Promoting active site renewal in heterogeneous olefin metathesis catalysts.

As an atom-efficient strategy for the large-scale interconversion of olefins, heterogeneously catalysed olefin metathesis sees commercial applications in the petrochemical, polymer and speciality chemical industries1. Notably, the thermoneutral and highly selective cross-metathesis of ethylene and 2-butenes1 offers an appealing route for the on-purpose production of propylene to address the C3 shortfall caused by using shale gas as a feedstock in steam crackers2,3. However, key mechanistic details have remained ambiguous for decades, hindering process development and adversely affecting economic viability4 relative to other propylene production technologies2,5. Here, from rigorous kinetic measurements and spectroscopic studies of propylene metathesis over model and industrial WOx/SiO2 catalysts, we identify a hitherto unknown dynamic site renewal and decay cycle, mediated by proton transfers involving proximal Brønsted acidic OH groups, which operates concurrently with the classical Chauvin cycle. We show how this cycle can be manipulated using small quantities of promoter olefins to drastically increase steady-state propylene metathesis rates by up to 30-fold at 250 °C with negligible promoter consumption. The increase in activity and considerable reduction of operating temperature requirements were also observed on MoOx/SiO2 catalysts, showing that this strategy is possibly applicable to other reactions and can address major roadblocks associated with industrial metathesis processes.

Efficient epoxidation over dinuclear sites in titanium silicalite-1.

Titanium silicalite-1 (TS-1) is a zeolitic material with MFI framework structure, in which 1 to 2 per cent of the silicon atoms are substituted for titanium atoms. It is widely used in industry owing to its ability to catalytically epoxidize olefins with hydrogen peroxide (H2O2), leaving only water as a byproduct1,2; around one million tonnes of propylene oxide are produced each year using this process3. The catalytic properties of TS-1 are generally attributed to the presence of isolated Ti(IV) sites within the zeolite framework1. However, despite almost 40 years of experimental and computational investigation4-10, the structure of these active Ti(IV) sites is unconfirmed, owing to the challenges of fully characterizing TS-1. Here, using a combination of spectroscopy and microscopy, we characterize in detail a series of highly active and selective TS-1 propylene epoxidation catalysts with well dispersed titanium atoms. We find that, on contact with H217O2, all samples exhibit a characteristic solid-state 17O nuclear magnetic resonance signature that is indicative of the formation of bridging peroxo species on dinuclear titanium sites. Further, density functional theory calculations indicate that cooperativity between two titanium atoms enables propylene epoxidation via a low-energy reaction pathway with a key oxygen-transfer transition state similar to that of olefin epoxidation by peracids. We therefore propose that dinuclear titanium sites, rather than isolated titanium atoms in the framework, explain the high efficiency of TS-1 in propylene epoxidation with H2O2. This revised view of the active-site structure may enable further optimization of TS-1 and the industrial epoxidation process.

NMR Spectroscopic Signatures of Cationic Surface Sites from Supported Coinage Metals Interacting with N-Heterocyclic Carbenes.

N-heterocyclic carbenes (NHCs) have been extensively studied to modulate the reactivity of molecular catalysts, colloids, and their supported analogues, being isolated sites, clusters, or nanoparticles. While the interaction of NHCs on metal surfaces has been discussed in great detail, showing specific coordination chemistry depending on the type of NHC ligands, much less is known when the metal is dispersed on oxide supports, as in heterogeneous catalysts. Herein, we study the interaction of NHC ligands with Au surface sites dispersed on silica, a nonreducible oxide support. We identify the easy formation of bis-NHC ligated Au(I) surface sites parallel to what is found on metallic Au surfaces. These species display a specific 13C NMR spectroscopic signature that clearly distinguishes them from the mono-NHC Au(I) surface sites or supported imidazoliums. We find that bis-ligated surface species are not unique to supported Au(I) species and are found for the corresponding Ag(I) and Cu(I) species, as well as for the isolobal surface silanols. Furthermore, the interaction of NHC ligand with silica-supported Au nanoparticles also yields bis-NHC ligated Au(I) surface sites, indicating that metal atoms can also be easily extracted from nanoparticles, further illustrating the dynamics of these systems and the overall favorable formation of such bis-ligated species across a range of systems, besides what has been found on crystalline metal facets.

Reactivity Switch of Platinum with Gallium: From Reverse Water Gas Shift to Methanol Synthesis.

The development of efficient catalysts for the hydrogenation of CO2 to methanol using "green" H2 is foreseen to be a key step to close the carbon cycle. In this study, we show that small and narrowly distributed alloyed PtGa nanoparticles supported on silica, prepared via a surface organometallic chemistry (SOMC) approach, display notable activity for the hydrogenation of CO2 to methanol, reaching a 7.2 molCH3OH h-1 molPt-1 methanol formation rate with a 54% intrinsic CH3OH selectivity. This reactivity sharply contrasts with what is expected for Pt, which favors the reverse water gas shift reaction, albeit with poor activity (2.6 molCO2 h-1 molPt-1). In situ XAS studies indicate that ca. 50% of Ga is reduced to Ga0 yielding alloyed PtGa nanoparticles, while the remaining 50% persist as isolated GaIII sites. The PtGa catalyst slightly dealloys under CO2 hydrogenation conditions and displays redox dynamics with PtGa-GaOx interfaces responsible for promoting both the CO2 hydrogenation activity and methanol selectivity. Further tailoring the catalyst interface by using a carbon support in place of silica enables to improve the methanol formation rate by a factor of ∼5.

Probing Homogeneous Catalysts and Precatalysts in Solution by Exchange-Mediated Overhauser Dynamic Nuclear Polarization NMR.

Triphenylphosphine (PPh3) is a ubiquitous ligand in organometallic chemistry that has been shown to give enhanced 31P NMR signals at high magnetic field via a scalar-dominated Overhauser effect dynamic nuclear polarization (OE DNP). However, PPh3 can only be polarized via DNP in the free form, while the coordinated form is DNP-inactive. Here, we demonstrate the possibility of enhancing the 31P NMR signals of coordinated PPh3 in metal complexes in solution at room temperature by combining Overhauser effect DNP and chemical exchange between the free and coordinated PPh3 forms. With this method, we successfully obtain 31P DNP enhancements of up to 2 orders of magnitude for the PPh3 ligands in Rh(I), Ru(II), Pd(II), and Pt(II) complexes, and we show that the DNP enhancements can be used to determine the activation energy of the ligand exchange reaction.

Bonding and Reactivity of d0 Transition Metal Imido Complexes Encoded in Their 15N NMR Signatures.

Terminal imido complexes containing metal-nitrogen multiple bonds have been widely used in organometallic chemistry and homogeneous catalysis. The role of terminal imido ligands spans from reactive sites to spectator motifs, largely depending on the nature of the metal center and its specific coordination sphere. Aiming at identifying reactivity descriptors for M-N multiple bonds, we herein explore solid-state 15N NMR spectroscopy (ssNMR) on early transition metal terminal imido complexes augmented by computational studies and show that the asymmetry parameter, κ (skew, 1 ≥ κ ≥ -1), readily available from experiments or calculations, is diagnostic for the reactivity of M-N multiple bonds in imido complexes. While inert imido ligands exhibit skew values (κ) close to 1, highly reactive imido moieties display significantly lower skew values (κ ≪ 1) as found in metallocene or bis-imido complexes. Natural chemical shielding analysis shows that skew values away from 1 are associated with an asymmetric development of π-orbitals around the M-N multiple bond of the imido moiety, with a larger double-bond character for reactive imido. Notably, this descriptor does not directly relate to the M-N-C bond angle, illustrating the shortcoming of evaluating bonding and hybridization from geometrical parameters alone. Overall, this descriptor enables to obtain direct experimental evidence for the π-loading effect seen in bis(imido) and related complexes, thus explaining their bonding/reactivity.

Tracking Coordination Environment and Reaction Intermediates in Homogeneous and Heterogeneous Epoxidation Catalysts via Ti L2,3-Edge Near-Edge X-ray Absorption Fine Structures.

Ti-based molecules and materials are ubiquitous and play a major role in both homogeneous and heterogeneous catalytic processes. Understanding the electronic structures of their active sites (oxidation state, local symmetry, and ligand environment) is key to developing molecular-level structure-property relationships. In that context, X-ray absorption spectroscopy (XAS) offers a unique combination of elemental selectivity and sensitivity to local symmetry. Commonly, for early transition metals such as Ti, K-edge XAS is applied for in situ characterization and subsequent structural analysis with high sensitivity toward tetrahedral species. Ti L2,3-edge spectroscopy is in principle complementary and offers specific opportunities to interrogate the electronic structure of five-and six-coordinated species. It is, however, much more rarely implemented because the use of soft X-rays implies ultrahigh vacuum conditions. Furthermore, the interpretation of the data can be challenging. Here, we show how Ti L2,3-edge spectroscopy can help to obtain unique information about both homogeneous and heterogeneous epoxidation catalysts and develop a molecular-level relationship between spectroscopic signatures and electronic structures. Toward this goal, we first establish a spectral library of molecular Ti reference compounds, comprising various coordination environments with mono- and dimeric Ti species having O, N, and Cl ligands. We next implemented a computational methodology based on multiplet ligand field theory and maximally localized Wannier orbitals benchmarked on our library to understand Ti L2,3-edge spectroscopic signatures. We finally used this approach to track and predict the spectra of catalytically relevant intermediates, focusing on Ti-based olefin epoxidation catalysts.

Geometry and electronic structure of Yb(III)[CH(SiMe3)2]3 from EPR and solid-state NMR augmented by computations.

Characterization of paramagnetic compounds, in particular regarding the detailed conformation and electronic structure, remains a challenge, and - still today it often relies solely on the use of X-ray crystallography, thus limiting the access to electronic structure information. This is particularly true for lanthanide elements that are often associated with peculiar structural and electronic features in relation to their partially filled f-shell. Here, we develop a methodology based on the combined use of state-of-the-art magnetic resonance spectroscopies (EPR and solid-state NMR) and computational approaches as well as magnetic susceptibility measurements to determine the electronic structure and geometry of a paramagnetic Yb(III) alkyl complex, Yb(III)[CH(SiMe3)2]3, a prototypical example, which contains notable structural features according to X-ray crystallography. Each of these techniques revealed specific information about the geometry and electronic structure of the complex. Taken together, both EPR and NMR, augmented by quantum chemical calculations, provide a detailed and complementary understanding of such paramagnetic compounds. In particular, the EPR and NMR signatures point to the presence of three-centre-two-electron Yb-γ-Me-ß-Si secondary metal-ligand interactions in this otherwise tri-coordinate metal complex, similarly to its diamagnetic Lu analogues. The electronic structure of Yb(III) can be described as a single 4f13 configuration, while an unusually large crystal-field splitting results in a thermally isolated ground Kramers doublet. Furthermore, the computational data indicate that the Yb-carbon bond contains some π-character, reminiscent of the so-called α-H agostic interaction.

Active Sites in Cr(III)-Based Ethylene Polymerization Catalysts from Machine-Learning-Supported XAS and EPR Spectroscopy.

The ethylene polymerization Phillips catalyst has been employed for decades and is central to the polymer industry. While Cr(III) alkyl species are proposed to be the propagating sites, there is so far no direct experimental evidence for such proposal. In this work, by coupling Surface organometallic chemistry, EPR spectroscopy, and machine learning-supported XAS studies, we have studied the electronic structure of well-defined silica-supported Cr(III) alkyls and identified the presence of several surface species in high and low-spin states, associated with different coordination environments. Notably, low-spin Cr(III) sites are shown to participate in ethylene polymerization, indicating that similar Cr(III) alkyl species could be involved in the related Phillips catalyst.

Surface Redox Dynamics in Gold-Zinc CO2 Hydrogenation Catalysts.

Au-Zn catalysts have previously been shown to promote the hydrogenation of CO2 to methanol, but their active state is poorly understood. Here, silica-supported bimetallic Au-Zn alloys, prepared by surface organometallic chemistry (SOMC), are shown to be proficient catalysts for hydrogenation of CO2 to methanol. In situ X-ray absorption spectroscopy (XAS), in conjunction with gas-switching experiments, is used to amplify subtle changes occurring at the surface of this tailored catalyst during reaction. Consequently, an Au-Zn alloy is identified and is shown to undergo subsequent reversible redox changes under reaction conditions according to multivariate curve resolution alternating least-squares (MCR-ALS) analysis. These results highlight the role of alloying and dealloying in Au-based CO2 hydrogenation catalysts and illustrate the role of these reversible processes in driving reactivity.

Geometry and Local Environment of Surface Sites in Vanadium-Based Ziegler-Natta Catalysts from 51V Solid-State NMR Spectroscopy.

Since its emergence over 50 years ago, the structure of surface sites in Ziegler-Natta catalysts, which are responsible for a major fraction of the world's supply of polyethylene (PE) and polypropylene (PP), has remained elusive. This is in part due to the complexity of these systems that involve multiple synthetic steps and components, namely, the MgCl2 support, a transition-metal chloride, and several organic modifiers, known as donors, that are used prior and in some instances during the activation step with alkyl aluminum. Due to the favorable nuclear magnetic resonance (NMR) properties of V and its use in Ziegler-Natta catalysts, we utilize 51V solid-state NMR spectroscopy to investigate the structure of VOCl3 on MgCl2(thf)1.5. The resulting catalyst shows ethylene polymerization activity similar to that of its Ti analogues. Using carefully benchmarked density functional theory (DFT) calculations, the experimental 51V NMR signature was analyzed to elucidate the structure of the surface sites. Using this approach, we demonstrate that the 51V NMR signature contains information about the coordination environment, i.e., the type of ancillary ligand, and the morphology of the MgCl2 support. Analysis of the NMR signature shows that the adsorption of VOCl3 on MgCl2(thf)1.5 generates a well-defined hexacoordinated V-oxo species containing one alkoxy and four chloride ligands, whose local geometry results from the interaction with an amorphous MgCl2 surface. This study illustrates how NMR spectroscopy, which is highly sensitive to the local environment of the investigated nuclei, here V, enables us to identify the exact coordination sphere and to address the effect of the support morphology on surface site structures.

Tailored Lewis Acid Sites for High-Temperature Supported Single-Molecule Magnetism.

Generating or even retaining slow magnetic relaxation in surface immobilized single-molecule magnets (SMMs) from promising molecular precursors remains a great challenge. Illustrative examples are organolanthanide compounds that show promising SMM properties in molecular systems, though surface immobilization generally diminishes their magnetic performance. Here, we show how tailored Lewis acidic Al(III) sites on a silica surface enable generation of a material with SMM characteristics via chemisorption of (Cpttt)2DyCl ((Cpttt)- = 1,2,4-tri(tert-butyl)-cyclopentadienide). Detailed studies of this system and its diamagnetic Y analogue indicate that the interaction of the metal chloride with surface Al sites results in a change of the coordination sphere around the metal center inducing for the dysprosium-containing material slow magnetic relaxation up to 51 K with hysteresis up to 8 K and an effective energy barrier (Ueff) of 449 cm-1, the highest reported thus far for a supported SMM.

Selective Oxidation of Methane to Methanol over Au/H-MOR.

Selective oxidation of methane to methanol by dioxygen (O2) is an appealing route for upgrading abundant methane resource and represents one of the most challenging reactions in chemistry due to the overwhelmingly higher reactivity of the product (methanol) versus the reactant (methane). Here, we report that gold nanoparticles dispersed on mordenite efficiently catalyze the selective oxidation of methane to methanol by molecular oxygen in aqueous medium in the presence of carbon monoxide. The methanol productivity reaches 1300 µmol gcat-1 h-1 or 280 mmol gAu-1 h-1 with 75% selectivity at 150 °C, outperforming most catalysts reported under comparable conditions. Both hydroxyl radicals and hydroperoxide species participate in the activation and conversion of methane, while it is shown that the lower affinity of methanol on gold mainly accounts for higher methanol selectivity.

NMR Signatures and Electronic Structure of Ti Sites in Titanosilicalite-1 from Solid-State 47/49Ti NMR Spectroscopy.

Although titanosilicalite-1 (TS-1) is among the most successful oxidation catalysts used in industry, its active site structure is still debated. Recent efforts have mostly focused on understanding the role of defect sites and extraframework Ti. Here, we report the 47/49Ti signature of TS-1 and molecular analogues [Ti(OTBOS)4] and [Ti(OTBOS)3(OiPr)] using novel MAS CryoProbe to enhance the sensitivity. While the dehydrated TS-1 displays chemical shifts similar to those of molecular homologues, confirming the tetrahedral environment of Ti consistent with X-ray absorption spectroscopy, it is associated with a distribution of larger quadrupolar coupling constants, indicating an asymmetric environment. Detailed computational studies on cluster models highlights the high sensitivity of the NMR signatures (chemical shift and quadrupolar coupling constant) to small local structural changes. These calculations show that, while it will be difficult to distinguish mono- vs dinuclear sites, the sensitivity of the 47/49Ti NMR signature should enable distinguishing the Ti location among specific T site positions.

Active Site Descriptors from 95Mo NMR Signatures of Silica-Supported Mo-Based Olefin Metathesis Catalysts.

The olefin metathesis activity of silica-supported molybdenum oxides depends strongly on metal loading and preparation conditions, indicating that the nature and/or amounts of the active sites vary across compositionally similar catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared by impregnation (2.5-15.6 wt % Mo) and a model material (2.3 wt % Mo) synthesized via surface organometallic chemistry (SOMC). Analyses of FTIR, UV-vis, and Mo K-edge X-ray absorption spectra show that these (pre)catalysts are composed predominantly of similar isolated Mo dioxo sites. However, they exhibit different reaction properties in both liquid and gas-phase olefin metathesis with the SOMC-derived catalyst outperforming a classical catalyst of a similar Mo loading by ×1.5-2.0. Notably, solid-state 95Mo NMR analyses leveraging state-of-the-art high-field (28.2 T) measurement conditions resolve four distinct surface Mo dioxo sites with distributions that depend on the (pre)catalyst preparation methods. The intensity of a specific deshielded 95Mo NMR signal, which is most prominent in the SOMC-derived catalyst, is linked to reducibility and catalytic activity. First-principles calculations show that 95Mo NMR parameters directly manifest the local strain and coordination environment: acute (SiO-Mo(O)2-OSi) angles and low coordination numbers at Mo lead to highly deshielded 95Mo chemical shifts and small quadrupolar coupling constants, respectively. Natural chemical shift analyses relate the 95Mo NMR signature of strained species to low LUMO energies, which is consistent with their high reducibility and corresponding reactivity. The 95Mo chemical shifts of supported Mo dioxo sites are thus linked to their specific electronic structures, providing a powerful descriptor for their propensity toward reduction and formation of active sites.

Non-Oxidative Coupling of Methane: Interplay of Catalyst Interface and Gas Phase Mechanisms.

Non-oxidative coupling of methane (NOCM) is a sought-after reaction that has been studied for decades. Harsh reaction conditions (T >800°C) in the face of limited catalyst stability lead to rapid catalyst deactivation and strong coking, preventing application thus far. Recent reports have shown the significance of an interplay of catalyst nature and reaction conditions, whereas metal carbides have prevailed to play a crucial role which involves incorporation of carbidic carbon in C2Hx and aromatic products. This perspective gives an overview of proposed mechanistic pathways and considerations about experiment conditions in order to foster a rational catalyst design platform for NOCM.

Swiss CAT+, a Data-driven Infrastructure for Accelerated Catalysts Discovery and Optimization.

The Catalysis Hub - Swiss CAT+ is a new infrastructure project funded by ETH-domain, co-headed by EPFL and ETHZ. It offers the scientific community a unique integrated technology platform combining automated and high-throughput experimentation with advanced computational data analysis to accelerate the discoveries in the field of sustainable catalytic technologies. Divided into two hubs of expertise, homogeneous catalysis at EPFL and heterogeneous catalysis at ETHZ, the platform is open to academic and private research groups. Following a multi-year investment plan, both hubs have acquired and developed several high-end robotic platforms devoted to the synthesis, characterization, and testing of large numbers of molecular and solid catalysts. The hardware is associated with a fully digitalized experimental workflow and a specific data management strategy to support closed-loop experimentation and advanced computational data analysis.

Small Cobalt Nanoparticles Favor Reverse Water-Gas Shift Reaction Over Methanation Under CO2 Hydrogenation Conditions.

Cobalt-based catalysts are well-known to convert syngas into a variety of Fischer-Tropsch (FTS) products depending on the various reaction parameters, in particular particle size. In contrast, the reactivity of these particles has been much less investigated in the context of CO2 hydrogenation. In that context, Surface organometallic chemistry (SOMC) was employed to synthesize highly dispersed cobalt nanoparticles (Co-NPs) with particle sizes ranging from 1.6 to 3.0 nm. These SOMC-derived Co-NPs display significantly different catalytic performances under CO2 hydrogenation conditions: while the smallest cobalt nanoparticles (1.6 nm) catalyze mainly the reverse water-gas shift (rWGS) reaction, the larger nanoparticles (2.1-3.0 nm) favor the expected methanation activity. Operando X-ray absorption spectroscopy shows that the smaller cobalt particles are fully oxidized under CO2 hydrogenation conditions, while the larger ones remain mostly metallic, paralleling the observed difference of catalytic performances. This fundamental shift of selectivity, away from methanation to reverse water-gas shift for the smaller nanoparticles is noteworthy and correlates with the formation of CoO under CO2 hydrogenation conditions.

Surface Sites and Ligation in Amine-capped CdSe Nanocrystals.

Converting colloidal nanocrystals (NCs) into devices for various applications is facilitated by designing and controlling their surface properties. One key strategy for tailoring surface properties is thus to choose tailored surface ligands. In that context, amines have been universally used, with the goal to improve NCs synthesis, processing and performances. However, understanding the nature of surface sites in amine-capped NCs remains challenging, due to the complex surface compositions as well as surface ligands dynamic. Here, we investigate both surface sites and amine ligation in CdSe NCs by combining advanced NMR spectroscopy and computational modelling. Notably, dynamic nuclear polarization (DNP) enhanced 113 Cd and 77 Se 1D NMR helps to identify both bulk and surface sites of NCs, while 113 Cd 2D NMR spectroscopy enables to resolve amines terminated sites on both Se-rich and nonpolar surfaces. In addition to directly bonding to surface sites, amines are shown to also interact through hydrogen-bonding with absorbed water as revealed by 15 N NMR, augmented with computations. The characterization methodology developed for this work provides unique molecular-level insight into the surface sites of a range of amine-capped CdSe NCs, and paves the way to identify structure-function relationships and rational approaches towards colloidal NCs with tailored properties.

Lithium Promotes Acetylide Formation on MgO During Methane Coupling Under Non-Oxidative Conditions.

A prototypical material for the oxidative coupling of methane (OCM) is Li/MgO, for which Li is known to be essential as a dopant to obtain high C2 selectivities. Herein, Li/MgO is demonstrated to be an effective catalyst for non-oxidative coupling of methane (NOCM). Moreover, the presence of Li is shown to favor the formation of magnesium acetylide (MgC2 ), while pure MgO promotes coke formation as evidenced by solid-state 13 C NMR, thus indicating that Li promotes C-C bond formation. Metadynamic simulations of the carbon mobility in MgC2 and Li2 C2 at the density functional theory (DFT) level show that carbon easily diffuses as a C2 unit at 1000 °C. These insights suggest that the enhanced C2 selectivity for Li-doped MgO is related to the formation of Li and Mg acetylides.