Heterogeneous Trimetallic Nanoparticles as Catalysts.

The development and application of trimetallic nanoparticles continues to accelerate rapidly as a result of advances in materials design, synthetic control, and reaction characterization. Following the technological successes of multicomponent materials in automotive exhausts and photovoltaics, synergistic effects are now accessible through the careful preparation of multielement particles, presenting exciting opportunities in the field of catalysis. In this review, we explore the methods currently used in the design, synthesis, analysis, and application of trimetallic nanoparticles across both the experimental and computational realms and provide a critical perspective on the emergent field of trimetallic nanocatalysts. Trimetallic nanoparticles are typically supported on high-surface-area metal oxides for catalytic applications, synthesized via preparative conditions that are comparable to those applied for mono- and bimetallic nanoparticles. However, controlled elemental segregation and subsequent characterization remain challenging because of the heterogeneous nature of the systems. The multielement composition exhibits beneficial synergy for important oxidation, dehydrogenation, and hydrogenation reactions; in some cases, this is realized through higher selectivity, while activity improvements are also observed. However, challenges related to identifying and harnessing influential characteristics for maximum productivity remain. Computation provides support for the experimental endeavors, for example in electrocatalysis, and a clear need is identified for the marriage of simulation, with respect to both combinatorial element screening and optimal reaction design, to experiment in order to maximize productivity from this nascent field. Clear challenges remain with respect to identifying, making, and applying trimetallic catalysts efficiently, but the foundations are now visible, and the outlook is strong for this exciting chemical field.

Integrated workflows and interfaces for data-driven semi-empirical electronic structure calculations.

Modern software engineering of electronic structure codes has seen a paradigm shift from monolithic workflows toward object-based modularity. Software objectivity allows for greater flexibility in the application of electronic structure calculations, with particular benefits when integrated with approaches for data-driven analysis. Here, we discuss different approaches to create deep modular interfaces that connect big-data workflows and electronic structure codes and explore the diversity of use cases that they can enable. We present two such interface approaches for the semi-empirical electronic structure package, DFTB+. In one case, DFTB+ is applied as a library and provides data to an external workflow; in another, DFTB+receives data via external bindings and processes the information subsequently within an internal workflow. We provide a general framework to enable data exchange workflows for embedding new machine-learning-based Hamiltonians within DFTB+ or enabling deep integration of DFTB+ in multiscale embedding workflows. These modular interfaces demonstrate opportunities in emergent software and workflows to accelerate scientific discovery by harnessing existing software capabilities.

Fundamental Structural and Electronic Understanding of Palladium Catalysts on Nitride and Oxide Supports.

The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single-atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non-metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non-metal and metal oxide). Through thorough oxidation state investigations by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), CO-DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd-N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity.

Methanol synthesis from CO2 and H2 using supported Pd alloy catalysts.

A number of Pd based materials have been synthesised and evaluated as catalysts for the conversion of carbon dioxide and hydrogen to methanol, a useful platform chemical and hydrogen storage molecule. Monometallic Pd catalysts show poor methanol selectivity, but this is improved through the formation of Pd alloys, with both PdZn and PdGa alloys showing greatly enhanced methanol productivity compared with monometallic Pd/Al2O3 and Pd/TiO2 catalysts. Catalyst characterisation shows that the 1 : 1 ß-PdZn alloy is present in all Zn containing post-reaction samples, including PdZn/Ga2O3, with the Pd2Ga alloy formed for the Pd/Ga2O3 sample. The heat of mixing was calculated for a variety of alloy compositions with high values determined for both PdZn and Pd2Ga alloys, at ca. -0.6 eV per atom and ca. -0.8 eV per atom, respectively. However, ZnO is more readily reduced than Ga2O3, providing a possible explanation for the preferential formation of the PdZn alloy, rather than PdGa, when in the presence of Ga2O3.

Computational infrared and Raman spectra by hybrid QM/MM techniques: a study on molecular and catalytic material systems.

Vibrational spectroscopy is one of the most well-established and important techniques for characterizing chemical systems. To aid the interpretation of experimental infrared and Raman spectra, we report on recent theoretical developments in the ChemShell computational chemistry environment for modelling vibrational signatures. The hybrid quantum mechanical and molecular mechanical approach is employed, using density functional theory for the electronic structure calculations and classical forcefields for the environment. Computational vibrational intensities at chemical active sites are reported using electrostatic and fully polarizable embedding environments to achieve more realistic vibrational signatures for materials and molecular systems, including solvated molecules, proteins, zeolites and metal oxide surfaces, providing useful insight into the effect of the chemical environment on the signatures obtained from experiment. This work has been enabled by the efficient task-farming parallelism implemented in ChemShell for high-performance computing platforms.  This article is part of a discussion meeting issue 'Supercomputing simulations of advanced materials'.

The application of QM/MM simulations in heterogeneous catalysis.

The QM/MM simulation method is provenly efficient for the simulation of biological systems, where an interplay of extensive environment and delicate local interactions drives a process of interest through a funnel on a complex energy landscape. Recent advances in quantum chemistry and force-field methods present opportunities for the adoption of QM/MM to simulate heterogeneous catalytic processes, and their related systems, where similar intricacies exist on the energy landscape. Herein, the fundamental theoretical considerations for performing QM/MM simulations, and the practical considerations for setting up QM/MM simulations of catalytic systems, are introduced; then, areas of heterogeneous catalysis are explored where QM/MM methods have been most fruitfully applied. The discussion includes simulations performed for adsorption processes in solvent at metallic interfaces, reaction mechanisms within zeolitic systems, nanoparticles, and defect chemistry within ionic solids. We conclude with a perspective on the current state of the field and areas where future opportunities for development and application exist.

Multiscale QM/MM modelling of catalytic systems with ChemShell.

Hybrid quantum mechanical/molecular mechanical (QM/MM) methods are a powerful computational tool for the investigation of all forms of catalysis, as they allow for an accurate description of reactions occurring at catalytic sites in the context of a complicated electrostatic environment. The scriptable computational chemistry environment ChemShell is a leading software package for QM/MM calculations, providing a flexible, high performance framework for modelling both biomolecular and materials catalysis. We present an overview of recent applications of ChemShell to problems in catalysis and review new functionality introduced into the redeveloped Python-based version of ChemShell to support catalytic modelling. These include a fully guided workflow for biomolecular QM/MM modelling, starting from an experimental structure, a periodic QM/MM embedding scheme to support modelling of metallic materials, and a comprehensive set of tutorials for biomolecular and materials modelling.

Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts.

In this review, we discuss selected examples from recent literature on the role of the support on directing the nanostructures of Au-based monometallic and bimetallic nanoparticles. The role of support is then discussed in relation to the catalytic properties of Au-based monometallic and bimetallic nanoparticles using different gas phase and liquid phase reactions. The reactions discussed include CO oxidation, aerobic oxidation of monohydric and polyhydric alcohols, selective hydrogenation of alkynes, hydrogenation of nitroaromatics, CO2 hydrogenation, C-C coupling, and methane oxidation. Only studies where the role of support has been explicitly studied in detail have been selected for discussion. However, the role of support is also examined using examples of reactions involving unsupported metal nanoparticles (i.e., colloidal nanoparticles). It is clear that the support functionality can play a crucial role in tuning the catalytic activity that is observed and that advanced theory and characterization add greatly to our understanding of these fascinating catalysts.

A computational study of direct CO2 hydrogenation to methanol on Pd surfaces.

The reaction mechanism of direct CO2 hydrogenation to methanol is investigated in detail on Pd (111), (100) and (110) surfaces using density functional theory (DFT), supporting investigations into emergent Pd-based catalysts. Hydrogen adsorption and surface mobility are firstly considered, with high-coordination surface sites having the largest adsorption energy and being connected by diffusion channels with low energy barriers. Surface chemisorption of CO2, forming a partially charged CO2δ-, is weakly endothermic on a Pd (111) whilst slightly exothermic on Pd (100) and (110), with adsorption enthalpies of 0.09, -0.09 and -0.19 eV, respectively; the low stability of CO2δ- on the Pd (111) surface is attributed to negative charge accumulating on the surface Pd atoms that interact directly with the CO2δ- adsorbate. Detailed consideration for sequential hydrogenation of the CO2 shows that HCOOH hydrogenation to H2COOH would be the rate determining step in the conversion to methanol, for all surfaces, with activation barriers of 1.41, 1.51, and 0.84 eV on Pd (111), (100) and (110) facets, respectively. The Pd (110) surface exhibits overall lower activation energies than the most studied Pd (111) and (100) surfaces, and therefore should be considered in more detail in future Pd catalytic studies.

Dehydrogenation and dehydration of formic acid over orthorhombic molybdenum carbide.

The dehydrogenation and dehydration of formic acid is investigated on the ß-Mo2C (100) catalyst surface using time independent density functional theory. The energetics of the two mechanisms are calculated, and the thermochemistry and kinetics are discussed using the transition state theory. Subsequently, microkinetic modelling of the system is conducted, considering the batch reactor model. The potential energy landscape of the reaction shows a thermodynamically favourable cleavage of H-COOH to form CO; however, the kinetics show that the dehydrogenation mechanism is faster and CO2 is continuously formed. The effect of HCOOH adsorption on the surface is also analysed, in a temperature-programmed desorption, with the conversion proceeding at under 350 K and desorption of CO2 is observed with a selectivity of about 100 %, in line with the experimental reports.

A combined periodic DFT and QM/MM approach to understand the radical mechanism of the catalytic production of methanol from glycerol.

The production of methanol from glycerol over a basic oxide, such as MgO, using high reaction temperatures (320 °C) is a promising new approach to improving atom efficiency in the production of biofuels. The mechanism of this reaction involves the homolytic cleavage of the C3 feedstock, or its dehydration product hydroxyacetone, to produce a hydroxymethyl radical species which can then abstract an H atom from other species. Obtaining a detailed reaction mechanism for this type of chemistry is difficult due to the large number of products present when the system is operated at high conversions. In this contribution we show how DFT based modelling studies can provide new insights into likely reaction pathways, in particular the source of H atoms for the final step of converting hydroxymethyl radicals to methanol. We show that water is unlikely to be important in this stage of the process, C-H bonds of C2 and C3 species can give an energetically favourable pathway and that the disproportionation of hydroxymethyl radicals to methanol and formaldehyde produces a very favourable route. Experimental analysis of reaction products confirms the presence of formaldehyde. The calculations presented in this work also provide new insight into the role of the catalyst surface in the reaction showing that the base sites of the MgO(100) are able to deprotonate hydroxymethyl radicals but not methanol itself. In carrying out the calculations we also show how periodic DFT and QM/MM approaches can be used together to obtain a rounded picture of molecular adsorption to surfaces and homolytic bond cleavage which are both central to the reactions studied.

QM/MM study of the stability of dimethyl ether in zeolites H-ZSM-5 and H-Y.

The methanol-to-hydrocarbons (MTH) process transforms C1 carbon sources to higher hydrocarbons, but details of the mechanism that leads to the formation of the first carbon-carbon bond remain unclear. Here, we present a computational investigation of how a crucial intermediate, dimethyl ether (DME), interacts with different zeolite catalysts (H-ZSM-5, H-Y) to gain insight into the initial stages in the MTH process. We use QM/MM computational simulations to model the conversion of methanol to DME in H-ZSM-5, which is a well characterised and important reaction intermediate. We analyse and compare the stability of DME on several acid sites in H-ZSM-5 and H-Y, and show that the more acidic and open "intersection sites" in the H-ZSM-5 framework are able to bond strongest with DME, with complete deprotonation of the acid site occurring. The conversion of methanol to DME in H-ZSM-5 is calculated as requiring a higher activation energy than framework methoxylation, which indicates that a stepwise (indirect) mechanism, through a methoxy intermediate, is the most likely route to DME formation during the initiation of the MTH process.

A computational study of the properties of low- and high-index Pd, Cu and Zn surfaces.

We report a detailed Density Functional Theory (DFT) based investigation of the structure and stability of bulk and surface structures for the Group 10-12 elements Pd, Cu and Zn, considering the effect of the choice of exchange-correlation density functional and computation parameters. For the initial bulk structures, the lattice parameter and cohesive energy are calculated, which are then augmented by calculation of surface energies and work functions for the lower-index surfaces. Of the 22 density functionals considered, we highlight the mBEEF density functional as providing the best overall agreement with experimental data. The optimal density functional choice is applied to the study of higher index surfaces for the three metals, and Wulff constructions performed for nanoparticles with a radius of 11 nm, commensurate with nanoparticle sizes commonly employed in catalytic chemistry. For Pd and Cu, the low-index (111) facet is dominant in the constructed nanoparticles, covering ∼50% of the surface, with (100) facets covering a further 10 to 25%; however, non-negligible coverage from higher index (332), (332) and (210) facets is also observed for Pd, and (322), (221) and (210) surfaces are observed for Cu. In contrast, only the (0001) and (10-10) facets are observed for Zn. Overall, our results highlight the need for careful validation of computational settings before performing extensive density functional theory investigations of surface properties and nanoparticle structures of metals.

QM/MM study of the reactivity of zeolite bound methoxy and carbene groups.

The conversion of methanol-to-hydrocarbons (MTH) is known to occur via an autocatalytic process in zeolites, where framework-bound methoxy species play a pivotal role, especially during catalyst induction. Recent NMR and FT-IR experimental studies suggest that methoxylated zeolites are able to produce hydrocarbons by a mechanism involving carbene migration and association. In order to understand these observations, we have performed QM/MM computational investigations on a range of reaction mechanisms for the reaction of zeolite bound methoxy and carbene groups, which are proposed to initiate hydrocarbon formation in the MTH process. Our simulations demonstrate that it is kinetically unfavourable for methyl species to form on the framework away from the zeolite acid site, and both kinetically and thermodynamically unfavourable for methyl groups to migrate through the framework and aggregate around an acid site. Formation of carbene moieties was considered as an alternative pathway to the formation of C-C bonds; however, the reaction energy for conversion of a methyl to a carbene is unfavourable. Metadynamics simulations help confirm further that methyl species at the framework acid sites would be more reactive towards formed C2+ species, rather than inter-framework migration, and that the role of carbenes in the formation of the first C-C bond will be via a concerted type of mechanism rather than stepwise.

A quantitative multiscale perspective on primary olefin formation from methanol.

The formation of the first C-C bond and primary olefins from methanol over zeolite and zeotype catalysts has been studied for over 40 years. Over 20 mechanisms have been proposed for the formation of the first C-C bond. In this quantitative multiscale perspective, we decouple the adsorption, desorption, mobility, and surface reactions of early species through a combination of vacuum and sub-vacuum studies using temporal analysis of products (TAP) reactor systems, and through studies with atmospheric fixed bed reactors. These results are supplemented with density functional theory calculations and data-driven physical models, using partial differential equations, that describe the temporal and spatial evolution of species. We consider the effects of steam, early degradation species, and product masking due to the inherent autocatalytic nature of the process, which all complicate the observation of the primary olefin(s). Although quantitative spectroscopic determination of the lifetimes, surface mobility, and reactivity of adspecies is still lacking in the literature, we observe that reaction barriers are competitive with adsorption enthalpies and/or activation energies of desorption, while facile diffusion occurs in the porous structures of the zeolite/zeotype catalysts. Understanding the various processes allows for quantitative evaluation of their competing energetics, which leads to molecular insights as to what governs the catalytic activity during the conversion of methanol to primary olefins over zeolite/zeotype catalysts.

Tuning the transition barrier of H2 dissociation in the hydrogenation of CO2 to formic acid on Ti-doped Sn2O4 clusters.

A density functional theory study has been performed to investigate cation-doped Sn2O4 clusters for selective catalytic reduction of CO2. We study the influence of Si and Ti dopants on the height of the H2 dissociation barrier for the doped systems, and then the subsequent mechanism for the conversion of CO2 into formic acid (FA) via a hydride pinning pathway. The lowest barrier height for H2 dissociation is observed across the 'Ti-O' bond of the Ti-doped Sn2O4 cluster, with a negatively charged hydride (Ti-H) formed during the heterolytic H2 dissociation, bringing selectivity towards the desired FA product. The formation of a formate intermediate is identified as the rate-determining step (RDS) for the whole pathway, but the barrier height is substantially reduced for the Ti-doped system when compared to the same steps on the undoped Sn2O4 cluster. The free energy of formate formation in the RDS is calculated to be negative, which reveals that the hydride transfer would occur spontaneously. Overall, our results show that the small-sized Ti-doped Sn2O4 clusters exhibit better catalytic activity than undoped clusters in the important process of reducing CO2 to FA when proceeding via the hydride pinning pathway.

Hydride Pinning Pathway in the Hydrogenation of CO2 to Formic Acid on Dimeric Tin Dioxide.

Capture of CO2 and its conversion into organic feedstocks are increasingly needed as society moves towards a renewable energy economy. Here, a hydride-assisted selective reduction pathway is proposed for the conversion of CO2 to formic acid (FA) over SnO2 monomers and dimers. Our density functional theory calculations infer a strong chemisorption of CO2 on SnO2 clusters forming a carbonate structure, whereas heterolytic cleavage of H2 provides a new pathway for the selective reduction of CO2 to formic acid at low overpotential. Among the two investigated pathways for reduction of CO2 to HCOOH, the hydride pinning pathway is found promising with a unique selectivity for HCOOH. The negatively-charged hydride forms on the cluster during the dissociation of H2 and facilitates the formation of a formate intermediate, which determines the selectivity for FA over the alternative CO and H2 evolution reaction. It is confirmed that SnO2 clusters exhibit a different catalytic behaviour from their surface equivalents, thus offering promise for future work investigating the reduction of CO2 to FA via a hydride pinning pathway at low overpotential and CO2 capturing.

Polymorphism of l-Tryptophan.

A new polymorph of l-tryptophan was prepared through crystallization from the gas phase, with structure determination carried out directly from powder XRD data augmented by periodic DFT-D calculations. The new polymorph (denoted ß) and the previously reported polymorph (denoted α) are both based on alternating hydrophilic and hydrophobic layers, but with substantially different hydrogen-bonding arrangements. The ß polymorph exhibits the energetically favourable l2-l2 hydrogen-bonding arrangement, which is unprecedented for amino acids with aromatic side chains. The specific molecular conformations adopted in the ß polymorph facilitate this hydrogen-bonding scheme while avoiding steric conflict of the side chains.

Modelling the chemistry of Mn-doped MgO for bulk and (100) surfaces.

We have investigated the energetic properties of Mn-doped MgO bulk and (100) surfaces using a QM/MM embedding computational method, calculating the formation energy for doped systems, as well as for surface defects, and the subsequent effect on chemical reactivity. Low-concentration Mn doping is endothermic for isovalent species in the bulk but exothermic for higher oxidation states under p-type conditions, and compensated by electrons going to the Fermi level rather than cation vacancies. The highest occupied dopant Mn 3d states are positioned in the MgO band gap, about 4.2 eV below the vacuum level. Surface Mn-doping is more favourable than subsurface doping, and marginally exothermic on a (100) surface at high O2 pressures. For both types of isovalent Mn-doped (100) surfaces, the formation energy for catalytically important oxygen defects is less than for pristine MgO, with F0 and F2+-centres favoured in n- and p-type conditions, respectively. In addition, F+-centres are stabilised by favourable exchange coupling between the Mn 3d states and the vacancy-localised electrons, as verified through calculation of the vertical ionisation potential. The adsorption of CO2 on to the pristine and defective (100) surface is used as a probe of chemical reactivity, with isovalent subsurface Mn dopants mildly affecting reactivity, whereas isovalent surface-positioned Mn strongly alters the chemical interactions between the substrate and adsorbate. The differing chemical reactivity, when compared to pristine MgO, justifies further detailed investigations for more varied oxidation states and dopant species.

Band alignment of rutile and anatase TiO2.

The most widely used oxide for photocatalytic applications owing to its low cost and high activity is TiO2. The discovery of the photolysis of water on the surface of TiO2 in 1972 launched four decades of intensive research into the underlying chemical and physical processes involved. Despite much collected evidence, a thoroughly convincing explanation of why mixed-phase samples of anatase and rutile outperform the individual polymorphs has remained elusive. One long-standing controversy is the energetic alignment of the band edges of the rutile and anatase polymorphs of TiO2 (ref. ). We demonstrate, through a combination of state-of-the-art materials simulation techniques and X-ray photoemission experiments, that a type-II, staggered, band alignment of ~ 0.4 eV exists between anatase and rutile with anatase possessing the higher electron affinity, or work function. Our results help to explain the robust separation of photoexcited charge carriers between the two phases and highlight a route to improved photocatalysts.