Search Results (352)

The escalating problem of nitrate pollution, coupled with the environmental burden of the Haber-Bosch process, has spurred intense interest in the electrocatalytic nitrate reduction reaction (eNO₃RR) as a sustainable route for simultaneous wastewater treatment and ammonia production. However, the efficiency and selectivity of eNO₃RR are hampered by the multi-step proton-coupled electron transfer process and the competing hydrogen evolution reaction. This review provides a comprehensive and critical overview of recent advances in understanding and designing catalysts for eNO₃RR. We begin by elucidating the fundamental mechanisms and key reaction pathways, followed by a discussion on how critical parameters (e.g., electrolyte microenvironment, applied potential, reactor design) dictate performance. Further discussion of recent advances in catalysts, including single-metal catalysts, alloy catalysts, transition metal compounds, single-atom catalysts, carbon-based non-metal catalysts, and composite catalysts, highlights their significant roles in enhancing both the efficiency and selectivity. A distinctive feature of this review is its consistent critical assessment of catalysts through the dual lenses of practicality and sustainable development. Finally, we outline prevailing challenges and propose future research directions aimed at developing scalable and commercially viable electrocatalytic systems for green nitrogen management. Full article

H₂ has become one of the most attractive alternatives to replace fossil fuels in clean energy production, but large-scale production remains a challenge. A key step toward this goal is to develop new efficient electrocatalysts for H₂ production. This work presents a new mixed metal oxides-decorated CNT paste electrode (MMO@C), which is highly electrocatalytic, for use in the hydrogen evolution reaction (HER). MMO@C is synthesized by a solvothermal method and used as an easy-to-prepare paste electrode. XPS and X-ray analysis indicate that the electrocatalyst corresponds to a mixed surface of Ga₂O₃-CuO-Cu₂O-Cu(OH)₂@C. The MMO@C electrocatalyst shows a positive E_o of 0.12 V vs. RHE at −10 mA cm⁻² towards the HER in a neutral medium. In neutral and alkaline media, the presence of Ga₂O₃ facilitates the reduction of CuO to Cu(I) species, which is followed by the formation of Cu(s) active sites. Therefore, the excellent electrocatalytic performance toward the HER in a neutral medium is attributed to the synergistic effect between gallium and copper oxides on the electrode surface. The prominent H₂ production using MMO@C electrocatalyst is 1.31 × 10⁻² mol cm⁻², with a turnover number (TON) of 39,423, a turnover frequency (TOF) of 13,141 h⁻¹, and a faradaic efficiency (FE) of 94.3%. Although the Tafel slope reveals slow reaction kinetics, the outstanding onset potential allows for the coupling of the electrocatalyst to renewable energy production systems, making it an attractive candidate for producing green H₂ and for application in membrane water electrolyzers. Full article

Carbon-based metal-free catalysts, particularly those such as biomass-derived mesoporous activated carbon (AC) nanostructures, hold great promises for cost-effective and sustainable electrocatalysis for enhancing hydrogen evolution reaction (HER) performance in green energy technology. Neem and ginkgo leaves are rich in bioactive compounds and self-doping heteroatoms with naturally porous structures and act as a low-cost, sustainable biomass precursors for high-performance HER catalysts. In this study, mesoporous AC nanoflakes and nanosponges were synthesized using biomass precursors of neem and ginkgo leaves through a KOH activation process. Notably, AC nanosponges derived from ginkgo leaves exhibited outstanding physicochemical characteristics, including a sponge-like porous morphology with a large specific surface area of 1025 m²/g. For electrochemical evaluation in 0.5 M H₂SO₄, the G-AC sample revealed superior electrocatalytic HER performance, with a remarkably low overpotential of 26 mV at −10 mA/cm², a small Tafel slope of 24 mV/dec, and long-term durability over 30 h. These results depict biomass-derived mesoporous AC nanosponges to hold substantial potential for highly efficient hydrogen production, contributing significantly to the advancement of eco-friendly energy solutions. Full article

The advancement of efficient energy conversion and storage technologies is fundamentally linked to the development of electrochemical systems, including fuel cells, batteries, and electrolyzers, whose performance depends on key electrocatalytic reactions: hydrogen evolution (HER), oxygen evolution (OER), oxygen reduction (ORR), carbon dioxide reduction (CO₂RR), and nitrogen reduction (NRR). Beyond catalyst design, the electrolyte microenvironment significantly influences these reactions by modulating charge transfer, intermediate stabilization, and mass transport, making electrolyte engineering a powerful tool for enhancing performance. This review provides a comprehensive analysis of how fundamental electrolyte properties, including pH, ionic strength, ion identity, and solvent structure, affect the mechanisms and kinetics of these five reactions. We examine in detail how the electrolyte composition and individual ion contributions impact reaction pathways, catalytic activity, and product selectivity. For HER and OER, we discuss the interplay between acidic and alkaline environments, the effects of specific ions, interfacial electric fields, and catalyst stability. In ORR, we highlight pH-dependent activity, selectivity, and the roles of cations and anions in steering 2e⁻ versus 4e⁻ pathways. The CO₂RR and NRR sections explore how the electrolyte composition, local pH, buffering capacity, and proton sources influence activity and the product distribution. We also address challenges in electrolyte optimization, such as managing competing reactions and maximizing Faradaic efficiency. By comparing the electrolyte’s effects across these reactions, this review identifies general trends and design guidelines for enhancing electrocatalytic performance and outlines key open questions and future research directions relevant to practical energy technologies. Full article

The development of ternary metal oxide electrocatalysts with optimized electronic structures and surface morphologies has emerged as one of the effective strategies to improve the performance of electrochemical water splitting. In this work, ternary CoMoCe (CMC)-oxide electrocatalysts were successfully synthesized on nickel foam substrates via a hydrothermal technique and employed for their catalytic activity in an alkaline electrolyte. For comparison, binary counterparts (CoMo, CoCe, and MoCe) were also fabricated under similar conditions. The synthesized catalysts’ electrodes exhibited diverse surface architectures, including microporous-flake hybrids, ultrathin flakes, nanoneedle-assembled microspheres, and randomly oriented hexagonal structures. Among them, the ternary CoMoCe-oxide electrode exhibited outstanding bifunctional electrocatalytic activity, delivering low overpotentials of 124 mV for the hydrogen evolution reaction (HER) at −10 mA cm⁻², and 340 mV for the oxygen evolution reaction (OER) at 100 mA cm⁻², along with excellent durability. Furthermore, in full water-splitting configuration, the CMC||CMC and RuO₂||CMC electrolyzers required cell voltages of 1.69 V and 1.57 V, respectively, to reach a current density of 10 mA cm⁻². Remarkably, the CMC-based electrolyzer reached an industrially relevant current density of 1000 mA cm⁻² at a cell voltage of 2.18 V, maintaining excellent stability over 100 h of continuous operation. These findings underscore the impact of an optimized electronic structure and surface architecture on design strategies for high-performance ternary metal oxide electrocatalysts. Herein, a robust and straightforward approach is comprehensively presented for fabricating highly efficient ternary metal-oxide catalyst electrodes, offering significant potential for scalable water splitting. Full article

Spinels like Co₃O₄ have acquired relevance because of their photocatalytic, electrocatalytic, optical and magnetic properties. In this context, we investigated the defect structure evolution of compounds synthetized using the nitrate precursor method and after annealing cycles at temperatures ranging from 260 to 650 °C by means of thermogravimetric analysis (TGA), neutron powder diffraction (NPD), X-ray powder diffraction (XRPD) coupled to Pair Distribution Function (PDF) analysis, and Density Functional Theory (DFT) calculations. Deuterated and hydrogenated precursors were adopted to produce the samples for NPD and XRPD experiments, respectively. TGA measurements displayed weight losses, the extent of which increased on lowering the preparation annealing temperature, suggesting that the adopted wet synthesis introduces structural water in the sample. Both XRPD and NPD revealed the presence of vacancies in tetrahedral cobalt sites ($V_{Co1}^{″}$) whose concentration at RT decreases on raising the annealing temperatures, while octahedral cobalt and oxygen sites were fully occupied in all the samples. In addition, the $V_{Co1}^{″}$ presence induces a shrinking of the volume of the CoO₄ tetrahedra. The combination of DFT calculation and diffraction revealed that deuterium/hydrogen ions ($D_i^{•}$/$H_i^{•}$), introduced during the synthesis by the nitrate precursor balanced the $V_{Co1}^{″}$. Finally, DFT calculations revealed that ($D_i^{•}$/$H_i^{•}$) in Co₃O₄ forms hydroxyl groups. Full article

Hydrogen generation has become a popular research subject in light of currently pressing issues, such as the rapidly increasing environmental pollution, the depleting fossil fuel reserves, and the looming energy crisis. Sustainable electrochemical water splitting is regarded as one of the most desirable methods for obtaining green hydrogen. Considering this state of affairs, the water splitting electrocatalytic activity of glassy carbon electrodes modified with birnessite-type K₂Mn₄O₈ and mixed-valence iron phosphate Fe₃(PO₃OH)₄(H₂O)₄ materials were evaluated in electrolyte solutions having different pH values. Both compounds were characterized by X-ray diffraction and FT-IR spectroscopy in order to analyze their phase purity and their structural features. The most catalytically active birnessite-type K₂Mn₄O₈-based electrode was manufactured using a catalyst ink containing only the electrocatalyst dispersed in ethanol and Nafion solution. In 0.1 M H₂SO₄, it exhibited an oxygen evolution reaction (OER) overpotential of 1.07 V and a hydrogen evolution reaction (HER) overpotential of 0.957 V. The Tafel slopes obtained in the OER and HER experiments were 0.180 and 0.142 V/dec, respectively. The most catalytically active mixed-valence iron phosphate Fe₃(PO₃OH)₄(H₂O)₄-based electrode was obtained with a catalyst ink containing the specified material mixed with carbon black and dispersed in ethanol and Nafion solution. In a strongly alkaline medium, it displayed a HER overpotential of 0.515 V and a Tafel slope value of 0.122 V/dec. The two electrocatalysts have not been previously investigated in this way, and the acquired data provide insights into their electrocatalytic activity and improve the scientific understanding of their properties and applicative potential. Full article

The continuous increase in global energy demand necessitates the development of sustainable, clean, and highly efficient methods of energy generation. Electrochemical water splitting, comprising hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), represents a promising strategy but remains hindered by sluggish reaction kinetics and limited availability of highly active electrocatalysts especially under alkaline conditions. Addressing this challenge, we successfully synthesized a rGO-VO₂/W₅O₁₄ (rG-VO₂/W₅O₁₄) hydrogel electrocatalyst through a facile hydrothermal approach. The prepared composite distinctly reveals an advantageous hierarchical microstructure characterized by VO₂ nanoflakes uniformly distributed on the surface of rGO nanosheets, intricately integrated with W₅O₁₄ nanorods. Evaluated in a 1.0 M KOH electrolyte, the optimized rG-VO₂/W₅O₁₄-2 catalyst demonstrates remarkable electrocatalytic performance towards OER, achieving a low overpotential of 265.8 mV and a reduced Tafel slope of 81.9 mV dec⁻¹. Furthermore, the catalyst maintains robust stability with minimal performance degradation, exhibiting an overpotential of only 273.0 mV after 5000 cyclic stability tests. The superior catalytic activity and durability are attributed to the synergistic combination of enriched chemical composition, effective electron transfer, and abundant catalytic active sites inherent in the well-optimized rG-VO₂/W₅O₁₄-2 composite. Full article

Developing efficient and sustainable hydrogen production technologies is critical for advancing the global clean energy transition. This review highlights recent progress in the design, synthesis, and electrocatalytic applications of MXene-based materials for electrochemical water splitting. It discusses the fundamental mechanisms of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the structure–function relationships that govern electrocatalytic behavior. Emphasis is placed on the intrinsic structural and surface properties of MXenes, such as their layered architecture and tunable surface chemistry, which render them promising candidates for electrocatalysis. Despite these advantages, several practical limitations hinder their full potential, including oxidation susceptibility, restacking, and a limited number of active sites. Several studies have addressed these challenges using diverse engineering strategies, such as heteroatom doping; surface functionalization; and constructing MXene-based composites with metal chalcogenides, oxides, phosphides, and conductive polymers. These modifications have significantly improved catalytic activity, charge transfer kinetics, and long-term operational stability under various electrochemical conditions. Finally, this review outlines key knowledge gaps and emerging research directions, including defect engineering, single-atom integration, and system-level design, to accelerate the development of MXene-based electrocatalysts for sustainable hydrogen production. Full article

Improving the catalytic performance of the oxygen evolution reaction (OER) for water splitting in acidic media is crucial for the production of clean and renewable hydrogen energy. Herein, we study the OER electrocatalytic properties of various active sites on four exposed (110) and ($\overline{1}$10) surfaces of Sn-doped RuO₂ (Sn/RuO₂) with antiferromagnetic arrangements in acidic environments. The Sn/RuO₂ bulk structure with the Cm space group exhibits favorable thermodynamic stability. The coordinatively unsaturated metal (M_cus) sites distributed on the right branch of the volcano plot are generally more active than the bridge-bonded lattice oxygen (O_br) sites located on the left. Different from the conventional knowledge that the most active site is located in the nearest neighbor of the doped atom, it has a lower OER overpotential when the active site is 3.6 Å away from the doped Sn atom. Among the sites studied, the 46-Ru_cus site exhibits the optimal OER catalytic performance. The inherent factors affecting the OER activity of each site on the Sn/RuO₂ surface are further analyzed, including the center of the d/p band at the active sites, the average electrostatic potential of the ions, and the number of transferred electrons. This work provides a reminder for the selection of active sites used to evaluate catalytic performance, which will benefit the development of efficient OER electrocatalysts. Full article

The high cost of hydrogen production is the primary factor limiting the development of the hydrogen energy industry chain. Additionally, due to the inefficiency of hydrogen production by water electrolysis technology, the development of high-performance catalysts is an effective means of producing low-cost hydrogen. In water electrolysis technology, the electrocatalytic activity of the electrode affects the kinetics of the oxygen evolution reaction (OER) and the hydrogen evolution rate. This study utilizes the liquid phase co-precipitation method to synthesize three types of Prussian blue analog (PBA) electrocatalytic materials: Fe/PBA(Fe₄[Fe(CN)₆]₃), Fe-Mn/PBA((Fe, Mn)₃[Fe(CN)₆]₂·nH₂O), and Fe-Mn-Co/PBA((Mn, Co, Fe)₃^II[Fe^III(CN)₆]₂·nH₂O). X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses show that Fe-Mn-Co/PBA has a smaller particle size and higher crystallinity, and its grain boundary defects provide more active sites for electrochemical reactions. The electrochemical test shows that Fe-Mn-Co/PBA exhibits the best electrochemical performance. The overpotential of the oxygen evolution reaction (OER) under 1 M alkaline electrolyte at 10/50 mA·cm⁻² is 270/350 mV, with a Tafel slope of 48 mV·dec⁻¹, and stable electrocatalytic activity is maintained at 5 mA·cm⁻². All of these are attributed to the synergistic effect of Fe, Mn, and Co metal ions, grain refinement, and the generation of grain boundary defects and internal stresses. Full article

Electrochemical water splitting represents a sustainable approach for hydrogen production, yet efficient hydrogen evolution reaction (HER) catalysts operating in alkaline environments remain critically needed. Herein, we report the fabrication of Co₃O₄–NiS₂ nanocomposites synthesized through a facile coprecipitation and subsequent thermal treatment method. Detailed characterization via physicochemical techniques confirmed the successful formation of a hybrid Co₃O₄–NiS₂ heterostructure with tunable compositional and morphological characteristics. Among the synthesized catalysts (Co–Ni–1, Co–Ni–2, and Co–Ni–3), the Co–Ni–2 sample demonstrated optimal structural integration, displaying interconnected nanosheet morphologies and balanced elemental distribution. Remarkably, Co–Ni–2 achieved exceptional HER performance in 1 M KOH electrolyte, requiring an ultralow overpotential of only 84 mV at 10 mA cm⁻² and exhibiting a favorable Tafel slope of 67.5 mV dec⁻¹. Electrochemical impedance spectroscopy and electrochemical surface area measurements further substantiated the superior electrocatalytic kinetics, rapid charge transport, and abundant active site accessibility in the optimized Co–Ni–2 composite. Additionally, Co–Ni–2 demonstrated outstanding durability with negligible activity decay over 5000 cycles. This study not only highlights the strategic synthesis of Co₃O₄–NiS₂ nanostructures but also provides valuable insights for designing advanced, stable, and efficient non-noble electrocatalysts for sustainable hydrogen generation. Full article

Hydrogen, as a renewable and clean energy with a high energy density, is of great significance to the realization of carbon neutrality. In recent years, extensive research has been conducted on the electrocatalytic hydrogen evolution reaction (HER) by splitting water, with a focus on developing efficient electrocatalysts that can perform the HER at an overpotential with minimal power consumption. Tungsten oxide (WO₃), a non-noble-metal-based material, has great potential in hydrogen evolution due to its excellent redox capability, low cost, and high stability. However, it cannot meet practical needs because of its poor electrical conductivity and the limited number of active sites; thus, it is necessary to further improve HER performance. In this review, recent advances related to WO3-based electrocatalysts for the HER are introduced. Most importantly, several tactics for optimizing the electrocatalytic HER activity of WO₃ are summarized, such as controlling its morphology, phase transition, defect engineering (anion vacancies, cation doping, and interstitial atoms), constructing a heterostructure, and the microenvironment effect. This review can provide insight into the development of novel catalysts with high activity for the HER and other renewable energy applications. 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