Evaluation of Sonocatalytic and Photocatalytic Processes Efficiency for Degradation of Humic Compounds Using Synthesized Transition-Metal-Doped ZnO Nanoparticles in Aqueous Solution

The existence of a humic substance in water causes the growth of microorganisms and reduces the quality of water; therefore, the removal of these materials is crucial. Here, the ZnO nanoparticles doped using transition metals, copper (Cu) and manganese (Mn), were used as an effective catalyst for photocatalytic removal of humic substances in an aqueous environment under ultraviolet, visible light, and light-emitting diode irradiations. Also, we study the effect of the sonocatalytic method. A solvothermal procedure is used for doping, and the Cu- and Mn-doped ZnO nanocatalyst were characterized by means of FTIR, XRD, AFM, SEM, and EDAX analyses. We investigate the effect of operational variables, including doping ratio, initial pH, catalyst dose, initial HS content, and illuminance on the removal efficiency of the processes. The findings of the analyses used for the characterization of the nanoparticles illustrate the appropriate synthesis of the Cu- and Mn-doped ZnO nanocatalysts. We observe the highest removal efficiency rate under acidic conditions and the process efficiency decreased with increasing solution pH, when we tested it in the range of 3–7. Photocatalytic decomposition of HS increases with a rise in catalyst dose, but an increase in initial HS content results in decreasing the removal efficiency. We observe the highest photocatalytic degradation of humic acid while using the visible light, and the highest removal efficiency is obtained using Cu.ZnO. The Cu.ZnO also shows better performance under ultraviolet irradiation compared to other agents

Experimental evaluation and application of genetic programming to develop predictive correlations for hydrochar higher heating value and yield to optimize the energy content

The hydrothermal carbonization (HTC) process has been found to consistently improve biomass fuel characteristics by raising the higher heating value (HHV) of the hydrochar as process severity is increased. However, this is usually associated with a decrease in the solid yield (SY) of hydrochar, making it difficult to determine the optimal operating conditions to obtain the highest energy yield (EY), which combines the two parameters. In this study, a graph-based genetic programming (GP) method was used for developing correlations to predict HHV, SY, and EY for hydrochars based on published values from 42 biomasses and a broad range of HTC experimental systems and operating conditions, i.e., 5 ≤ holding time (min) ≤ 2208, 120 ≤ temperature (°C) ≤ 300, and 0. 0096 ≤ biomass to water ratio ≤ 0.5. In addition, experiments were carried out with 5 pomaces at 4 temperatures and two reactor scales, 1 L and 18.75 L. The correlations were evaluated using this experimental data set in order to estimate prediction errors in similar experimental systems. The use of the correlations to predict HTC conditions to achieve the maximum EY is demonstrated for three common feedstocks, wheat straw, sewage sludge, and a fruit pomace. The prediction was confirmed experimentally with pomace at the optimized HTC conditions; we observed 6.9 % error between the measured and predicted EY %. The results show that the correlations can be used to predict the optimal operating conditions to produce hydrochar with the desired fuel characteristics with a minimum of actual HTC runs

Changes in Selected Organic and Inorganic Compounds in the Hydrothermal Carbonization Process Liquid While in Storage

Although many studies have investigated the hydrothermal transformation of feedstock biomass, little is known about the stability of the compounds present in the process liquid after the carbonization process is completed. The physicochemical characteristics of hydrothermal carbonization (HTC) liquid products may change over storage time, diminishing the amount of desired products or producing unwanted contaminants. These changes may restrict the use of HTC liquid products. Here, we investigate the effect of storage temperature (20, 4, and −18 °C) and time (weeks 1-12) on structural and compositional changes of selected organic compounds and physicochemical characteristics of the process liquid from the HTC of digested cow manure. ANOVA showed that the storage time has a significant effect on the concentrations of almost all of the selected organic compounds, except acetic acid. Considerable changes in the composition of the process liquid took place at all studied temperatures, including deep freezing at −18 °C. Prominent is the polymerization of aromatic compounds with the formation of precipitates, which settle over time. This, in turn, influences the inorganic compounds present in the liquid phase by chelating or selectively adsorbing them. The implications of these results on the further processing of the process liquid for various applications are discussed

Advances in Research and Technology of Hydrothermal Carbonization: Achievements and Future Directions

Hydrothermal carbonization (HTC) has emerged as a pivotal technology in the battle against climate change and fosters circular economies. Operating within a unique reaction environment characterized by water as a solvent and moderate temperatures at self-generated pressures, HTC efficiently converts biomass residues into valuable bio-based products. Despite HTC’s potential—from the management of challenging biomass wastes to the synthesis of advanced carbons and the implementation of biorefineries—it encounters hurdles transitioning from academic exploration to industrial implementation. Gaps persist, from a general comprehension of reaction intricacies to the difficulty of large-scale integration with wastewater treatments, to the management of process water, to the absence of standardized assessment techniques for HTC products. Addressing these challenges demands collaboration to bridge the many scientific sectors touched by HTC. Thus, this article reviews the current state of some hot topics considered crucial for HTC development: It emphasizes the role of HTC as a cornerstone for waste management and biorefineries, highlighting potentialities and challenges for its development. In particular, it surveys fundamental research aspects, delving into reaction pathways, predictive models, analytical techniques, and HTC modifications while exploring HTC’s crucial technological applications and challenges, with a peculiar focus on combined HTC, wastewater integration, and plant energy efficiency

Analysis of Spatial Memory Cell Types Projections in Entorhino-Entorhinal Circuitry Using Electronphysiological Neural Recordings Combined with Optogenetics Application

Recent studies have revealed that all functional cell types in superficial layers of medial entorhinal cortex have projections to the hippocampus. Furthermore, hippocampal functions in connection with neural circuits in medial entorhinal cortex offer a good systems approach to understanding the basic functions of episodic memory formation. Then, we draw our attentions to the connections complexity between both medial entorhinal cortex (MEC) hemispheres to investigate the pattern of connectivity of MEC-MEC functional cell type neurons, furthermore, providing further data associated with spatial memory formation for future research. There are several functional spatial cell types in superficial layer 2 of MEC that code various spatially information in navigational system. These cells including; grid cells, head-direction cells, border cells, conjunctive grid x head-direction cells, conjunctive border x head-direction cells, unknown principal cells and interneurons. By injecting retrogradely transportable recombinant adeno-associated virus carrying channelrhodopsin-2 transgene in the left MEC of two rats and also right MEC of three rats, optogenetic control over entorhinal neurons with direct projections to the contralateral MEC has been presented. Optogenetics application together with electrophysiological recordings in vivo, enabled us to determine functionally specialized spatial cell types in MEC projecting to the contralateral MEC, as these cells contained minimal response latencies to laser stimulations in MEC. We here show that, unknown principal cells and interneurons, among all functional cell types presented in MEC, had a strong projection from left MEC to the contralateral right MEC and vise versa. Grid cells that are recently found to have a massive projections to the hippocampus, here in our study, only a small number, showed responses to light that might suggest the probability of their contralateral MEC connections. However, these responses were too much weak to convince us that these cells had projections to contralateral MEC. No more data were discovered to support projections of other detected spatial cell types to the contralateral MEC at this study

Evaluation of Sonocatalytic and Photocatalytic Processes Efficiency for Degradation of Humic Compounds Using Synthesized Transition-Metal-Doped ZnO Nanoparticles in Aqueous Solution

The existence of a humic substance in water causes the growth of microorganisms and reduces the quality of water; therefore, the removal of these materials is crucial. Here, the ZnO nanoparticles doped using transition metals, copper (Cu) and manganese (Mn), were used as an effective catalyst for photocatalytic removal of humic substances in an aqueous environment under ultraviolet, visible light, and light-emitting diode irradiations. Also, we study the effect of the sonocatalytic method. A solvothermal procedure is used for doping, and the Cu- and Mn-doped ZnO nanocatalyst were characterized by means of FTIR, XRD, AFM, SEM, and EDAX analyses. We investigate the effect of operational variables, including doping ratio, initial pH, catalyst dose, initial HS content, and illuminance on the removal efficiency of the processes. The findings of the analyses used for the characterization of the nanoparticles illustrate the appropriate synthesis of the Cu- and Mn-doped ZnO nanocatalysts. We observe the highest removal efficiency rate under acidic conditions and the process efficiency decreased with increasing solution pH, when we tested it in the range of 3–7. Photocatalytic decomposition of HS increases with a rise in catalyst dose, but an increase in initial HS content results in decreasing the removal efficiency. We observe the highest photocatalytic degradation of humic acid while using the visible light, and the highest removal efficiency is obtained using Cu.ZnO. The Cu.ZnO also shows better performance under ultraviolet irradiation compared to other agents

Effect of Hydrochar Modification on the Adsorption of Methylene Blue from Aqueous Solution: An Experimental Study Followed by Intelligent Modeling

Wheat straw, which is a carbon-rich precursor and a common agriculture waste in Sanandaj, was modified to produce hydrochar with high adsorption capacity by the hydrothermal carbonization (HTC) method. The hydrochars were tested as adsorbents to remove methylene blue (MB) from aqueous solution, and the effects of various interfering parameters, including pH, MB concentration, and adsorbent dosage, were investigated using artificial neural networks (ANNs) on adsorption modeling. Adsorption isotherms and kinetics were studied to explain the MB adsorption process. The prepared hydrochars were characterized using Brunauer–Emmett–Teller (BET), scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDAX), and high-performance liquid chromatography (HPLC) instruments. The maximum MB removal efficiency achieved by hydrochar modified by KOH (0.1 M) and adsorption data fitted well with the Langmuir isotherm and pseudo-second-order kinetics. In terms of elemental composition, the hydrochar sample contained 52.19% carbon (C), 3.37% hydrogen (H), 0.1% nitrogen (N), 0.15% sulfur (S), and 35.66% oxygen (O). The ash content in the sample was 8.50%. The recorded hydrogen-to-carbon ratio (H/C) and oxygen-to-carbon ratio (O/C) indicated a shift towards humification, implying the influence of KOH addition during the hydrochar production process. Additionally, the specific surface area of the hydrochar, as measured by the BET method, was found to be 11.54 m²/g. Among the aromatics, a significant presence of hydroxymethylfurfural (HMF) was detected, with a concentration of 4.70 g/kg DM. The modeling results demonstrated that the concentration of MB had the most substantial impact on the predicted removal, followed by pH, adsorbent dosage, and contact time

Development of a nano alumina-zirconia composite catalyst as an active thin film in biodiesel production

A Nano-alumina-zirconia composite catalyst was synthesized by a simple aqueous sol-gel method using AlCl3.6H2O and ZrCl4 as precursors. Thermal decomposition of the precursor and subsequent formation of γ-Al2O3 and t-ZrO2 were investigated by thermal analysis. XRD analysis showed that γ-Al2O3 and t-ZrO2 phases were formed at 700 °C. FT-IR analysis also indicated the phase transition to γ-Al2O3 occurred in corroboration with X-ray studies. TEM analysis of the calcined powder revealed that spherical particles were in the range of 8-12 nm. The nano alumina-zirconia composite particles were mesoporous and uniformly distributed in their crystalline phase. In order to measure the catalytic activity, esterification reaction was carried out. Biodiesel, as a renewable fuel, was formed in a continuous packed column reactor. Free fatty acid (FFA) was esterified with ethanol in a heterogeneous catalytic reactor. It was found that the synthesized γ-Al2O3/ZrO2 composite had the potential to be used as a heterogeneous base catalyst for biodiesel production processes

Chemical insights into the base-tuned hydrothermal treatment of side stream biomasses

Herein, we analyzed the hydrothermal processes applied to four very different side stream biomasses (chestnut foliage, sugar beet pressing chips, pine bark and branches from park cleaning, bamboo cuts) and identified diverse soluble products depending on the starting pH of the reaction, covering mild to strong basic pH conditions. Despite the biological diversity of the starting products, hydrothermal disintegration of biomass results in a remarkable reduction of chemical diversity towards a controllable number of molecular products, and the well-resolved and rather simple NMR-spectra allow the assignment of the products to only a few families of compounds. It has been revealed that in comparison with the classical hydrothermal treatment, where mostly hydrochar is produced, molar excess of base shifts the hydrothermal treatment towards a humification process. A further increase of the base content causes destruction of the biomass into the more oxygenated homogeneous colloid and thus, for the first time, it can be assigned to the hydrothermal fulvication process. We discuss diverse valorization schemes depending on the biomass and conditions applied

Artificial humic substances as sustainable carriers for manganese: Development of a novel bio-based microfertilizer

This study presents a new strategy for the production of sustainable manganese fertilizer based on artificial humic substances (AHS). AHS with different manganese concentrations (0‒20%) were synthesized from poplar bark under alkaline conditions via hydrothermal treatment. For the 20% manganese formulation, the interaction of manganese with AHS resulted in reduced solubility (from 25.2% to 12.3% organic carbon) and average molecular weight of humic acids (from 11.6 to 3.9 KDa), indicating preferential binding of the high-molecular-weight fraction. The formulation with 5% of manganese achieved optimal manganese loading without compromising the AHS solubility (19.4%). Structural analyses showed only minor changes in AHS in the presence of manganese, indicating that the main structural fragments of the AHS were preserved. Structural, morphological, and spectroscopic characterizations confirmed the formation of amorphous manganese complexes within the AHS matrix, primarily in the plant-available Mn(II) oxidation state. Plant bioassays showed increased manganese uptake with the application of AHS containing 5% Mn compared to MnCl2 alone (64 mg/kg vs. 40 mg/kg in dry cucumber biomass). Interestingly, unmodified AHS at higher concentrations (50 mg/L) further enhanced manganese (67 mg/kg) and iron (up to 209 mg/kg) uptake, highlighting the potential role of AHS in facilitating metal transport