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Although biomass-based alternatives for the manufacturing of bioplastic films are an important aspect of a more sustainable future, their physicochemical properties need to be able to compete with the existing market to establish them as a viable alternative. One important factor that is often neglected is the long-term stability of renewables-based functional materials, as they should neither degrade after a day or week, nor last forever. One material showing high potential in this regard, also due to its intrinsic biodegradability and antibacterial properties, is chitosan, which can form stable, self-standing films. We previously showed that green additives introduce a broad tunability of the chitosan-based material properties. In this work, we investigate the long-term stability and related degradation processes of chitosan-based bioplastics by assessing their physicochemical properties over 400 days. It was found that the film properties change similarly for samples stored in the fridge (4 °C, dark) as at ambient conditions (20 °C, light/dark cycles of the day). Additives with high vapor pressure, such as glycerol, evaporate and degrade, causing both brittleness and discoloration. In contrast, films with the addition of crosslinking additives, such as citric acid, show high stability also over a long time, bearing great preconditions for practical applications. This knowledge serves as a stepping-stone to utilizing chitosan as an alternative material for renewable-resourced bioplastic products.

To switch to alternatives for fossil-fuel-based polymer materials, renewable raw materials from green resources should be utilized. Chitosan is such a material that is a strong, but workable derivative from chitin, obtained from crustaceans. However, various applications ask for specific plastic properties, such as certain flexibility, hardness and transparency. With different additives, also obtainable from green resources, chitosan-based composites in the form of self-supporting films, ranging from very hard and brittle to soft and flexible were successfully produced. The additives turned out to belong to one of three categories, namely linear, non-linear, or crosslinking additives. The non-linear additives could only be taken up to a certain relative amount, whereas the uptake of linear additives was not limited within the range of our experiments. Additives with multiple functional groups tend to crosslink chitosan even at room temperature in an acidic medium. Finally, it was shown that dissolving the chitosan in acetic acid and subsequently drying the matrix as a film results in reacetylation compared to the starting chitosan source, resulting in a harder material. With these findings, it is possible to tune the properties of chitosan-based polymer materials, making a big step towards application of this renewable polymer within consumer goods.

Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10-20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Lastly, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.

The valorization of low-grade industrial residues into valuable materials has been a way to reduce the impact of the industry on planetary boundaries. Silicon-rich wastes have been used for zeolite synthesis while the impurities originating from wastes have a vital role in the physicochemical properties and the catalytic performance of waste-derived zeolites. Here, the effect of steaming and the impact of impurities on waste-derived zeolites were investigated. Steamed waste-derived zeolite ZSM-5 maintained their structure while their Brønsted acidity was decreased significantly due to dealumination. Electron paramagnetic resonance revealed that steaming of the samples resulted in the re-dispersion of Fe impurities phases. The waste-derived zeolites exhibited a high amount of weak and intermediate acidity upon steaming. Interestingly, the waste-derived sample with a higher amount of impurities had an increase in Lewis acidity upon steaming, while catalytic testing in the Methanol-to-Hydrocarbons reaction exhibited 10 % higher conversion and 4 % in propylene yield.

Laboratory-based X-ray absorption spectroscopy (XAS) and especially X-ray absorption near-edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory-based setup for performing operando , quasi-simultaneous XANES analysis at multiple K edges, more specifically, operando XANES of mono-, bi-, and trimetallic CO 2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multi-element solid catalysts revealed metal-dependent differences in the reducibility and re-oxidation behavior and their influence on the catalytic performance in CO 2 hydrogenation. The applicability of operando laboratory-based XANES at multiple K edges paves the way for advanced multi-element catalyst characterization complementing detailed studies at synchrotron facilities.

Understanding the impact of shaping processes on solid adsorbents is critical for the implementation of MOFs in industrial separation processes or as catalytic materials. Production of MOF-containing shaped particles is typically associated with loss of porosity and modification of acid sites, two phenomena that affect their performance. Herein, we report a detailed study on how extrusion affects the crystallinity, porosity, and acidity of the aluminium fumarate MOF with clays or SiO2 gel binders. Thorough characterization showed that the clay binders confer the extrudates a good mechanical robustness at the expense of porosity, while silica gel shows an opposite trend. The CO2 selectivity towards CH4, of interest for natural gas separation processes, is maintained upon the extrusion process. Moreover, probe FTIR spectroscopy revealed no major changes in the types of acid sites. This study highlights that these abundant and inexpensive clay materials may be used for scaling MOFs as active adsorbents.

The development of improved zeolite materials for applications in separation and catalysis requires understanding of mass transport. Herein, diffusion of single molecules is tracked in the straight and sinusoidal channels of the industrially relevant ZSM-5 zeolites using a combination of single-molecule localization microscopy and uniformly oriented zeolite thin films. Distinct motion behaviors are observed in zeolite channels with the same geometry, suggesting heterogeneous guest-host interactions. Quantification of the diffusion heterogeneities in the sinusoidal and straight channels suggests that the geometry of zeolite channels dictates the mobility and motion behavior of the guest molecules, resulting in diffusion anisotropy. The study of hierarchical zeolites shows that the addition of secondary pore networks primarily enhances the diffusivity of sinusoidal zeolite channels, and thus alleviating the diffusion limitations of microporous zeolites.