Labeling and Probing the Silica Surface Using Mechanochemistry and 17O NMR Spectroscopy**

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly ¹⁷O enrichment protocols to help to understand the structure and reactivity of materials by using ¹⁷O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision ¹⁷O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution ¹⁷O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si−O−Si) and silanols (Si−OH), while DNP analyses, performed by using direct ¹⁷O polarization and indirect ¹⁷O{¹H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si−OH environments at the surface was obtained from 2D ¹H−¹⁷O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using ¹⁷O DNP, their common interface was probed and Si−O−Ti bonds identified.     

Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina

Recent studies have shown that dynamic nuclear polarization (DNP) can be used to detect ¹⁷O solid-state NMR spectra of naturally abundant samples within a reasonable experimental time. Observations using indirect DNP, which relies on ¹H mediation in transferring electron hyperpolarization to ¹⁷O, are currently limited mostly to hydroxyls. Direct DNP schemes can hyperpolarize non-protonated oxygen near the radicals; however, they generally offer much lower signal enhancements. In this study, we demonstrate the detection of signals from non-protonated ¹⁷O in materials containing silicon. The sensitivity boost that made the experiment possible originates from three sources: indirect DNP excitation of ²⁹Si via protons, indirect detection of ¹⁷O through ²⁹Si nuclei using two-dimensional ²⁹Si{¹⁷O} D-HMQC, and Carr-Purcell-Meiboom-Gill refocusing of ²⁹Si magnetization during acquisition. This ²⁹Si-detected scheme enabled, for the first time, 2D ¹⁷O−²⁹Si heteronuclear correlation spectroscopy in mesoporous silica and silica-alumina surfaces at natural abundance. In contrast to the silanols showing motion-averaged ¹⁷O signals, the framework oxygens exhibit unperturbed powder patterns as unambiguous fingerprints of surface sites. Along with hydroxyl oxygens, detection of these moieties will help in gaining more atomistic-scale insights into surface chemistry.     

Unleashing the Potential of 17O NMR Spectroscopy Using Mechanochemistry

¹⁷O NMR spectroscopy has been the subject of vivid interest in recent years, because there is increasing evidence that it can provide unique insight into the structure and reactivity of many molecules and materials. However, due to the very poor natural abundance of oxygen‐17, ¹⁷O labeling is generally a prerequisite. This is a real obstacle for most research groups, because of the high costs and/or strong experimental constraints of the most frequently used ¹⁷O‐labeling schemes. Here, we show for the first time that mechanosynthesis offers unique opportunities for enriching in ¹⁷O a variety of organic and inorganic precursors of synthetic interest. The protocols are fast, user‐friendly, and low‐cost, which makes them highly attractive for a broad research community, and their suitability for ¹⁷O solid‐state NMR applications is demonstrated.     

Atomistic Description of Reaction Intermediates for Supported Metathesis Catalysts Enabled by DNP SENS

Obtaining detailed structural information of reaction intermediates remains a key challenge in heterogeneous catalysis because of the amorphous nature of the support and/or the support interface that prohibits the use of diffraction‐based techniques. Combining isotopic labeling and dynamic nuclear polarization (DNP) increases the sensitivity of surface enhanced solid‐state NMR spectroscopy (SENS) towards surface species in heterogeneous alkene metathesis catalysts; this in turn allows direct determination of the bond connectivity and measurement of the carbon–carbon bond distance in metallacycles, which are the cycloaddition intermediates in the alkene metathesis catalytic cycle. Furthermore, this approach makes possible the understanding of the slow initiation and deactivation steps in these heterogeneous metathesis catalysts.     

Unleashing the Potential of 17O NMR Spectroscopy Using Mechanochemistry

¹⁷O NMR spectroscopy has been the subject of vivid interest in recent years, because there is increasing evidence that it can provide unique insight into the structure and reactivity of many molecules and materials. However, due to the very poor natural abundance of oxygen-17, ¹⁷O labeling is generally a prerequisite. This is a real obstacle for most research groups, because of the high costs and/or strong experimental constraints of the most frequently used ¹⁷O-labeling schemes. Here, we show for the first time that mechanosynthesis offers unique opportunities for enriching in ¹⁷O a variety of organic and inorganic precursors of synthetic interest. The protocols are fast, user-friendly, and low-cost, which makes them highly attractive for a broad research community, and their suitability for ¹⁷O solid-state NMR applications is demonstrated.     

Natural Abundance 17O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by ¹⁷O DNP surface‐enhanced NMR spectroscopy (SENS). We additionally show that the O−H bond length in these catalysts can be measured with sub‐picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. Experiments performed on materials impregnated with pyridine also allow for the direct detection of intermolecular hydrogen bonding interactions through the lengthening of O−H bonds.     

Quantitative Structural Constraints for Organic Powders at Natural Isotopic Abundance Using Dynamic Nuclear Polarization Solid‐State NMR Spectroscopy

A straightforward method is reported to quantitatively relate structural constraints based on ¹³C–¹³C double‐quantum build‐up curves obtained by dynamic nuclear polarization (DNP) solid‐state NMR to the crystal structure of organic powders at natural isotopic abundance. This method relies on the significant gain in NMR sensitivity provided by DNP (approximately 50‐fold, lowering the experimental time from a few years to a few days), and is sensitive to the molecular conformation and crystal packing of the studied powder sample (in this case theophylline). This method allows trial crystal structures to be rapidly and effectively discriminated, and paves the way to three‐dimensional structure elucidation of powders through combination with powder X‐ray diffraction, crystal‐structure prediction, and density functional theory computation of NMR chemical shifts.     

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 ¹¹³Cd and ⁷⁷Se 1D NMR helps to identify both bulk and surface sites of NCs, while ¹¹³Cd 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 ¹⁵N 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.     

Ce3+掺杂La2O3的17O固体核磁共振研究

本文用水热共沉淀法制备Ce³⁺掺杂La₂O₃的前驱体,随后在H₂/N₂气氛下用高温煅烧法合成了不同Ce³⁺浓度的掺杂La₂O₃。由于Ce³⁺的掺杂,¹⁷O固体核磁共振谱图中在698、650和558处出现了新的共振峰;随着Ce³⁺掺杂浓度的增加,这些峰的强度也随之增强。根据谱峰位置和强度,对谱图进行了归属：698、650处的共振峰应源自与Ce³⁺相连的四配位O(OCeLa₃),558处的信号则来自于与Ce³⁺相连的六配位O(OCeLa₅)。通过¹⁷O固体核磁共振能够直接观测与Ce³⁺直接相连的O显示该方法将可能用于研究稀土掺杂氧化物功能材料。     

Natural Abundance 17O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by ¹⁷O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O−H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. Experiments performed on materials impregnated with pyridine also allow for the direct detection of intermolecular hydrogen bonding interactions through the lengthening of O−H bonds.     

Ce3+掺杂La2O3的17O固体核磁共振研究

本文用水热共沉淀法制备Ce³⁺掺杂La₂O₃的前驱体,随后在H₂/N₂气氛下用高温煅烧法合成了不同Ce³⁺浓度的掺杂La₂O₃。由于Ce³⁺的掺杂,¹⁷O固体核磁共振谱图中在698、650和558处出现了新的共振峰;随着Ce³⁺掺杂浓度的增加,这些峰的强度也随之增强。根据谱峰位置和强度,对谱图进行了归属:698、650处的共振峰应源自与Ce³⁺相连的四配位O(OCeLa₃),558处的信号则来自于与Ce³⁺相连的六配位O(OCeLa₅)。通过¹⁷O固体核磁共振能够直接观测与Ce³⁺直接相连的O显示该方法将可能用于研究稀土掺杂氧化物功能材料。     

Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid‐State NMR Spectroscopy

Molecular orientation in amorphous organic semiconducting thin‐film devices is an important issue affecting device performance. However, to date it has not been possible to analyze the “distribution” of the orientations. Although solid‐state NMR (ssNMR) spectroscopy can provide information on the “distribution” of molecular orientations, the technique is limited because of the small amount of sample in the device and the low sensitivity of ssNMR. Here, we report the first application of dynamic nuclear polarization enhanced ssNMR (DNP‐ssNMR) spectroscopy for the orientational analysis of amorphous phenyldi(pyren‐1‐yl)phosphine oxide (POPy₂). The ³¹P DNP‐ssNMR spectra exhibited a sufficient signal‐to‐noise ratio to quantify the distribution of molecular orientations in amorphous films: the P=O axis of the vacuum‐deposited and drop‐cast POPy₂ shows anisotropic and isotropic distribution, respectively. The different molecular orientations reflect the molecular origin of the different charge transport behaviors.     

Fast characterization of functionalized silica materials by silicon-29 surface-enhanced NMR spectroscopy using dynamic nuclear polarization

We demonstrate fast characterization of the distribution of surface bonding modes and interactions in a series of functionalized materials via surface-enhanced nuclear magnetic resonance spectroscopy using dynamic nuclear polarization (DNP). Surface-enhanced silicon-29 DNP NMR spectra were obtained by using incipient wetness impregnation of the sample with a solution containing a polarizing radical (TOTAPOL). We identify and compare the bonding topology of functional groups in materials obtained via a sol-gel process and in materials prepared by post-grafting reactions. Furthermore, the remarkable gain in time provided by surface-enhanced silicon-29 DNP NMR spectroscopy (typically on the order of a factor 400) allows the facile acquisition of two-dimensional correlation spectra.     

Structure and acid-basic properties of the surface of titanium oxides modified by phosphorus and aluminum and prepared by the alkoxo method. 2. Study of the active surface of titanium oxides

The data of temperature-programmed desorption of ammonia from the surface of oxide systems and IR spectroscopy were used to demonstrate that the strength of the surface acid sites in titanium oxides prepared by the alkoxo method and modified by aluminum decreases with respect to that in nonmodified titanium oxide. Modification of titanium oxide with P³⁺ ions from ethriol phosphite almost completely suppresses the acid properties. Modified oxides are able to chemisorb water. XANES data suggest that modification of titanium oxide with phosphorus ions increases the electron density on the titanium atoms and, correspondingly, the basicity of the materials.     

Centrifugal distortion and oxygen-17 quadrupole coupling in ethylene oxide

The microwave spectrum of ethylene oxide has been reinvestigated to determine its quartic centrifugal distortion constants and the quadrupole coupling constants of the ¹⁷O species. The measurements of the quadrupole structure were done in natural isotopic abundance (0.037%) using a computer coupled spectrograph.     

17O NMR spectroscopy of crystalline microporous materials

Microporous materials, containing pores and channels of similar dimensions to small molecules have a range of applications in catalysis, gas storage and separation and in drug delivery. Their complex structure, often containing different types and levels of positional, compositional and temporal disorder, makes structural characterisation challenging, with information on both long-range order and the local environment required to understand the structure–property relationships and improve the future design of functional materials. In principle, ¹⁷O NMR spectroscopy should offer an ideal tool, with oxygen atoms lining the pores of many zeolites and phosphate frameworks, playing a vital role in host–guest chemistry and reactivity, and linking the organic and inorganic components of metal–organic frameworks (MOFs). However, routine study is challenging, primarily as a result of the low natural abundance of this isotope (0.037%), exacerbated by the presence of the quadrupolar interaction that broadens the spectral lines and hinders the extraction of information. In this Perspective, we will highlight the current state-of-the-art for ¹⁷O NMR of microporous materials, focusing in particular on cost-effective and atom-efficient approaches to enrichment, the use of enrichment to explore chemical reactivity, the challenge of spectral interpretation and the approaches used to help this and the information that can be obtained from NMR spectra. Finally, we will turn to the remaining challenges, including further improving sensitivity, the high-throughput generation of multiple structural models for computational study and the possibility of in situ and in operando measurements, and give a personal perspective on how these required improvements can be used to help solve important problems in microporous materials chemistry.

Cost-effective and atom-efficient isotopic enrichment enables ¹⁷O NMR spectroscopy of microporous materials to be used to probe local structure and disorder and to explore chemical reactivity.     

Sulfide Catalysts Supported on Al2O3: VI. Synthesis of Catalysts with the Use of Binuclear Molybdenum(V) Complexes with Sulfur-Containing Ligands

A new method was developed for the preparation of sulfide catalysts supported on aluminum oxide. The surface assembling of a direct precursor of the active component was used in this method. The method consists in the sequential immobilization of binuclear molybdenum complexes with S-containing ligands on the support surface followed by the immobilization of nickel (cobalt) compounds at the surface molybdenum complexes. The complexation and structure of the resulting complexes in solution and the structure of surface complexes were studied by ⁹⁵Mo and ¹⁷O NMR, IR, and EXAFS spectroscopy. The surface assembling of a direct precursor of the active component of sulfide hydrodesulfurization catalysts was demonstrated using IR and EXAFS spectroscopy. The activity of the resulting catalysts in a model reaction of thiophene hydrogenolysis was comparable to the activity of sulfide catalysts of the metal complex origin and was much higher than the activity of commercial catalysts and catalysts prepared by impregnation.     

Structural Insights into Peptides Bound to the Surface of Silica Nanopores

The structure and surface functionalization of biologically relevant silica-based hybrid materials was investigated by 2D solid-state NMR techniques combined with dynamic nuclear polarization (DNP). This approach was applied to a model system of mesoporous silica, which was modified through in-pore grafting of small peptides by solid-phase peptide synthesis (SPPS). To prove the covalent binding of the peptides on the surface, DNP-enhanced solid-state NMR was used for the detection of ¹⁵N NMR signals in natural abundance. DNP-enhanced heterocorrelation experiments with frequency switched Lee–Goldburg homonuclear proton decoupling (¹H–¹³C and ¹H–¹⁵N CP MAS FSLG HETCOR) were performed to verify the primary structure and configuration of the synthesized peptides. ¹H FSLG spectra and ¹H-²⁹Si FSLG HETCOR correlation spectra were recorded to investigate the orientation of the amino acid residues with respect to the silica surface. The combination of these NMR techniques provides detailed insights into the structure of amino acid functionalized hybrid compounds and allows for the understanding for each synthesis step during the in-pore SPPS.     

Efficient Building Blocks for Solid-Phase Peptide Synthesis of Spin Labeled Peptides for Electron Paramagnetic Resonance and Dynamic Nuclear Polarization Applications

Specific spin labeling allows the site-selective investigation of biomolecules by EPR and DNP enhanced NMR spectroscopy. A novel spin labeling strategy for commercially available Fmoc-amino acids is developed. In this approach, the PROXYL spin label is covalently attached to the hydroxyl side chain of three amino acids hydroxyproline (Hyp), serine (Ser) and tyrosine (Tyr) by a simple three-step synthesis route. The obtained PROXYL containing building-blocks are N-terminally protected by the Fmoc-protection group, which makes them applicable for the use in solid-phase peptide synthesis (SPPS). This approach allows the insertion of the spin label at any desired position during SPPS, which makes it more versatile than the widely used post synthetic spin labeling strategies. For the final building-blocks, the radical activity is proven by EPR. DNP enhanced solid-state NMR experiments employing these building-blocks in a TCE solution show enhancement factors of up to 26 for ¹H and ¹³C (¹H→¹³C cross-polarization). To proof the viability of the presented building-blocks for insertion of the spin label during SPPS the penta-peptide Acetyl-Gly-Ser(PROXYL)-Gly-Gly-Gly was synthesized employing the spin labeled Ser building-block. This peptide could successfully be isolated and the spin label activity proved by EPR and DNP NMR measurements, showing enhancement factors of 12.1±0.1 for ¹H and 13.9±0.5 for ¹³C (direct polarization).     

Bis‐Gadolinium Complexes for Solid Effect and Cross Effect Dynamic Nuclear Polarization

High‐spin complexes act as polarizing agents (PAs) for dynamic nuclear polarization (DNP) in solid‐state NMR spectroscopy and feature promising aspects towards biomolecular DNP. We present a study on bis(Gd‐chelate)s which enable cross effect (CE) DNP owing to spatial confinement of two dipolar‐coupled electron spins. Their well‐defined Gd⋅⋅⋅Gd distances in the range of 1.2–3.4 nm allowed us to elucidate the Gd⋅⋅⋅Gd distance dependence of the DNP mechanism and NMR signal enhancement. We found that Gd⋅⋅⋅Gd distances above 2.1 nm result in solid effect DNP while distances between 1.2 and 2.1 nm enable CE for ¹H, ¹³C, and ¹⁵N nuclear spins. We compare 263 GHz electron paramagnetic resonance (EPR) spectra with the obtained DNP field profiles and discuss possible CE matching conditions within the high‐spin system and the influence of dipolar broadening of the EPR signal. Our findings foster the understanding of the CE mechanism and the design of high‐spin PAs for specific applications of DNP.