Search Results (306)

The ability of earth-abundant metals to serve as catalysts for the oxygen reduction reaction is of increasing importance given the prominence of this reaction in several emerging technologies. It is now recognized that both the primary and secondary coordination environments of these catalysts can be modulated to optimize their performance. In this present work, we describe two Co^II complexes [Co^II(PaPy₂Q)](OTf) (1) and [Co^II(PaPy₂N)](OTf) (2) that catalyze chemical and electrochemical dioxygen reduction. Both 1 and 2 contain Co^II centers in a N₅⁻ coordination environment, but 2 has a naphthyridine group that places a nitrogen atom in the secondary coordination sphere. Solid-state X-ray crystallography and solution-state spectroscopic measurements reveal that, apart from this second-sphere nitrogen in 2, complexes 1 and 2 have essentially identical properties. Despite these similarities, 2 performs the chemical reduction of dioxygen ~10-fold more rapidly than 1. In addition, 2 has an enhanced performance in the electrochemical reduction of dioxygen compared to 1. Both complexes yield a significant amount of H₂O₂ in the chemical reduction of dioxygen (>25%). The enhanced catalytic performance of 2 is attributed to the presence of the second-sphere nitrogen atom, which might enable the efficient protonation of cobalt–oxygen intermediates formed during turnover. Full article

The commercialization of proton-conducting fuel cells (PCFCs) is hindered by the limited electroactivity and durability of cathodes at intermediate temperatures ranging from 400 to 700 °C, a challenge exacerbated by an insufficient understanding of high-entropy perovskite (HEP) materials for oxygen reduction reaction (ORR) optimization. This study introduces an yttrium-doped HEP to address these limitations. A comparative analysis of Ce_0.2−xY_xBa_0.2Sr_0.2La_0.2Ca_0.2CoO_3−δ (x = 0, 0.2; designated as CBSLCC and YBSLCC) revealed that yttrium doping enhanced the ORR activity, reduced the thermal expansion coefficient (19.9 × 10⁻⁶ K⁻¹, 30–900 °C), and improved the thermomechanical compatibility with the BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ electrolytes. Electrochemical testing demonstrated a peak power density equal to 586 mW cm⁻² at 700 °C, with a polarization resistance equaling 0.3 Ω cm². Yttrium-induced lattice distortion promotes proton adsorption while suppressing detrimental Co spin-state transitions. These findings advance the development of durable, high-efficiency PCFC cathodes, offering immediate applications in clean energy systems, particularly for distributed power generation. Full article

The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In this paper, oxygen-functionalised activated carbon (FAC) with controllable oxygen-containing functional groups was prepared by adjusting the volume ratio of H₂SO₃/HNO₃ mixed acid, and Pd/AC and Pd/FAC catalysts were synthesised via the hydrazine hydrate reduction method. A series of characterisation techniques and electrochemical performance tests were used to study the catalyst. The results showed that when V(H₂SO₃):V(HNO₃) = 2:3, more defects were generated on the surface of the AC, and more oxygen-containing functional groups represented by C=O and C–OH were attached to the surface of the support, which increased the anchor sites of Pd and improved the dispersion of Pd nanoparticles (Pd NPs) on the support. At the same time, the mass–specific activity of Pd/FAC for MOR was 2320 mA·mg_Pd, which is 1.5 times that of Pd/AC, and the stability was also improved to a certain extent. In situ infrared spectroscopy further confirmed that oxygen functionalisation treatment promoted the formation and transformation of *COOH intermediates, accelerated the transformation of CO_L into CO_B, reduced the poisoning of CO_ads species adsorbed to the catalyst, optimised the reaction path and improved the catalytic kinetic performance. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) offers an energy-saving and environmentally friendly approach to producing hydrocarbon fuels. The use of a gas diffusion electrode (GDE) flow cell has generally improved the rate of CO₂RR, while the gas diffusion layer (GDL) remains a significant challenge. In this study, we successfully engineered a novel metal–organic framework (MOF) heterojunction through the controlled coating of zeolitic imidazolate framework (ZIF-L) on ultrathin nickel—metal–organic framework (Ni-MOF) nanosheets. This innovative architecture simultaneously integrates GDL functionality and exposes abundant solid–liquid–gas triple-phase boundaries. The resulting Ni-MOF@ZIF-L heterostructure demonstrates exceptional performance, achieving a formate Faradaic efficiency of 92.4% while suppressing the hydrogen evolution reaction (HER) to 6.7%. Through computational modeling of the optimized heterojunction configuration, we further elucidated its competitive adsorption behavior and electronic modulation effects. The experimental and theoretical results demonstrate an improvement in electrochemical CO₂ reduction activity with suppressed hydrogen evolution for the heterojunction because of its hydrophobic interface, good electron transfer capability, and high CO₂ adsorption at the catalyst interface. This work provides a new insight into the rational design of porous crystalline materials in electrocatalytic CO₂RR. Full article

Amidst global imperatives for sustainable energy and environmental remediation, carbon aerogels (CAs) present a transformative alternative to conventional carbon materials (e.g., activated carbon, carbon fibers), overcoming limitations of disordered pore structures, unmodifiable surface chemistry, and functional inflexibility. This review systematically examines CA-based electrochemical systems as its primary focus, analyzing fundamental charge-storage mechanisms and establishing structure–property–application relationships critical to energy storage performance. We critically assess synthesis methodologies, emphasizing how stage-specific parameters govern structural/functional traits, and detail multifunctional modification strategies (e.g., heteroatom doping, composite engineering) that enhance electrochemical behavior through pore architecture optimization, surface chemistry tuning, and charge-transfer kinetics acceleration. Electrochemical applications are extensively explored, including the following: 1. Energy storage: supercapacitors (dual EDLC/pseudocapacitive mechanisms) and battery hybrids. 2. Electrocatalysis: HER, OER, ORR, and CO₂ reduction reaction (CO₂RR). 3. Electrochemical processing: capacitive deionization (CDI) and electrosorption. Beyond this core scope, we briefly acknowledge CA versatility in ancillary domains: environmental remediation (heavy metal removal, oil/water separation), flame retardancy, microwave absorption, and CO₂ capture. Full article

The degradation of electrochemical materials during energy conversion and storage, in particular the electrocatalyst materials, is becoming increasingly important. The selection and design of sustainable materials is an important task. This work examines the synthesis, characterization, and application of an electrocatalyst (based on an amorphous alloy Co75Si15Fe5Cr4.5) having a structured surface in the form of nanocells for a “green” nitrate reduction reaction (NO₃RR), which can serve as an alternative to the well-known Haber-Bosch process for the synthesis of ammonia. The material for the electrocatalyst was obtained by anodizing the alloy in the ionic liquid BmimNTf₂ and characterized by using a combination of modern physicochemical and electrochemical methods. The Faradaic efficiency (FE) for the nanocell catalyst exceeds by more than three-fold and seven-fold catalyst with a polished surface and the initial catalyst having a natural oxide on the surface, respectively. A mechanism of this reaction on the studied electrocatalysts with structured and non-structured surfaces is proposed. It is mentioned that the nanocell electrocatalyst is an extremely stable material that passes all tests without visible changes. The authors consider their work as a starting point for the application of a nanostructured Co-electrocatalyst in NO₃RR. Full article

The conventional spent lithium-ion batteries (LIBs) recycling method suffers from complex processes and excessive chemical consumption. Hence, this study proposes an electrochemical strategy for achieving reductant-free leaching of high-valence transition metals and efficient separation of valuable components from spent cathode sheets (CSs). An innovatively designed sandwich-structured electrochemical reactor achieved efficient reductive dissolution of cathode materials (CMs) while maintaining the structural integrity of aluminum (Al) foils in a dilute sulfuric acid system. Optimized current enabled leaching efficiencies exceeding 93% for lithium (Li), cobalt (Co), manganese (Mn), and nickel (Ni), with 88% metallic Al foil recovery via cathodic protection. Multi-scale characterization systematically elucidated metal valence evolution and interfacial reaction mechanisms, validating the technology’s tripartite innovation: simultaneous high metal extraction efficiency, high value-added Al foil recovery, and organic removal through single-step electrochemical treatment. The process synergized the dissolution of CM particles and hydrogen bubble-induced physical liberation to achieve clean separation of polyvinylidene difluoride (PVDF) and carbon black (CB) layers from Al foil substrates. This method eliminates crushing pretreatment, high-temperature reduction, and any other reductant consumption, establishing an environmentally friendly and efficient method of comprehensive recycling of battery materials. Full article

Methane (CH₄) has attracted much attention regarding its use in electrochemical carbon dioxide reduction reaction (CO₂RR) due to its high mass-energy density; however, the uneven adsorption of intermediates on copper sites by conventional Cu-based catalysts limits the selective production of CH₄. The introduction of a second metal can effectively regulate the adsorption energy of intermediates on the Cu site. In this paper, a method of alloying Cu with oxyphilic metals (M) using rapid electrodeposition is presented; the synergistic effect of the bimetal effectively directed the reaction pathway toward CH₄. The best Faraday efficiency for methane occurred in the optimized Cu₃₀La₂₀ electrode, reaching 66.9% at −1.7 V vs. RHE potential. In situ infrared testing revealed that the *CHO intermediate—a critical species for the electrocatalytic conversion of CO₂ to CH₄—was detected on the Cu₃₀La₂₀ catalytic electrode. However, no *CHO intermediate was observed on the Cu₂₀La₃₀ electrode. Instead, the characteristic peak of the *OCCHO intermediate associated with C-C coupling emerged on the Cu₂₀La₃₀ catalyst. This indicates that the adsorbed oxygen-containing groups on lanthanum sites reacted with carbon-containing groups on copper sites to form C₂ products, serving as the primary reason for the shift in reduction products from methane to ethylene. Full article

Photocatalytic CO₂ conversion is one of the ideal approaches to address both topics of solar energy shortage and carbon neutrality. Cobalt(II) centers coordinated with bipyridines have been designed and evaluated as catalysts for CO₂ conversion under light irradiation. Herein, we report a series of pyridine-based cobalt complexes with alkyl substituents as molecular photocatalysts, aiming to elucidate the effects of alkyl type and substitution position on catalytic performance through spectroscopic and electrochemical measurements. The substitution of the hydrogen at 4,4′-positions on the bipyridine ring with a methyl group, a tert-butyl group, and a nonyl group led to a decrease in the conversion rate of CO₂ by 13.2%, 29.6%, and 98%, respectively. The methyl substituents at the 5, 5′-positions of the bipyridine ring resulted in a 71.1% decrease in the CO₂ conversion rate. The usage of either 6, 6′-Me₂-2,2′-bipy, 2,4-bipy, or 3,3′-bipy resulted in no detectable activity for CO₂ conversion in the current system. Both photo- and electrochemical analyses have been employed to reveal the relationship between changing ligands and photocatalytic performance on the molecular scale. These results demonstrate that bulky ligands significantly hinder CO₂ reduction by cobalt complexes due to steric interference with coordination and active-site accessibility. This study demonstrates that the substituent effect of ligands on photocatalytic reactions for CO₂ conversion provides valuable insight into a deeper understanding of molecular catalysis. Full article

Lithium–air batteries (LABs) possess the highest energy density among all energy storage systems, and have drawn widespread interest in academia and industry. However, many arduous challenges are still to be conquered, one of them is Li₂CO₃, which is a ubiquitous product in LABs. It is inevitably produced but difficult to decompose; therefore, Li₂CO₃ is perceived as the “Achilles’ heel of LABs”. Among various approaches to addressing the Li₂CO₃ issue, developing Li₂CO₃-decomposing redox mediators (RMs) is one of the most convenient and versatile, because they can be electrochemically oxidized at the gas cathode surface, then they diffuse to the solid-state products and chemically oxidize them, recovering the RMs to a pristine state and avoiding solid-state catalysts’ contact instability with Li₂CO₃. Furthermore, because of their function mechanism, they can double as catalysts for Li₂O₂/LiOH decomposition, which are needed in LABs/LOBs anyway regardless of Li₂CO₃ incorporation due to the sluggish kinetics of oxygen reduction/evolution reactions. This review summarizes the progress in Li₂CO₃-decomposing RMs, including halides, metal–chelate complexes, and metal-free organic compounds. The insights into and discrepancies in the mechanisms of Li₂CO₃ decomposition and corresponding catalysis processes are also discussed. Full article

The core challenge of integrated carbon capture and utilization (ICCU) technology lies in developing electrolytes that combine efficient carbon dioxide (CO₂) capture with electrocatalytic conversion capabilities. This review analyzes the structure–performance relationship between electrolyte properties and CO₂ electrochemical reduction (eCO₂RR), revealing the key regulatory mechanisms. Research shows that the performance of bicarbonate electrolytes heavily depends on the cation type, where Cs⁺ can achieve over 90% CO selectivity by suppressing the hydrogen evolution reaction (HER) and stabilizing reaction intermediates, though its strong corrosiveness limits practical applications. Although amine absorbents excel in carbon capture (efficiency > 90%), they tend to undergo competitive adsorption during electrocatalysis, making formic acid the primary product (FE = 15%); modifying electrodes with ionomers can enhance their activity by 1.15 times. Ionic liquids (ILs) demonstrate unique advantages due to their tunability: imidazolium-based ILs improve formate selectivity to 85% via carboxylate intermediate formation, while amino-functionalized task-specific ILs (TSILs) achieve a 1:1 stoichiometric CO₂ absorption ratio. Recent breakthroughs reveal that ternary IL hybrid electrolytes can achieve nearly 100% CO Faradaic efficiency (FE) through microenvironment modulation, while L-histidine additives boost CH₄ selectivity by 23% via interface modification. Notably, constructing a “bulk acidic–interfacial neutral” pH gradient system addresses carbonate deposition issues in traditional alkaline conditions, increasing C₂₊ product efficiency to 50%. Studies also highlight that cation–anion synergy (e.g., K⁺/I⁻) significantly enhances C-C coupling through electrostatic interactions, achieving 97% C₂₊ selectivity on Ag electrodes. These findings provide new insights for ICCU electrolyte design, with future research focusing on machine learning-assisted material optimization and reactor engineering to advance industrial applications. 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 current work examines the effect of acetone on the electrochemical characteristics of a polycrystalline nickel electrode in a 0.1 M NaOH electrolyte, with respect to the kinetics of alkaline water electrolysis (HER: hydrogen evolution reaction, and OER: oxygen evolution reaction). Cyclic voltammetry (CV) and impedance spectroscopy (EIS) electrochemical techniques were employed to examine these processes for acetone concentrations stretching from 1.0 × 10⁻⁷ to 1.0 × 10⁻³ M. The introduction of small amounts of (CH₃)₂C=O clearly facilitated the catalytic efficiency of both examined electrochemical gas evolution processes. The latter is believed to result from a significant reduction in the surface tension parameter, due to the mutual interactions of acetone and water molecules, thus facilitating the detachment of gas bubbles from the nickel electrode surface. These findings suggest considerable opportunities for the introduction of tiny amounts of organic additives into alkaline electrolytes to improve the industrial alkaline water electrolysis process that is performed on technologically valuable electrode materials. Full article

The cobalt crystalline islands (Co_cryst) were electrochemically deposited onto a glassy carbon (GC) support and then modified by a facile spontaneous deposition of platinum. The electrocatalytic activity of the resulting Co_cryst-Pt core-shell catalyst was evaluated for the oxygen reduction reaction (ORR) in an alkaline medium. The XRD characterization of the Co_cryst-Pt islands revealed that the cobalt core had a hexagonal close-packed (hcp) crystalline structure, and that the platinum shell exhibited a crystalline structure with a preferential (111) orientation. SEM images showed that the average lateral size of the Co_cryst islands was 1.17 μm, which increased to 1.32 μm after adding platinum. The XPS analysis indicated that the outer layer of the bulk metallic Co_cryst islands was fully oxidized. During the spontaneous deposition of platinum, the outer Co(OH)₂ layer was dissolved, leaving the cobalt core in a metallic state, while the platinum shell remained only partially oxidized. The high electrochemically active surface area of the Co_cryst-Pt/GC electrode, along with a suitable crystalline structure of the Co_cryst-Pt islands, contributes to enhancing its ORR activity by providing a greater number of surface active sites for oxygen adsorption and subsequent reduction. The ORR on the Co_cryst-Pt catalyst occurs via a four-electron reaction pathway, with onset and half-wave potentials of 1.07 V and 0.87 V, respectively, which exceed those of polycrystalline platinum and a commercial benchmark Pt/C. Full article

The conversion of CO₂ through the electrochemical reduction reaction (ECO₂RR) into chemicals or fuels is regarded as one of the effective ways to decrease atmospheric CO₂ concentrations. In this study, a Cu-Sn bimetallic electrocatalyst (ER-Sn_mCu_nO_x-t/CC) was successfully prepared via a chemical foaming method and electrochemical reduction. SEM showed that ER-Sn₁Cu₁O_x-500 nanoparticles were uniformly distributed on the carbon cloth, which benefited from foaming. The XPS results demonstrated the synergistic interaction between Cu and Sn and the existence of oxygen vacancies originating from the electroreduction. Due to the above features, ER-Sn₁Cu₁O_x-500/CC achieved 84.1% FE for HCOOH at −1.1 V vs. RHE, and the corresponding J_HCOOH was up to 32.4 mA·cm⁻² in the H-type cell. Especially in the flow cell, ER-Sn₁Cu₁O_x-500/GDE could reach a high J_HCOOH of 190 mA·cm⁻² at −1.1 V vs. RHE and maintained J_HCOOH higher than 100 mA·cm⁻² for 24 h with a formic acid selectivity over 70%, indicating both excellent catalytic activity and high HCOOH selectivity. In situ FTIR results revealed that synergism between Cu and Sn could regulate the adsorption of intermediates, thus enhancing the catalytic performance of ER-Sn₁Cu₁O_x-500 for ECO₂RR. Full article