Search Results (26)

This study reports a binder-free, catalyst-free method for fabricating vertically aligned carbon nanotubes (VACNTs) directly on copper (Cu) foil using plasma-enhanced chemical vapor deposition (PECVD) for electrochemical double-layer capacitor (EDLC) applications. This approach eliminates the need for catalyst layers, polymeric binders, or substrate pre-treatments, simplifying electrode design and enhancing electrical integration. The resulting VACNTs form a dense, uniform, and porous array with strong adhesion to the Cu substrate, minimizing contact resistance and improving conductivity. Electrochemical analysis shows gravimetric specific capacitance (C_grav) and areal specific capacitance (C_areal) of 8 F g⁻¹ and 3.5 mF cm⁻² at a scan rate of 5 mV/s, with low equivalent series resistance (3.70 Ω) and charge transfer resistance (0.48 Ω), enabling efficient electron transport and rapid ion diffusion. The electrode demonstrates excellent rate capability and retains 92% of its initial specific capacitance after 3000 charge–discharge cycles, indicating strong cycling stability. These results demonstrate the potential of directly grown VACNT-based electrodes for high-performance EDLCs, particularly in applications requiring rapid charge–discharge cycles and sustained energy delivery. Full article

Waste lithium-ion batteries (LIBs), which usually contain dangerous organic electrolytes and transition metals, including nickel, cobalt, iron, and manganese, can hurt the environment and human health. Substantial advancements have been achieved in employing high-efficiency, economical, and environmentally sustainable techniques for the recycling of spent LIBs. Converting exhausted LIBs into efficient energy conversion catalysts straightforwardly is a good strategy for addressing metal resource constraints and clean energy concerns. This transforms waste cathodes, anodes, binders, and separators from depleted LIBs into electrocatalysts free of platinum group metals for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). The composite, including transition metal oxide, graphene oxide, and carbon mass, will be synthesized from spent LIBs, demonstrating enhanced electrocatalytic activity. Utilizing “waste-to-energy” methods for used LIBs as catalysts would provide substantial benefits in environmental preservation and the effective production of functional materials in metal–air batteries. Full article

In this work, the effect of the palladium precursor on the Oxygen Reduction Reaction (ORR) performance of lignin-based electrospun carbon fibers was studied. The fibers were spun from a lignin-ethanol solution free of any binder, where different Pd salts were added at two concentration levels. The system implemented to perform the spinning was a coaxial setup in which the internal flow contains the precursor dispersion with the metallic precursor, and ethanol was used as external flow to help fiber formation and prevent drying before generating the Taylor cone. The obtained cloths were thermostabilized in air at 200 °C and carbonized in nitrogen at 900 °C. The resulting carbon fibers were characterized by physicochemical and electrochemical techniques. The palladium precursor significantly affects nanoparticle distribution and size, fiber diameter, pore distribution, surface area and electrochemical behavior. The fibers prepared with palladium acetylacetonate at high Pd loading and carbonized at 900 °C under a CO₂ atmosphere showed high mechanical stability and the best ORR activity, showing near total selectivity towards the 4-electron path. These features are comparable to those of the commercial Pt/C catalyst but much lower metal loading (10.6 wt.% vs. 20 wt.%). The most promising fibers have been evaluated as cathodes in a zinc–air battery, delivering astonishing stability results that surpassed the performance of commercial Pt/C materials in both charging and discharging processes. Full article

The development of efficient, sustainable, and cost-effective catalysts is crucial for energy storage technologies, such as zinc–air batteries (ZABs). These batteries require bifunctional catalysts capable of efficiently and selectively catalyzing oxygen redox reactions. However, the high cost and low selectivity of conventional catalysts hinder the large-scale integration of ZABs into the electric grid. This study presents binder-free Fe-based bifunctional electrocatalysts synthesized via a sol–gel method, followed by thermal treatment under ammonia flow. Supported on nickel foam, the catalyst exhibits enhanced activity for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), essential for ZAB operation. This work addresses two critical challenges in the development of ZABs: first, the replacement of costly cobalt or platinum-group-metal (PGM)-based catalysts with an efficient alternative; second, the achievement of prolonged battery performance under real conditions without passivation. Structural analysis confirms the integration of iron nitrides, oxides, and carbon, resulting in high conductivity and catalytic stability without relying on precious or cobalt-based metals. Electrochemical tests reveal that the catalyst calcined at 800 °C delivers superior performance, achieving a four-electron ORR mechanism and prolonged operational life compared to its 900 °C counterpart. Both catalysts outperform conventional Pt/C-RuO₂ systems in stability and selective bifunctionality, offering a more sustainable and cost-effective alternative. The innovative combination of nitrogen, carbon, and iron compounds overcomes limitations associated with traditional materials, paving the way for scalable, high-performance applications in renewable energy storage. This work underscores the potential of transition metal-based catalysts in advancing the commercial viability of ZABs. Full article

The incorporation of waste fluid catalytic cracking (FCC) catalysts (WFCs) into asphalt pavements represents an effective strategy for resource utilization. However, the influences of the composition of the waste catalyst and its surface characteristics on the performance of asphalt mortars are still unclear. Herein, five WFCs were selected as powder filler to replace partial mineral powder (MP) to prepare five asphalt mortars. The diffusion behaviors of asphalt binder on the components of WFCs were investigated based upon molecular dynamic simulation, as was the interfacial energy between them. The adhesion work values between asphalt and WFCs were evaluated based upon the surface free energy theory. A dynamic shear rheology test and multiple stress creep recovery test on the WFC asphalt mortar were also conducted. Furthermore, the gray correlation analysis (GCA) method was employed to analyze the correlation between the diffusion coefficient and interfacial energy with the performance of WFC asphalt mortar. The results showed that the asphalt exhibited a low diffusion coefficient and high interfacial energy with the alkaline components of WFCs. The adhesion work values between asphalt and WFCs are higher than those with MP. The addition of WFCs can enhance the anti-rutting property of asphalt mortar significantly. Among the five WFCs, 2# exhibited the best improvement effect on the anti-permanent deformation ability of asphalt mortar, which may be due to its large specific surface area and moderate pore width. The GCA results suggest that the diffusion coefficient and interfacial energy strongly correlated with the performance of asphalt mortar, with an order of adhesion > permanent deformation resistance > rutting resistance. This study provides both theoretical and experimental support for the application of WFCs in asphalt materials. Full article

The formation of metal soaps or carboxylates in oil paintings is a widely studied topic. Expanding upon the extant research on the subject, this work investigates the formation of metal soaps as pertaining to alkyd-based media. Especially popular in modern and contemporary art, alkyd paints are complex commercial formulations mainly containing a polyester backbone obtained by the condensation of glycerol and phthalic acids, where the third free alcoholic function is esterified with a blend of saturated and unsaturated fatty acids. The formulation may also contain cross-linking agents, dries, and catalysts. Compared to drying oils, alkyd systems have different stability and mobility, likely prompting different kinetics in the formation of metal soaps. This work explores the formation of metal carboxylates in mock-up paints prepared as mixtures of an alkyd binder with potassium hydroxide and three commonly used pigments (smalt, zinc white, and lead white) at ambient conditions and upon artificial aging. As a second step, samples from two contemporary works by Italian artists Franco Garelli and Luciano Minguzzi were investigated for comparison. The results confirm the formation of metal soaps in both mock-up and real paints, paving the way for future research, with significant implications especially for the conservation of modern and contemporary artworks. Full article

The elaborate design of inexpensive, high-performance electrocatalysts from earth-abundant elements toward oxygen evolution reaction (OER) is critical in various (electro)chemical processes. Herein, a novel binder-free catalyst of Ce-coupled Ni₃S₂/NiS supported on Ni foam (Ce-Ni₃S₂/NiS@NF) is successfully synthesized via a facile one-step hydrothermal method that enables practical feasibility with a significant enhancement of OER activity through anchoring Ce dopants on an Ni₃S₂/NiS nanobud host. Ce species coupling can modulate electronic structure, which reduces the reaction energy barrier and optimizes OER catalytic activity. More profoundly, the superhydrophilic and superaerophobic properties of the Ce-Ni₃S₂/NiS@NF electrode further promote mass transfer. As a result, the Ce-Ni₃S₂/NiS@NF electrode exhibits excellent OER activity with a low overpotential of 236 and 350 mV to achieve current densities of 10 and 100 mA cm⁻², respectively, and long-term durability for 24 h in alkaline medium. These results could supply valuable guidelines for the design of other OER catalysts and beyond. Full article

The porous architectures of oxygen cathodes are highly desired for high-capacity lithium–oxygen batteries (LOBs) to support cathodic catalysts and provide accommodation for discharge products. However, controllable porosity is still a challenge for laminated cathodes with cathode materials and binders, since polymer binders usually shield the active sites of catalysts and block the pores of cathodes. In addition, polymer binders such as poly(vinylidene fluoride) (PVDF) are not stable under the nucleophilic attack of intermediate product superoxide radicals in the oxygen electrochemical environment. The parasitic reactions and blocking effect of binders deteriorate and then quickly shut down the operation of LOBs. Herein, the present work proposes a binder-free three-dimensional (3D) porous graphene (PG) cathode for LOBs, which is prepared by the self-assembly and the chemical reduction of GO with triblock copolymer soft templates (Pluronic F127). The interconnected mesoporous architecture of resultant 3D PG cathodes achieved an ultrahigh capacity of 10,300 mAh g⁻¹ for LOBs. Further, the cathodic catalysts ruthenium (Ru) and manganese dioxide (MnO₂) were, respectively, loaded onto the inner surface of PG cathodes to lower the polarization and enhance the cycling performance of LOBs. This work provides an effective way to fabricate free-standing 3D porous oxygen cathodes for high-performance LOBs. Full article

In this research, a thin layer of multi-metallic non-precious catalyst is prepared by electroplating from an electrolyte bath containing Ni, Co, and Fe sulfates over pressed commercial nickel foam electrode. The composition of the deposited catalytic film and its morphology are characterized by scanning electron microscopy (SEM) with energy dispersion X-ray (EDX) techniques. The efficiency of the prepared binder-free electrodes for electrochemical water splitting is investigated in a self-designed short water electrolysis stack with zero-gap configuration of the integrated single cells and hybrid electrical connections. The separator used is a commercial Zirfon Perl 500 membrane, doped with 25% KOH. The performance of the catalyst, the single cells, and the developed electrolyzer stack are examined by steady state polarization curves and stationery galvanostatic stability tests in the temperature range 20 °C to 80 °C. The NiFeCoP multi-metallic alloy demonstrates superior catalytic efficiency compared to the pure nickel foam electrodes and reliable stability with time. The single cells in the stack show identical performance and the cumulative stack parameters strictly follow the theoretical considerations. The applied hybrid electrical connections enable scaling of both the stack voltage and the passing current, which in turn ensures flexibility with regard to the input power and the hydrogen production capacity. Full article

In this work, a 3D printing methodology based on the robocasting of catalytic ink pastes was applied to obtain structured matrix-like cylinders as innovative materials for an effective utilization of carbon dioxide. The influence of three different binders (i.e., PEI, HPMC and MC) on the physio-chemical, mechanical and catalytic properties of multi-channel monoliths was studied against a reference binder-free powdered system in order to envisage the effectiveness of the printing procedure in realizing hybrid advanced materials at a higher control and reproducibility than from traditional preparation techniques. In terms of textural and structural properties, the micro-extruded 3D cylinders only evidenced a slight difference in terms of relative crystallinity, with minor effects on the surface area exposure in relation to the specific binder used during the direct ink writing process. More importantly, the typology of binder significantly affected the rheological properties of the catalytic ink, with the need of a controlled viscosity to ensure a suitable thixotropic behaviour of the extrudable pastes, finally determining an optimal mechanical resistance of the final 3D monolith. The experimental validation of the hybrid multi-channel cylinders under conditions of CO₂ hydrogenation demonstrated the great potential of additive manufacturing in the realization of catalyst architectures characterized by unique features and fidelity scarcely reproducible via conventional synthetic techniques. Full article

The electro-Fenton process is based on the generation of hydroxyl radicals (OH•) from hydroxide peroxide (H₂O₂) generated in situ by an oxygen reduction reaction (ORR). Catalysts based on carbon gels have aroused the interest of researchers as ORR catalysts due to their textural, chemical and even electrical properties. In this work, we synthesized metal-free electrocatalysts based on carbon gels doped with graphene oxide, which were conformed to a working electrode. The catalysts were prepared from organic-gel-based inks using painted (brush) and screen-printed methods free of binders. These new methods of electrode preparation were compared with the conventional pasted method on graphite supports using a binder. All these materials were tested for the electro-Fenton degradation of amoxicillin using a homemade magnetite coated with carbon (Fe₃O₄/C) as a Fenton catalyst. All catalysts showed very good behavior, but the one prepared by ink painting (brush) was the best one. The degradation of amoxicillin was close to 90% under optimal conditions ([Fe₃O₄/C] = 100 mg L⁻¹, −0.55 V) with the catalyst prepared using the painted method with a brush, which had 14.59 mA cm⁻² as J_K and a H₂O₂ electrogeneration close to 100% at the optimal voltage. These results show that carbon-gel-based electrocatalysts are not only very good at this type of application but can be adhered to graphite free of binders, thus enhancing all their catalytic properties. Full article

A series of robust energetic polyurethane binders was developed by in situ grafting reactive spiranes to achieve the migration-resistant processing aid and compensate for the energy output. The reactive grafting spiranes (RGSs), bearing two highly ring-strained spiranes, were synthesized sequentially to provide a promising ring strain energy up to a maximum value of 290 kJ mol⁻¹. The thermodynamic compatibility of the RGS with uncured glycidyl azido polymer (GAP) was studied quantitatively by analyzing the glass transition temperature of their blendings. The reactivity study of the catalyst-free click reaction with respect to spacer-dependent species was amplified by tracing the extent of the reaction and measuring the activation energy. The faster reactivity of propargyl species was evident from two experimental approaches, which were verified further by theoretical predictions. Interestingly, the energy gap difference in the frontier molecular orbitals agreed well with the difference in activation energy between the two types of spacer-dependent species. The mechanical and thermochemical enhancements of GAP-based polyurethane with RGS were basically gained from those highly ring-strained moieties. Full article

A [3 + 2] cycloaddition reaction using dialkyne and diazide comonomers, both bearing explosophoric groups, to synthesize energetic polymers containing furazan and 1,2,3-triazole ring as well as nitramine group in the polymer chain have been described. The developed solvent- and catalyst-free approach is methodologically simple and effective, the comonomers used are easily available, and the resulting polymer does not need any purification. All this makes it a promising tool for the synthesis of energetic polymers. The protocol was utilized to generate multigram quantities of the target polymer, which has been comprehensively investigated. The resulting polymer was fully characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers, thermochemical characteristics, and combustion features indicate the prospects of this polymer as a binder base for energetic materials. The polymer of this study surpasses the benchmark energetic polymer, nitrocellulose (NC), in a number of properties. Full article

Although direct methanol fuel cells (DMFCs) have been spotlighted in the past decade, their commercialization has been hampered by the poor efficiency of the methanol oxidation reaction (MOR) due to the unsatisfactory performance of currently available electrocatalysts. Herein, we developed a binder-free, copper-based, self-supported electrode consisting of a heterostructure of Cu₃P and mixed copper oxides, i.e., cuprous–cupric oxide (Cu-O), as a high-performance catalyst for the electro-oxidation of methanol. We synthesized a self-supported electrode composed of Cu-O|Cu₃P using a two-furnace atmospheric pressure–chemical vapor deposition (AP-CVD) process. High-resolution transmission electron microscopy analysis revealed the formation of 3D nanocrystals with defects and pores. Cu-O|Cu₃P outperformed the MOR activity of individual Cu₃P and Cu-O owing to the synergistic interaction between them. Cu₃P|Cu-O exhibited a highest anodic current density of 232.5 mAcm⁻² at the low potential of 0.65 V vs. Hg/HgO, which is impressive and superior to the electrocatalytic activity of its individual counterparts. The formation of defects, 3D morphology, and the synergistic effect between Cu₃P and Cu-O play a crucial role in facilitating the electron transport between electrode and electrolyte to obtain the optimal MOR activity. Cu-O|Cu₃P shows outstanding MOR stability for about 3600 s with 100% retention of the current density, which proves its robustness alongside CO intermediate. Full article

In this paper, a facile and rapid aqueous-based electrochemical technique was used for the phase conversion of Ni into Ni(OH)₂ thin film. The Ni(OH)₂ thin film was directly converted and coated onto the network surface of Ni foam (NF) via the self-hydroxylation process under alkaline conditions using a simple cyclic voltammetry (CV) strategy. The as-formed and coated Ni(OH)₂ thin film on the NF was used as the catalyst layer for the direct growth of carbon nanotubes (CNTs). The self-converted Ni(OH)₂ thin film is a good catalytic layer for the growth of CNTs due to the fact that the OH⁻ of the Ni(OH)₂ can be reduced to H₂O to promote the growth of CNTs during the CVD process, and therefore enabling the dense and uniform CNTs growth on the NF substrate. This binder-free CNTs/NF electrode displayed outstanding behavior as an electric double-layer capacitor (EDLC) due to the large surface area of the CNTs, showing excellent specific capacitance values of 737.4 mF cm⁻² in the three-electrode configuration and 319.1 mF cm⁻² in the two-electrode configuration, at the current density of 1 mA cm⁻² in a 6 M KOH electrolyte. The CNTs/NF electrode also displayed good cycling stability, with a capacitance retention of 96.41% after 10,000 cycles, and this the excellent cycling performance can be attributed to the stable structure of the direct growth of CNTs with a strong attachment to the NF current collector, ensuring a good mechanical and electrical connection between the NF collector and the CNTs. Full article