Spatial Distribution of Silica-Bound Catalytic Organic Functional Groups Can Now Be Revealed by Conventional and DNP-Enhanced Solid-State NMR Methods

Understanding the spatial distribution of functionalities on surfaces with atomic-scale resolution is very important for catalytic applications, yet very challenging for analytical inquiry. Recent advances in solid-state nuclear magnetic resonance (SSNMR), especially in dynamic nuclear polarization and fast magic-angle spinning, offer new tools for examining this longstanding problem. The aim of this Perspective is to showcase how these SSNMR methods can shed light on the uniformity of surface functionalities deployed on mesoporous silica-based catalysts using post-synthesis grafting and co-condensation methods. The results are discussed in the context of earlier landmark studies on the spatial distributions of surface species using probe molecules and reactions

Growing Signals from the Noise: Challenging Nuclei in Materials DNP

The polarization of nuclear spins by dynamic nuclear polarization (DNP) has redefined the sensitivity limits of solid‐state (SS) NMR spectroscopy. Materials science has been arguably one of the key beneficiaries of the recent remarkable advances of the technique, which included low‐temperature magic angle spinning (MAS), modern gyrotrons, and biradical agents for polarization transfer via the cross‐effect. In many classes of materials, DNP offers the capability of selectively sensitizing progressively smaller surface and interfacial regions of materials and eliciting responses from previously undetectable nuclei, with no detrimental effect on resolution. We review the most recent applications of DNP‐enhanced SSNMR to materials, focusing specifically on measurements that pose insurmountable challenges to conventional SSNMR, including the detection of 15N, 17O, 25Mg, 35Cl, 43Ca, 79Br, 89Y, 119Sn, and 195Pt by one‐dimensional MAS methods, ultrawideline NMR, as well as two‐dimensional homo‐ and heteronuclear correlation spectroscopy

Measuring Long-Range 13C–13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance

We report that spatial (\u3c1 \u3enm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C–13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution

In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP‐MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. Generally, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near‐optimal DNP performance. Our results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter‐radical distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Lastly, the calculations showed that the electron T1e value should be near 500 μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non‐nitroxide radicals, as well as improvements in sample formulations to advance high‐temperature DNP and limit quenching and reactivity

Reducing t1 noise through rapid scanning

The so-called t1 noise, which arises due to random instabilities in the spectrometer hardware, remains the primary source of noise that limits the sensitivity of most 2D NMR experiments, particularly in the expanding group of solid-state NMR methods that utilize dipolar-recoupling. In this communication we revisit the relationship between the signal intensity and the t1 noise produced. It is shown that since the latter scales linearly with the signal strength, the use of a conventional relaxation delay of 1.3T1 may prove far from optimal. In cases where the fluctuations occur on a shorter timescale than the recycle delay, a considerably faster repetition rate should be used to maximize the time sensitivity in a 2D experiment than what is used to maximize the sensitivity in 1D. This is demonstrated with the acquisition of 1H{13C} Dipolar-mediated Heteronuclear Multiple-Quantum Correlation (D-HMQC) type spectra in which the sensitivity could be nearly doubled by choosing a very short relaxation delay corresponding to 0.2T1

Comparison of Nitroaldol Reaction Mechanisms Using Accurate Ab Initio Calculations

In the nitroaldol reaction, condensation between a nitroalkane and an aldehyde yields a nitroalcohol that can undergo dehydration to yield a nitroalkene. Amine-functionalized, MCM-41-type mesoporous silica nanosphere (MSN) materials have been shown to selectively catalyze this reaction. Gas-phase reaction paths for the several competing mechanisms for the nitroaldol reaction have been mapped out using second-order perturbation theory (MP2). Improved relative energies were determined using singles and doubles coupled cluster theory with perturbative triples, CCSD(T). The mechanism in the absence of a catalyst was used to provide a baseline against which to assess the impact of the catalyst on both the mechanism and the related energetics. Catalyzed mechanisms can either pass through a nitroalcohol intermediate as in the classical mechanism or an imine intermediate

Linear-scaling ab initio simulations of spin diffusion in rotating solids

We investigated the utility of locally restricting the basis sets involved in low-order correlations in Liouville space (LCL) calculations of spin diffusion. Using well-known classical models of spin diffusion, we describe a rationale for selecting the optimal basis set for such calculations. We then show that the use of these locally restricted basis sets provides the same computational accuracy as the full LCL set while reducing the computational time by several orders of magnitude. Speeding up the calculations also enables us to use higher maximum spin orders and increase the computational accuracy. Furthermore, unlike exact and full LCL calculations, locally restricted LCL calculations scale linearly with the system size and should thus enable the ab initio study of spin diffusion in spin systems containing several thousand spins

Large-scale ab initio simulations of MAS DNP enhancements using a Monte Carlo optimization strategy

Magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) has recently emerged as a powerful technology enabling otherwise unrealistic solid-state NMR experiments. The simulation of DNP processes which might, for example, aid in refining the experimental conditions or the design of better performing polarizing agents, is, however, plagued with significant challenges, often limiting the system size to only 3 spins. Here, we present the first approach to fully ab initio large-scale simulations of MAS DNP enhancements. The Landau-Zener equation is used to treat all interactions concerning electron spins, and the low-order correlations in the Liouville space method is used to accurately treat the spin diffusion, as well as its MAS speed dependence. As the propagator cannot be stored, a Monte Carlo optimization method is used to determine the steady-state enhancement factors. This new software is employed to investigate the MAS speed dependence of the enhancement factors in large spin systems where spin diffusion is of importance, as well as to investigate the impacts of solvent and polarizing agent deuteration on the performance of MAS DNP