•Simultaneous analysis of heavy pyrolyzates and quantification of light pyrolysis gases.•Deans switch enables time-efficient analysis of broad pyrolysis product spectra.•Hard coal released increased amounts of light hydrocarbons as pyrolysis products.•Lignites mainly released oxygenated pyrolysis gases.•Phenol derivatives and long-chain hydrocarbons identified as condensable pyrolyzates.

The applied pyrolysis temperature was found to strongly affect composition, structure, and oxidation behavior of pure and iron oxide nanoparticle (NP)-loaded carbon materials originating from hydrothermal carbonization (HTC) of cellulose. A strong loss of functional groups during pyrolysis at temperatures beyond 300 °C of the HTC-derived hydrochars was observed, resulting in an increase of the carbon content up to 95 wt% for the carbon materials pyrolyzed at 800 °C and an increase of the specific surface area with a maximum of 520 m2 g-1 at a pyrolysis temperature of 600 °C. Devolatilization mainly took place in the range from 300 to 500 °C, releasing light pyrolysis gases such as CO, CO2, H2O and larger oxygen-containing molecules up to C11. The presence of iron oxide NPs lowered the specific surface areas by about 200 m2 g-1 and resulted in the formation of mesopores. For the iron oxide-containing composites pyrolyzed up to 500 °C, the oxidation temperature was decreased by about 100 °C, indicating tight contact between the iron oxide NPs and the carbon matrix. For higher pyrolysis temperatures, this catalytic effect of iron oxide on carbon oxidation vanished due to carbothermal reduction to iron and iron carbide, which, however, catalyzed the graphitization of the carbon matrix. Thus, the well-controlled two-step synthesis based on a biomass-derived precursor yielded stably embedded iron NPs in a corrosion-resistant graphitic carbon matrix.

Development of metal-free carbon-based electrocatalysts for reducing oxygen to water (ORR), preferentially following a 4 electron transfer pathway, is of high importance. We present a two-step synthesis of N-doped carbon-based ORR electrocatalysts by using an efficient thermal treatment of hydrothermally carbonized cellulose in ammonia combining devolatilization, reduction and nitrogen doping. The influence of the synthesis temperature as well as of the ammonia concentration used during the synthesis on the electrocatalytic ORR activity was analyzed using bulk- and surface-sensitive techniques. Correlation of electrocatalytic activity with structural features of the catalysts provided deeper mechanistic understanding and enabled us to optimize the synthesis conditions. The nitrogen-doped metal-free catalyst originating from the treatment in 100 % NH3 at 800 degrees C achieved a current density of -1 mA cm(-2) at 0.83 V vs. RHE positioning it among the most active noble-metal free and biomass-based ORR catalysts reported so far.

The high temperatures and heating rates typical of PF are known to induce thermal annealing of char and loss of its reactivity. Several authors investigated this effect for coals in inert atmospheres, while little is known about the effects of CO2-rich atmospheres, typical of oxy-combustion and gasification, on the course of thermal annealing. Thermal annealing of biomass has been scarcely investigated in the literature; however, available studies reported that also biomass can suffer from thermo-deactivation. The present study aims to provide further insight on thermal annealing of biomass in the context of gasification and oxy-combustion. A lignin-rich biomass (walnut shells) has been heat-treated in a heated strip reactor at temperatures of 1573-2073 K with a holding time of 3 s using atmospheres of either N-2 or CO2. Similar experiments have been performed with a high volatile bituminous coal (Colombian coal) used as reference. The char samples have been analyzed by thermogravimetric analysis and Raman spectroscopy. Results have been further compared with those reported in previous studies where heat-treatment of the same fuels were performed in fixed bed, fluidized bed, and drop tube reactors at lower temperature or shorter holding time. Two remarkable results have been obtained: (1) Loss of reactivity by thermal annealing and structural reorganization follow similar pathways for coal and biomass. (2) The effect of CO2 on pyrolysis and thermal annealing is non-monotonic along with heat treatment: in the early instances of heat treatment (T = 1573 K, t < 0.1 s), CO2 fosters pyrolysis and thermal annealing, increasing structural ordering. At longer holding times (T > 1573 K, t > 1 s), instead, CO2 somewhat hampers thermal annealing.

Char emissivity of burning particles is an important factor for heat transfer calculations in pulverized fuel boilers. As the chemical composition is known to influence the emissivity in general, a coal sample has been prepared by a leaching method to reduce the mineral content. A flat flame burner was used for the combustion of the particles in oxyfuel atmosphere, providing boundary conditions comparable to pulverized coal applications. The burnout-dependent emissivity of the sample was measured in a defined spectral range and compared with data for an unleached sample of the same coal, indicating that the mineral content has minor effect for the investigated conversion levels, although clear changes in the emissivity show that conversion in general is not negligible.

Synthetic lignite was prepared by hydrothermal carbonization, in which minerals typical for coal ashes were incorporated during hydrothermal carbonization allowing us to study the catalytic effect of ash components on the oxidation rate of the fuel. Chemically leached lignite using hydrochloric acid was applied as reference material. Combustion experiments were performed by thermogravimetric analysis under chemically controlled conditions and in a laminar flow reactor under pore-diffusion limitation. The investigation of the hydrochar in the laminar flow reactor provided gas temperatures and heating rates typical for pulverized coal combustion. The combustion rate of the chemically leached lignite was found to be comparable to the hydrochar. Furthermore, the catalytic effect of incorporated iron oxide was detected in both combustion experiments.

•Hydrothermal conversion of cellulose leads to H/C and O/C ratios close to real lignite.•Leaching of rhenish lignite with acids changes the oxidation temperatures.•Synthetic lignite was obtained by hydrothermal conversion of cellulose at 48h at 200°.•Synthetic lignite has a similar oxidation profile as acid-leached rhenish lignite.•ATR-IR and NMR spectroscopy are highly useful tools to analyze synthetic and real lignites.

The catalytic effect of iron oxide on the oxidation kinetics of synthetic char was investigated in a fixed-bed reactor and in a conventional thermobalance for comparison. Synthetic char doped with iron oxide was obtained by pyrolyzing hydrochar at 800°C, which had been synthesized by hydrothermal carbonization of cellulose in the presence of iron oxide. Isothermal char oxidation in the fixed-bed reactor resulted in the most reliable kinetic results. According to model-free kinetic analysis of these experiments at 15% conversion, iron oxide decreased the activation energy of char oxidation from 149kJ/mol to 133kJ/mol. Modeling of the conversion-time curves was first performed by using the uniform reaction model and then improved by using a n-th order power law. In the temperature range of 440–490°C a very good agreement with the experimental data was achieved using n=0.6. Activation energies amounting to 149kJ/mol and 134kJ/mol were derived for the undoped and iron oxide-doped char, respectively, well in line with the model-free analysis.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Flexible metal-organic frameworks (MOFs), also referred to as soft porous crystals (SPCs), show reversible structural transitions dependent on the nature and quantity of adsorbed guest molecules. In recent studies it has been reported that covalent functionalization of the organic linker can influence or even integrate framework flexibility ("breathing") in MOFs. However, rational fine-tuning of such responsive properties is very desirable but challenging as well. Here we present a powerful approach for the targeted manipulation of responsiveness and framework flexibility of an important family of pillared-layered MOFs based on the parent structure [Zn(2)(bdc)(2)(dabco)](n) (bdc = 1,4-benzenedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane). A library of functionalized bdc-type linkers (fu-bdc), which bear additional dangling side groups at different positions of the benzene core (alkoxy groups of varying chain length with diverse functionalities and polarity), was generated. Synthesis of the materials [Zn(2)(fu-bdc)(2)(dabco)](n) yields the respective collection of highly responsive MOFs. The parent MOF is only weakly flexible; however, the substituted frameworks of [Zn(2)(fu-bdc)(2)(dabco)](n) contract drastically upon guest removal and expand again upon adsorption of DMF (N,N-dimethylformamide), EtOH, or CO(2), etc., while N(2) is hardly adsorbed and does not open the narrow-pored form. These "breathing" dynamics are attributed to the dangling side chains that act as immobilized "guests", which interact with mobile guest molecules as well as with themselves and with the framework backbone. The structural details of the guest-free, contracted form and the gas sorption behavior (phase transition pressure, hysteresis loop) are highly dependent on the nature of the substituent at the linker and can therefore be adjusted using our approach. Combining our library of functionalized linkers with the concept of mixed-component MOFs (solid solutions) offers very rich additional dimensions of tailoring the structural dynamics and responsiveness. Implementation of two differently functionalized linkers in varying ratios yields multicomponent single-phased [Zn(2)(fu-bdc')(2x)(fu-bdc″)(2-2x)(dabco)](n) MOFs (0 < x < 1) of increased inherent complexity, which feature a non-linear dependence of their gas sorption properties on the applied ratio of components. Hence, the responsive behavior of such pillared-layered MOFs can be extensively tuned via an intelligent combination of functionalized linkers.