Unravelling CO Activation on Flat and Stepped Co Surfaces: A Molecular Orbital Analysis.

Structure sensitivity in heterogeneous catalysis dictates the overall activity and selectivity of a catalyst whose origins lie in the atomic configurations of the active sites. We explored the influence of the active site geometry on the dissociation activity of CO by investigating the electronic structure of CO adsorbed on 12 different Co sites and correlating its electronic structure features to the corresponding C-O dissociation barrier. By including the electronic structure analyses of CO adsorbed on step-edge sites, we expand upon the current models that primarily pertain to flat sites. The most important descriptors for activation of the C-O bond are the decrease in electron density in CO's 1π orbital , the occupation of 2π anti-bonding orbitals and the redistribution of electrons in the 3σ orbital. The enhanced weakening of the C-O bond that occurs when CO adsorbs on sites with a step-edge motif as compared to flat sites is caused by a distancing of the 1π orbital with respect to Co. This distancing reduces the electron-electron repulsion with the Co d-band. These results deepen our understanding of the electronic phenomena that enable the breaking of a molecular bond on a metal surface.

Descriptor for C2N-Supported Single-Cluster Catalysts in Bifunctional Oxygen Evolution and Reduction Reactions.

Developing highly active cluster catalysts for the bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is significant for future renewable energy technology. Here, we employ first-principles calculations combined with a genetic algorithm to explore the activity trends of transition metal clusters supported on C2N. Our results indicate that the supported clusters, as bifunctional catalysts for the OER and the ORR, may outperform single-atom catalysts. In particular, the C2N-supported Ag6 cluster exhibits outstanding bifunctional activity with low overpotentials. Mechanistic analysis indicates that the activity of the cluster is related to the number of atoms in the active site as well as the interaction between the intermediate and the cluster. Accordingly, we identify a descriptor that links the intrinsic properties of the clusters with the activity of both the OER and the ORR. This work provides guidelines and strategies for the rational design of highly efficient bifunctional cluster catalysts.

The Promoting Role of Ni on In2O3 for CO2 Hydrogenation to Methanol.

Ni-promoted indium oxide (In2O3) is a promising catalyst for the selective hydrogenation of CO2 to CH3OH, but the nature of the active Ni sites remains unknown. By employing density functional theory and microkinetic modeling, we elucidate the promoting role of Ni in In2O3-catalyzed CO2 hydrogenation. Three representative models have been investigated: (i) a single Ni atom doped in the In2O3(111) surface, (ii) a Ni atom adsorbed on In2O3(111), and (iii) a small cluster of eight Ni atoms adsorbed on In2O3(111). Genetic algorithms (GAs) are used to identify the optimum structure of the Ni8 clusters on the In2O3 surface. Compared to the pristine In2O3(111) surface, the Ni8-cluster model offers a lower overall barrier to oxygen vacancy formation, whereas, on both single-atom models, higher overall barriers are found. Microkinetic simulations reveal that only the supported Ni8 cluster can lead to high methanol selectivity, whereas single Ni atoms either doped in or adsorbed on the In2O3 surface mainly catalyze CO formation. Hydride species obtained by facile H2 dissociation on the Ni8 cluster are involved in the hydrogenation of adsorbed CO2 to formate intermediates and methanol. At higher temperatures, the decreasing hydride coverage shifts the selectivity to CO. On the Ni8-cluster model, the formation of methane is inhibited by high barriers associated with either direct or H-assisted CO activation. A comparison with a smaller Ni6 cluster also obtained with GAs exhibits similar barriers for key rate-limiting steps for the formation of CO, CH4, and CH3OH. Further microkinetic simulations show that this model also has appreciable selectivity to methanol at low temperatures. The formation of CO over single Ni atoms either doped in or adsorbed on the In2O3 surface takes place via a redox pathway involving the formation of oxygen vacancies and direct CO2 dissociation.

Near-Unity Electrochemical CO2 to CO Conversion over Sn-Doped Copper Oxide Nanoparticles.

Bimetallic electrocatalysts have emerged as a viable strategy to tune the electrocatalytic CO2 reduction reaction (eCO2RR) for the selective production of valuable base chemicals and fuels. However, obtaining high product selectivity and catalyst stability remain challenging, which hinders the practical application of eCO2RR. In this work, it was found that a small doping concentration of tin (Sn) in copper oxide (CuO) has profound influence on the catalytic performance, boosting the Faradaic efficiency (FE) up to 98% for carbon monoxide (CO) at -0.75 V versus RHE, with prolonged stable performance (FE > 90%) for up to 15 h. Through a combination of ex situ and in situ characterization techniques, the in situ activation and reaction mechanism of the electrocatalyst at work was elucidated. In situ Raman spectroscopy measurements revealed that the binding energy of the crucial adsorbed *CO intermediate was lowered through Sn doping, thereby favoring gaseous CO desorption. This observation was confirmed by density functional theory, which further indicated that hydrogen adsorption and subsequent hydrogen evolution were hampered on the Sn-doped electrocatalysts, resulting in boosted CO formation. It was found that the pristine electrocatalysts consisted of CuO nanoparticles decorated with SnO2 domains, as characterized by ex situ high-resolution scanning transmission electron microscopy and X-ray photoelectron spectroscopy measurements. These pristine nanoparticles were subsequently in situ converted into a catalytically active bimetallic Sn-doped Cu phase. Our work sheds light on the intimate relationship between the bimetallic structure and catalytic behavior, resulting in stable and selective oxide-derived Sn-doped Cu electrocatalysts.

What Happens at Surfaces and Grain Boundaries of Halide Perovskites: Insights from Reactive Molecular Dynamics Simulations of CsPbI3.

The commercialization of perovskite solar cells is hindered by the poor long-term stability of the metal halide perovskite (MHP) light-absorbing layer. Solution processing, the common fabrication method for MHPs, produces polycrystalline films with a wide variety of defects, such as point defects, surfaces, and grain boundaries. Although the optoelectronic effects of such defects have been widely studied, the evaluation of their impact on the long-term stability remains challenging. In particular, an understanding of the dynamics of degradation reactions at the atomistic scale is lacking. In this work, using reactive force field (ReaxFF) molecular dynamics simulations, we investigate the effects of defects, in the forms of surfaces, surface defects, and grain boundaries, on the stability of the inorganic halide perovskite CsPbI3. Our simulations establish a stability trend for a variety of surfaces, which correlates well with the occurrence of these surfaces in experiments. We find that a perovskite surface degrades by progressively changing the local geometry of PbIx octahedra from corner- to edge- to face-sharing. Importantly, we find that Pb dangling bonds and the lack of steric hindrance of I species are two crucial factors that induce degradation reactions. Finally, we show that the stability of these surfaces can be modulated by adjusting their atomistic details, by either creating additional point defects or merging them to form grain boundaries. While in general additional defects, particularly when clustered, have a negative impact on the material stability, some grain boundaries have a stabilizing effect, primarily because of the additional steric hindrance.

On the Potential of Gallium- and Indium-Based Liquid Metal Membranes for Hydrogen Separation.

The concept of liquid metal membranes for hydrogen separation, based on gallium or indium, was recently introduced as an alternative to conventional palladium-based membranes. The potential of this class of gas separation materials was mainly attributed to the promise of higher hydrogen diffusivity. The postulated improvements are only beneficial to the flux if diffusion through the membrane is the rate-determining step in the permeation sequence. Whilst this is a valid assumption for hydrogen transport through palladium-based membranes, the relatively low adsorption energy of hydrogen on both liquid metals suggests that other phenomena may be relevant. In the current study, a microkinetic modeling approach is used to enable simulations based on a five-step permeation mechanism. The calculation results show that for the liquid metal membranes, the flux is limited by the dissociative adsorption over a large temperature range, and that the membrane flux is expected to be orders of magnitude lower compared to the membrane flux through pure palladium membranes. Even when accounting for the lower cost of the liquid metals compared to palladium, the latter still outperforms both gallium and indium in all realistic scenarios, in part due to the practical difficulties associated with making liquid metal thin films.

Structure Sensitivity of CO2 Conversion over Nickel Metal Nanoparticles Explained by Micro-Kinetics Simulations.

Nickel metal nanoparticles are intensively researched for the catalytic conversion of carbon dioxide. They are commercially explored in the so-called power-to-methane application in which renewably resourced H2 reacts with CO2 to produce CH4, which is better known as the Sabatier reaction. Previous work has shown that this reaction is structure-sensitive. For instance, Ni/SiO2 catalysts reveal a maximum performance when nickel metal nanoparticles of ∼2-3 nm are used. Particularly important to a better understanding of the structure sensitivity of the Sabatier reaction over nickel-based catalysts is to understand all relevant elementary reaction steps over various nickel metal facets because this will tell as to which type of nickel facets and which elementary reaction steps are crucial for designing an efficient nickel-based methanation catalyst. In this work, we have determined by density functional theory (DFT) calculations and micro-kinetics modeling (MKM) simulations that the two terrace facets Ni(111) and Ni(100) and the stepped facet Ni(211) barely show any activity in CO2 methanation. The stepped facet Ni(110) turned out to be the most effective in CO2 methanation. Herein, it was found that the dominant kinetic route corresponds to a combination of the carbide and formate reaction pathways. It was found that the dissociation of H2CO* toward CH2* and O* is the most critical elementary reaction step on this Ni(110) facet. The calculated activity of a range of Wulff-constructed nickel metal nanoparticles, accounting for varying ratios of the different facets and undercoordinated atoms exposed, reveals the same trend of activity-versus-nanoparticle size, as was observed in previous experimental work from our research group, thereby providing an explanation for the structure-sensitive nature of the Sabatier reaction.

Ni-In Synergy in CO2 Hydrogenation to Methanol.

Indium oxide (In2O3) is a promising catalyst for selective CH3OH synthesis from CO2 but displays insufficient activity at low reaction temperatures. By screening a range of promoters (Co, Ni, Cu, and Pd) in combination with In2O3 using flame spray pyrolysis (FSP) synthesis, Ni is identified as the most suitable first-row transition-metal promoter with similar performance as Pd-In2O3. NiO-In2O3 was optimized by varying the Ni/In ratio using FSP. The resulting catalysts including In2O3 and NiO end members have similar high specific surface areas and morphology. The main products of CO2 hydrogenation are CH3OH and CO with CH4 being only observed at high NiO loading (≥75 wt %). The highest CH3OH rate (∼0.25 gMeOH/(gcat h), 250 °C, and 30 bar) is obtained for a NiO loading of 6 wt %. Characterization of the as-prepared catalysts reveals a strong interaction between Ni cations and In2O3 at low NiO loading (≤6 wt %). H2-TPR points to a higher surface density of oxygen vacancy (Ov) due to Ni substitution. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and electron paramagnetic resonance analysis of the used catalysts suggest that Ni cations can be reduced to Ni as single atoms and very small clusters during CO2 hydrogenation. Supportive density functional theory calculations indicate that Ni promotion of CH3OH synthesis from CO2 is mainly due to low-barrier H2 dissociation on the reduced Ni surface species, facilitating hydrogenation of adsorbed CO2 on Ov.

Enumerating Active Sites on Metal Nanoparticles: Understanding the Size Dependence of Cobalt Particles for CO Dissociation.

Detailed understanding of structure sensitivity, a central theme in heterogeneous catalysis, is important to guide the synthesis of improved catalysts. Progress is hampered by our inability to accurately enumerate specific active sites on ubiquitous metal nanoparticle catalysts. We employ herein atomistic simulations based on a force field trained with quantum-chemical data to sample the shape of cobalt particles as a function of their size. Algorithms rooted in pattern recognition are used to identify surface atom arrangements relevant to CO dissociation, the key step in the Fischer-Tropsch (FT) reaction. The number of step-edge sites that can catalyze C-O bond scission with a low barrier strongly increases for larger nanoparticles in the range of 1-6 nm. Combined with microkinetics of the FT reaction, we can reproduce experimental FT activity trends. The stabilization of step-edge sites correlates with increasing stability of terrace nanoislands on larger nanoparticles.

Improved Pd/CeO2 Catalysts for Low-Temperature NO Reduction: Activation of CeO2 Lattice Oxygen by Fe Doping.

Developing better three-way catalysts with improved low-temperature performance is essential for cold start emission control. Density functional theory in combination with microkinetics simulations is used to predict reactivity of CO/NO/H2 mixtures on a small Pd cluster on CeO2(111). At low temperatures, N2O formation occurs via a N2O2 dimer over metallic Pd3. Part of the N2O intermediate product re-oxidizes Pd, limiting NO conversion and requiring rich conditions to obtain high N2 selectivity. High N2 selectivity at elevated temperatures is due to N2O decomposition on oxygen vacancies. Doping CeO2 by Fe is predicted to lead to more oxygen vacancies and a higher N2 selectivity, which is validated by the lower onset of N2 formation for a Pd catalyst supported on Fe-doped CeO2 prepared by flame spray pyrolysis. Activating ceria surface oxygen by transition metal doping is a promising strategy to improve the performance of three-way catalysts.

Consequences of Amide Connectivity in the Supramolecular Polymerization of Porphyrins: Spectroscopic Observations Rationalized by Theoretical Modelling.

The correlation between molecular structure and mechanism of supramolecular polymerizations is a topic of great interest, with a special focus on the pathway complexity of porphyrin assemblies. Their cooperative polymerization typically yields highly ordered, long 1D polymers and is driven by a combination of π-stacking due to solvophobic effects and hydrogen bonding interactions. Subtle changes in molecular structure, however, have significant influence on the cooperativity factor and yield different aggregate types (J- versus H-aggregates) of different lengths. In this study, the influence of amide connectivity on the self-assembly behavior of porphyrin-based supramolecular monomers was investigated. While in nonpolar solvents, C=O centered monomers readily assemble into helical supramolecular polymers via a cooperative mechanism, their NH centered counterparts form short, non-helical J-type aggregates via an isodesmic pathway. A combination of spectroscopy and density functional theory modelling sheds light on the molecular origins causing this stunning difference in assembly properties and demonstrates the importance of molecular connectivity in the design of supramolecular systems. Finally, their mutual interference in copolymerization experiments is presented.

Design of Nonideal Eutectic Mixtures Based on Correlations with Molecular Properties.

In this work, a statistical analysis was performed to reveal how the molecular properties are correlated with the nonideal behavior observed in eutectic mixtures. From this, a statistical model, combined with theory and experimental results, was developed to predict the nonideal behavior of a specific set of eutectic mixtures, consisting of quaternary ammonium bromides with dicarboxylic acids and polyols. The combination of this analysis and this model can be considered as a first step toward the a priori design of eutectic mixtures. The analysis performed is based on principal components. The descriptors used for this are molecular properties of the constituents of these mixtures. The molecular properties are a combination of experimental, theoretical, and computed properties. The analysis reveals that there are strong correlations between the nonideality of the mixtures and a measure of the acidity of the hydrogen bond donating protons, the displacement of the bromide anion, and the bulkiness of the quaternary ammonium salt. Our analysis highlights the design rules of deep eutectic systems (DES), enabling control over the extent of the liquid window. Our model enables prediction of the eutectic temperature for a range of related mixtures.

Bioorthogonal Tetrazine Carbamate Cleavage by Highly Reactive trans-Cyclooctene.

The high rate of the 'click-to-release' reaction between an allylic substituted trans-cyclooctene linker and a tetrazine activator has enabled exceptional control over chemical and biological processes. Here we report the development of a new bioorthogonal cleavage reaction based on trans-cyclooctene and tetrazine, which allows the use of highly reactive trans-cyclooctenes, leading to 3 orders of magnitude higher click rates compared to the parent reaction, and 4 to 6 orders higher than other cleavage reactions. In this new pyridazine elimination mechanism, wherein the roles are reversed, a trans-cyclooctene activator reacts with a tetrazine linker that is substituted with a methylene-linked carbamate, leading to a 1,4-elimination of the carbamate and liberation of a secondary amine. Through a series of mechanistic studies, we identified the 2,5-dihydropyridazine tautomer as the releasing species and found factors that govern its formation and subsequent fragmentation. The bioorthogonal utility was demonstrated by the selective cleavage of a tetrazine-linked antibody-drug conjugate by trans-cyclooctenes, affording efficient drug liberation in plasma and cell culture. Finally, the parent and the new reaction were compared at low concentration, showing that the use of a highly reactive trans-cyclooctene as the activator leads to a complete cycloaddition reaction with the antibody-drug conjugate in seconds vs hours for the parent system. Although the subsequent release from the IEDDA adduct is slower, we believe that this new reaction may allow markedly reduced click-to-release reagent doses in vitro and in vivo and could expand the application scope to conditions wherein the trans-cyclooctene has limited stability.

Supramolecular interactions between catalytic species allow rational control over reaction kinetics.

The adaptivity of biological reaction networks largely arises through non-covalent regulation of catalysts' activity. Such type of catalyst control is still nascent in synthetic chemical networks and thereby hampers their ability to display life-like behavior. Here, we report a bio-inspired system in which non-covalent interactions between two complementary phase-transfer catalysts are used to regulate reaction kinetics. While one catalyst gives bimolecular kinetics, the second displays autoinductive feedback, resulting in sigmoidal kinetics. When both catalysts are combined, the interactions between them allow rational control over the shape of the kinetic curves. Computational models are used to gain insight into the structure, interplay, and activity of each catalytic species, and the scope of the system is examined by optimizing the linearity of the kinetic curves. Combined, our findings highlight the effectiveness of regulating reaction kinetics using non-covalent catalyst interactions, but also emphasize the risk for unforeseen catalytic contributions in complex systems and the necessity to combine detailed experiments with kinetic modelling.

Understanding carbon dioxide activation and carbon-carbon coupling over nickel.

Carbon dioxide is a desired feedstock for platform molecules, such as carbon monoxide or higher hydrocarbons, from which we will be able to make many different useful, value-added chemicals. Its catalytic hydrogenation over abundant metals requires the amalgamation of theoretical knowledge with materials design. Here we leverage a theoretical understanding of structure sensitivity, along with a library of different supports, to tune the selectivity of methanation in the Power-to-Gas concept over nickel. For example, we show that carbon dioxide hydrogenation over nickel can and does form propane, and that activity and selectivity can be tuned by supporting different nickel particle sizes on various oxides. This theoretical and experimental toolbox is not only useful for the highly selective production of methane, but also provides new insights for carbon dioxide activation and subsequent carbon-carbon coupling towards value-added products thereby reducing the deleterious effects of this environmentally harmful molecule.

Understanding the Impact of Defects on Catalytic CO Oxidation of LaFeO3-Supported Rh, Pd, and Pt Single-Atom Catalysts.

Understanding the intrinsic catalytic properties of perovskite materials can accelerate the development of highly active and abundant complex oxide catalysts. Here, we performed a first-principles density functional theory study combined with a microkinetics analysis to comprehensively investigate the influence of defects on catalytic CO oxidation of LaFeO3 catalysts containing single atoms of Rh, Pd, and Pt. La defects and subsurface O vacancies considerably affect the local electronic structure of these single atoms adsorbed at the surface or replacing Fe in the surface of the perovskite. As a consequence, not only the stability of the introduced single atoms is enhanced but also the CO and O2 adsorption energies are modified. This also affects the barriers for CO oxidation. Uniquely, we find that the presence of La defects results in a much higher CO oxidation rate for the doped perovskite surface. A linear correlation between the activation barrier for CO oxidation and the surface O vacancy formation energy for these models is identified. Additionally, the presence of subsurface O vacancies only slightly promotes CO oxidation on the LaFeO3 surface with an adsorbed Rh atom. Our findings suggest that the introduction of La defects in LaFeO3-based environmental catalysts could be a promising strategy toward improved oxidation performance. The insights revealed herein guide the design of the perovskite-based three-way catalyst through compositional variation.

Linear Activation Energy-Reaction Energy Relations for LaBO3 (B = Mn, Fe, Co, Ni) Supported Single-Atom Platinum Group Metal Catalysts for CO Oxidation.

Single-atom catalysts are at the center of attention of the heterogeneous catalysis community because they exhibit unique electronic structures distinct from nanoparticulate forms, resulting in very different catalytic performance combined with increased usage of often costly transition metals. Proper selection of a support that can stably keep the metal in a high dispersion is crucial. Here, we employ spin-polarized density functional theory and microkinetics simulations to identify optimum LaBO3 (B = Mn, Fe, Co, Ni) supported catalysts dispersing platinum group metals as atoms on their surface. We identify a strong correlation between the CO adsorption energy and the d-band center of the doped metal atom. These CO adsorption strength differences are explained in terms of the electronic structure. In general, Pd-doped surfaces exhibit substantially lower activation barriers for CO2 formation than the Rh- and Pt-doped surfaces. Strong Brønsted-Evans-Polanyi correlations are found for CO oxidation on these single-atom catalysts, providing a tool to predict promising compositions. Microkinetics simulations show that Pd-doped LaCoO3 is the most active catalyst for low-temperature CO oxidation. Moderate CO adsorption strength and low reaction barriers explain the high activity of this composition. Our approach provides guidelines for the design of highly active and cost-effective perovskite supported single-atom catalysts.

Reversible Restructuring of Silver Particles during Ethylene Epoxidation.

The restructuring of a silver catalyst during ethylene epoxidation under industrially relevant conditions was investigated without and with vinyl chloride (VC) promotion. During non-VC-promoted ethylene epoxidation, the silver particles grow and voids are formed at the surface and in the bulk. Electron tomography highlighted the presence of voids below the Ag surface. A mechanism is proposed involving reconstruction of the silver lattice and defect sites induced by oxygen adsorption on the external surface and grain boundaries, which finally create pores. Promotion of the catalytic reaction by VC suppresses to a significant extent void formation. The use of VC also redisperses silver particles, initially grown during ethylene epoxidation without VC. This process is rapid as the average size decreased from 172 to 136 nm within 2 h. These insights emphasize the dynamic nature of the silver particles during the ongoing ethylene epoxidation reaction and indicate that particle size and morphology strongly depend on reaction conditions.

Highly Active and Stable CH4 Oxidation by Substitution of Ce4+ by Two Pd2+ Ions in CeO2(111).

Methane (CH4) combustion is an increasingly important reaction for environmental protection, for which Pd/CeO2 has emerged as the preferred catalyst. There is a lack of understanding of the nature of the active site in these catalysts. Here, we use density functional theory to understand the role of doping of Pd in the ceria surface for generating sites highly active toward the C-H bonds in CH4. Specifically, we demonstrate that two Pd2+ ions can substitute one Ce4+ ion, resulting in a very stable structure containing a highly coordinated unsaturated Pd cation that can strongly adsorb CH4 and dissociate the first C-H bond with a low energy barrier. An important aspect of the high activity of the stabilized isolated Pd cation is its ability to form a strong σ-complex with CH4, which leads to effective activation of CH4. We show that also other transition metals like Pt, Rh, and Ni can give rise to similar structures with high activity toward C-H bond dissociation. These insights provide us with a novel structural view of solid solutions of transition metals such as Pt, Pd, Ni, and Rh in CeO2, known to exhibit high activity in CH4 combustion.

Potential enthalpic energy of water in oils exploited to control supramolecular structure.

Water directs the self-assembly of both natural1,2 and synthetic3-9 molecules to form precise yet dynamic structures. Nevertheless, our molecular understanding of the role of water in such systems is incomplete, which represents a fundamental constraint in the development of supramolecular materials for use in biomaterials, nanoelectronics and catalysis 10 . In particular, despite the widespread use of alkanes as solvents in supramolecular chemistry11,12, the role of water in the formation of aggregates in oils is not clear, probably because water is only sparingly miscible in these solvents-typical alkanes contain less than 0.01 per cent water by weight at room temperature 13 . A notable and unused feature of this water is that it is essentially monomeric 14 . It has been determined previously 15 that the free energy cost of forming a cavity in alkanes that is large enough for a water molecule is only just compensated by its interaction with the interior of the cavity; this cost is therefore too high to accommodate clusters of water. As such, water molecules in alkanes possess potential enthalpic energy in the form of unrealized hydrogen bonds. Here we report that this energy is a thermodynamic driving force for water molecules to interact with co-dissolved hydrogen-bond-based aggregates in oils. By using a combination of spectroscopic, calorimetric, light-scattering and theoretical techniques, we demonstrate that this interaction can be exploited to modulate the structure of one-dimensional supramolecular polymers.