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"Salmi, Tapio"
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Recent Advances in C5 and C6 Sugar Alcohol Synthesis by Hydrogenation of Monosaccharides and Cellulose Hydrolytic Hydrogenation over Non-Noble Metal Catalysts
2022
A new reality of the 21st century is the transition to a new type of economy and energy concepts characterized by the replacement of existing petrochemical routes to a bio-based circular economy. The needs for new strategies in obtaining basic products from bio-based resources with minimum CO2 traces has become mandatory. In this review, recent trends in the conversion of biomass-derived molecules, such as simple monomeric sugars and cellulose, to industrially important C5 and C6 sugar alcohols on heterogeneous catalysts based on non-noble metals are discussed focusing on the influence of catalyst structures and reaction conditions used on the substrate conversion and product selectivity. The challenges and prominent ideas are suggested for the further development of catalytic hydrogenation of naturally abundant carbohydrates to value-added chemicals on non-noble metal catalysts.
Journal Article
Microwave Synthesis of Copper Phyllosilicates as Effective Catalysts for Hydrogenation of C≡C Bonds
by
Kostyukhin, Egor
,
Shesterkina, Anastasiya
,
Vikanova, Kseniia
in
1,4-butenediol
,
1,4-butynediol
,
Copper
2022
For the first time, the new microwave-assisted method for the synthesis of copper phyllosilicates on a commercial SiO2 carrier was developed. The application of microwave synthesis allowed to decrease the synthesis time from 9 to 6 h compared to the traditional DPU method of preparing chrysocolla. The synthesized catalysts were studied by N2 adsorption, TEM and XRD methods. Catalysts prepared by microwave method are highly effective in the selective hydrogenation of the С≡С bond in 1,4-butynediol to 1,4-butenediol and 2-phenylethinylaniline with a selectivity of 96.5% and 100% at full conversion for 2 and 0.5 h of the reaction, respectively.
Journal Article
Microwave-Assisted Conversion of Carbohydrates
by
Kustov, Alexander L.
,
Salmi, Tapio
,
Kustov, Leonid M.
in
5-hydroxymethylfurfural
,
Acids
,
alcohols
2022
Catalytic conversion of carbohydrates into value-added products and platform chemicals became a trend in recent years. Microwave activation used in the processes of carbohydrate conversion coupled with the proper choice of catalysts makes it possible to enhance dramatically the efficiency and sometimes the selectivity of catalysts. This mini-review presents a brief literature survey related to state-of-the-art methods developed recently by the world research community to solve the problem of rational conversion of carbohydrates, mostly produced from natural resources and wastes (forestry and agriculture wastes) including production of hydrogen, synthesis gas, furanics, and alcohols. The focus is made on microwave technologies used for processing carbohydrates. Of particular interest is the use of heterogeneous catalysts and hybrid materials in processing carbohydrates.
Journal Article
Zeta Potential of Beta Zeolites: Influence of Structure, Acidity, pH, Temperature and Concentration
by
Liu, Xuan
,
Vajglova, Zuzana
,
Kumar, Narendra
in
Acids - chemistry
,
beta
,
Hydrogen-Ion Concentration
2018
Measurements of the zeta potential of solid heterogeneous supports are important for preparation of metal supported catalysts and for shaping zeolites into extrudates. In the current work, different types of heterogeneous support materials such as SiO2, Al2O3, and a range of beta zeolites of different silica- to-alumina ratio were analysed. It was observed that parameters such as temperature, pH and acidity significantly affect the zeta potential. In several instances, depending on the materials’ acidity and microstructure, maxima in zeta potential were observed. The solid materials were thoroughly characterized using XRD, SEM, EDX, TEM, nitrogen physisorption, Al-NMR and FTIR with pyridine before zeta potential measurements.
Journal Article
Performance Degradation and Regeneration of Palladium Catalysts for Hybrid Rockets
by
Guida, Riccardo
,
Cassese, Sergio
,
Russo, Vincenzo
in
Advertising campaigns
,
Aluminum oxide
,
Analysis
2026
The renewed interest in hydrogen peroxide-based space propulsion systems has highlighted the persistent issue of catalyst degradation during long-term operation. Although several studies have investigated the underlying causes of this phenomenon, effective regeneration techniques capable of restoring catalytic activity have not yet been clearly demonstrated. This study investigates the mechanisms responsible for performance degradation and proposes a viable regeneration strategy for palladium-based catalysts. Experimental analyses were conducted on a batch of commercial Al2O3/Pd pellets subjected to multiple firing cycles in a 10 N-class hybrid mini-thruster. Monitoring of the propulsive performance revealed a progressive decline in catalytic activity, ultimately preventing ignition of the hybrid rocket engine. To characterize the degradation mechanisms, the pellets were examined through visual inspection, static hydrogen peroxide decomposition tests, and Temperature Programmed Reduction (TPR) analysis. The results indicated significant surface oxidation of palladium, leading to reduced decomposition efficiency. A chemical regeneration procedure based on sodium borohydride (NaBH4) treatment was subsequently developed to restore catalytic performance. The regenerated pellets were tested under the same experimental conditions that had previously led to ignition failure. Their propulsive performance was then compared with both the degraded pellets and a new batch of equivalent catalysts. The results demonstrate that the regeneration process successfully restored the catalytic activity to levels comparable with the original state, enabling stable and efficient hybrid combustion. These findings confirm the role of surface oxidation in catalyst degradation and demonstrate that targeted chemical treatment can significantly extend catalyst lifetime. The proposed regeneration strategy offers a practical method to reduce costs of ground-based experimental campaigns and support the future deployment of hydrogen peroxide-based propulsion systems in space applications by providing insights into the mechanisms that can degrade the performance of palladium catalysts.
Journal Article
Ozonation of carbamazepine and its main transformation products: product determination and reaction mechanisms
by
Eklund, Patrik
,
Kumar, Narendra
,
Kronberg, Leif
in
Aquatic Pollution
,
Benzaldehyde
,
Carbamazepine
2020
Carbamazepine (CBZ) is a recalcitrant pharmaceutical often detected in wastewater and in the environment. CBZ can be removed from wastewater through advanced oxidation treatment methods such as ozonation. In this study, CBZ and its transformation product 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD) were ozonated, and the formation and transformation of their ozonation products were investigated using liquid chromatography coupled to ion trap mass spectrometry and high-resolution mass spectrometry as well as nuclear magnetic resonance (NMR). The main products, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM) and BQD were quantified using isolated standards and LC-UV. Of the original CBZ concentration, 74% was transformed into BQM and 83% of BQM was further transformed into BQD. Both products are more stable than CBZ and could still be detected after 240 min of ozonation. Another major product, 2,2′-azanediyldibenzaldehyde (TP225) was for the first time identified using NMR. Twelve further CBZ products were identified.
Journal Article
Thermal risk assessment for the epoxidation of linseed oil by classical Prisleschajew epoxidation and by direct epoxidation by H2O2 on alumina
by
Leveneur, Sébastien
,
Estel, Lionel
,
Pérez-Sena, Wander Y
in
Adiabatic conditions
,
Alumina
,
Aluminum oxide
2020
Substitution of fossil feedstock by vegetable oils is growing due to environmental constraints and oil depletion. Among the different valorization routes for vegetable oils, epoxidation of their unsaturation is widely used. The epoxidation is an exothermic reaction which could lead to a thermal runaway. There are different routes for the vegetable oil epoxidation: Prileschajew by performic and peracetic acid, which are the most used. Another promising alternative is the direct epoxidation by hydrogen peroxide by alumina. The goal of this manuscript is to rank the thermal risk of these three epoxidation routes by determining the safety parameter time to maximum rate under adiabatic condition. The Advanced Reactive System Screening Tool was used to conduct these experiments. It was found that the direct epoxidation is safer than the two other routes.
Journal Article
Microwave-Assisted Synthesis, Characterization and Modeling of CPO-27-Mg Metal-Organic Framework for Drug Delivery
by
Caro, Juergen
,
Isaeva, Vera
,
Kustov, Leonid M.
in
Acetaminophen - administration & dosage
,
Acetaminophen - chemistry
,
Acids
2021
The coordination polymer CPO-27-Mg was rapidly synthesized under microwave irradiation. This material exhibits a sufficiently high drug loading towards aspirin (~8% wt.) and paracetamol (~14% wt.). The binding of these two molecules with the inner surface of the metal-organic framework was studied employing the Gaussian and Plane Wave approach of the Density Functional Theory. The structure of CPO-27-Mg persists after the adsorption of aspirin or paracetamol and their desorption energies, being quite high, decrease under solvent conditions.
Journal Article
Supported Ionic Liquid Catalysts (SILCA) for Preparation of Organic Chemicals
2010
Supported Ionic Liquid Catalysts (SILCA) designed by immobilization of catalytic species residing in an ionic liquid layer, which in turn was immobilized on a solid support, were applied on the selective hydrogenation of citral in a batch reactor and in a continuous reactor. Different ionic liquids with and without addition of acid modificators were studied in terms of the catalyst activity and product selectivity. Consequently, mechanistic kinetic models describing the differences in the activity and selectivity of the catalysts consisting different ionic liquids, were developed.
Journal Article
The Effect of Alkoxide Ionic Liquids on the Synthesis of Dimethyl Carbonate from CO2 and Methanol over ZrO2–MgO
by
Eta, Valerie
,
Salminen, Eero
,
Mikkola, Jyri-Pekka
in
Additives
,
Alkoxide ionic liquid
,
Alkoxides
2011
The use of carbon dioxide in the synthesis of chemicals, such as dimethyl carbonate (DMC), constitutes an environmentally attractive alternative to hazardous and toxic reagents. However, the direct synthesis of DMC from methanol and CO
2
is characterized by low yields due to the reaction equilibrium and the thermodynamic limitations
. Alkoxide ionic liquids possessing alkylimidazolium and benzalkonium cations were prepared, characterised and tested together with ZrO
2
–MgO catalyst for the synthesis of DMC from methanol and CO
2
. By using the novel ionic liquid as additives, ca. 12% conversion of methanol, and 90% selectivity to DMC was obtained at 120 °C and 7.5 MPa. The water abstracting potential of the ionic liquids influenced the conversion of methanol and the selectivity to DMC. The alkoxide ionic liquids were recovered and reused in DMC synthesis without loss in activity and selectivity.
Graphical abstract
Synthesis of DMC from CO
2
and methanol catalysed by ZrO
2
–MgO using ionic liquid alkoxides as water abstracting additives. Comparison of the fresh and regenerated ionic liquid at 120 °C.
Journal Article