Daina Upskuvienė

The development of sustainable electrocatalysts for clean energy by modifying biomass-derived activated carbon with nitrogen and transition metals is presented. Activated carbon (AWC) material was obtained using alder wood char as a precursor, while nitrogen and cobalt or copper nanoparticles were incorporated with the aim of creating efficient materials for hydrazine oxidation (HzOR) and direct hydrazine–hydrogen peroxide fuel cells (DHHPFC, N₂H₄–H₂O₂). The composition, structure, and surface morphology of the created materials were examined using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and inductively coupled plasma optical emission spectroscopy (ICP-OES). The activity of the AWC, AWC–Co–N, and AWC–Cu–N catalysts for HzOR was investigated using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). N₂H₄–H₂O₂ fuel-cell tests were performed by applying the catalysts as both the anode and cathode. It was found that all materials retained a hierarchical porous carbon framework, while metal incorporation altered surface compactness. Cobalt doping produced well-dispersed Co nanoparticles and abundant Co–N–C coordination sites, whereas Cu introduction resulted in moderately compact structures with uniformly distributed Cu-based nanoparticles. Electrochemical measurements demonstrated that both metal dopants enhanced HzOR activity, with the catalytic performance following the order of AWC–Co–N > AWC–Cu–N > AWC. Fuel-cell testing further confirmed this trend: AWC–Co–N achieved the highest maximum power density (30.4 mW cm⁻²), outperforming AWC–Cu–N (17.7 mW cm⁻²). These results identify AWC–Co–N as a highly effective bifunctional electrocatalyst for DHHPFCs.

In this study the development of sustainable electrocatalysts for clean energy by modifying biomass-derived activated carbon with nitrogen and transition metals is presented. Activated carbon (AWC) was synthesized using alder wood char as a precursor, while nitrogen and cobalt or copper nanoparticles were incorporated with the aim to create efficient materials for hydrazine oxidation (HzOR) and direct hydrazine-hydrogen peroxide fuel cells (DHHPFC, N2H4–H2O2). The composition, structure, and surface morphology of the created catalysts were examined using inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy and energy dispersive X-ray analysis (SEM/EDX). The activity of the AWC, AWC–Co–N, and AWC–Cu–N catalysts for HzOR was evaluated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). N2H4–H2O2 fuel cell tests were carried out by employing the catalysts both as the anode and cathode. It was found that all materials retained a hierarchical porous carbon framework, while metal incorporation altered surface compactness Cobalt doping produced well-dispersed Co nanoparticles and abundant Co–N–C coordination sites, whereas Cu introduction resulted in moderately compact structures with uniformly distributed Cu-based nanoparticles. Electrochemical measurements demonstrated that both metal dopants enhanced HzOR activity, with the catalytic performance following the order AWC–Co–N > AWC–Cu–N > AWC. Fuel-cell testing further confirmed this trend: AWC–Co–N achieved the highest maximum power density (30.4 mW cm–2), outperforming AWC–Cu–N (17.7 mW cm–2). These results identify AWC–Co–N as a highly effective bifunctional electrocatalyst for DHHPFCs.

Electrocatalytic seawater splitting is an ideal strategy for the large-scale production of green hydrogen. Compared to scarce freshwater, oceanic seawater electrolysis represents a game-changer for the hydrogen economy. Herein, we report a cost-effective one-step synthesis of binder-free, self-supported 3D nickel–manganese–cobalt (NiMnCo) coatings on titanium (Ti) substrates and evaluated their electrocatalytic performance for the hydrogen evolution reactions (HERs) in alkaline media (1.0 M KOH), simulated seawater (SSW, 1.0 M KOH + 0.5 M NaCl) and alkaline natural seawater (ASW, 1.0 M KOH + natural seawater). These ternary coatings were electrodeposited on Ti substrates using an electrochemical deposition method via a dynamic hydrogen bubble template (DHBT) technique. The optimized ternary NiMnCo/Ti-2 electrocatalyst exhibited an enhanced HER activity in both alkaline and seawater media, achieving an ultra-low overpotential of 29, 59 and 66 mV to reach the benchmark current density of 10 mA cm⁻² in SSW, ASW and 1.0 M KOH, respectively. This efficient 3D ternary NiMnCo/Ti-2 electrocatalyst demonstrated stable long-term performance at a constant potential of −0.23 V (vs. RHE) and a constant current density of 10 mA cm⁻² for 50 h without any significant degradation. Furthermore, it exhibited long-term stability in alkaline electrolyte and simulated seawater during multi-step chronopotentiometric testing at variable current densities from 20 mA cm⁻² to 100 mA cm⁻² for 18 h. This superior performance can be attributed to its unique intermetallic structure and multi-component composition, which provides good Cl⁻ resistance, electrochemical stability and synergistic effects among its constituents. Therefore, the optimized NiMnCo/Ti-2 electrocatalyst is a promising candidate for practical seawater electrolysis aiming at green hydrogen production.

In this study we present an application of wood biomass—alder wood char—as the carbon precursor for the synthesis of novel and sustainable nitrogen-doped activated-carbon-supported nickel nanoparticle catalyst (AWC-Ni-N) for hydrazine oxidation. For comparison, the wood-based carbon material doped with nitrogen only (AWC-N) was also synthesized. Extensive characterization, including SEM, Raman spectroscopy, XPS, and XRD revealed the catalysts’ microstructure and properties. Electrochemical testing demonstrated that the AWC-Ni-N catalyst significantly enhanced the efficiency of the hydrazine oxidation reaction. In addition, direct N₂H₄-H₂O₂ single-fuel-cell tests were conducted using the prepared AWC-N and AWC-Ni-N catalysts as the anodes and cathodes. Peak power densities of up to 10.8 mW cm⁻² were achieved at 25 °C, corresponding to a current density of 27 mA cm⁻² and a cell voltage of 0.4 V when the AWC-Ni-N catalyst was used as both the anode and cathode. Furthermore, the peak power density increased by approximately 1.6 and 2.9 times, respectively, when the operating temperature was raised from 25 °C to 55 °C for the AWC-N and AWC-Ni-N catalysts. Overall, the AWC-N and AWC-Ni-N catalysts demonstrated significant potential as anode and cathode materials in direct N₂H₄-H₂O₂ fuel cells.

In this study we present an application of wood biomass - alder wood char as the carbon precursor for the synthesis of novel and sustainable nitrogen-doped activated carbon supported nickel nanoparticle catalyst (AWC-Ni-N) for hydrazine oxidation. For comparison, the wood-based carbon material doped with nitrogen only (AWC-N) was also synthesized. Extensive characterization, including SEM, Raman spectroscopy, XPS, and XRD revealed the catalysts' microstructure and properties. Electrochemical testing demonstrated that the AWC-Ni-N catalyst significantly enhanced the efficiency of the hydrazine oxidation reaction. In addition, direct N2H4-H2O2 single fuel cell tests were conducted using the prepared AWC-N and AWC-Ni-N catalysts as the anodes and cathodes. Peak power densities of up to 10.8 mW cm⁻² were achieved at 25 °C, corresponding to a current density of 27 mA cm⁻² and a cell voltage of 0.4 V when the AWC-Ni-N catalyst was used as both the anode and cathode. Furthermore, the peak power density increased by approximately 1.6 and 2.9 times, respectively, when the operating temperature was raised from 25 °C to 55 °C for the AWC-N and AWC-Ni-N catalysts. Overall, the AWC-N and AWC-Ni-N catalysts demonstrate significant potential as anode and cathode materials in direct N2H4-H2O2 fuel cells.

The perfect strategy for the generation of green and renewable hydrogen (H₂) fuels is the direct electrocatalytic splitting of plentiful seawater rather than scarce freshwater. One of the half-reactions taking place during the electrocatalytic splitting of seawater is oxygen evolution (OER). However, the OER is affected by slow four-electron transfer kinetics as well as competitive chlorine evolution reactions (CERs) in seawater. To overcome the kinematic and competitive barriers of seawater splitting and achieve an excellent overall performance of seawater splitting, we herein report a facile, low-cost, one-step fabrication procedure of 3D structured nickel–manganese (NiMn) coatings using a dynamic hydrogen bubble template (DHBT) technique. The electrocatalytic activities of the thus synthesized catalytic materials for OER in simulated seawater (0.5 M NaCl + 1 M KOH, denoted as SSW) and alkaline natural seawater (natural seawater + 1 M KOH, denoted as ASW) were investigated using linear sweep voltammetry (LSV) at varying temperatures from 25 to 75 °C. Scanning electron microscopy (SEM) and inductively coupled plasma–optical emission spectroscopy (ICP–OES) were used to examine the surface morphology and composition of the prepared catalysts. It was found that the prepared NiMn/Ti-1 catalyst in a plating bath containing a molar ratio of 1:1 Ni²⁺:Mn²⁺ and having the lowest Mn loading of 13.43 µg cm⁻² exhibited quite reasonable activity for OER in Cl⁻ ion rich SSW and ASW. To achieve the benchmark current density of 10 mA cm⁻² in SSW and ASW, the NiMn/Ti-1 electrocatalyst requires overpotentials of 386 and 388 mV, respectively. In addition, this optimal bimetallic electrocatalyst also demonstrated superior long-run stability at 1.81 V (vs. RHE) and 10 mA cm⁻² for 24 h in both working electrolytes. Impressively, the two-electrode electrolyzer—NiMn/Ti-5₍₋₎||NiMn/Ti-1₍₊₎—needs only 1.619 V to deliver 10 mA cm⁻² current density for overall alkaline seawater electrolysis, which is even 0.075 V lower than the noble metal-based electrolyzer (Pt₍₋₎||NiMn/Ti-1₍₊₎).

Carbonization of biomass residues followed by activation has great potential to become a safe process for the production of various carbon materials for various applications. Demand for commercial use of biomass-based carbon materials is growing rapidly in advanced technologies, including in the energy sector, as catalysts, batteries and capacitor electrodes. In this study, carbon materials were synthesized from hardwood using two carbonization methods, followed by activation with H₃PO₄, KOH and NaOH and doping with nitrogen. Their chemical composition, porous structure, thermal stability and structural order of samples were studied. It was shown that, despite the differences, the synthesized carbon materials are active catalysts for oxygen reduction reactions. Among the investigated carbon materials, NaOH-activated samples exhibited the lowest Tafel slope values, of −90.6 and −88.0 mV dec^–1, which are very close to the values of commercial Pt/C at −86.6 mV dec^–1.

A Pt-coated Ni layer supported on a Ni foam catalyst (denoted PtNi/Ni_foam) was investigated for the electro-oxidation of the formic acid (FAO) in acidic media. The prepared PtNi/Ni_foam catalyst was studied as a function of the formic acid (FA) concentration at bare Pt and PtNi/Ni_foam catalysts. The catalytic activity of the PtNi/Ni_foam catalysts, studied on the basis of the ratio of the direct and indirect current peaks (j^d)/(j^nd) for the FAO reaction, showed values approximately 10 times higher compared to those on bare Pt, particularly at low FA concentrations, reflecting the superiority of the former catalysts for the electro-oxidation of FA to CO₂. Ni foams provide a large surface area for the FAO, while synergistic effects between Pt nanoparticles and Ni-oxy species layer on Ni foams contribute significantly to the enhanced electro-oxidation of FA via the direct pathway, making it almost equal to the indirect pathway, particularly at low FA concentrations.

Pt-coated Ni layer supported on Ni foam catalyst (denoted PtNi/Nifoam) was investigated for the oxidation of the formic acid (FAO) in acidic media. The prepared PtNi/Ni foam catalyst was studied as a function of the formic acid (FA) concentration at bare Pt and PtNi/Nifoam catalysts. The catalytic activity of the PtNi/Nifoam catalysts, studied on the basis of the ratio of the direct and indirect current peaks (jd)/(jnd) for the FAO reaction, showed values about 10 times higher compared to those on bare Pt, particularly at a low formic acid concentrations, reflecting the superiority of the former catalysts for the oxidation of FA to CO2. Ni foams provide a large surface area for the FOR while synergistic effects between Pt nanoparticles and Ni-oxy species layer on Ni foams contribute significantly to the enhanced oxidation of FA via the direct pathway, making it almost equal to the indirect pathway, particularly at low formic acid concentrations.

Nitrogen-doped activated carbons with controlled micro- and mesoporosity were obtained from wood and wastes via chemical processing using pre-treatment (pyrolysis at 500 °C and hydrothermally carbonization at 250 °C) and evaluated as oxygen reduction catalysts for further application in fuel cells. The elemental and chemical composition, structure and porosity, and types of nitrogen bonds of obtained catalyst materials were studied. The catalytic activity was evaluated in an alkaline medium using the rotating disk electrode method. It was shown that an increase in the volume of mesopores in the porous structure of a carbon catalyst promotes the diffusion of reagents and the reactions proceed more efficiently. The competitiveness of the obtained carbon materials compared to Pt/C for the reaction of catalytic oxygen reduction is shown.