Inspired by geological ore formation processes, we apply one-step hydrothermal (HT) polymerization to the toughest existing high-performance polymer, poly(p-phenyl pyromellitimide) (PPPI). We obtain highlyordered and fully imidized PPPI as crystalline flakes and flowers on the micrometer scale. In contrast to classical 2-step procedures that require long reaction times and toxic solvents and catalysts, HT polymerization allows for full conversion in only 1 h at 200 C, in nothing but hot water. Investigation of the crystal growth mechanism via scanning electron microscopy (SEM) suggests that PPPI aggregates form via a dissolution-polymerization-crystallization process, which is uniquely facilitated by the reaction conditions in the HT regime. A conventionally prefabricated polyimide did not recrystallize hydrothermally, indicating that the HT polymerization and crystallization occur simultaneously. The obtained material shows excellent crystallinity and remarkable thermal stability (600 C under N 2 ) that stem from a combination of a strong, covalent polymer backbone and interchain hydrogen bonding.

Hydrothermal polymerization (HTP) yields highly crystalline polyimides. A general picture of the mechanisms leading to crystallinity and morphology is provided.

High-purity, symmetrically substituted perylene and naphthalene bisimides were obtained by hydrothermal condensation of monoamines with the corresponding bisanhydride. The hydrothermal imidization proceeds quantitatively, without the need for organic solvents, catalysts or excess of the amines.

Adsorption of molecules on high-surface-area materials is a fundamental process critical to many fields of basic and applied chemical research; for instance, it is among the simplest and most efficient principles for separating and remediating polluted water. However, established experimental approaches for investigating this fundamental process preclude in situ monitoring and thus obtaining real-time information about the ongoing processes. In this work, mid-infrared attenuated total reflection (ATR) spectroscopy is introduced as a powerful technique for quantitative in situ monitoring of adsorption processes and thus enrichment of traces of organic pollutants from aqueous solution in ordered mesoporous silica films. The synthesis, functionalization, and characterization of two silica films with 3D hexagonal and cubic pore structure on silicon ATR crystals are presented. Benzonitrile and valeronitrile as model compounds for aromatic and aliphatic water pollutants are enriched in hydrophobic films, while the matrix, water, is excluded from the volume probed by the evanescent field. Enrichment times of <5 s are observed during in situ measurements of benzonitrile adsorbing onto the film from aqueous solution. The sensing system is calibrated using the Freundlich adsorption equation as calibration function. Enrichment factors of benzonitrile and valeronitrile within the film were determined to be >200 and >100, respectively, yielding detection limits in the low ppm range. Furthermore, fast and complete desorption of the analyte, ensuring reliable regeneration of the sensor, was verified. Lastly, we derive and experimentally validate equations for ATR spectroscopy with thin film adsorption layers to quantify the absolute mass of adsorbed pollutant in the film. The excellent agreement between recorded absorptions at target wavenumbers of the target analytes and corresponding simulations corroborates the validity of the chosen approach.

The local structure of water on chemically and structurally different surfaces is subject of ongoing research. In particular, confined spaces as found in mesoporous silica have a pronounced effect on the interplay between adsorbate-adsorbate and adsorbate-surface interactions. Mid-infrared spectroscopy is ideally suited to quantitatively and qualitatively study such systems as the probed molecular vibrations are highly sensitive to intermolecular interactions. Here, the quantity and structure of water adsorbed from the gas phase into silica mesopores at different water vapor pressures was monitored using mid-infrared attenuated total reflection (ATR) spectroscopy. Germanium ATR crystals were coated with different mesoporous silica films prepared by evaporation induced self-assembly. Quantitative analysis of the water bending vibration at 1640 cm-1 at varying vapor pressure allowed for retrieving porosity and pore size distribution of the mesoporous films. The results were in excellent agreement with those obtained from ellipsometric porosimetry. In addition, different degrees of hydrogen bonding of water as reflected in the band position and shape of the stretching vibrations (3000-3750 cm-1) were analyzed and attributed to high-density, unordered bulk and low-density, surface-induced ordered water. Thereby, the progression of surface-induced ordered water and bulk water as a function of water vapor pressure was studied for different pore sizes. Small pores with 5 nm diameter showed a number of two ordered monolayers, while for pores > 12 nm the number of ordered monolayers is significantly larger and agrees with the number observed on planar SiO2 surfaces.

Hydrothermal polymerization (HTP) is a technique to synthesize highly crystalline polyimides in solely water. The process involves monomer salt intermediates also able to undergo other polymerizations during the HTP experiment: sub‐hydrothermal polymerization (sHTP) and solid‐state polycondensation (SSP). Both processes yield semicrystalline polyimides at best. This is widely believed to result from irreversible bond‐formation and the incorporation of conformational defects during chain growth. Here, microwave‐assisted HTP is used, allowing for controlling the heating time to the reaction temperature, and thus to strongly reduce sHTP. Moreover, we show that highest crystallinity can be obtained in the higher hydrothermal regime (≈200 °C), and synthesize two polyimides of sufficient crystallinity to refine their crystal structures from powder X‐ray diffraction data. This study brings us one step closer to a general picture and rational design of the hydrothermal synthesis of polyimides.

Polarization-dependent infrared spectroscopy of oriented metal organic framework films fills the information gap left by diffraction methods and gives access to the orientation of the aromatic linker and initial orientation of ultra-thin films.

The sensitivity of quartz-enhanced photoacoustic spectroscopy (QEPAS) can be drastically increased using the power enhancement in high-finesse cavities. Here, low noise resonant power enhancement to 6.3 W was achieved in a linear Brewster window cavity by exploiting optical feedback locking of a quantum cascade laser. The high intracavity intensity of up to 73 W mm −2 in between the prongs of a custom tuning fork resulted in strong optical saturation of CO at 4.59 µm. Saturated absorption is discussed theoretically and experimentally for photoacoustic measurements in general and intracavity QEPAS (I-QEPAS) in particular. The saturation intensity of CO's R9 transition was retrieved from power-dependent I-QEPAS signals. This allowed for sensing CO independently from varying degrees of saturation caused by absorption induced changes of intracavity power. Figures of merit of the I-QEPAS setup for sensing of CO and H 2 O are compared to standard wavelength modulation QEPAS without cavity enhancement. For H 2 O, the sensitivity was increased by a factor of 230, practically identical to the power enhancement, while the sensitivity gain for CO detection was limited to 57 by optical saturation.