Detection of the Surface of Crystalline Y2O3 Using Direct 89Y Dynamic Nuclear Polarization.

Nuclei with low gyromagnetic ratio (γ) present a serious sensitivity challenge for nulear magnetic resonance (NMR) spectroscopy. Recently, dynamic nuclear polarization (DNP) has shown great promise in overcoming this hurdle by indirect hyperpolarization (via 1H) of these low-γ nuclei. Here we show that at a magnetic field of 9.4 T and cryogenic temperature of about 110 K direct DNP of 89Y in a frozen solution of Y(NO3)3 can offer signal enhancements greater than 80 times using exogeneous trityl OX063 monoradical by satisfying the cross effect magic angle spinning (MAS) DNP mechanism. The large signal enhancement achieved permits 89Y NMR spectra of Y2O3 and Gd2O3-added Y2O3 materials to be obtained quickly (∼30 min), revealing a range of surface yttrium hydroxyl groups in addition to the two octahedral yttrium signals of the core. The results open up promises for the observation of low gyromagnetic ratio nuclei and the detection of corresponding surface and (sub-)surface sites.

Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR.

Acidic zeolites are porous aluminosilicates used in a wide range of industrial processes such as adsorption and catalysis. The formation of carbocation intermediates plays a key role in reactivity, selectivity and deactivation in heterogeneous catalytic processes. However, the observation and determination of carbocations remain a significant challenge in heterogeneous catalysis due to the lack of selective techniques of sufficient sensitivity to detect their low concentrations. Here, we combine 13C isotopic enrichment and efficient dynamic nuclear polarization magic angle spinning nuclear magnetic resonance spectroscopy to detect carbocations in zeolites. We use two dimensional 13C-13C through-bond correlations to establish their structures and 29Si-13C through-space experiments to quantitatively probe the interaction between multiple surface sites of the zeolites and the confined hydrocarbon pool species. We show that a range of various membered ring carbocations are intermediates in the methanol to hydrocarbons reaction catalysed by different microstructural ß-zeolites and highlight that different reaction routes for the formation of both targeted hydrocarbon products and coke exist. These species have strong van der Waals interaction with the zeolite framework demonstrating that their accumulation in the channels of the zeolites leads to deactivation. These results enable understanding of deactivation pathways and open up opportunities for the design of catalysts with improved performances.

Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution.

Conjugated polymers have sparked much interest as photocatalysts for hydrogen production. However, beyond basic considerations such as spectral absorption, the factors that dictate their photocatalytic activity are poorly understood. Here we investigate a series of linear conjugated polymers with external quantum efficiencies for hydrogen production between 0.4 and 11.6%. We monitor the generation of the photoactive species from femtoseconds to seconds after light absorption using transient spectroscopy and correlate their yield with the measured photocatalytic activity. Experiments coupled with modeling suggest that the localization of water around the polymer chain due to the incorporation of sulfone groups into an otherwise hydrophobic backbone is crucial for charge generation. Calculations of solution redox potentials and charge transfer free energies demonstrate that electron transfer from the sacrificial donor becomes thermodynamically favored as a result of the more polar local environment, leading to the production of long-lived electrons in these amphiphilic polymers.

Publisher Correction: Liquid phase blending of metal-organic frameworks.

The original version of this Article contained an error in Figure 1b, where the blue '(ZIF-4-Zn)0.5 (ZIF-62)0.5 blend' data curve was omitted from the enthalpy response plot. This has now been corrected in both the PDF and HTML versions of the Article.

Liquid phase blending of metal-organic frameworks.

The liquid and glass states of metal-organic frameworks (MOFs) have recently become of interest due to the potential for liquid-phase separations and ion transport, alongside the fundamental nature of the latter as a new, fourth category of melt-quenched glass. Here we show that the MOF liquid state can be blended with another MOF component, resulting in a domain structured MOF glass with a single, tailorable glass transition. Intra-domain connectivity and short range order is confirmed by nuclear magnetic resonance spectroscopy and pair distribution function measurements. The interfacial binding between MOF domains in the glass state is evidenced by electron tomography, and the relationship between domain size and Tg investigated. Nanoindentation experiments are also performed to place this new class of MOF materials into context with organic blends and inorganic alloys.

Ultra-Fast Molecular Rotors within Porous Organic Cages.

Using variable temperature 2 H static NMR spectra and 13 C spin-lattice relaxation times (T1 ), we show that two different porous organic cages with tubular architectures are ultra-fast molecular rotors. The central para-phenylene rings that frame the "windows" to the cage voids display very rapid rotational rates of the order of 1.2-8×106  Hz at 230 K with low activation energy barriers in the 12-18 kJ mol-1 range. These cages act as hosts to iodine guest molecules, which dramatically slows down the rotational rates of the phenylene groups (5-10×104  Hz at 230 K), demonstrating potential use in applications that require molecular capture and release.

Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T.

We report 17O dynamic nuclear polarisation (DNP) enhanced solid-state NMR experiments at 18.8 T. Several formulations were investigated on the Mg(OH)2 compound. A signal enhancement factor of 17 could be obtained when the solid particles were incorporated into a glassy o-terphenyl matrix doped with BDPA using the Overhauser polarisation transfer scheme whilst the cross effect mechanism enabled by TEKPol yielded a slightly lower enhancement but more time efficient data acquisition.

Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts.

Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO2, but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co-polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.

A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling.

X-ray diffraction has been used to investigate the kinetics of amorphization through ball-milling at 20 Hz, for five zeolitic imidazolate frameworks (ZIFs) - ZIF-8, ZIF-4, ZIF-zni, BIF-1-Li and CdIF-1. We find that the rates of amorphization for the zinc-containing ZIFs increase with increasing solvent accessible volume (SAV) in the sequence ZIF-8 > ZIF-4 > ZIF-zni. The Li-B analogue of the dense ZIF-zni amorphizes more slowly than the corresponding zinc phase, with the behaviour showing a correlation with their relative bulk moduli and SAVs. The cadmium analogue of ZIF-8 (CdIF-1) amorphizes more rapidly than the zinc counterpart, which we ascribe primarily to its relatively weak M-N bonds as well as the higher SAV. The results for the ZIFs are compared to three classical zeolites - Na-X, Na-Y and ZSM-5 - with these taking up to four times longer to amorphize. The presence of adsorbed solvent in the pores is found to render both ZIF and zeolite frameworks more resistant to amorphization. X-ray total scattering measurements show that amorphous ZIF-zni is structurally indistinguishable from amorphous ZIF-4 with both structures retaining the same short-range order that is present in their crystalline precursors. By contrast, both X-ray total scattering measurements and (113)Cd NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor.

Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts.

Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO2, but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co-polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.

Influence of Functionalization of Nanocontainers on Self-Healing Anticorrosive Coatings.

Feedback coating based on pH-induced release of inhibitor from organosilyl-functionalized containers is considered as a compelling candidate to achieve smart self-healing corrosion protection. Four key factors that determine the overall coating performance include (1) the uptake and release capacity of containers, (2) prevention of the premature leakage, (3) compatibility of containers in coating matrix, and (4) cost and procedure simplicity consideration. The critical influence introduced by organosilyl-functionalization of containers is systematically demonstrated by investigating MCM-41 silica nanoparticles modified with ethylenediamine (en), en-4-oxobutanoic acid salt (en-COO(-)), and en-triacetate (en-(COO(-))3) with higher and lower organic contents. The properties of the modified silica nanoparticles as containers were mainly characterized by solid-state (13)C nuclear magnetic resonance, scanning and transmission electron microscopy, N2 sorption, thermogravimetric analysis, small-angle X-ray scattering, dynamic light scattering, and UV-vis spectroscopy. Finally, the self-healing ability and anticorrosive performances of hybrid coatings were examined through scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS). We found that en-(COO(-))3-type functionalization with content of only 0.23 mmol/g performed the best as a candidate for establishing pH-induced release system because the resulting capped and loaded (C-L) functionalized silica nanocontainers (FSNs) exhibit high loading (26 wt %) and release (80%) capacities for inhibitor, prevention of premature leakage (less than 2%), good dispersibility in coating matrix, and cost effectiveness.