Search Results (151)

Olive mill wastewater (OMW) is a highly polluting effluent rich in organic pollutant compounds derived from olive oil production. In this work, the steam reforming reaction of OMW (OMWSR) was performed in a traditional reactor at 400 °C and different pressures (1–4 bar) to treat and valorize this effluent. A commercial catalyst (Rh/Al₂O₃) was used as a reference sample and several new catalysts were prepared (Ni-Ru/Ce-SiO₂) using different preparation methods to study their effect on the activity and stability. The best-performing catalysts were also subjected to long-term operation experimental tests (24 h). It was observed that the preparation method used for the catalysts synthesis influenced the catalytic performance of the samples. In addition, temperature-programmed oxidation (TPO) analysis of the used catalyst showed the presence of carbon deposits: the results showed that periodic oxidative regeneration improved the catalyst stability and sustained H₂ production. Finally, it was verified that the Ni-Ru/Ce³ catalyst stood out during the experimental tests, exhibiting high catalytic activity along the stability test at 400 °C and 1 bar: H₂ yield always over 7 mol_H2·mol_OMW⁻¹ and total organic carbon (TOC) conversion always higher than 94%. Despite these promising results, further research is needed to assess the economic feasibility of scaling up the process. Additionally, future work could explore the development of catalysts with enhanced resistance to deactivation by carbon deposition. Full article

Developing efficient and durable electrocatalysts for the alkaline hydrogen evolution reaction (HER) is crucial for sustainable hydrogen production. Herein, we report a novel RuP₂/Mn₂P₂O₇ heterojunction anchored on a three-dimensional nitrogen and phosphorus co-doped porous carbon (RuP₂/Mn₂P₂O₇/NPC) framework as a high-performance HER catalyst, synthesized via a controlled pyrolysis–phosphidation strategy. The heterostructure achieves uniform dispersion of ultrafine RuP₂/Mn₂P₂O₇ heterojunctions with well-defined interfaces. Furthermore, phosphorus doping restructures the electronic configuration of Mn and Ru species at the RuP₂/Mn₂P₂O₇ heterointerface, enabling enhanced catalytic activity through the accelerated electron transfer and kinetics of the HER. This RuP₂/Mn₂P₂O₇/NPC catalyst exhibits exceptional HER activity with 1 M KOH, requiring only 69 mV of overpotential to deliver 10 mA·cm⁻² and displaying a small Tafel slope of 69 mV·dec⁻¹, rivaling commercial 20% Pt/C. Stability tests reveal negligible activity loss over 48 h, underscoring the robustness of the heterostructure. The RuP₂/Mn₂P₂O₇ heterojunction demonstrates markedly reduced overpotentials for the electrochemical HER process, highlighting its enhanced catalytic efficiency and improved cost-effectiveness compared to the conventional catalytic systems. This work establishes a strategy for designing a transition metal phosphide heterostructure through interfacial electronic modulation, offering broad implications for energy conversion technologies. Full article

The CO₂ (Dry) Reforming of Methane (DRM) is a key process for reducing CO₂ and CH₄ emissions while producing syngas with an H₂/CO ratio of 1, ideal for Fischer–Tropsch synthesis. This study explores DRM and the Reverse Water Gas Shift (RWGS) reaction under mild conditions using Ru-based catalysts supported on CeO₂, YSZ, TiO₂, and SiO₂, with three reactant ratios: (i) stoichiometric, PCO₂ = 1 kPa, PCH₄ = 1 kPa, (ii) oxidizing, PCO₂ = 2 kPa, PCH₄ = 1 kPa, and (iii) reducing, PCO₂ = 1 kPa, PCH₄ = 4 kPa. The results highlight the importance of redox support for catalyst stability, with mobile lattice oxygen aiding carbon gasification. While Ru/CeO₂ is stable at high temperatures, it rapidly deactivates at low temperatures, emphasizing the need for precise metal particle size control. This work demonstrates the necessity of fine-tuning catalyst properties for more sustainable DRM, offering insights for next-generation CO₂ utilization catalysts. Full article

Ru-based catalysts manifest unparalleled hydrogen evolution reaction (HER) performance, but the hydrolysis of Ru species and the accumulation of corresponding reaction intermediates greatly limit HER activity and stability. Herein, Ru nanoparticle assemblies modified with single Mo atoms and supported on N-incorporated graphene (referred to as MoRu-NG) are compounded via hydrothermal and chemical vapor deposition (CVD) methods. The incorporation of single Mo atoms into Ru lattices modifies the local atomic milieu around Ru centers, significantly improving HER catalytic behavior and stability. More specifically, MoRu-NG achieves overpotentials of 53 mV and 28 mV at 10 mA cm⁻², with exceptional stability in acidic and alkaline seawater solutions, respectively. In MoRu-NG, Ru atoms have a special electronic structure and thus possess optimal hydrogen adsorption energy, which indicates that excellent HER activity mainly hinges upon Ru centers. To be specific, the d-electron orbitals of Ru atoms are close to half full, giving Ru atoms moderate bond energy for the assimilation and release of hydrogen, which is beneficial for the conversion of reaction intermediates. Moreover, the incorporation of single Mo atoms facilitates the formation of O and O’-bidentate ligands, significantly enhancing the structural stability of MoRu-NG in universal-pH seawater electrolysis. This work advances a feasible construction method of hexagonal octahedral configuration (Ru-O-Mo-N-C) and provides a route to synthesize an efficient and stable catalyst for electrocatalytic HER in universal-pH seawater. Full article

Metal carbonyl clusters, which can be seen as monodispersed and atomically defined nanoparticles stabilized by CO ligands, were used to prepare Ru-based catalysts with tuned basic properties to conduct the 5-hydroxymethylfurfural (HMF) aerobic oxidation to produce 2,5-furandicarboxylic acid (FDCA) in base-free conditions. The controlled decomposition of the carbonyl cluster [HRu₃(CO)₁₁]⁻, a methodology not yet applied to Ru catalysts for this reaction, on different supports focusing on controlling and tuning the basic properties of support allowed the formation of small Ru nanoparticles with a mean diameter of around 1 nm. The catalytic systems obtained resulted in more activity in the HMF oxidation than those prepared through a more common salt-impregnation technique, and the deposition of Ru nanoparticles on materials with basic functionalities has allowed avoiding the use of basic solutions in the reaction. The characterization by CO₂-TPD of Mg(Al)O catalysts obtained from decomposition of layered double hydroxide hydrotalcites with different composition and activation has allowed disclosure of an important correlation between the selectivity of FDCA and the fraction of weak basic sites, which is decreased by the calcination treatment at increased temperature. 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

Photocatalytic H₂ production is one of the most promising approaches for sustainable energy. The literature presents a plethora of carefully designed systems aimed at harnessing solar energy and converting it into chemical energy. However, the main drawback of the reported photocatalysts is their stability. Thus, the development of a cost-effective and stable photocatalyst, suitable for real-world applications remains a challenge. An ideal photocatalyst for H₂ production must possess appropriate band-edge energy positions, an effective sacrificial agent, and a suitable cocatalyst. Among the various photocatalysts studied, TiO₂ stands out due to its stability, abundance, and non-toxicity. However, its efficiency in the visible spectrum is limited by its wide bandgap. Metal doping is an effective strategy to enhance electron–hole separation and improve light absorption efficiency, thereby boosting H₂ synthesis. Common metal cocatalysts used as TiO₂ dopants include platinum (Pt), gold (Au), copper (Cu), nickel (Ni), cobalt (Co), ruthenium (Ru), iron (Fe), and silver (Ag), as well as bimetallic combinations such as Ni-Fe, Ni-Cu, Nb-Ta, and Ni-Pt. In all cases, doped TiO₂ exhibits higher H₂ production performance compared to undoped TiO₂, as metals provide additional reaction sites and enhance charge separation. The use of bimetallic dopants further optimizes the hydrogen evolution reaction. Additionally, porphyrins, with their strong visible light absorption and efficient electron transfer properties, have demonstrated potential in TiO₂ photocatalysis. Their incorporation expands the photocatalyst’s light absorption range into the visible spectrum, enhancing H₂ production efficiency. This review paper explores the principles and advancements in metal- and porphyrin-doped TiO₂ photocatalysts, highlighting their potential for sustainable hydrogen production. Full article

BaTiO₃ (BTO), a lead-free chalcogenide ferroelectric material, has emerged as a promising candidate for ferroelectric memories due to its advantageous ferroelectric properties, notable flexibility, and mechanical stability, along with a high dielectric constant and minimal leakage. These attributes lay a crucial foundation for multi-value storage. In this study, high-quality BaTiO₃ ferroelectric thin films have been successfully prepared on STO substrates by pulsed laser deposition (PLD), and Pt/BaTiO₃/SrRuO₃/SrTiO₃ ferroelectric heterojunctions were finally prepared by a combination of UV lithography and magnetron sputtering. Characterization and performance tests were carried out by AFM, XRD, and a semiconductor analyzer. The results demonstrate that the ferroelectric heterojunction prepared in this study exhibits excellent ferroelectric properties. Furthermore, the device demonstrates fatigue-free operation after 10⁷ bipolar switching cycle tests, and the polarization value exhibits no significant decrease in the holding characteristic test at 10⁴ s, thereby further substantiating its exceptional reliability and durability. These findings underscore the considerable promise of BTO ferroelectric memories for nonvolatile storage applications and lay the foundation for the development in the fields of both in-memory computing systems and neuromorphic computing. Full article

In this study, a sulfur-doped cobalt–iron catalyst (CoFeS/NF) was synthesized on a nickel foam (NF) substrate via a facile one-step electrodeposition method, and its performance in urea electrolysis for hydrogen production was systematically investigated. Sulfur doping induced significant morphology optimization, forming a highly dispersed nanosheet structure, which enhanced the specific surface area increase by 1.9 times compared with the undoped sample, exposing abundant active sites. Meanwhile, the introduction of sulfur facilitated electron redistribution at the surface modulated the valence states of nickel and cobalt, promoted the formation of high-valence Ni³⁺/Co³⁺, optimized the adsorption energy of the reaction intermediates, and reduced the charge transfer resistance. Electrochemical evaluations revealed that CoFeS/NF achieves a current density of 10 mA cm⁻² at a remarkably low potential of 1.18 V for the urea oxidation reaction (UOR), outperforming both the undoped catalyst (1.24 V) and commercial RuO₂ (1.35 V). In addition, the catalyst also exhibited excellent catalytic activity and long-term stability in the total urea decomposition process, which was attributed to the amorphous structure and the synergistic enhancement of corrosion resistance by sulfur doping. This study provides a new idea for the application of sulfur doping strategy in the design of multifunctional electrocatalysts, which promotes the coupled development of urea wastewater treatment and efficient hydrogen production technology. Full article

Electrocatalytic water splitting is a critical approach for achieving carbon neutrality, playing an essential role in clean energy conversion. However, the slow kinetics of the oxygen evolution reaction (OER) remains a major bottleneck hindering energy conversion efficiency. Although noble metal catalysts (e.g., IrO₂ and RuO₂) show excellent catalytic activity, their high cost and scarcity limit their applicability in large-scale industrial processes. In this study, we introduce a novel electrocatalyst based on selenized NiFe-layered double hydroxides (NiFe-LDHs), synthesized via a simple hydrothermal method. Its key innovation lies in the selenization process, during which Ni atoms lose electrons to form selenides, while selenium (Se) gains electrons. This leads to a significant increase in the concentration of high-valent metal ions, enhances electronic mobility, and improves the structural stability of the catalyst through the formation of Ni-Se bonds. Experimental results show that selenized NiFe-LDHs exhibit excellent electrocatalytic performance in 1 M KOH alkaline solution. In the oxygen evolution reaction (OER), the catalyst achieved an ultra-low overpotential of 286 mV at a current density of 10 mA cm⁻², with a Tafel slope of 63.6 mV dec⁻¹. After 60 h of continuous testing, the catalyst showed almost no degradation, far outperforming conventional catalysts. These results highlight the potential of NiFe-LDH@selenized catalysts in large-scale industrial water electrolysis applications, providing an effective solution for efficient and sustainable clean energy production. Full article

Water is critical for the sustenance of life and pH is an important parameter in monitoring its quality. Solid-state pH sensors provide a worthy alternative to glass-based electrodes due to many advantages such as low cost, longer shelf life, simpler manufacturing, easier operation, miniaturization, and integration into electronic systems. Cobalt oxides are relatively cheaper and more abundantly available than ruthenium oxide. This work aims to reduce the environmental impact of screen-printed pH sensors by mixing Co₃O₄ and RuO₂ in five molar proportions (30%, 40%, 50%, 60%, and 70%) and investigating the influence of oxide proportions on the pH-sensing properties of the resulting composition using potentiometric characterization, scanning electron microscopy, X-ray diffraction, surface profilometry, and electron dispersive spectroscopy. Although all the developed compositions showed super- or near-Nernstian sensitivity with good linearity, the sensors based on 50 mol% Co₃O₄-50 mol% RuO₂ were the best due to superior sensitivity, selectivity, and stability. Fabricated sensors were applied in real-life environmental, municipal, and commercial water samples, including those from various depths in the Baltic Sea, and were found to be accurate in comparison to a glass electrode. Full article

This study explores poly(methyl methacrylate) (PMMA)-based composites as potential alternatives to conventional TiO₂-based photocatalysts. Specifically, it examines PMMA composites enriched with oxo–titanium(IV) complexes, [Ti₈O₂(OⁱPr)₂₀(man)₄] (1), [Ti₄O(OⁱPr)₁₀(O₃C₁₄H₈)₂] (2), and [Ti₆O₄(OⁱPr)₂(O₃C₁₄H₈)₄(O₂CEt)₆] (3), alongside ruthenium(III) complexes, K[Ru(Hedta)Cl]∙2H₂O (4) and [Ru(pic)₃]·H₂O (5). We assessed the physicochemical, adsorption, and photocatalytic properties of these composites with structural analyses (Raman spectroscopy, X-ray absorption (XAS), and SEM-EDX), confirming the stability of complexes within the PMMA matrix. Composites containing titanium(IV) compounds demonstrated notably higher photocatalytic efficiency than those with ruthenium(III) complexes. Based on activity profiles, composites were categorized into three types: (i) UV-light active (complexes (1) and (2)), (ii) visible-light active (complexes (4) and (5)), and (iii) dual-range active (complex (3)). The results highlight the strong potential of titanium(IV)–PMMA composites for UV-driven photocatalysis. Moreover, their activity can be extended to the visible range after structural modifications. Ruthenium(III)–PMMA composites, in turn, showed superior performance under visible light. Overall, PMMA composites with titanium(IV) or ruthenium(III) complexes demonstrate promising photocatalytic properties for applications using both UV and visible light ranges. Full article

A CuNiCe-O nanocomposite was fabricated on the Cu₄₀Ni₂₀Al₁₀Ce₂₆Pt₃Ru₁ metallic glass (MG) ribbon surface by dealloying. The influences of Ni and dealloying time on the morphology and EOR performance were analyzed. The results suggest that the catalytic activity and stability of the dealloyed MG ribbon could be significantly enhanced owing to the alloying of Ni to the Cu₆₀Al₁₀Ce₂₆Pt₃Ru₁ MG ribbon precursor. The activated D-Cu₄₀Ni₂₀Al₁₀Ce₂₆Pt₃Ru₁ ribbon obtained at an etching time of 3 h had a better electrochemical ethanol oxidation reaction (EOR) performance than other dealloyed samples due to the formation of abundant active sites and the presence of defects within the CuNiCe-O composite. Full article

CeO₂-supported noble metal catalysts show great application potential in the catalytic oxidation of volatile organic compounds and hazardous organic wastewater. In this paper, an efficient Ru/CeO₂ catalyst is developed by combining the oxygen affinity of noble metals and the redox of supports for catalytic wet air oxidation (CWAO) of reconstituted tobacco wastewater. First, what factors affect the catalytic performance are studied by investigating the effect of supports (C, TiO₂, Al₂O₃, and CeO₂) and noble metals (Pt, Pd, and Ru) on the activity. Second, the catalytic performance of Ru/CeO₂ is further enhanced by tuning the morphology of CeO₂ supports. The results indicate that the Ru/CeO₂-R (rod-like) catalyst is highly active and can reach a high TOC conversion of 97.6% at 220 °C in 1 h. In contrast, the TOC conversions of Ru/CeO₂-MOF, Ru/CeO₂-NP (nanoparticle), and Ru/CeO₂-C (cube-like) are 93.3, 77.9, and 68.2%, respectively. Ru/CeO₂-R also presented good stability. The TOC conversion can be maintained at approximately 85% in four consecutive cycles. The characterization results indicate that better Ru dispersion, higher Ce³⁺ content, more surface reactive oxygen species, electron transfer between Ru and CeO₂-R, and oxygen transfer from CeO₂-R to Ru are the main reasons for the best catalytic performance of the Ru/CeO₂-R catalyst. Full article

Acidic oxygen evolution reaction (OER) electrocatalysts that provide high activity, lower costs, and long-term stability are needed for the wide-scale adoption of proton-exchange membrane (PEM) water electrolyzers for generating hydrogen through electrochemical water splitting. We report the effects of chromium substitution and temperature treatments on the structure, OER activity, and electrochemical stability of ruthenium oxide (RuO₂) aerogel OER electrocatalysts. RuO₂ and Cr-substituted RuO₂ aerogels (Ru_0.6Cr_0.4O₂) were synthesized using sol–gel chemistry and then thermally treated at different temperatures. Introducing chromium into the synthesis increased the surface area (7–11 times higher) and pore volume (5–6 times higher) relative to RuO₂ aerogels. X-ray diffraction analysis is consistent with s that Cr was substituted into the rutile RuO₂ structure. X-ray photoelectron spectroscopy showed that trivalent Cr substitution altered the surface electronic structure and ratio of surface hydroxides. The specific capacitance values of Cr-substituted RuO₂ aerogels were consistent with charge storage within a hydrous surface. Cr-substituted RuO₂ aerogels exhibited 26 times the OER mass activity and 3.5 times the OER specific activity of RuO₂ aerogels. Electrochemical stability tests show that Cr-substituted RuO₂ aerogels exhibit similar stability to commercial RuO₂. Understanding how metal substituents can be used to alter OER activity and stability furthers our ability to obtain highly active, durable, and lower-cost OER electrocatalysts for PEM electrolyzers. Full article