex materials with multiple interfaces. A critical proposition in exploiting bifunctionality in alloy catalysts is to achieve surface migration across interfaces separating functionally dissimilar regions. Herein, we demonstrate the enhancement of more than 104 in the rate of molecular hydrogen reduction of a silver surface oxide in the presence of palladium oxide compared to pure silver oxide resulting from the transfer of atomic hydrogen from palladium oxide islands onto the surrounding surface formed from oxidation of a palladium-silver alloy. The palladium-silver interface also dynamically restructures during reduction, resulting in silver-palladium intermixing. This study clearly demonstrates the migration of reaction intermediates and catalyst material across surface interfacial boundaries in alloys with a significant effect on surface reactivity, having broad implications for the catalytic function of bimetallic materials.

Predicting a Sharp Decline in Selectivity for Catalytic Esterification of Alcohols from van der Waals Interactions.

Controlling the selectivity of catalytic reactions is a critical aspect of improving energy efficiency in the chemical industry; thus, predictive models are of key importance. Herein the performance of a heterogeneous, nanoporous Au catalyst is predicted for the complex catalytic self-coupling of the series of C2 -C4 alkyl alcohols, based solely on the known kinetics of the elementary steps of the catalytic cycle for methanol coupling, using scaling methods augmented by density functional theory. Notably, a sharp decrease in selectivity for ester formation with increasing molecular weight to favor the aldehyde due to van der Waals interactions of reaction intermediates with the surface was predicted and subsequently verified quantitatively by experiment. Further, the agreement between theory and experiment clearly demonstrates the efficacy of this approach for building a predictive model of catalytic behavior for a homologous set of reactants using a small set of experimental information.

Growth and auto-oxidation of Pd on single-layer AgOx/Ag(111).

We investigated the growth and auto-oxidation of Pd deposited onto a AgOx single-layer on Ag(111) using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Palladium initially grows as well-dispersed, single-layer clusters that adopt the same triangular shape and orientation of Agn units in the underlying AgOx layer. Bi-layer clusters preferentially form upon increasing the Pd coverage to ∼0.30 ML (monolayer) and continue to develop until aggregating and forming a nearly conformal Pd bi-layer at a coverage near 2 ML. Analysis of the STM images provides quantitative evidence of a transition from single to bi-layer Pd growth on the AgOx layer, and a continuation of bi-layer growth with increasing Pd coverage from ∼0.3 to 2 ML. XPS further demonstrates that the AgOx layer efficiently transfers oxygen to Pd at 300 K, and that the fraction of Pd that oxidizes is approximately equal to the local oxygen coverage in the AgOx layer for Pd coverages up to at least ∼0.7 ML. Our results show that oxygen in the initial AgOx layer mediates the growth and structural properties of Pd on the AgOx/Ag(111) surface, enabling the preparation of model PdAg surfaces with uniformly distributed single or bi-layer Pd clusters. Facile auto-oxidation of Pd by AgOx further suggests that oxygen transfer from Ag to Pd could play a role in promoting oxidation chemistry of adsorbed molecules on PdAg surfaces.

Enhancing catalytic performance of dilute metal alloy nanomaterials.

Dilute alloys are promising materials for sustainable chemical production; however, their composition and structure affect their performance. Herein, a comprehensive study of the effects of pretreatment conditions on the materials properties of Pd0.04Au0.96 nanoparticles partially embedded in porous silica is related to the activity for catalytic hydrogenation of 1-hexyne to 1-hexene. A combination of in situ characterization and theoretical calculations provide evidence that changes in palladium surface content are induced by treatment in oxygen, hydrogen and carbon monoxide at various temperatures. In turn, there are changes in hydrogenation activity because surface palladium is necessary for H2 dissociation. These Pd0.04Au0.96 nanoparticles in the porous silica remain structurally intact under many cycles of activation and deactivation and are remarkably resistant to sintering, demonstrating that dilute alloy catalysts are highly dynamic systems that can be tuned and maintained in a active state.

Tuning reactivity layer-by-layer: formic acid activation on Ag/Pd(111).

The potential for tuning the electronic structure of materials to control reactivity and selectivity in heterogenous catalysis has driven interest in ultrathin metal films which may differ from their bulk form. Herein, a 1-atomic layer Ag film on Pd(111) (Ag/Pd(111)) is demonstrated to have dramatically different reactivity towards formic acid compared to bulk Ag. Formic acid decomposition is of interest as a source of H2 for fuel cell applications and modification of Pd by Ag reduces poisoning by CO and increases the selectivity for H2 formation. Formic acid reacts below room temperature on the 1-atomic layer Ag film, whereas no reaction occurs on pristine bulk Ag. Notably, 2 monolayer films of Ag again become unreactive towards formic acid, indicating a reversion to bulk behavior. A combination of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) was used to establish that the Ag monolayer is continuous and electronically modified compared to bulk Ag. The work establishes a demonstration of the altered electronic structure of Ag monolayers on Pd(111) and an associated change in reactivity. The effect on reactivity only persists for the first layer, demonstrating the need for precise control of materials to exploit the modification in electronic properties.

Spatially Nonuniform Reaction Rates during Selective Oxidation on Gold.

The nonuniform reactivity of adsorbed oxygen during the selective oxidation of methanol on Au(110)-(1×2) was demonstrated using in situ scanning tunneling microscopy (STM), establishing the importance of both atomic and mesoscale structure in determining reaction kinetics. At coverages above 0.06 ML, oxygen consumption occurs preferentially along [11̅0] direction, creating local regions completely devoid of oxygen between oxygen islands. The directionally specific reactivity is attributed to a combination of the weaker binding of oxygen atoms at chain termini and the release of surface strain induced by O bonding to Au. The generality of this phenomenon is illustrated by analogous, but kinetically contrasting behavior, for reaction of 2-propanol with oxygen covered Au(110)-(1×2). Even at low O coverages, there are structurally related changes in the reactivity for the reaction with methanol. With decreasing O coverage, a slow reaction period is followed by a fast reaction period, the latter starting when oxygen coverage decreases to ∼0.06 monolayer, independent of the initial coverage. This increase in reactivity is attributed to a sudden destabilization of the island structure. These results demonstrate that both local and mesocale structures can affect reactivity.

Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110).

The relative stability of carboxylates on Au(110) was investigated as part of a comprehensive study of adsorbate binding on Group IB metals that can be used to predict and understand how to control reactivity in heterogeneous catalysis. The binding efficacy of carboxylates is only weakly dependent on alkyl chain length for relatively short-chain molecules, as demonstrated using quantitative temperature-programmed reaction spectroscopy. Corresponding density functional theory (DFT) calculations demonstrated that the bidentate anchoring geometry is rigid and restricts the amount of additional stabilization through adsorbate-surface van der Waals (vdW) interactions which control stability for alkoxides. A combination of scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) shows that carboxylates form dense local islands on Au(110). Complementary DFT calculations demonstrate that adsorbate-adsorbate interactions provide additional stabilization that increases as a function of alkyl chain length for C2 and C3 carboxylates. Hence, overall stability is generally a function of the anchoring group to the surface and the inter-adsorbate interaction. This study demonstrates the importance of these two important factors in describing binding of key catalytic intermediates.

New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica.

A highly modular synthesis of designed catalysts with controlled bimetallic nanoparticle size and composition and a well-defined structural hierarchy is demonstrated. Exemplary catalysts-bimetallic dilute Ag-in-Au nanoparticles partially embedded in a porous SiO2 matrix (SiO2 -Agx Auy )-were synthesized by the decoration of polymeric colloids with the bimetallic nanoparticles followed by assembly into a colloidal crystal backfilled with the matrix precursor and subsequent removal of the polymeric template. This work reports that these new catalyst architectures are significantly better than nanoporous dilute AgAu alloy catalysts (nanoporous Ag3 Au97 ) while retaining a clear predictive relationship between their surface reactivity with that of single-crystal Au surfaces. This paves the way for broadening the range of new catalyst architectures required for translating the designed principles developed under controlled conditions to designed catalysts under operating conditions for highly selective coupling of alcohols to form esters. Excellent catalytic performance of the porous SiO2 -Agx Auy structure for selective oxidation of both methanol and ethanol to produce esters with high conversion efficiency, selectivity, and stability was demonstrated, illustrating the ability to translate design principles developed for support-free materials to the colloid-templated structures. The synthetic methodology reported is customizable for the design of a wide range of robust catalytic systems inspired by design principles derived from model studies. Fine control over the composition, morphology, size, distribution, and availability of the supported nanoparticles was demonstrated.

O2 Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts.

The activation of O2 on metal surfaces is a critical process for heterogeneous catalysis and materials oxidation. Fundamental studies of well-defined metal surfaces using a variety of techniques have given crucial insight into the mechanisms, energetics, and dynamics of O2 adsorption and dissociation. Here, trends in the activation of O2 on transition metal surfaces are discussed, and various O2 adsorption states are described in terms of both electronic structure and geometry. The mechanism and dynamics of O2 dissociation are also reviewed, including the importance of the spin transition. The reactivity of O2 and O toward reactant molecules is also briefly discussed in the context of catalysis. The reactivity of a surface toward O2 generally correlates with the adsorption strength of O, the tendency to oxidize, and the heat of formation of the oxide. Periodic trends can be rationalized in terms of attractive and repulsive interactions with the d-band, such that inert metals tend to feature a full d band that is low energy and has a large spatial overlap with adsorbate states. More open surfaces or undercoordinated defect sites can be much more reactive than close-packed surfaces. Reactions between O and other species tend to be more prevalent than reactions between O2 and other species, particularly on more reactive surfaces.

Water facilitates oxygen migration on gold surfaces.

The water-oxygen-gold interface is important in many surface processes and has potential influence on heterogeneous catalysis. Herein, it is shown that water facilitates the migration of atomic oxygen on Au(110), demonstrating the dynamic nature of surface adsorption. We demonstrate this effect for the first time, using in situ scanning tunnelling microscopy (STM), temperature-programmed reaction spectroscopy (TPRS) and first-principles theoretical calculations. The dynamic interaction of water with adsorbed O maintains a high dispersion of O on the surface, potentially creating reactive transient species. At low temperature and pressure, isotopic experiments show that adsorbed oxygen on the Au(110) surface exchanges with oxygen in H218O. The presence of water modulates local electronic properties and facilitates oxygen exchange. Combining experimental results and theory, we propose that hydroxyl is transiently formed via proton transfer from the water to adsorbed oxygen. Hydroxyl groups easily recombine to regenerate water and adsorbed oxygen atoms, the net result of which is migration of the adsorbed oxygen without significant change in its overall distribution on the surface. The presence of water creates a dynamic surface where mobile surface oxygen atoms and hydroxyls are present, which can lead to a better performance of gold catalysis in oxidation reactions.

General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces.

The critical role of noncovalent van der Waals (vdW) interactions in determining the relative thermodynamic stability of alkoxy intermediates has been demonstrated for the Cu(110) surface using a combination of experiment and theory. The results may be significant for the selectivity control of copper-based reactions of alcohols. Previous examination of this effect on Au(110) was also extended to include higher molecular weight alcohols; on Cu(110) and Au(110) the hierarchy for the strength of binding of the alkoxys was found to be the same within experimental accuracy, with alkoxy species of greater chain length being more stable. The equilibrium constants governing the competition of alcohol pairs for binding sites of the alkoxys are also similar on the two surfaces. These results reveal the generality of such vdW effects. This work expands the understanding of the role of vdW interactions on the binding efficacy of key reactive intermediates on metal surfaces, a key factor in the rational design of complex and selective catalytic processes.

Dynamic restructuring drives catalytic activity on nanoporous gold-silver alloy catalysts.

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver-gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changes occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.