Search Results (198)

Catalytic upgrading of pyrolysis oils is an important step for producing replacement hydrocarbon-rich liquid biofuels from biomass and can help to advance pyrolysis technology. Catalysts play a pivotal role in influencing the selectivity of chemical reactions leading to the formation of main compounds in the final upgraded liquid products. The present work involved a systematic study of solvent-free catalytic reactions of cyclohexanone in the presence of hydrogen gas at 160 °C for 3 h in a batch reactor. Cyclohexanone can be produced from biomass through the selective hydrogenation of lignin-derived phenolics. Three types of catalysts comprising undoped NbOPO₄, 10 wt% NiO/NbOPO₄, and 30 wt% NiO/NbOPO₄ were studied. Undoped NbOPO₄ promoted both aldol condensation and the dehydration of cyclohexanol, producing fused ring aromatic hydrocarbons and hard char. With 30 wt% NiO/NbOPO₄, extensive competitive hydrogenation of cyclohexanone to cyclohexanol was observed, along with the formation of C₆ cyclic hydrocarbons. When compared to NbOPO₄ and 30 wt% NiO/NbOPO₄, the use of 10 wt% NiO/NbOPO₄ produced superior selectivity towards bi-cycloalkanones (i.e., C₁₂) at cyclohexanone conversion of 66.8 ± 1.82%. Overall, the 10 wt% NiO/NbOPO₄ catalyst exhibited the best performance towards the production of precursor compounds that can be further hydrodeoxygenated into energy-dense aviation fuel hydrocarbons. Hence, the presence and loading of NiO was able to tune the activity and selectivity of NbOPO₄, thereby influencing the final products obtained from the same cyclohexanone feedstock. This study underscores the potential of lignin-derived pyrolysis oils as important renewable feedstocks for producing replacement hydrocarbon solvents or feedstocks and high-density sustainable liquid hydrocarbon fuels via sequential and selective catalytic upgrading. Full article

The physicochemical processes that occur during selective transfer in the contact area of a bronze/steel friction pair lubricated with glycerin are experimentally studied by the polarization method to observe how they influence the tribological properties (friction and wear) of the pair. The proposed method allows for the study of tribochemical transformations of glycerin and the friction pair materials during the work process with selective transfer. The analysis of the experimental results allows for the establishment of the conditions for a stable and stationary selective transfer during the operation of the bronze/steel pair, by friction, at which the friction coefficient (COF) values and wear are low. This was achieved by implementing continuous lubrication with fresh glycerin in the contact area, choosing the optimal flow rate, and maintaining an optimal ratio between glycerin and the chemical transformation products, within well-established limits, to avoid undesirable consequences. Acrolein, as a product of chemical transformation (resulting from the catalytic dehydration of glycerin), is the most important for the initiation and stability of the selective transfer, and as the main reaction product, also represents a pathway of regeneration. Thus, it was found that the friction relative moments and the acrolein concentration presented conclusive/specific results at loads of 4–15 MPa and a sliding speed of 0.3 m/s. The optimum lubricant entry speed is 15–30 mg/min, for a minimum COF and reduced wear (about 0.028–0.03 at relatively high operating temperatures (45 and 60 °C)), and at low temperatures (30 °C) the minimum COF is about 0.038, but the lubricant inlet entry speed increases considerably, by around 1000 mg/min. Therefore, this paper aims to demonstrate the possibility of moving to another stage of practical use of a friction pair (with greatly improved tribological properties) that operates with selective transfer, much different from the ones still present, using a lubricant with special properties (glycerin). The research method used (polarization) highlights the physicochemical properties, tribochemical transformations of the lubricant, and the friction pair materials present in the contact area, for the understanding, maintenance, and stability of selective transfer, based on experiments, as a novelty compared to other studies. Full article

This article presents a review of several non-exclusive pathways for the sequestration of soil organic carbon, which can be classified into two large classical groups: the modification of plant and microbial macromolecules and the abiotic and microbial neoformation of humic substances. Classical studies have established a causal relationship between aromatic structures and the stability of soil humus (traditional hypotheses regarding lignin and aromatic microbial metabolites as primary precursors for soil organic matter). However, further evidence has emerged that underscores the significance of humification mechanisms based solely on aliphatics. The precursors may be carbohydrates, which may be transformed by the effects of fire or catalytic dehydration reactions in soil. Furthermore, humic-type structures may be formed through the condensation of unsaturated fatty acids or the alteration of aliphatic biomacromolecules, such as cutins, suberins, and non-hydrolysable plant polyesters. In addition to the intrinsic value of understanding the potential for carbon sequestration in diverse soil types, biogeochemical models of the carbon cycle necessitate the assessment of the total quantity, nature, provenance, and resilience of the sequestered organic matter. This emphasises the necessity of applying specific techniques to gain insights into their molecular structures. The application of appropriate analytical techniques to soil organic matter, including sequential chemolysis or thermal degradation combined with isotopic analysis and high-resolution mass spectrometry, derivative spectroscopy (visible and infrared), or ¹³C magnetic resonance after selective degradation, enables the simultaneous assessment of the concurrent biophysicochemical stabilisation mechanisms of C in soils. Full article

5-Hydroxymethylfurfural (HMF) is a versatile platform molecule with the potential to replace many fossil fuel derivatives. It can be obtained through the dehydration of carbohydrates. In this study, we present a simple and cost-effective microwave-assisted method for producing HMF. This method involves the use of readily available sucrose as a substrate and glucose-derived bifunctional hydrochars as carbocatalysts. These catalysts were produced via hydrothermal carbonisation using thiourea and urea as nitrogen and sulphur sources, respectively, to introduce Brønsted acidic and basic sites into the materials. Using a microwave reactor, we found that the S, N-doped hydrochars were active in sucrose dehydration in water. Catalytic results showed that HMF yield depended on the balance between acidic and basic sites as well as the types of S and N species present on the surfaces of these hydrochars. The best-performing catalyst achieved an encouraging HMF yield of 37%. The potential of N, S-co-doped biochar as a green solid catalyst for various biorefinery processes was demonstrated. A simple kinetic model was developed to elucidate the kinetics of the main reaction pathways of this cascade process, showing a very good fit with the experimental results. The calculated rate constants revealed that reactions with a 5% sucrose loading exhibited significantly higher fructose dehydration rates and produced fewer side products than reactions using a more diluted substrate. No isomerisation of glucose into fructose was observed in an air atmosphere. On the contrary, a limited rate of isomerisation of glucose into fructose was recorded in an oxygen atmosphere. Therefore, efforts should focus on achieving a high glucose-to-fructose isomerisation rate (an intermediate reaction step) to improve HMF selectivity by reducing humin formation. Full article

ZSM-22 zeolites with different Si/Al ratios (38, 50, 80) were prepared via a hydrothermal synthesis method, investigated for the catalytic dehydration of 1,3-butanediol (1,3-BDO) to butadiene (BD) at 300 °C. The catalytic performance of the synthesized materials was related to their properties and compared to a commercial ZSM-22 zeolite (Si/Al = 30). ZSM-22 (50) exhibited a quick decline in conversion, a lower BD selectivity, and higher propylene selectivity compared to the other materials, which could be attributed to the presence of strong Lewis acid sites and silanol nests. The Lewis sites favor the cracking of the intermediate 3-buten-1-ol (3B1OL) into propylene, while the silanol nests interact with the free hydroxyl group of 3B1OL, potentially inhibiting further dehydration towards BD. The highest initial BD yield of 74% was observed over ZSM-22 (80), while the highest initial BD productivity of 2.7 g_BD·g⁻¹_cata·h⁻¹ was achieved over ZSM-22 (38). After 22 h time on stream (TOS), c-ZSM-22 and ZSM-22 (38) outperformed previously reported catalysts from the literature, with productivities amounting to 1.3 g_BD·g⁻¹_cata·h⁻¹ and 1.2 g_BD·g⁻¹_cata·h⁻¹, respectively, at a site time of 6.6 mol_H+·s·mol⁻¹_1,3-BDO. Full article

2,5-Furandicarboxylic acid (FDCA) is a bio-based platform chemical with high potential to replace terephthalic acid in polymer production, particularly for polyethylene furanoate (PEF), a biopolymer with superior thermal and barrier properties. This study investigates the selective oxidation of 5-hydroxymethylfurfural (HMF) into FDCA using nickel-based heterogeneous catalysts, aiming at a cost-effective and sustainable alternative to noble metal catalysts. A series of nickel oxide catalysts were synthesized and screened. The NiOx catalyst synthesized without thermal treatment via Route B showed the best performance, achieving a FDCA yield of 11.77%, selectivity of 27.41%, and concentration of 0.9 g/L under preliminary conditions. Reaction kinetics revealed that the controlled addition of NaClO enhanced FDCA yield by 2.28 times. Optimization using a 2³ factorial design identified the optimal conditions as 6% (w/v) catalyst concentration, 25 °C, and a NaClO:HMF molar ratio of 12:1, leading to 34.14% yield and 42.57% selectivity. The NiOx catalyst maintained its activity over five successive cycles, indicating good recyclability. Moreover, NiOx demonstrated catalytic activity with crude HMF derived from glucose dehydration, confirming its practical applicability. These results support the potential of nickel-based catalysts in sustainable FDCA production, contributing to the advancement of bio-based polymer synthesis. Full article

Chicken manure (CM) is a nutrient-rich but environmentally problematic biomass that requires sustainable management. This study applied a three-step process consisting of hydrothermal activation (ZnCl₂ or H₃PO₄), catalytic hydrothermal carbonization (HCl or FeCl₃), and low-temperature pyrolysis (250 °C) to develop an energy-efficient method for producing biochar. The resulting biochars were systematically analyzed for their physicochemical properties, heavy metal content, and carbon sequestration potential, and compared with conventional pyrolysis-based biochars. Among the tested samples, the biochar produced via H₃PO₄ activation and HCl-catalyzed HTC [P-HTC(HCl)] exhibited the most favorable characteristics, including the highest carbon content (59.5 wt.%) and the lowest H/C ratio (0.65). As a result, it achieved the highest total potential carbon (TPC, 158.8 g_carbon/kg_biochar) and CO₂ reduction potential (CRP, 465.9 g_CO2-eq/kg_biochar), attributed to the strong dehydration and decarboxylation reactions and effective inorganic removal induced by Brønsted acid action. In contrast, conventional pyrolysis biochars showed significantly higher concentrations of heavy metals—up to 633 mg/kg of Cu and 2331 mg/kg of Zn—due to thermal concentration effects, whereas P-HTC(HCl) biochar presented a more balanced and environmentally acceptable heavy metal profile. In conclusion, the proposed low-temperature hydrothermal-assisted process demonstrates great potential for producing high-performance biochar from chicken manure with enhanced environmental safety and carbon storage efficiency. Full article

The lactic acid (LA) production from corn stover using Lewis acid catalysts was optimized. Initially, an equimolar mixture of Al(III)/Sn(II) was used as a catalytic system at 190 °C with 5 wt% biomass. Increasing the catalyst concentration led to higher LA production, showing the optimal results at 16 mM. A low catalyst concentration mainly produced furfural and HMF, dehydration products from the corn stover sugars. Higher catalyst concentration increased LA yield but also produced the degradation of the glucose dehydration products into levulinic and formic acids, reducing LA selectivity. Al(III) was essential for LA formation, while Sn(II) was less effective due to its lower solubility, shown by the presence of Sn(II) in the solid residue after treatments. A total of 16 mM Al(III) yielded the highest LA levels at 190 °C, 7.4 g/L, and 20.7% yield. Increasing the temperature to 210 °C accelerated the LA production while also achieving the lowest energy consumption, which was 0.47 kWh/g LA at the highest LA production point. However, longer treatments at this temperature caused LA degradation. AlCl₃ has been identified as an ideal catalyst for biomass conversion to LA, being inexpensive and low in toxicity. Full article

Sulfation is a common strategy to enhance the acidity and modify the adsorption properties of metal–organic frameworks (MOFs), yet its impact on the coordination and accessibility of active sites remains unclear. In this study, we investigate two structurally related systems—sulfated UiO-66 (UiO-66-SO₄) and sulfated tetragonal zirconia (S-ZrO₂)—by FTIR spectroscopy with probe molecules. Isotope exchange experiments on S-ZrO₂ reveal that dehydration above 250 °C induces tridentate SO₄ coordination, while hydration leads to a reversible transition to a bidentate coordination mode. In UiO-66-SO₄, sulfates are coordinated in a bidentate fashion to Zr₆O₆ clusters, significantly affecting the accessibility of Zr sites in defective pores. This coordination prevents CO adsorption but allows acetonitrile adsorption even after room temperature activation. Unlike S-ZrO₂, due to its lower thermal stability, UiO-66-SO₄ cannot be evacuated at high temperatures and dehydration at 250 °C does not induce tridentate coordination. The presence of H-bonded hydroxyls in UiO-66-SO₄ after activation at 250 °C supports this coordination model, indicating the formation of OH-coordinated Zr sites that are inaccessible to CO but interact with stronger bases like acetonitrile. Overall, this study provides new insights into the coordination chemistry of sulfated UiO-66 and highlights that sulfation can tune acidity and adsorption in MOFs for potential catalytic and adsorption applications. Full article

The rational development of single-atom catalysts (SACs) for selective formic acid dehydrogenation (FAD) requires an atomic-scale understanding of metal–support interactions and electronic modulation. In this study, spin-polarized density functional theory (DFT) calculations were performed to systematically examine platinum-group SACs anchored on graphitic carbon nitride (g-C₃N₄). The findings reveal that Pd and Au SACs exhibit superior selectivity toward the dehydrogenation pathway, lowering the free energy barrier by 1.42 eV and 1.39 eV, respectively, compared to the competing dehydration route. Conversely, Rh SACs demonstrate limited selectivity due to nearly equivalent energy barriers for both reaction pathways. Stability assessments indicate robust metal–support interactions driven by d–p orbital hybridization, while a linear correlation is established between the d-band center position relative to the Fermi level and catalytic selectivity. Additionally, charge transfer (ranging from 0.029 to 0.467 e) substantially modulates the electronic structure of the active sites. These insights define a key electronic descriptor for SAC design and offer a mechanistic framework for optimizing selective hydrogen production. Full article

Sorption-enhanced reverse water–gas shift (SE-RWGS), designated as COMAX, was studied using a Pt4A bifunctional catalyst (reactive adsorbent). The bifunctional Pt4A catalyst integrates CO₂ activation and reaction with water adsorption functionality, where the active phase is loaded onto a carrier that provides a surface area for Pt dispersion as well as H₂O adsorption capacity. The 0.3 wt% Pt-4A molecular sieve reactive sorbent was tested at a kg scale in a pressure swing (reactive) adsorption–regeneration process. More than 400 cycles over 50 days of operation were successfully demonstrated without significant decay. Cyclic stability was achieved, provided that the regeneration temperature was sufficiently high to ensure near-complete dehydration. The single-bead structure withstood the pressure swing operation effectively, with only a maximum of 2% of the total recovered reactive sorbent turning to fines (<500 μm). The successful integration of catalytic activity and water adsorption capacity into a single particle presents opportunities for the further intensification of sorption-enhanced reactions for CO₂ conversion. Full article

With the rapid development of biorefinery technology, the efficient conversion of lignocellulose into high-value platform chemicals is of great significance for enhancing the value of renewable carbon resources. In this study, a hydroxyl-functionalized covalent organic framework (COF), TAPB-DHPA, was synthesized via an in situ method and innovatively applied to the catalytic conversion of xylo-oligosaccharides (XOS) into furfural. The results demonstrated that TAPB-DHPA possesses a large specific surface area, a well-developed porous structure, and excellent thermal stability, with abundant Brønsted acid (B acid) sites, exhibiting outstanding catalytic activity. Under optimal conditions, including a catalyst loading of 0.16 wt%, a reaction temperature of 180 °C, and a reaction time of 3 h, a furfural yield of up to 65.4% was achieved. The high selectivity was primarily attributed to the p-π conjugation effect between the benzene ring and the phenolic hydroxyl group, which enhanced the ionization ability of hydroxyl hydrogen, thereby effectively promoting the hydrolysis of XOS and subsequent dehydration. Furthermore, TAPB-DHPA exhibited excellent recyclability and stability, maintaining a furfural yield of over 59.9% after six cycles. This study provides new insights into the application of functionalized COF in biomass catalytic conversion and contributes to the green transformation of the pulp and paper industry into a biorefinery-based model. Full article

Polybutylene succinate (PBS) is a biodegradable aliphatic polyester with excellent thermal stability, mechanical properties, and processability. The synthesis of PBS typically employs titanium-based catalysts like tetrabutyl titanate (TBT) to accelerate the reaction. However, TBT acts as a homogeneous catalyst and is non-recyclable. This study aims to minimize the cost of recovering liquid TBT catalyst during PBS synthesis by using TBT-loaded activated carbon for direct esterification and optimizing the process conditions. The catalyst was analyzed using inductively coupled plasma emission spectroscopy, automated specific surface area and pore size analysis, X-ray diffraction, and Fourier-transform infrared spectroscopy. The product was evaluated through infrared spectroscopy, nuclear magnetic resonance hydrogen spectra, and gel permeation chromatography. The optimal process parameters were determined to be an esterification temperature of 170 °C, a polycondensation temperature of 235 °C, an acid-to-alcohol molar ratio of 1:1.2, a catalyst amount of 0.06 g, and a dehydration time of 3 h. Under these conditions, the weight-average molecular weight of PBS reached 47,655, reducing the catalyst usage from 0.5% to 0.3%, resulting in a 24.7% increase in catalytic efficiency compared to TBT, significantly lowering costs. After five cycles of reuse, the weight-average molecular weight of the product remained above 35,000. This study demonstrates that TBT-loaded activated carbon exhibits superior catalytic performance, offering a cost-effective and efficient method for industrial PBS production with broad application potential. Full article

In this work, we review some illustrative examples to evidence the potential of two archetypal Zr-containing MOFs, UiO-66 and MOF-808, as heterogeneous catalysts for converting biomass-derived products into valuable chemicals. The reactions are organized in three blocks, depending on the biomass source: carbohydrates, lipids, and other sources. Through this review, we will show that the chemical properties of these two Zr-MOFs are significantly different in terms of the nature and strength of acid sites, which largely depends on the number of missing linker defects of the solid and its hydration state. While hydrated UiO-66 bears relatively strong Brønsted-induced acid sites, dehydrated MOF-808 is more than competent as a Lewis acid catalyst. Therefore, we will pick one or the other catalyst depending on the particular demands of the catalytic transformation that we want to carry out. Full article

This study investigated the production of high-performance biochar from swine manure using a sequential carbonization process combining hydrothermal carbonization (HTC) and pyrolysis. Biochar produced through HCl-assisted sequential carbonization exhibited superior properties, including the highest fixed carbon (70.0%), higher heating value (28.48 MJ/kg, ~18.8% increase over HTC-Py), and BET surface area (279.66 m²/g, ~17 times higher than other biochars). These improvements were attributed to the catalytic role of HCl in promoting dehydration, hydrolysis, and decarboxylation, leading to a more condensed and stabilized carbon structure. Furthermore, HCl significantly enhanced heavy metal removal, reducing Zn to 343.17 mg/kg (compared to HTC-Py 1324.15 mg/kg) and lowering Cd, As, Cu, Pb, Ni, and Cr by 70–80%, demonstrating effective demineralization. This approach presents a practical strategy for producing high-quality biochar with improved carbonization, energy properties, and pollutant removal, offering potential applications in environmental and agricultural fields. Full article