Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49Ti Solid-State Nuclear Magnetic Resonance Spectroscopy.

Treatment of Ziegler-Natta (ZN) catalysts with BCl3 improves their activity by increasing the number of active sites. Here we show how 47/49Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (∼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of 47/49Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit 49Ti NMR signatures (δiso, exp = -170 ppm; CQ, exp = 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl2 support, formed upon post-treatment with BCl3 and removal of the alkoxo ligands, paralleling the increased polymerization activity.

109Ag NMR chemical shift as a descriptor for Brønsted acidity from molecules to materials.

Molecular-level understanding of the acid/base properties of heterogeneous catalysts requires the development of selective spectroscopic probes to establish structure-activity relationships. In this work we show that substituting the surface protons in oxide supports by isolobal N-heterocyclic carbene (NHC) Ag cations and measuring their 109Ag nuclear magnetic resonance (NMR) signatures enables to probe the speciation and to evaluate the corresponding Brønsted acidity of the substituted OH surface sites. Specifically, a series of silver N-heterocyclic carbene (NHC) Ag(i) complexes of general formula [(NHC)AgX] are synthesized and characterized, showing that the 109Ag NMR chemical shift of the series correlates with the Brønsted acidity of the conjugate acid of X- (i.e., HX), thus establishing an acidity scale based on 109Ag NMR chemical shift. The methodology is then used to evaluate the Brønsted acidity of the OH sites of representative oxide materials using Dynamic Nuclear Polarization (DNP-)enhanced solid-state NMR spectroscopy.

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.

Nature of GaOx Shells Grown on Silica by Atomic Layer Deposition.

Gallia-based shells with a thickness varying from a submonolayer to ca. 2.5 nm were prepared by atomic layer deposition (ALD) using trimethylgallium, ozone, and partially dehydroxylated silica, followed by calcination at 500 °C. Insight into the atomic-scale structure of these shells was obtained by high-field 71Ga solid-state nuclear magnetic resonance (NMR) experiments and the modeling of X-ray differential pair distribution function data, complemented by Ga K-edge X-ray absorption spectroscopy and 29Si dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) studies. When applying one ALD cycle, the grown submonolayer contains mostly tetracoordinate Ga sites with Si atoms in the second coordination sphere ([4]Ga(Si)) and, according to 15N DNP SENS using pyridine as the probe molecule, both strong Lewis acid sites (LAS) and strong Brønsted acid sites (BAS), consistent with the formation of gallosilicate Ga-O-Si and Ga-µ2-OH-Si species. The shells obtained using five and ten ALD cycles display characteristics of amorphous gallia (GaOx), i.e., an increased relative fraction of pentacoordinate sites ([5]Ga(Ga)), the presence of mild LAS, and a decreased relative abundance of strong BAS. The prepared Ga1-, Ga5-, and Ga10-SiO2-500 materials catalyze the dehydrogenation of isobutane to isobutene, and their catalytic performance correlates with the relative abundance and strength of LAS and BAS, viz., Ga1-SiO2-500, a material with a higher relative fraction of strong LAS, is more active and stable compared to Ga5- and Ga10-SiO2-500. In contrast, related ALD-derived Al1-, Al5-, and Al10-SiO2-500 materials do not catalyze the dehydrogenation of isobutane and this correlates with the lack of strong LAS in these materials that instead feature abundant strong BAS formed via the atomic-scale mixing of Al sites with silica, leading to Al-µ2-OH-Si sites. Our results suggest that [4]Ga(Si) sites provide strong Lewis acidity and drive the dehydrogenation activity, while the appearance of [5]Ga(Ga) sites with mild Lewis activity is associated with catalyst deactivation through coking. Overall, the atomic-level insights into the structure of the GaOx-based materials prepared in this work provide a guide to design active Ga-based catalysts by a rational tailoring of Lewis and Brønsted acidity (nature, strength, and abundance).

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.

Direct Identification of Zeolite Beta Polymorphs by Solid-State 29Si Nuclear Magnetic Resonance Spectroscopy.

Stacking disorder and polymorphism in zeolite and zeolite-like materials hinder their structural characterization. In this work, we propose an advanced approach based on applying "pure shift" solid-state 29Si nuclear magnetic resonance (NMR) spectroscopy for the structural investigation of zeolitic materials containing intergrown polymorphs. The approach developed in the case study of zeolite beta allows for the resolution of 21 29Si signals, attributing them to non-equivalent T sites in polymorphs A, B, and C, reconstruction of individual 29Si magic angle spinning NMR spectra for each polymorph, and determination of the polymorph composition with higher accuracy than X-ray diffraction. The results reveal that two widely used synthetic routes for zeolite beta, alkaline and fluoride synthesis, lead to different polymorph compositions. These findings indicate that "pure shift" solid-state 29Si NMR can serve as a superior tool for the elucidation of polymorphism in zeolites.

Atomic-scale changes of silica-supported catalysts with nanocrystalline or amorphous gallia phases: implications of hydrogen pretreatment on their selectivity for propane dehydrogenation.

This work explores how H2 pretreatment at 550 °C induces structural transformation of two gallia-based propane dehydrogenation (PDH) catalysts, viz. nanocrystalline γ/ß-Ga2O3 and amorphous Ga2O3 (GaO x ) supported on silica (γ-Ga2O3/SiO2 and Ga/SiO2, respectively) and how it affects their activity, propene selectivity and stability with time on stream (TOS). Ga/SiO2-H2 shows poor activity and propene selectivity, no coking and no deactivation with TOS, similar to Ga/SiO2. In contrast, the high initial activity and propene selectivity of γ-Ga2O3/SiO2-H2 decline with TOS but to a lesser extent than in calcined γ-Ga2O3/SiO2. In addition, γ-Ga2O3/SiO2-H2 cokes less than γ-Ga2O3/SiO2. Ga K-edge X-ray absorption spectroscopy suggests an increased disorder of the nanocrystalline γ/ß-Ga2O3 phases in γ-Ga2O3/SiO2-H2 and the emergence of additional tetrahedral Ga sites (GaIV). Such GaIV sites are strong Lewis acid sites (LAS) according to studies using adsorbed pyridine and CO probe molecules, i.e., the abundance of strong LAS is higher in γ-Ga2O3/SiO2-H2 compared to γ-Ga2O3/SiO2 but lower than in Ga/SiO2 and Ga/SiO2-H2. Dissociation of H2 on the Ga-O linkages in γ-Ga2O3/SiO2-H2 yields high-frequency Ga-H bands that are observed in Ga/SiO2 and Ga/SiO2-H2 but not detected in γ-Ga2O3/SiO2. We attribute the increased amount of GaIV sites in γ-Ga2O3/SiO2-H2 mostly to an increased disorder in γ/ß-Ga2O3. X-ray photoelectron spectroscopy detects the formation of Ga+ and Ga0 species in both Ga/SiO2-H2 and γ-Ga2O3/SiO2-H2. Therefore, it is likely that a minor amount of GaIV sites also forms through the interaction of Ga+ (such as Ga2O) and/or Ga0 with silanol groups of SiO2.

Structure and Framework Association of Lewis Acid Sites in MOR Zeolite.

Zeolites, although key materials used in industrial processes, remain poorly understood on a molecular level despite their well-defined crystal lattices. In fact, obtaining a direct spectroscopic signatures and resolving the structure of Lewis acid sites (LAS) has remained a challenge. In this work, thanks to 1D and 2D 1H, 15N, and 27Al MAS NMR spectroscopy, carried out at different temperatures (from 298 down to 107 K), we were able to obtain the NMR spectroscopic signatures of LAS and Brønsted acid sites (BAS) in mordenite zeolite in the presence and the absence of adsorbed pyridine (Py). Combined with DFT modeling, this information enabled the structure of LAS to be revealed, namely (≡SiO)3Al sites interacting with pyridine, thus indicating that the corresponding base-free framework-associated sites are pseudo tricoordinated Al sites, namely tricoordinated Al sites interacting with an additional coordinated adjacent siloxane bridge. With this information in hand, we propose a molecular-level understanding on how the AlIV and AlVI framework and framework-associated sites evolve upon dehydration and exposure to Py into BAS and LAS, and their associated Py adducts. By measuring and analyzing the changes in quadrupolar coupling constants (CQ) that reflect electrical charge distribution around the nuclei, we further show that the lower CQ values observed at 298 K are due to residual dynamics that makes the electric field around aluminum nuclei more symmetric. Thus, NMR spectroscopic signatures of 27Al greatly vary with temperature; this information illustrates the importance of accounting for the temperature effect when confronting experimental and calculated CQ values of the corresponding aluminum sites in zeolites in order to obtain accurate structural assessment.

Single-Site Iridium Picolinamide Catalyst Immobilized onto Silica for the Hydrogenation of CO2 and the Dehydrogenation of Formic Acid.

The development of an efficient heterogeneous catalyst for storing H2 into CO2 and releasing it from the produced formic acid, when needed, is a crucial target for overcoming some intrinsic criticalities of green hydrogen exploitation, such as high flammability, low density, and handling. Herein, we report an efficient heterogeneous catalyst for both reactions prepared by immobilizing a molecular iridium organometallic catalyst onto a high-surface mesoporous silica, through a sol-gel methodology. The presence of tailored single-metal catalytic sites, derived by a suitable choice of ligands with desired steric and electronic characteristics, in combination with optimized support features, makes the immobilized catalyst highly active. Furthermore, the information derived from multinuclear DNP-enhanced NMR spectroscopy, elemental analysis, and Ir L3-edge XAS indicates the formation of cationic iridium sites. It is quite remarkable to note that the immobilized catalyst shows essentially the same catalytic activity as its molecular analogue in the hydrogenation of CO2. In the reverse reaction of HCOOH dehydrogenation, it is approximately twice less active but has no induction period.

A Formulation Protocol with Pyridine to Enable Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy on Reactive Surface Sites: Case Study with Olefin Polymerization and Metathesis Catalysts.

Dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP-SENS) has emerged as a powerful characterization tool in material chemistry and heterogeneous catalysis by dramatically increasing, by up to 2 orders of magnitude, the NMR signals associated with surface sites. DNP-SENS mostly relies on using exogenous polarizing agents (PAs), typically dinitroxyl radicals, to boost the NMR signals. However, the PAs may interact with the surface or even react with surface sites, thus leading to loss or quenching of DNP enhancements. Herein, we describe the development of a DNP-SENS formulation that allows broadening the application of DNP-SENS to samples containing highly reactive surface sites, namely a Ziegler-Natta propylene polymerization catalyst, a sulfated zirconia-supported metallocene, and a silica-supported cationic Mo alkylidene. The protocol consists of adsorbing pyridine prior to the DNP formulation (TEKPol/TCE). The addition of pyridine not only preserves the PAs and thereby restores the DNP enhancement but also allows probing Lewis/Brønsted acid surface sites that are often present on these catalysts.

Direct Observation of Tin in Different T-Sites of Sn-BEA by One- and Two-Dimensional 119Sn MAS NMR Spectroscopy.

The direct and quantitative identification of active sites is crucial for the development of zeolite catalysts and their implementation in industry. Herein we report on the application of one-dimensional 119Sn direct polarization (DP) and rotational echo double-resonance (REDOR) and two-dimensional 119Sn magic-angle tuning (MAT) NMR spectroscopy for the identification of different Sn sites in fully dehydrated Sn-BEA zeolite. It is demonstrated that 119Sn magic-angle spinning (MAS) NMR techniques, modified by Carr-Purcell-Meiboom-Gill (CPMG) echo-train acquisition allow to resolve three groups of NMR signals, which can be attributed to three groups of nonequivalent T-sites based on the existing theoretical predictions: (I) T9, T4, and T3; (II) T2, T1, and T8; and (III) T7, T5, and T6. Results suggest that the sites attributed to group III are the most populated in Sn-BEA samples obtained via the fluoride route. The attribution of NMR lines to different T-sites in the structure of BEA allows for the establishment of structure-reactivity relationship and therefore for further improvement of Sn-BEA catalysts.

Time-Resolved In†Situ MAS NMR Monitoring of the Nucleation and Growth of Zeolite BEA Catalysts under Hydrothermal Conditions.

Time-resolved 13 C, 23 Na, 27 Al, and 29 Si MAS NMR has been applied in situ for monitoring the hydrothermal synthesis of zeolite BEA. Isotopic labelling with 29 Si and 13 C isotopes has been used to follow the fate of siliceous species and structure directing agent ((13 CH3 -CH2 )4 NOH). Two mechanistic pathways, namely solution-mediated and solid-solid hydrogel rearrangement have been distinguished for two synthesis procedures studied. The mechanisms of structure-directing behavior of TEA+ cations in two reaction pathways have been elucidated. The results show that multinuclear MAS NMR can serve as a superior tool for monitoring hydrothermal synthesis of various solids including zeolites, zeotypes, mesoporous materials, metal-organic frameworks and so on and for the design of novel outstanding materials for different applications.

Application of (119)Sn CPMG MAS NMR for Fast Characterization of Sn Sites in Zeolites with Natural (119)Sn Isotope Abundance.

(119)Sn CPMG MAS NMR is demonstrated to be a fast and efficient method for characterization of Sn-sites in Sn-containing zeolites. Tuning of the CPMG echo-train sequence decreases the experimental time by a factor of 5-40 in the case of as-synthesized and hydrated Sn-BEA samples and by 3 orders of magnitude in the case of dehydrated Sn-BEA samples as compared to conventional methods. In the latter case, the reconstruction of the quantitative spectrum without the loss of sensitivity is shown to be possible. The method proposed allows obtaining (119)Sn MAS NMR spectra with improved resolution for Sn-BEA zeolites with natural (119)Sn isotope abundance using conventional MAS NMR equipment.