Search Results (542)

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

Adipic acid (AA), a pivotal precursor for nylon-6,6 and polyurethane, was synthesized via an innovative catalytic electrocatalytic oxidation strategy in this study. Four distinct MnO_x/CNT nanocatalysts were prepared by hydrothermal and co-precipitation methods and fabricated into electrodes for the oxidation of cyclohexanol (Cy-OH) in a K₂SO₄ neutral solution. Comprehensive characterization revealed that the catalytic performance depended on both crystalline phase configuration and manganese valence states. MnO(OH) and MnO_x were identified as the main active species, with the synergy between MnO species and carbon nanotubes significantly enhancing catalytic activity. Mechanistic investigations demonstrated that under Mn⁴⁺-dominant conditions, low-valence manganese species facilitated Cy-OH-to-cyclohexanone (Cy=O) conversion, while an optimal O_ads/O_lat ratio (≈1) effectively promoted subsequent Cy=O oxidation to AA. Under optimized conditions (1.25 V vs. Ag/AgCl, 80 °C, 15 h), complete Cy-OH conversion was achieved with 56.4% AA yield and exceptional Faradaic efficiency exceeding 94%. This work elucidates manganese-based electrocatalytic oxidation mechanisms, proposes a sequential reaction pathway, and establishes an environmentally benign synthesis protocol for AA, advancing sustainable industrial chemistry. Full article

The catalytic conversion of bio-based glycerol (Gly) into high-value glycerol carbonate (GC) has received great attention from both the academic and industrial fields. The development of highly efficient catalysts and economical industrial processes remains a challenging subject. In this mini-review, we summary the recent advances in catalyst design, characterization, mechanism, and catalytic process optimization, including the various synthetic strategies of GC, such as the coupling of CO₂ and Gly or its derivatives like glycidol (GD), the transesterification of Gly with small carbonate-containing molecules, and the carbonylation of Gly with urea. The main difficulties and challenges faced by constructing high-performance catalysts and achieving scale production of GC have been put forward, and the future research directions and opportunities in catalyst innovation, reaction mechanism exploration, and continuous catalytic process improvement have also been suggested. Full article

Metallo-phthalocyanines (MPcs) are versatile materials with applications in electroanalysis because of their superior catalytic properties. This review presents the electrochemical methods based on MPc-modified electrodes and reports some of their remarkable properties and applications in the electroanalysis of monoamine neurotransmitters and biomolecules that play a crucial role in vital functions of the human body. The development of electrocatalytic chemically modified electrodes is based on their ability to provide a selective and rapid response toward a specific analyte in complex media without the need for sample pretreatment. The explanation of several phenomena occurring at the MPc-modified electrode surface (e.g., MPc-mediated electrocatalysis), the advantages of promoting different electron transfer reactions, and the detection mechanism are also presented. The types of MPcs and different materials, such as carbon nanotubes and graphene, used as substrates for modified working electrodes are discussed. Modifying the properties of MPcs through various interactions, or combining MPcs with carbonaceous materials, creates a synergistic effect. Such hybrid materials present both extraordinary catalytic and increased conductivity properties. We conducted a compilation study based on recent works to demonstrate the efficacy of the developed sensors and methods in sensing monoamine neurotransmitters. We emphasize the analyte type, optimized experimental parameters, working range, limits of detection and quantification, and application to real samples. MPc–carbon hybrids have led to the development of sensors with superior sensitivity and improved selectivity, enabling the detection of analytes at lower concentrations. We highlight the main advantages and drawbacks of the discussed methods. This review summarizes recent progress in the development and application of metallo-phthalocyanine-modified electrodes in the electroanalysis of monoamine neurotransmitters. Some possible future trends are highlighted. 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

Ammonia is increasingly recognised as a promising carbon-free fuel and hydrogen carrier due to its high hydrogen content, ease of liquefaction, and existing global infrastructure. However, its direct utilisation in combustion systems poses significant challenges, including low flame speed, high ignition temperature, and the formation of nitrogen oxides (NO_X). This review explores catalytic ammonia cracking as a viable method to enhance combustion through in situ hydrogen production. It evaluates traditional catalytic burner designs originally developed for hydrocarbon fuels and assesses their adaptability for ammonia-based applications. Special attention is given to ruthenium- and nickel-based catalysts supported on various oxides and nanostructured materials, evaluating their ammonia conversion efficiency, resistance to sintering, and thermal stability. The impact of the main operational parameters, including reaction temperature and gas hourly space velocity (GHSV), is also discussed. Strategies for combining partial ammonia cracking with stable combustion are studied, with practical issues such as catalyst degradation, NO_X regulation, and system scalability. The analysis highlights recent advancements in structural catalyst support, which have potential for industrial-scale application. This review aims to provide future development of low-emission, high-efficiency catalytic burner systems and advance ammonia’s role in next-generation hydrogen energy technologies. Full article

The dry reforming of methane (DRM) converts two greenhouse gases, CH₄ and CO₂, into H₂ and CO, offering a crucial technological pathway for reducing greenhouse gas emissions and producing clean energy. However, the reaction faces two main challenges: high activation energy barriers require high temperatures to drive the reaction, while sintering and carbon deactivation at high temperatures are common with conventional nickel-based catalysts, which severely limit the further development of the methane dry reforming reaction. In this study, a nitrogen-doped carbon nanotube-loaded nickel catalytic system (Ni/NCNT) was developed to overcome the challenges caused by limited active sites while maintaining the stable structure of the Ni/CNT system. Ni/NCNT catalysts were prepared using different nitrogen precursors, and the impact of the mixing method on catalytic performance was examined. Characterization using H₂-TPR, XPS, and TEM revealed that nitrogen doping enhanced the metal–support interaction (MSI). Additionally, pyridine nitrogen species synergistically interact with nickel particles, modulating the electronic environment on the carbon nanotube surface and increasing catalyst active site density. The Ni/NCNT-IU catalyst, prepared with impregnated urea, exhibited excellent stability, with methane conversion decreasing from 85.0% to 82.9% over 24 h of continuous reaction. This study supports the use of non-precious-metal carbon-based catalysts in high-temperature catalytic systems, which is strategically important for the industrialization of DRM and the development of decarbonized energy conversion. Full article

Biodiesel is obtained by transesterification of triglycerides using catalysts. The possibilities of using a natural catalyst—dolomite in the synthesis of biodiesel are explored in this article. The conditions for preparing dolomite are presented, with considerable emphasis placed on the dependence of the structural changes and activity of dolomite on the calcination conditions. The optimal conditions for the transesterification of triglycerides with methanol are discussed, along with the possibilities for dolomite regeneration and reuse. It has been established that the calcination temperature of dolomite ranges from 800 to 900 °C, and using it can produce biodiesel that meets standard requirements, but this requires a large excess of alcohol in the transesterification reaction medium. The main issues related to the use of dolomite are linked to increasing catalytic activity and the possibilities of regenerating and reusing it. Researchers have recently focused on this by studying the possibilities of modifying dolomite using physical and chemical processes. The findings are contradictory and further studies are necessary, the possibilities for reuse have also been insufficiently explored. It is appropriate to analyze the economic indicators of dolomite preparation, modification, and regeneration in comparison with the preparation of other catalysts, so that the use of this catalyst aligns with the principles of sustainable synthesis. Full article

This study employed a two-stage fixed-bed pyrolysis-reforming reactor to investigate H₂ production behaviors from municipal solid waste (MSW) and biomass with their self-derived catalysts under different operating parameters. The self-derived catalysts are prepared by mechanically mixing pyrolysis-derived chars with CaO and iron powders. The main results are as follows: (1) The higher oxygen content in biomass facilitates oxidative dehydrogenation reactions, enabling in situ generation of H₂O, which results in a higher H₂/CO ratio for biomass compared to MSW under steam-free conditions. (2) There are optimal values for the reforming temperature and steam-to-feedstock ratio (S/F) to achieve best performance. In the presence of steam, MSW generally exhibits superior H₂ and syngas production performance to biomass; (3) Both MSW char (MSWC)- and biomass char (BC)-based catalysts showed satisfied H₂ production and tar cracking performance at 850–900 °C, and the MSWC-based catalyst demonstrated better catalytic activity than the BC-based catalyst due to its higher contents of several active metals. In addition, the iron powder can be recycled easily, proving the effectiveness of the self-derived convenient and cheap catalysts. Full article

Covalent organic frameworks hold great promise for heterogeneous catalysis because of their porous structure for gas adsorption and tunable functionality. Two triazine support materials (MAmPA-COF and MAoPA-COF) were prepared by using melamine as the linked monomer and meta-phthalaldehyde (MPA) or ortho-phthalaldehyde (OPA) as the sub-construction monomer. Two nickel(II) complexes (Ni@MAmPA-COF and Ni@MAoPA-COF) based on the synthesized COFs were prepared to use for ethylene oligomerization. The nickel(II) complexes had good catalytic activities in ethylene oligomerization. Moreover, the substituent position of the aldehyde group in the sub-construction monomer had a certain influence on the specific surface area, morphology and catalytic activity. The morphology of Ni@MAmPA-COF was spherical, while Ni@MAoPA-COF exhibited layered stacking shapes and had a large specific surface area. Ni@MAoPA-COF has a higher catalytic activity and higher selectivity for low-carbon olefins in ethylene oligomerization due to its larger specific surface area and smaller pore width. Ni@MAoPA-COF has good recyclability and still had excellent catalytic activity after three cycles. Based on the gray correlation analysis and single factor experiment, the reaction pressure was the most important factor affecting the activity of Ni@MAoPA-COF in ethylene oligomerization, and the molar ratio of Al/Ni was the main important factor affecting the selectivity. Full article

Avocado is a rich source of numerous nutrients, such as micro- and macroelements, essential unsaturated fatty acids, and vitamins essential for the correct functioning of the body. Consequently, its consumption has significantly increased in recent years. The primary edible part of the fruit is the flesh, while the seed is still considered biowaste. Currently, various methods for utilization of this biowaste are being explored, prompting the authors of this work to investigate the catalytic properties of ground avocado seeds. Dried, ground avocado seeds were used as the catalyst in the environmentally friendly oxidation of limonene with oxygen. The process was carried out in mild conditions, without the use of any solvent and at atmospheric pressure. The studies examined the influence of temperature (70–110 °C), the amount of the catalyst (0.5–5.0 wt%), and the reaction time (15–360 min). The analyses of the post-reaction mixtures were performed using the gas chromatography method (GC). The maximum value of the conversion of limonene obtained during the tests was 36 mol%. The main products of this process were as follows: 1,2-epoxylimonene, carveol, and perillyl alcohol. Also, the following compounds were determined in the post-reaction mixtures: carvone and 1,2-epoxylimonene diol. The studied process is interesting, taking into account both the management of waste in the form of avocado seeds and possible wide applications of limonene transformation products in medicine, cosmetics and the food industry. Given that limonene is now increasingly being extracted from waste orange peels, this is also a good way to manage the future naturally derived limonene and reduce the amount of waste orange peels. The presented studies fit perfectly with the goals of sustainable development and circular economy and may be the basis for the future development of “green technology” for obtaining value-added oxygenated derivatives of limonene. These studies show the use of waste biomass in the form of avocado seeds to obtain a green catalyst. In this context, our research presents an effective way of waste valorization. Full article

The efficient utilization of heavy oil is of great significance to alleviating the global energy crisis. How to efficiently convert heavy oil into high-value-added light fuel oil has become a hot issue in the field of petrochemicals. As the residual part of crude oil processing, heavy oil has a complex composition and contains polycyclic aromatic hydrocarbons, long-chain alkanes, and heteroatom compounds, which makes it difficult to process directly. Zeolite, as an important type of solid acid catalyst, has a unique pore structure, adjustable acidity, and good thermal stability. It can promote the efficient cracking and conversion of heavy oil molecules, reduce coke formation, and improve the yield and quality of light oil products. This paper systematically reviews the development status of heavy oil cracking technology, focusing on the structural characteristics, acidity regulation of zeolite catalysts, and their applications in heavy oil cracking and hydrocracking. The mechanism of the cracking reaction of polycyclic aromatic hydrocarbons and long-chain alkanes is analyzed in detail, and the catalytic characteristics and modification methods of zeolite in the reaction process are explained. In addition, this paper summarizes the main challenges faced by zeolite catalysts in practical applications, including uneven acidity distribution, limited pore diffusion, and easy catalyst deactivation, and proposes targeted development strategies. Finally, this paper looks forward to the future development direction of zeolite catalysts in the field of heavy oil cracking and upgrading reactions, emphasizes the importance of structural optimization and multi-scale characterization, and provides theoretical support and practical reference for the design and industrial application of efficient zeolite catalysts. Full article

The production of formic acid (FA) from lignocellulose and its derived sugars represents a pivotal upgrading reaction in biorefinery. This work prepared a Mn-Mo doped carbon nanotube composite catalyst for the catalytic oxidation of glucose into FA in an O₂ atmosphere, under extremely low Mn (3.27%) and Mo (0.40%) loading conditions, displaying a comparable performance with the traditional vanadium-based catalyst suffering from toxicity issues. It was confirmed that the doping of Mo led to the formation of MnMoO_X and increased the contents of low-valence Mn species (Mn²⁺ + Mn³⁺), lattice oxygen (O_latt), and surface adsorbed oxygen (O_ads) based on various characterization methods, such as XRD, XPS, TEM and ICP, which were beneficial to improve the catalytic performance. The maximum FA yield of 58.8% could be achieved over Mn₉Mo₁O_X@MWCNT after reaction for 6 h at 140 °C, which was far more than that obtained with undoped MnO_X@MWCNT (14.5%) at the identical conditions. Glyoxylic acid and arabinose were identified as two main intermediates, suggesting that the transformation of glucose into FA over Mn₉Mo₁O_X@MWCNT involved two different paths. This work proved that manganese-based catalyst was a green alternative for upgrading lignocellulose via catalytic oxidation. Full article

Methane is the second most prevalent greenhouse gas after carbon dioxide in global climate change, and catalytic oxidation technology is a very effective way to eliminate methane. However, the high reaction temperature of methane catalytic oxidation is an urgent problem that needs to be solved. In this work, a series of MnCo₂O_4.5 catalysts were prepared using carbon spheres as templates, combined with metal ion adsorption and calcination processes. Excitingly, the catalytic oxidation activity of MnCo₂O_4.5 spherical catalyst with irregular nanoparticles on the surface for lean methane (T₉₀ = 395 °C) is higher than that of pure phase Co₃O₄ (T₉₀ = 538 °C) and Mo₃O₄ (T₉₀ = 581 °C) spherical catalysts and even surpasses most precious metal catalysts. The main reasons are as follows: (1) The spherical core with irregular nanoparticle morphology significantly increases the specific surface area, creating abundant active sites; (2) through the optimized distribution of oxygen vacancies, rapid oxygen migration through this structure can quickly enter the catalytic zone; (3) the hierarchical wall structure expands the interface and provides spatial accommodation for the catalytic process. Meanwhile, the structure of the ball wall further expands the reaction interface, providing sufficient space for the occurrence of reactions. Rich and highly active oxygen vacancies are evenly distributed on the surface and inside of the ball. The extraordinary performance of low-temperature methane combustion catalysts has opened a promising new path, which is expected to inject strong impetus into the global energy transition and environmental protection. Full article