Umeå University's logo

NbOPO4 supported TiO2 materials were demonstrated to be excellent catalysts for selective conversion of C6-carbohydrates to 5-hydroxymethylfurfural in an environmentally benign dimethyl carbonate-water solvent system. The materials presented high activity and excellent stability in sub-critical water conditions (upto 180 °C and 20 bar), enabling continuous 5-hydroxymethylfurfural production from highly concentrated sugars (35 wt% fructose, glucose and glucose:fructose mixtures) in a micro fixed-bed reactor. The high catalytic activity (6–27.3 KgHMFKgCat−1day−1) and good-to-excellent HMF selectivity (55–91 %) and exceptional hydrolytic stability and regenerability observed under process conditions was attributed to a highly crystalline NbOPO4 phase with Q2 and Q3 phosphates stabilized on a TiO2 framework with tunable acidity (0.11–0.52 mmolH+g−1 and Brønsted/Lewis ratio) and acidic strength comparable to bulk-NbOPO4. Furthermore, our experiments also revealed the importance of organic solvents in modulating catalyst acidic properties, particularly the strength of Brønsted acid sites which, in turn, influenced the HMF productivity.

Water pollutants such as synthetic dyes can cause significant problems for human health and ecosystems due to their chemical properties and environmental interactions. Contamination of surface and underground water caused by the discharge of synthetic dyes is a widespread problem that arises primarily from industrial activities such as textile manufacturing, leather processing, paper production, and plastics industries. Since adsorption is one of the most efficient and reliable methods to remove pollutants from water, in this work, pine tree logging residues (LR) were used to produce boron/sulfur chemically modified biochars with superior adsorption performance and recyclability. The biochars were produced using a two-step pyrolysis procedure with potassium hydroxide as a chemical activator. The specific surface areas (B.E.T.) of the biochars were 2645 m2 g−1 for the boron-treated biochar (LR-Boron), 2524 m2 g−1 for the sulfur-treated (LR-Sulfur), and 3141 m2 g−1 for the control biochar (LR-Control, without boron or sulfur), respectively. The LR-Boron biochar showed an exceptional degree of graphitization of (ID/IG=0.45), while the LR-Sulfur biochar displayed an ID/IG= 1.02; for comparison, the LR-Control exhibited an ID/IG= 0.81, showing that the sample subjected to boron treatment created carbon-rich in graphitic structures. The three biochars were evaluated as adsorbents for removing reactive black-5 azo dye (RB-5) from water and mixtures of several dyes in synthetic aqueous effluents. The adsorption data showed that all carbons exhibited outstanding RB-5 removal performance. Kinetic measurements were well fitted by the Avrami fractional order model, and the LR-sulfur carbon displayed the fastest adsorption kinetics. Isotherm measurements were well fitted by the Liu model, with a theoretical Qmax of around 1419 mg g−1 (LR-Control), 1586 mg g−1 (LR-Boron), and 1766 mg g−1 (LR-Sulfur) at 316 K. The presence of sulfur-functional groups on the LR-Sulfur biochar surface was probably the reason for the superior adsorption performance of this biochar. Both sulfur and boron-treated biochars exhibited higher regeneration potentials, maintaining around 60–67 % removal capacity after 7 cycles compared to 35 % for the LR-Control biochar. Thermodynamic adsorption studies showed that the adsorption process was endothermic, favorable, and compatible with physical adsorption. All produced biochars were highly efficient for removal of pollutants from concentrated synthetic effluents.

The current study presented a porous liquid (PL) prepared from propylene glycol-based deep eutectic solvent (DES) and hyper-crosslinked polymers (HCP) that are liquids over wide temperature ranges, including ambient temperature. It was shown that the solvent molecules are too large to penetrate the pores of HCP, so the PL is maintained as a suspension with permanent free volume for several months and can absorb large amounts of gases. This study marks the pioneering use of DESs as the liquid medium, replacing ionic liquids due to their closely matched properties. The structural features of both DES and HCP are retained; the increase in CO2 absorption capacity compared to pure DES is due to the presence of a porous solid and is proportional to the amount of solid. The absorbed CO2 amount rises from 1.0105 mmol·g−1 in pure DES to 1.3232, 1.6027, and 1.2168 mmol·g−1 in PL-1, PL-2, and PL-3, respectively. Thermodynamic analysis revealed that the enthalpy of gas absorption allows straightforward regeneration of the PLs in the studied cases. The investigated PLs show great potential as gas absorbents, with the incorporation of just 0.5 wt% of porous polymer material leading to an impressive increase in solvent absorption capacity, up to 59 %.

Lignin valorization has attracted significant attention in recent years due to its abundance and potential as a renewable organic carbon resource to produce a variety of value-added chemicals and fuel additives. Catalytic upgrading of lignin faces challenges due to its complex structure and an active catalyst with selective surface properties is needed to break the stable C–O and C–C interunit linkages. In the present work, we developed a series of multifunctional Ru/NbOPO₄/TiO₂ catalysts with varying surface acidic properties and explored their potential upon hydrogenolysis of lignin model compound eugenol. Textural and surface acidic properties of the prepared materials were studied by means of different techniques such as N₂-physisorption, NH₃-TPD, XRD, SEM-EDS, Raman spectra, FT-IR, and TEM. Our catalytic results revealed synergistic role of acid and metal sites upon catalyst performance, whereupon high yields of hydrocarbons (86.9–100 wt.%) were obtained with selective cleavage of the methoxy and hydroxy groups under milder conditions. A kinetic study further identified the reaction mechanism and determined a rate law and partial reaction orders. This research advances the understanding of catalyst design for upgrading of the lignin or lignin monomers into value added chemicals. and on the other hand, contributes to sustainable development by maximizing biomass usage and providing environmentally friendly alternatives in renewable energy.

ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure-directing agent, followed by homogenization and hydrothermal treatment. The as-prepared ZSM-5 was physicochemically characterized to assess its properties. Next, the as-prepared zeolite was employed as an adsorbent to remove rare earth elements, REEs from synthetic solutions and real phosphogypsum leachate under batch mode operation. As expected, the ZSM-5 adsorbent was discovered to be highly microporous with abundant surface functionalities, which could positively impact REE adsorption. The adsorption data indicated a high affinity between ZSM-5 and all three REEs with rapid kinetics and high adsorption capacities. The modeling study suggested that the adsorption kinetic data were well fitted by Avrami-fractional order, and Liu described the equilibrium data. The maximum adsorption capacity for Ce3+, La3+, and Nd3+ were 99.42 mg g−1, 96.43 mg g−1, 118.10 mg g−1, respectively. Further, the thermodynamic analysis revealed that the interaction between ZSM-5 and Ce3+, La3+, and Nd3+ was favorable, spontaneous, and endothermic. The efficiency of ZSM-5 adsorbent was also studied in recovering several REEs from leachate of phosphogypsum wastes, and the data results proved its potency to do so. The findings reported in this work support the idea that ZSM-5 can be successfully used as an adsorbent to recover REEs from synthetic and real samples.

Three short-alkyl-chain-modified [DBU][TFSI] ionic liquids (ILs) were synthesized and utilized in electrets. The electrets were prepared by mixing a UV-curable polymer with the ionic liquids followed by polymerization while applying an external electric field, thus forming spatially separated anions and cations in the proximity of opposing surfaces of the composite slabs. The immobilized surplus surface charge was measured by periodically engaging the electret with a metal counter electrode plate and detecting the displacement current using a charge amplifier. The results show that electrets based on polymerized [DBU][TFSI] ILs have a separated surface charge density of up to 64 nC × cm⁻², which equals an energy harvesting density of 7.0 nJ × cm⁻². Control measurements repeated after a few days to assess the stability and reproducibility of the systems showed that while charge separation reverses over time to some extent, the polymerized ionic liquid samples are resilient to exposure to atmospheric conditions and could be utilized in this type of energy harvesting scheme.

The development of biomass-based carbon materials has accelerated the research interest in environmental (e.g., adsorbents for wastewater decontamination) and energy applications (e.g., batteries). In this paper, we developed a series of carbon materials (CMs) using a sulfur doping strategy to improve the physicochemical, adsorptive and energy storage properties of the aforementioned CMs. CMs were prepared and optimized using an experimental design denoted as the Box-Behnken design approach with three independent factors (i.e., the temperature of pyrolysis, zinc chloride: biomass ratio and sulfur: biomass ratio), and the responses were evaluated, namely the Specific Surface Area (SBET), mesopore area (AMeso) and micropore area (AMicro) with the help of Nitrogen Physisorption. According to the statistical analysis, under the studied conditions, the responses were mainly influenced by the pyrolysis temperature and ZnCl2 ratio, while the sulfur content did not give rise to any remarkable differences in the selected responses. The physicochemical characterization of the CMs suggested that very high Specific Surface Areas ranging from 1069 to 1925 m2 g−1 were obtained. The sulfur doping resulted in up to 7.33wt.% of sulfur in the CM structure, which yielded CMs with more defects and hydrophilic surfaces. When tested as adsorbents, CMs exhibited a very high adsorption capacity (190 – 356mgg-1), and as anodes, they demonstrated a competitive Lithium Ion Battery (LIB) storage capacity, at least during the first five cycles (306 mAhg-1 at 1C for CM9). However, further studies on long-term cyclability are required to prove the CM materials suitability in LIBs. This work extends our understanding of how pyrolysis and sulfur doping of biomass feedstock affects carbon materials' usability, final characteristics and potential to use in wastewater decontamination by adsorption and as anodes in LIBs.

Poly-(3-hydroxybutyrate), PHB, is a bacterial polyester in industrial demand as a biodegradable alternative to fossil-derived nondegradable plastics. Moreover, apart from being used directly as a bioplastic, valorization of PHB to its monomer building blocks and other value-added chemicals is feasible but less explored. In this study, Brønsted acid ionic liquid (BAIL) catalyzed depolymerization of PHB was investigated as a highly selective route to 3-hydroxybutyric acid, 3-HBA. The hydrolysis of PHB to 3-HBA was performed in a biphasic solvent medium composed of methyl isobutyl ketone (MIBK) and water, where the organic phase had dual roles as an efficient medium for dissolution of the polymer and as solvent for the monomeric products, which were enriched in this phase after cooling, with the Brønsted acid ionic liquid (BAIL) catalyst partitioned into the aqueous phase for facile recycling. The effects of reaction parameters, including the temperature, types of IL in terms of cations and anions, and the amount of water and IL, were studied to assess the yield of 3-HBA. Furthermore, protic acids such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid (p-TsOH) were also applied for comparison as acid catalysts for the hydrolysis of PHB to 3-HBA. Among the tested catalysts, the ILs containing the p-TsO- as anion as well as p-TsOH alone were found to be highly selective in promoting hydrolysis to 3-HBA, with complete depolymerization of PHB at >90% yield of 3-HBA in 4 h at 120 °C using a BAIL with sulfobutylated 1-methylimidazolium as the cation component and p-TsO- as the anion ([ImSO3H+][p-TsO-]). Although the use of p-TsOH as the sole catalyst also yielded efficient PHB hydrolysis with high reaction rates, it had a disturbing effect on the biphasic MIBK-water system by forming a single-phase reaction mixture at high 3-HBA yields, obstructing the recoveries of the products as well as the catalyst. In contrast, the biphasic reaction mixture remained intact when using IL as catalyst, which allowed facile and efficient separation of the product from the catalyst. Both the 3-HBA and the [ImSO3H+][p-TsO-] IL were recovered in high purity, the latter after applying a solvent extraction scheme based on ethyl acetate, whereby the recoveries of 3-HBA and IL reached ≈90%. The compositions of the synthesized ILs and the progress of the hydrolysis process, as well as the purity of the recovered product, were confirmed by NMR analysis. This sustainable approach to selective hydrolytic transformation of PHB into 3-HBA using a recoverable acidic IL catalyst in a biphasic solvent media of aqueous methyl isobutyl ketone hence resulted in efficient product separation and catalyst recovery.

Anatase TiO₂ (TiO₂-A) has been utilized for biomass upgrading processes such as hydrodeoxygenation (HDO) and Carbon-Carbon (C-C) coupling reactions (ketonisation and aldol condensation), where Ti-O Lewis acid-base pairs (LABPs) serve as active sites. Altering the metal oxide’s reduction state can modify its acid-base properties, yet the effects of oxygen vacancy coverage on TiO₂ during biomass vapor upgrading remain unclear. This study investigates the dynamics between C-C coupling and HDO reactions in the ex-situ upgrading of beechwood pyrolysis vapors at 600 °C and 1 atm. LABPs properties were tuned by varying degrees of oxygen vacancy on TiO2, and the catalyst was characterized by BET, XRD, NH₃-TPD, CO2-TPD, H₂-TPR, Raman, UV–vis, SEM-EDX, and FTIR. Our study demonstrated that decreasing the O/Ti ratio (i.e., increasing oxygen vacancies) promotes C–C coupling and HDO reactions. The highest C-C coupling and moderate HDO observed on an O/Ti ratio of 1.7 produced the highest jet-fuel fraction (56.5%) compared to other TiO₂ variants. The C2+ selectivity shifted from 85.2% of hydropyrolysis oil to 99.2 wt%, while the O/C and H/C ratios changed from 0.45 and 1.55 of hydropyrolysis oil to 0.06 and 1.39, respectively, on TiO₂ with an O/Ti ratio of 1.7. The adsorption behavior of the acetone, furan, and guaiacol on LABPs was evaluated on the (1 0 1) plane of A-TiO₂ by DFT, which corroborated the experimental findings. This is the first time a deep correlation has been provided on the influence of oxygen vacancies on the vapor phase upgrading of real biomass feedstock.

The need of new electrolytes with wide electrochemical window, good stability and conductivity has promoted novel ionic liquids (ILs) as new solutions for supercapacitors. In this work, four hydrophobic room temperature ionic liquids based on organic superbase-derived cations and Trifluoromethanesulfonimide (TFSI) anion were synthetized. The structures of the novel ILs were analyzed, characterized and their performance as a supercapacitor electrolyte was evaluated. The ILs have high decomposition temperatures of up to 490 °C and electrochemical window up to 4.8 V. It was found that there was an optimal chemical structure providing the best stability and operational potential window coupled with moderate conductivity. The IL with the shortest alkyl chain structure provided the highest conductivity but suffered from instability. The performance of the ILs with longer alkyl chains was hindered by lower conductivities and, in the case of the largest chemical structures, also by reduced cyclic stabilities in open air. However, the ionic liquid with moderate alkyl chain length was found to be stable even in open air providing decent conductivity, which can be utilized in future research to develop other hydrophobic ionic liquids suitable as supercapacitor electrolytes.