A new category of crystalline polymer electrolyte prepared by the supramolecular self-assembly of polyethylene oxide (PEO), α-cyclodextrin (α-CD), and LiAsF6 is reported. The polymer electrolyte consists of the nanochannels formed by α-CDs in which the PEO/Li(+) complexes are confined. The nanochannels formed by α-CD provide the pathway for the directional motion of Li(+) ions and at the same time prevent the access of the anions by size exclusion, resulting in good separation of the Li(+) ions and the anions. The conductivity of the reported material is 30 times higher than that of the comparable PEO/Li(+) complex crystal at room temperature. By using state-of-art solid-state NMR spectroscopy, the structure and dynamics of the material were investigated in detail. The dynamics of the Li(+) ions was studied and correlated to the ionic conductivity of the material.

We present a novel concept for rf pulses and optimal control designed cross-polarization experiments for quadrupolar nuclei. The methods are demonstrated for (2)H CP-MAS and (2)H multiple-pulse NMR of perdeuterated proteins, for which sensitivity enhancements up to an order of magnitude are presented relative to commonly used approaches. The so-called RESPIRATION rf pulses combines the concept of short broad-band pulses with generation of pulses with large flip angles through distribution of the rf pulse over several rotor echoes. This lead to close-to-ideal rf pulses, facilitating implementation of experiments relying on the ability to realize high-performance 90 and 180° pulses, as, for example, in refocused INEPT and double-to-single quantum coherence experiments, or just pulses that provide a true representation of the quadrupolar powder pattern to extract information about the structure or dynamics. The optimal control (2)H → (13)C CP-MAS method demonstrates transfer efficiencies up to around 85% while being extremely robust toward rf inhomogeneity and resonance offsets.

Proton transfer (PT) processes in solid–liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid–liquid phases.

A new category of crystalline polymer electrolyte prepared by the supramolecular self‐assembly of polyethylene oxide (PEO), α‐cyclodextrin (α‐CD), and LiAsF6 is reported. The polymer electrolyte consists of the nanochannels formed by α‐CDs in which the PEO/Li+ complexes are confined. The nanochannels formed by α‐CD provide the pathway for the directional motion of Li+ ions and at the same time prevent the access of the anions by size exclusion, resulting in good separation of the Li+ ions and the anions. The conductivity of the reported material is 30 times higher than that of the comparable PEO/Li+ complex crystal at room temperature. By using state‐of‐art solid‐state NMR spectroscopy, the structure and dynamics of the material were investigated in detail. The dynamics of the Li+ ions was studied and correlated to the ionic conductivity of the material.