Search Results (573)

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

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

This review article describes the most recent studies carried out on the catalytic hydrodechlorination (HDC) of Diclofenac (DFC). In this context, the most commonly employed catalytic materials for the removal of DFC from aqueous matrices are reviewed, along with their main performance outcomes. Various strategies for the HDC of DFC are discussed, including conventional approaches that rely on molecular hydrogen as the electron donor, as well as emerging alternatives based on biocatalytic and electrocatalytic processes. Additionally, the optimized reaction conditions for each catalytic system are discussed, along with relevant kinetic models and mechanistic insights that contribute to a deeper understanding of the HDC of DFC. Future perspectives on the use of catalysts with alternative properties for DFC removal via HDC are also discussed, aiming to highlight potential applications in wastewater treatment and the broader field of heterogeneous catalysis. Full article

Metal–organic frameworks (MOFs) have characteristics such as a large specific surface area, distinct functional sites, and an adjustable pore size. However, the inherent low conductivity of MOFs significantly affects the charge transfer efficiency when they are used for electrocatalytic sensing. Combining MOFs with conductive materials can compensate for these deficiencies. For MOF/metal nanoparticle composites (e.g., composites with gold, silver, platinum, and bimetallic nanoparticles), the high electrical conductivity and catalytic activity of metal nanoparticles are utilized, and MOFs can inhibit the agglomeration of nanoparticles. MOF/carbon-based material composites integrate the high electrical conductivity and large specific surface area of carbon-based materials. MOF/conductive polymer composites offer good flexibility and tunability. MOF/multiple conductive material composites exhibit synergistic effects. Although MOF composites provide an ideal platform for electrocatalytic reactions, current research still suffers from several issues, including a lack of comparative studies, insufficient research on structure–property correlations, limited practical applications, and high synthesis costs. In the future, it is necessary to explore new synthetic pathways and seek; inexpensive alternative raw materials. Full article

Catalytic and bioelectrocatalytic properties of four white rot fungal laccases (Trametes hirsuta, ThL; Coriolopsis caperata, CcL; Steccherinum murashkinskyi, SmL; and Antrodiella faginea, AfL) from different orthologous groups were comparatively studied in homogeneous reactions of electron donor substrate oxidation and in a heterogeneous reaction of dioxygen electroreduction. The ThL and CcL laccases belong to high-redox-potential enzymes (E⁰_T1 = 780 mV), while the AfL and SmL laccases are medium-redox-potential enzymes (E⁰_T1 = 620 and 650 mV). We evaluated the efficiency of laccases in mediatorless bioelectrocatalytic dioxygen reduction by the steady-state potential (E_ss), onset potential (E_onset), half-wave potential (E_1/2), and the slope of the linear segment of the polarization curve. A good correlation was observed between the T1 center potential of the laccases and their electrocatalytic characteristics; however, no correlation with the homogeneous reactions of electron donor substrates’ oxidation was detected. The results obtained are discussed in the light of the known data on the three-dimensional structures of the laccases studied. Full article

In recent years, Ga-based liquid metals have emerged as a prominent research focus in catalysis, owing to their unique properties, including fluidity, low melting point, high thermal and electrical conductivity, and tunable surface characteristics. This review summarizes the synthesis strategies for Ga-based liquid metal catalysts, with a focus on recent advances in their applications across electrocatalysis, thermal catalysis, photocatalysis, and related fields. In electrocatalysis, these catalysts exhibit potential for reactions such as electrocatalytic CO₂ reduction, electrocatalytic ammonia synthesis, electrocatalytic hydrogen production, and the electrocatalytic oxidation of alcohols. As to thermal catalysis, these catalysts are employed in processes such as alkane dehydrogenation, selective hydrogenation, thermocatalytic CO₂ reduction, thermocatalytic ammonia synthesis, and thermocatalytic plastic degradation. In photocatalysis, they can be used in other photocatalytic reactions such as organic matter degradation and overall water splitting. Furthermore, Ga-based liquid metal catalysts also exhibit distinct advantages in catalytic reactions within battery systems and mechano-driven catalysis, offering innovative concepts and technical pathways for developing novel catalytic systems. Finally, this review discusses the current challenges and future prospects in Ga-based liquid metal catalysis. Full article

To address the low selectivity in the electrocatalytic conversion of furfural (FFR) to furfuryl alcohol (FFA) under alkaline conditions, a Zn-based metal–organic framework (MBON-2) featuring a 3D hierarchical flower-like architecture self-assembled from nanosheets was synthesized via a simple hydrothermal method. Under optimal conditions, MBON-2 exhibited an extremely high selectivity of FFA (100%) and a high Faradaic efficiency (FE) of 93.19% at −0.2 V vs. RHE. Electrochemical impedance spectroscopy (EIS) revealed the excellent electron transfer and mass transport properties of MBON-2. In addition, in situ Fourier transform infrared (FTIR) spectroscopy studies confirmed the adsorption of FFR molecules onto the Zn and B sites of MBON-2 during the ECH of FFR, providing key insights into the hydrogenation mechanism. The numerous exposed B and Zn sites of the MBON-2, as well as its robust structural stability contributed to its outstanding catalytic performance in the electrochemical hydrogenation (ECH) of FFR. This work provides valuable guidelines for developing efficient Zn-based catalysts for the ECH of FFR. Full article

Films of a Ni/Al-layered double hydroxide intercalated with reduced graphene oxide were deposited, by means of a simple and rapid electrochemical synthesis, on Pt electrodes previously submitted to a special cleaning procedure. The aim of the research was to determine whether the better electrocatalytic properties of the Ni(III)/Ni(II) couple, due to the presence of the carbon nanomaterial, as compared to the Ni/Al-LDH alone, could allow glucose detection at physiological pHs, as normally LDHs work as redox mediators in basic solutions. Chronoamperometric experiments were carried out by applying a potential of 1.0 V vs. SCE to the electrode soaked in solutions buffered at pHs from 5.0 to 9.0 to which glucose was continuously added. The steady-state currents increased as the pH solution increased, but at pH = 7.0 the modified electrode exhibited a fast and rather sensitive response, which was linear up to 10.0 mM glucose, with a sensitivity of 0.56 A M⁻¹ cm⁻² and a limit of detection of 0.05 mM. Our results suggest the potential application of Ni/Al-LDH(ERGO) composite for the non-enzymatic detection of glucose or other oxidizable analytes under biological conditions. Full article

Electrocatalytic CO₂ reduction reaction (CO₂RR) is a crucial technology for achieving carbon cycling and renewable energy conversion, yet it faces challenges such as complex reaction pathways, competition for intermediate adsorption, and low product selectivity. In recent years, molecular modification has emerged as a promising strategy. By adjusting the surface properties of catalysts, molecular modification alters the electronic structure, steric hindrance, promotes the adsorption of reactants, stabilizes intermediates, modifies the hydrophilic–hydrophobic environment, and regulates pH, thereby significantly enhancing the conversion efficiency and selectivity of CO₂RR. This paper systematically reviews the modification strategies and mechanisms of molecularly modified materials in CO₂RR. By summarizing and analyzing the existing literature, this review provides new perspectives and insights for future research on molecularly modified materials in electrocatalytic CO₂ reduction. Full article

Ferrocene (Fc) is a redox-active organometallic scaffold whose unique electronic properties, stability, and modularity have enabled a broad range of catalytic and sensing applications. This review critically examines recent advances in Fc-based systems for hydrogen evolution and carbon dioxide (CO₂) conversion, encompassing electrochemical, photochemical, and thermochemical strategies. Fc serves diverse functions: it operates as a reversible redox mediator, an electron reservoir, a ligand framework, and a structural modulator. Each role contributes differently to enhancing catalytic performance, improving selectivity, or increasing operational stability. We highlight how Fc integration facilitates proton-coupled electron transfer in hydrogen evolution, supports selective CO₂ reduction in molecular and hybrid catalysts, and promotes efficient CO₂ fixation and capture within functionalised frameworks. Emerging applications in electrosynthetic organic transformations are also discussed. Together, these findings position Fc as a foundational motif for designing future electrocatalytic and carbon management platforms. Full article

The rapid growth in population and industrialization have significantly increased global energy demand, placing immense pressure on finite and environmentally harmful conventional fossil fuel-based energy sources. In this context, the development of hybrid electrocatalysts presents a crucial solution for energy conversion and storage, addressing environmental challenges while meeting rising energy needs. In this study, the fabrication of a novel bifunctional catalyst, copper nickel aluminum spinel (Cu_0.5Ni_0.5Al₂O₄) supported on graphitic carbon nitride (GCN), using a solid-state synthesis process is reported. Because of its effective interface design and spinel cubic structure, the Cu_0.5Ni_0.5Al₂O₄/GCN nanocomposite, as synthesized, performs exceptionally well in electrochemical energy conversion, such as the oxygen evolution reaction (OER), the hydrogen evolution reaction (HER), and energy storage. In particular, compared to noble metals, Pt/C- and IrO₂-based water-splitting cells require higher voltages (1.70 V), while for the Cu_0.5Ni_0.5Al₂O₄/GCN nanocomposite, a voltage of 1.49 V is sufficient to generate a current density of 10 mA cm⁻² in an alkaline solution. When used as supercapacitor electrode materials, Cu_0.5Ni_0.5Al₂O₄/GCN nanocomposites show a specific capacitance of 1290 F g⁻¹ at a current density of 1 A g⁻¹ and maintain a specific capacitance of 609 F g⁻¹ even at a higher current density of 5 A g⁻¹, suggesting exceptional rate performance and charge storage capacity. The electrode’s exceptional capacitive properties were further confirmed through the determination of the roughness factor (Rf), which represents surface heterogeneity and active area enhancement, with a value of 345.5. These distinctive characteristics render the Cu_0.5Ni_0.5Al₂O₄/GCN composite a compelling alternative to fossil fuels in the ongoing quest for a viable replacement. Undoubtedly, the creation of the Cu_0.5Ni_0.5Al₂O₄/GCN composite represents a significant breakthrough in addressing the energy crisis and environmental concerns. Owing to its unique composition and electrocatalytic characteristics, it is considered a feasible choice in the pursuit of ecologically sustainable alternatives to fossil fuels. Full article

Metallo-phthalocyanines (MPcs) are versatile materials with applications in electroanalysis because of their superior catalytic properties. This review presents the electrochemical methods based on MPc-modified electrodes and reports some of their remarkable properties and applications in the electroanalysis of monoamine neurotransmitters and biomolecules that play a crucial role in vital functions of the human body. The development of electrocatalytic chemically modified electrodes is based on their ability to provide a selective and rapid response toward a specific analyte in complex media without the need for sample pretreatment. The explanation of several phenomena occurring at the MPc-modified electrode surface (e.g., MPc-mediated electrocatalysis), the advantages of promoting different electron transfer reactions, and the detection mechanism are also presented. The types of MPcs and different materials, such as carbon nanotubes and graphene, used as substrates for modified working electrodes are discussed. Modifying the properties of MPcs through various interactions, or combining MPcs with carbonaceous materials, creates a synergistic effect. Such hybrid materials present both extraordinary catalytic and increased conductivity properties. We conducted a compilation study based on recent works to demonstrate the efficacy of the developed sensors and methods in sensing monoamine neurotransmitters. We emphasize the analyte type, optimized experimental parameters, working range, limits of detection and quantification, and application to real samples. MPc–carbon hybrids have led to the development of sensors with superior sensitivity and improved selectivity, enabling the detection of analytes at lower concentrations. We highlight the main advantages and drawbacks of the discussed methods. This review summarizes recent progress in the development and application of metallo-phthalocyanine-modified electrodes in the electroanalysis of monoamine neurotransmitters. Some possible future trends are highlighted. Full article

Titanium dioxide (TiO₂) is a wide-bandgap semiconductor material with broad application potential, known for its excellent photocatalytic performance, high chemical stability, low cost, and non-toxicity. These properties make it highly attractive for applications in photovoltaic energy, environmental remediation, and optoelectronic devices. For instance, TiO₂ is widely used as a photocatalyst for hydrogen production via water splitting and for degrading organic pollutants, thanks to its efficient photo-generated electron–hole separation. Additionally, TiO₂ exhibits remarkable performance in dye-sensitized solar cells and photodetectors, providing critical support for advancements in green energy and photoelectric conversion technologies. Boron-doped diamond (BDD) is renowned for its exceptional electrical conductivity, high hardness, wide electrochemical window, and outstanding chemical inertness. These unique characteristics enable its extensive use in fields such as electrochemical analysis, electrocatalysis, sensors, and biomedicine. For example, BDD electrodes exhibit high sensitivity and stability in detecting trace chemicals and pollutants, while also demonstrating excellent performance in electrocatalytic water splitting and industrial wastewater treatment. Its chemical stability and biocompatibility make it an ideal material for biosensors and implantable devices. Research indicates that the combination of TiO₂ nanostructures and BDD into heterostructures can exhibit unexpected optical and electrical performance and transport behavior, opening up new possibilities for photoluminescence and rectifier diode devices. However, applications based on this heterostructure still face challenges, particularly in terms of photodetector, photoelectric emitter, optical modulator, and optical fiber devices under high-temperature conditions. This article explores the potential and prospects of their combined heterostructures in the field of optoelectronic devices such as photodetector, light emitting diode (LED), memory, field effect transistor (FET) and sensing. TiO₂/BDD heterojunction can enhance photoresponsivity and extend the spectral detection range which enables stability in high-temperature and harsh environments due to BDD’s thermal conductivity. This article proposes future research directions and prospects to facilitate the development of TiO₂ nanostructured materials and BDD-based heterostructures, providing a foundation for enhancing photoresponsivity and extending the spectral detection range enables stability in high-temperature and high-frequency optoelectronic devices field. Further research and exploration of optoelectronic devices based on TiO₂-BDD heterostructures hold significant importance, offering new breakthroughs and innovations for the future development of optoelectronic technology. Full article