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Herein, we present a synthesis route for high-efficiency nitrogen-doped carbon materials using kraft pulping residue, black liquor, and wood charcoal as carbon sources. The synthesized nitrogen-doped carbon materials, based on black liquor and its mixture with wood charcoal, exhibited high specific surface areas (SSAs) of 2481 and 2690 m2 g−1, respectively, as well as a high volume of mesopores with an average size of 2.9–4.6 nm. The nitrogen content was approximately 3–4 at% in the synthesized nitrogen-doped carbon materials. A specific capacitance of approximately 81–142 F g−1 was achieved in a 1 M Na2SO4 aqueous solution at a current density of 0.2 A g−1. In addition, the specific capacitance retention was 99% after 1000 cycles, indicating good electrochemical stability.

In this study, we present the synthesis of cationic brush-type polyelectrolytes and their use in the stabilization of GdPO4 particles in aqueous media. Polymers of various compositions were synthesized via the RAFT polymerization route. SEC equipped with triple detection (RI, DP, RALS, and LALS) was used to determine the molecular parameters (Mn, Mw, Mw/Mn). The exact composition of synthesized polymers was determined using NMR spectroscopy. Cationic brush-type polymers were used to improve the stability of aqueous GdPO4 particle dispersions. First, the IEPs of GdPO4 particles with different morphologies (nanorods, hexagonal nanoprisms, and submicrospheres) were determined by measuring the zeta potential of bare particle dispersions at various pH values. Afterward, cationic brush-type polyelectrolytes with different compositions were used for the surface modification of GdPO4 particles (negatively charged in alkaline media under a pH value of ∼10.6). The concentration and composition effects of used polymers on the change in particle surface potential and stability (DLS measurements) in dispersions were investigated and presented in this work. The most remarkable result of this study is redispersible GdPO4 nanoparticle colloids with increased biocompatibility and stability as well as new insights into possible cationic brush-type polyelectrolyte applicability in both scientific and commercial fields.

N-doped carbons are widely used in the energy storage and conversion field because of their excellent electrical conductivity, high specific surface area, and superb electrochemical stability. Herein, high-efficiency carbon material has been derived using the kraft pulping residues – black liquor as the carbon source. The carbon material was prepared from black liquor through a two-step process, including chemical activation with NaOH at high temperature and doping with nitrogen using dicyandiamide (DCDA). The synthesized catalyst's morphology, structure, and composition were characterized using TEM, XPS, Raman Spectroscopy, and ICP-OES. The electrochemical performance has been evaluated using cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) techniques. The synthesized nitrogen-doped carbon material had a high specific surface area of 2481 m2 g−1. Moreover, this catalyst had a high nitrogen content of 4.33 at%. Most of the nitrogen was in the pyridinic-N (66.58 at%) and graphitic-N forms (33.42 at%). It was found that the specific capacitance of catalysts depends on the catalyst loading. The specific capacitance of ca. 50 F g-1 was achieved in the 1 M Na2SO4 aqueous solution at the scan rate of 5 mV s-1. Besides, the specific capacitance retention was 99% after 100 cycles indicating good electrochemical stability. Our present results demonstrated that kraft pulping residue, such as black liquor, can be employed as a promising carbon precursor to synthesize low-cost and efficient catalysts for supercapacitors. Acknowledgment This project has received funding under the Baltic Research Programme project “Sustainably produced nanomaterials for energy applications (SuNaMa)” (No. S-BMT-21-12, LT08-2-LMT-K-01-055).

Recently, great attention has been focused on biomass-derived electrocatalysts for the oxygen reduction reaction (ORR). In the present study, the wood-derived nitrogen-doped carbon nanomaterials with graphene-like structures have been synthesized from wood biomass using a chemical activation method with NaOH to achieve a high specific surface area (SSA). Then, the activated carbon materials have been doped with nitrogen using dicyandiamide (DCDA) as a cheaper nitrogen precursor. The synthesized catalyst's morphology, structure, and composition have been characterized using TEM, XPS, Raman Spectroscopy, and ICP-OES. The activity of the prepared catalysts was evaluated for ORR in the 0.1 M KOH solution employing the rotating disk electrode (RDE) method. The nitrogen-doped carbon materials have been shown a high electrocatalytic activity and stability for the oxygen reduction reaction. The number of electrons transferred per O2 molecule is close to 4.0. Acknowledgment This project has received funding under the Baltic Research Programme project “Sustainably produced nanomaterials for energy applications (SuNaMa)” (No. S-BMT-21-12, LT08-2-LMT-K-01-055).

The synthesis of magnetic particles triggers the interest of many scientists due to their relevant properties and wide range of applications in the catalysis, nanomedicine, biosensing and magnetic separation fields. A fast synthesis of iron oxide magnetic particles using an eco-friendly and facile microwave-assisted solvothermal method is presented in this study. Submicron Fe3O4 spheres were prepared using FeCl3 as an iron source, ethylene glycol as a solvent and reductor and sodium acetate as a precipitating and nucleating agent. The influence of the presence of polyethylene glycol as an additional reductor and heat absorbent was also evaluated. We reduce the synthesis time to 1 min by increasing the reaction temperature using the microwave-assisted solvothermal synthesis method under pressure or by adding PEG at lower temperatures. The obtained magnetite spheres are 200–300 nm in size and are composed of 10–30 nm sized crystallites. The synthesized particles were investigated using the XRD, TGA, pulsed-field magnetometry, Raman and FTIR methods. It was determined that adding PEG results in spheres with mixed magnetite and maghemite compositions, and the synthesis time increases the size of the crystallites. The presented results provide insights into the microwave-assisted solvothermal synthesis method and ensure a fast route to obtaining spherical magnetic particles composed of different sized nanocrystallites.

In this study, we present the synthesis of cationic brush-type polyelectrolytes and their use in the stabilization of GdPO4 particles in aqueous media. Polymers of various compositions were synthesized via the RAFT polymerization route. SEC equipped with triple detection (RI, DP, RALS, and LALS) was used to determine the molecular parameters (Mn, Mw, Mw/Mn). The exact composition of synthesized polymers was determined using NMR spectroscopy. Cationic brush-type polymers were used to improve the stability of aqueous GdPO4 particle dispersions. First, the IEPs of GdPO4 particles with different morphologies (nanorods, hexagonal nanoprisms, and submicrospheres) were determined by measuring the zeta potential of bare particle dispersions at various pH values. Afterward, cationic brush-type polyelectrolytes with different compositions were used for the surface modification of GdPO4 particles (negatively charged in alkaline media under a pH value of ∼10.6). The concentration and composition effects of used polymers on the change in particle surface potential and stability (DLS measurements) in dispersions were investigated and presented in this work. The most remarkable result of this study is redispersible GdPO4 nanoparticle colloids with increased biocompatibility and stability as well as new insights into possible cationic brush-type polyelectrolyte applicability in both scientific and commercial fields.

A novel and simple method for CeO2 nanoscale particle synthesis in aqueous solutions via a photochemical route is reported in this paper. To this end, CeCl3·7H2O or Ce(NO3)3·6H2O was used as a Ce precursor, while NaN3 was chosen as the photoactive compound. Synthesis was carried out without any surfactants or by using polyvinylpyrrolidone (PVP). The synthesized samples were subsequently thermally treated at different temperatures between 100 and 900 °C. XRD patterns and Raman spectra indicated that CeO2 samples possess the fluorite structure. TEM analysis revealed that synthesis without surfactants leads to formation of highly agglomerated particles, while adding PVP to the primary solution resulted in decreased agglomeration and reduced particle size. The particle size was calculated from XRD and Raman line broadening and confirmed by TEM analysis. The average crystallite size for the unheated samples prepared without surfactant was hardly radiation exposure dependent and varied from 6.5 to 8.9 nm. Even smaller particles (3.3–7.0 nm) were formed by using PVP. It turned out that an increase of the calcination temperature causes significant crystallite growth. A strong interaction between CeO2 nanoparticles and PVP was revealed by TG analysis. The UV/VIS absorption spectra showed a strong absorption below 400 nm (3.10 eV) with a well-defined absorption peak at around 295–320 nm. The estimated band gap (Eg) of the obtained nanoscale particles was in the range of 2.90–3.57 eV, i.e. the values are higher than that of a bulk CeO2 powder (Eg = 3.19 eV), except for the sample calcined at 900 °C.

Among the different types of fuel cell technologies, direct methanol fuel cells (DMFCs) are the most suitable for mobile and portable electronic applications. The development of cost-effective, active, and stable catalysts, able to substitute Pt or allow reducing the amount of it in low temperature fuel cell anodes is still in progress. In our previous works [1, 2] it has been shown that the graphene supported platinum-cobalt catalysts prepared by means of microwave synthesis enhance electrocatalytic activity towards the oxidation of borohydride and ethanol in an alkaline medium and are promising anode materials for direct borohydride fuel cells (DBFCs) and ethanol fuel cells (DEFCs). In this study investigation of activity of the graphene supported platinum-cobalt catalysts with the different Pt:Co molar ratios, fabricated by the rapid microwave heating method, towards the electro-oxidation of methanol in an acidic medium is presented. The Pt-Co/GR catalysts with the Pt:Co molar ratios equal to 1:3, 1:6, 1:20, 1:50 and 1:60 were prepared by microwave-assisted heating of required amounts of Pt(IV), Co(II) and ethylene glycol at a temperature 170 oC for 30 min. For comparison, the graphene supported Pt catalyst was also prepared at 170 oC for 30 s. The Pt loading in the synthesized catalysts was near 0.1 mg Pt cm-2. The electrochemically active surface areas of Pt in the synthesized Pt/GR and Pt-Co/GR catalysts were determined from the cyclic voltammograms of the mentioned catalysts recorded in a deaerated 0.5 M H2SO4 solution at a sweep rate 50 mV s-1 by calculating the charge associated with hydrogen adsorption (220 µCcm-2) and are 0.7 cm2 for Pt/GR and 5.2, 2.9, 1.6, 1.0 and 0.5 cm2for the Pt-Co/GR catalysts with the Pt:Co molar ratios equal to 1:3, 1:6, 1:20, 1:50 and 1:60, respectively. Values of the electrochemically active surface areas of the investigated Pt-Co/GR catalysts are 1.4-7.5 times higher than those of the Pt/GR catalyst. Electrochemical properties of Pt-Co/GR were investigated towards the electro-oxidation of methanol in acidic medium by means of cyclic voltammetry and chronoamperometry and compared with those of the bare graphene supported Pt catalyst. It has been determined that the Pt-Co/GR catalysts with the Pt:Co molar ratios equal to 1:3, 1:6, 1:20 exhibit an enhanced electrocatalytic performance for methanol electro-oxidation as compared with that of bare graphene supported platinum catalyst. Methanol oxidation current density values are ca. 2.1-3.2 times higher at the Pt-Co/GR catalysts with the above mention Pt:Co molar ratios than those at the Pt/GR catalyst. Highest electrocatalytic activity towards the electro-oxidation of methanol in acidic medium shows the graphene supported Pt-Co catalyst with the Pt:Co molar ratios equal to 1:3 and 1:6 as compared with that of catalysts with higher Pt:Co molar ratios and Pt/GR. These results obtained show that the Pt-Co/GR catalysts with the different Pt:Co molar ratios could have promising future as catalysts for DMFC. References [1] L. Tamašauskaitë-Tamašiûnaitë, A. Radomskis, K. Antanavièiûtë, J. Jablonskienë, A. Balèiûnaitë, A. Þielienë, et al., Int. J. Hydrogen Energy, 39, 4282 (2014). [2] V. Kepenienë, L. Tamašauskaitë-Tamašiûnaitë, J. Jablonskienë, J. Vaièiûnienë, R. Kondrotas, R. Juškënas, E. Norkus, J. Electrochem. Soc., 161, F1354 (2014)