Abstract: This work aims to enhance the efficiency of integrated poultry waste management in bio-circular-green economy by maximizing the co-digestion of chicken manure and its digestate-grown biomass. In a series of batch assays, Napier grass (NG) was mixed with chicken manure (CM) at various proportions (100:0, 80:20, 60:40, 50:50, 40:60, 20:80 and 0:100) to identify co-substrate synergism, followed by physiochemical conditioning (size reduction and ultrasonication) of NG before co-digestion. Results indicated that NG mix of at least 80% was required to gain a full methanation potential of the individual substrates; no synergistic ratio above unity was found. However, the combined effect of size reduction and sonication was found to markedly improve the cosubstrate's biodegradability by 88.7%. The findings were then used to run continuous co-digestion at various operating regimes. In optimal continuous co-digestion condition, NG particle size of 0.6-2.4 mm combined with sonication intensity at 1111 kJ/kgTS improved biomethanation yield as high as 106.3%. Sub-thermophilic digestion at 45 degrees C was shown to give a higher and more stable CH4 yield than at 55 degrees C. Finally, it was also found that recycling liquid effluent at 40% to replace freshwater in feed, although showed no significant difference in CH4 yield (& alpha; = 0.05), noticeably increased system buffer capacity. This optimized biodegradation regime could give co-digestion waste management a higher overall plant efficiency and economic return.

Abstract: Two-dimensional (2D) honeycomb ferromagnets, such as monolayer chromium trihalides, are predicted to behave as topological magnon insulators, characterized by an insulating bulk and topologically protected edge states, giving rise to a thermal magnon Hall effect. Here we report the behavior of the topological magnons in monolayer CrI3 under external stimuli, including biaxial and uniaxial strain, electric gating, as well as in-plane and out-of-plane magnetic field, revealing that one can thereby tailor the magnetic states as well as the size and the topology of the magnonic bandgap. These findings broaden the perspective of using 2D magnetic materials to design topological magnonic devices.

Abstract: It remains a challenge to identify the active sites of bismuth catalysts in the electrochemical CO2 reduction reaction. Here we show through in situ characterization that the activation of bismuth oxyhalide electrocatalysts to metallic bismuth is guided by the halides. In situ X-ray diffraction results show that bromide promotes the selective exposure of planar bismuth surfaces, whereas chloride and iodide result in more disordered active sites. Furthermore, we find that bromide-activated bismuth catalysts outperform the chloride and iodide counterparts, achieving high current density (>100 mA cm(-2)) and formic acid selectivity (>90%), suggesting that planar bismuth surfaces are more active for the electrochemical CO2 reduction reaction. In addition, in situ X-ray absorption spectroscopy measurements reveal that the reconstruction proceeds rapidly in chloride-activated bismuth and gradually when bromide is present, facilitating the formation of ordered planar surfaces. These findings show the pivotal role of halogens on selective facet exposure in activated bismuth-based electrocatalysts during the electrochemical CO2 reduction reaction.

Abstract: In this work, the absorption–desorption performance of CO2 in six new solvent blends of amine (diisopropylamine (DPA), 2-amino-2-methyl-1-propanol (AMP), methyldiethanolamine (MDEA), diethanolamine (DEA), diisopropanolamine (DIPA), and ethanolamine (MEA)), sulfolane, and methanol has been monitored using ATR-FTIR spectroscopy. Additionally, NMR-based species confirmation and solvent viscosity analysis were done for DPA solvent samples. The identified CO2 capture products are monomethyl carbonate (MMC), carbamate, carbonate, and bicarbonate anions in different ratios. The DPA solvent formed MMC entirely with 0.88 molCO2/molamine capture capacity, 0.48 molCO2/molamine cyclic capacity, and 3.28 mPa·s CO2-loaded solvent viscosity. MEA, DEA, DIPA, and MDEA were shown to produce a low or a negligible amount of MMC while AMP occupied an intermediate position.

Abstract: In mainstream partial nitritation/anammox (PN/A), suppression of nitrite oxidizing bacteria (NOB) and mitigation of N2O emissions are two essential operational goals. The N2O emissions linked to three typical NOB suppression strategies were tested in a covered rotating biological contactor (RBC) biofilm system at 21 degrees C: (i) low dissolved oxygen (DO) concentrations, and treatments with (ii) free ammonia (FA), and (iii) free nitrous acids (FNA). Low emerged DO levels effectively minimized NOB activity and decreased N2O emissions, but NOB adaptation appeared after 200 days of operation. Further NOB suppression was successfully achieved by periodic (3 h per week) treatments with FA (29.3 & PLUSMN; 2.6 mg NH3-N L-1) or FNA (3.1 & PLUSMN; 0.3 mg HNO2-N L-1). FA treatment, however, promoted N2O emissions, while FNA did not affect these. Hence, biofilm PN/A should be operated at relatively low DO levels with periodic FNA treatment to maximize nitrogen removal efficiency while avoiding high greenhouse gas emissions.

Abstract: Microalgae can play a key role in the bioeconomy, particularly in combination with the valorisation of waste streams as cultivation media. Urine is an example of a widely available nutrient-rich waste stream, and alkaline stabilization and subsequent full nitrification in a bioreactor yields a stable nitrate-rich solution. In this study, such nitrified urine served as a culture medium for the edible microalga Limnospira indica. In batch cultivation, nitrified urine without additional supplements yielded a lower biomass concentration, nutrient uptake and protein content compared to modified Zarrouk medium, as standard medium. To enhance the nitrogen uptake efficiency and biomass production, nitrified urine was supplemented with potentially limiting elements. Limited amounts of phosphorus (36 mg L−1), magnesium (7.9 mg L−1), calcium (12.2 mg L−1), iron (2.0 mg L−1) and EDTA (88.5 mg Na2-EDTA.2H2O L−1) rendered the nitrified urine matrix as effective as modified Zarrouk medium in terms of biomass production (OD750 of 1.2), nutrient uptake (130 mg N L−1) and protein yield (47%) in batch culture. Urine precipitates formed by alkalinisation could in principle supply enough phosphorus, calcium and magnesium, requiring only external addition of iron, EDTA and inorganic carbon. Subsequently, the suitability of supplemented nitrified urine as a culture medium was confirmed in continuous Limnospira cultivation in a CSTR photobioreactor. This qualifies nitrified urine as a valuable and sustainable microalgae growth medium, thereby creating novel nutrient loops on Earth and in Space, i.e., in regenerative life support systems for human deep-space missions.

Abstract: In the present work, a method was utilized to control the in‐situ partial hydrolysis of a diphosphonate ester in presence of a titania precursor and in function of acid content and its impact on the hybrid nanoparticles was assessed. The hydrolysis degree of organodiphosphonate ester linkers during the formation of hybrid organic‐inorganic metal oxide nanoparticles, are relatively underexplored . Quantitative solution NMR spectroscopy revealed that during the synthesis of TiO2 nanoparticles, an increase in acid concentration introduces a higher degree of partial hydrolysis of the TEPD linker into diverse acid/ester derivatives of TEPD. Increasing the HCl/Ti ratio from 1 to 3, resulted in an increase in degree of partial hydrolysis of the TEPD linker in solution from 4% to 18.8% under the here applied conditions. As a result of the difference in partial hydrolysis, the linker‐TiO2 bonding was altered. Upon subsequent drying of the colloidal TiO2 solution, different textures, at nanoscale and macroscopic scale, were obtained dependent on the HCl/Ti ratio and thus the degree of hydrolysis of TEPD. Understanding such linker‐TiO2 nanoparticle surface dynamics is crucial for making hybrid organic‐inorganic materials (i.e. (porous) metal phosphonates) employed in applications such as electronic/photonic devices, separation technology and heterogeneous catalysts.

Abstract: Second-generation biofuels, starting from lignocellulosic biomass, are considered as a renewable alternative for fossil fuels with lower environmental impact and potentially higher supply and energy security. The economic and environmental performance of second-generation bioethanol production from corn stover in the European Union (EU) is studied, starting in Belgium as base case. A comparative environmental techno-economic assessment has been conducted, with process simulations in Aspen Plus and corn stover availability data in thirteen EU countries to calculate minimum ethanol selling prices (MESP) and Greenhouse gas emissions (GHGe). In this analysis, the emphasis is on the comparison of different pretreatment technologies, namely (i) dilute acid, (ii) alkaline, (iii) steam explosion and (iv) liquid hot water. Dilute acid showed the best economic and environmental performance for the base case scenario. Within the EU, Hungary and Romania presented the lowest MESP for the steam explosion model at 0.39 and 0.43 EUR/L respectively. Poland showed the lowest GHGe, at 0.46 kg CO2eq/L for the alkaline model, mainly due to the avoided product allocation on electricity and its high carbon intensity in the electricity generation sector. The second lowest GHGe were obtained in France for the dilute acid model and are attributed to its low agricultural emissions intensity. This study identifies a location-dependence of the economic and environmental performance of pretreatment technologies, which can be extrapolated from the EU to other large regions around the world and should be taken into consideration by decision-makers.

Abstract: Grafting organophosphonic acids modification (PAs) on metal oxides has shown to be a flexible technology to tune the surface properties of metal oxides for various applications. Nevertheless, there are still puzzles that need to be addressed, such as the correlations between metal oxides properties (types of surface reactive sites) and the modification (modification degree), the correlations between metal oxides properties and the properties of modified surfaces. Moreover, the currently used liquid-phase method for the grafting has associated impeding effects of solvent on tailoring the modification degrees, and also causes the formation of metal phosphonate side products. The solid-phase method can induce the unwanted changes in crystal phase of supports. Based on these questions, the three titania supports with divergent surface properties were selected as the metal oxides supports investigated, propylphosphonic acid (3PA) modification was carried out under the same synthesis conditions: four different concentrations, two solvents (water or toluene), and one reaction time (4 h) and temperature (90 ). MeOH chemisorption was introduced to probe the surface (un)reactive sites for 3PA modification. On the other hand, MeOH chemisorption and inverse gas chromatography (IGC) were combined to characterize the changes in surface polarity and acidic properties induced by the modification. Next, a solid-phase method, manual grinding, was proposed to graft 3PA on titania, avoiding the impeding effects of solvent on improving modification degree and the formation of the titania phosphonate side products, as well as preserving the crystal phase. The results indicate that methanol chemisorption can qualitatively analyze the surface active sites that are consumed by 3PA modification, its chemisorption capacity shows the consistent trend with the maximum modification degree, hereby revealing the kinds of interactions that are important in controlling surface coverage. Titania supports is found to play an important role in changes in surface polarity and acidic properties by charactering the three modified titania samples at a similar modification degree using the methanol chemisorption coupled with in-situ infrared and thermogravimetric-mass spectrometer, and the IGC. Moreover, IGC provides additional information about the changes in binding modes. Furthermore, grafting 3PA modification on titania was achieved by manual grinding. Compared to the liquid-phase method, the maximum modification degree obtained by the manual grinding is 25 % higher while using 83.3 % or 75.0% lower amounts of expensive 3PA and limiting the formation of titania phosphonate side products. Compared to the reactive milling method, the proposed manual grinding method preserves the crystal phase(s) of titania.

Abstract: Electron energy loss spectroscopy (EELS) is a well established technique in electron microscopy that yields information on the elemental content of a sample in a very direct manner. One of the persisting limitations of EELS is the requirement for manual identification of core-loss edges and their corresponding elements. This can be especially bothersome in spectrum imaging, where a large amount of spectra are recorded when spatially scanning over a sample area. This paper introduces a synthetic dataset with 736,000 labeled EELS spectra, computed from available generalized oscillator strength tables, that represents 107 K, L, M or N core-loss edges and 80 chemical elements. Generic lifetime broadened peaks are used to mimic the fine structure due to band structure effects present in experimental core-loss edges. The proposed dataset is used to train and evaluate a series of neural network architectures, being a multilayer perceptron, a convolutional neural network, a U-Net, a residual neural network, a vision transformer and a compact convolutional transformer. An ensemble of neural networks is used to further increase performance. The ensemble network is used to demonstrate fully automated elemental mapping in a spectrum image, both by directly mapping the predicted elemental content and by using the predicted content as input for a physical model-based mapping.

Abstract: In the recent advances towards more sustainable global energy supply, H2 is a possible alternative for large scale energy storage. In this view, Liquid Organic Hydrogen Carriers (LOHC) are a class of molecules that allow for easier long term energy storage compared to conventional H2 technologies. CFD simulations were used to showcase the hydrodynamics of the dehydrogenation of a LOHC in a new reactor unit, via a cold flow mock-up study. This reactor was designed to allow for a swirling motion of the liquid carrier material, favouring the removal of H2 gas from the flow and forcing the equilibrium of the reaction towards dehydrogenation, as well as to keep the catalyst particles in motion. The CFD simulations were validated qualitatively with experimental operation of the reactor, in a system with identical dimensionless numbers (Reynolds and Stokes), in order to use less costly products during the prototyping phase.

Abstract: Climate change is causing alterations in precipitation patterns, leading to adverse ecological consequences in many ecosystems. Recently, an increasingly persistent weather pattern has emerged, characterized by lengthening the duration of alternating dry and wet periods, which is more complex than exclusively drought or increasing precipitation. It is currently unclear how soil microbial communities respond to these new regimes in relation to their interactions with plants, especially in precipitation-sensitive ecosystems, such as tropical rainforests and grasslands. In this thesis, we explored responses of soil bacterial and fungal communities to increasing weather persistence in rainforests and grasslands, using high throughput sequencing technology. We firstly investigated the resistance and resilience of microbial communities to prolonged drought in a mature seasonal tropical rainforest which experiences unusually intensive dry seasons in the current century. Through excluding rainfall during and after the dry season, a simulated prolongation of the dry season by five months was compared to the control. Our results indicate that as rain exclusion progressed, the microbial communities increasingly diverged from the control, indicating a moderate resistance to prolonged drought. However, when the drought ceased, the composition and co-occurrence patterns of soil microbial communities immediately recovered to that in the control, implying a high resilience. To further investigate the ecological roles of soil microbial communities in response to increasing weather persistence, we set up grassland mesocosm experiments. In these experiments, precipitation frequency was adjusted along a series, ranging from 1 to 60 consecutive days alternating of dry and wet periods, while keeping the total precipitation constant. Our results show that microbial community assembly tended to be more stochastic processes at intermediate persistence of dry and wet alternations while more deterministic processes dominated at low and high persistence within 120 days regime exposure. Moreover, more persistent precipitation reduced the fungal diversity and network connectivity but barely impacted that of bacterial communities. The prior experiences of persistent weather events for one year caused legacy effects. The soil microbial legacy induced by soil microbial communities subjected to prior persistent weather events was more enduring in subsequent fungal communities than bacterial communities, likely due to slower growth of fungi compared to bacteria. However, a minor effect of soil microbial legacy  was observed on plant performance. In addition, we kept the grassland mesocosm experiment for two growing seasons. The effects of precipitation persistence on soil microbial communities increased in the second year. The dissimilarities of microbial communities between the first and second year were less with more persistent precipitation, potentially resulting in more vulnerable microbial communities, due to some taxa disappearing and a reduction in functional redundancy under more persistent weather. To conclude, our findings provide a comprehensive theoretical understanding of soil microbial communities in response to the current and future climate change, drawing from both natural and experimental systems. It helps in predicting and managing the impacts of future climate change on ecosystems mediated by microbial communities. Additionally, the findings of microbe-mediated legacy effects on grassland ecosystems can provide practical guidance for their application in agriculture, specifically for using an inoculum to mitigate the impacts of climate change.

Abstract: Two-dimensional (2D) perovskite oxide interfaces are ideal systems to uncover diverse emergent properties, such as the arising polaronic properties from short-range charge-lattice interactions. Thus, a technique to detect this quasiparticle phenomenon at the buried interface is highly coveted. Here, we report the observation of 2D small-polarons at the LaAlO3/SrTiO3 conducting interface using high-resolution spectroscopic ellipsometry. First-principles investigations show that interfacial electron-lattice coupling mediated by the longitudinal phonon mode facilitates the formation of these polarons. This study resolves the long-standing question by attributing the formation of interfacial 2D small polarons to the significant mismatch between experimentally measured interfacial carrier density and theoretical values. Our study sheds light on the complexity of broken periodic lattice-induced quasi-particle effects and its relationship with exotic phenomena at complex oxide interfaces. Meanwhile, this work establishes spectroscopic ellipsometry as a useful technique to detect and locate optical evidence of polaronic states and other emerging quantum properties at the buried interface.

Abstract: In this work, we have fabricatedan aryl amino-substitutedgraphiticcarbon nitride (g-C3N4) catalyst with atomicallydispersed Mn capable of generating hydrogen peroxide (H2O2) directly from seawater. This new catalyst exhibitedexcellent reactivity, obtaining up to 2230 & mu;M H2O2 in 7 h from alkaline water and up to 1800 & mu;Mfrom seawater under identical conditions. More importantly, the catalystwas quickly recovered for subsequent reuse without appreciable lossin performance. Interestingly, unlike the usual two-electron oxygenreduction reaction pathway, the generation of H2O2 was through a less common two-electron water oxidation reaction(WOR) process in which both the direct and indirect WOR processesoccurred; namely, photoinduced h(+) directly oxidized H2O to H2O2 via a one-step 2e(-) WOR, and photoinduced h(+) first oxidized a hydroxide (OH-) ion to generate a hydroxy radical ((OH)-O-& BULL;), and H2O2 was formed indirectly by thecombination of two (OH)-O-& BULL;. We have characterized thematerial, at the catalytic sites, at the atomic level using electronparamagnetic resonance, X-ray absorption near edge structure, extendedX-ray absorption fine structure, high-resolution transmission electronmicroscopy, X-ray photoelectron spectroscopy, magic-angle spinningsolid-state NMR spectroscopy, and multiscale molecular modeling, combiningclassical reactive molecular dynamics simulations and quantum chemistrycalculations.

Abstract: Hierarchicalassembly of arc-like fractal nanostructures not onlyhas its unique self-similarity feature for stability enhancement butalso possesses the structural advantages of highly exposed surface-activesites for activity enhancement, remaining a great challenge for high-performancemetallic nanocatalyst design. Herein, we report a facile strategyto synthesize a novel arc-like hierarchical fractal structure of PtPdbimetallic nanoparticles (h-PtPd) by using pyridinium-type ionic liquidsas the structure-directing agent. Growth mechanisms of the arc-likenanostructured PtPd nanoparticles have been fully studied, and precisecontrol of the particle sizes and pore sizes has been achieved. Dueto the structural features, such as size control by self-similaritygrowth of subunits, structural stability by nanofusion of subunits,and increased numbers of exposed active atoms by the curved homoepitaxialgrowth, h-PtPd displays outstanding electrocatalytic activity towardoxygen reduction reaction and excellent stability during hydrothermaltreatment and catalytic process.