Search Results (1,014)

Growing interest in sustainable hydrogen production has brought renewed attention to photoelectrochemical (PEC) water splitting as a promising route for direct solar-to-chemical energy conversion. This study explores how integrating hematite (α-Fe₂O₃) and cupric oxide (CuO) photoelectrodes with a series of nickel-based co-catalysts can improve photoelectrochemical activity. Photoanodic (NiO_x, NiFeO_x, NiWO₄) and photocathodic (Ni, NiCu, NiMo) co-catalysts were synthesized via co-precipitation and mechanochemical methods and characterized through X-ray Diffraction (XRD), X-ray Fluorescence (XRF), Transmission Electron Microscopy–Energy Dispersive X-ray Spectroscopy (TEM-EDX), Scanning Electron Microscopy–Energy Dispersive X-ray Spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) gas-adsorption analyses to clarify their crystallographic, morphological, and compositional properties, as well as their surface chemistry and textural properties (surface area and porosity). Electrochemical tests under 1 SUN illumination showed that NiO_x significantly improves the photocurrent of hematite photoanodes. Among the cathodic co-catalysts, NiMo demonstrated the best performance when combined with CuO photocathodes. For both photoelectrodes, an optimal co-catalyst loading was identified, beyond which performance declined due to potential charge transfer limitations and light attenuation. These findings highlight the critical role of co-catalyst composition and loading in optimizing the efficiency of PEC systems based on earth-abundant materials, offering a pathway toward scalable and cost-effective hydrogen production. Full article

CO₂ hydrogenation to methanol has attracted considerable attention as a promising catalytic route for both reducing CO₂ emissions and producing valuable chemical intermediates. Among various catalysts, Cu–ZnO-based systems are the most widely studied; however, their performance remains constrained by limited methanol selectivity and stability, highlighting the need for improved catalytic strategies. In this work, liquid metal gallium (Ga) was incorporated into Cu–ZnO catalysts as an additive for CO₂ hydrogenation to methanol. Owing to its high dispersibility and fluidity, Ga helps maintain long-term catalyst stability. We investigated different introduction methods for Ga promoters and found that the physical mixing approach generated the strongest alkaline sites, thereby enhancing CO₂ activation and increasing the CO₂ conversion to methanol. Moreover, this catalyst effectively suppressed carbon deposition, further improving its stability. These findings offer new insights into the use of liquid metal Ga in CO₂ hydrogenation and provide fresh perspectives for the rational design of efficient methanol synthesis catalysts. Full article

In this study, Cu(II) complexes containing the bidentate ligand N,N-dimethylethylendiamine (dmen), i.e., [Cu^II(dmen)₂(CH₃COO)₂], [Cu^II(dmen)₂(NO₃)₂], and [Cu^II(dmen)₂Cl₂], were developed to explore molecular catalysis for the oxygen reduction reaction (ORR). Cyclic voltammetry and UV–vis spectroelectrochemical and electrochemical impedance spectroscopy experiments were performed in the absence and presence of oxygen. The UV–vis spectroscopy results suggested that the aforementioned Cu(II) complexes present an octahedral geometry in the solid state; meanwhile, they show a square pyramidal geometry in an aqueous solution. It is proposed that the chemical species [Cu^I(dmen)₂H₂O]⁺ reacts with O₂, exhibiting an outer-sphere electron transfer mechanism. The same UV–vis spectroelectrochemical response obtained with and without O₂ indicated a direct electron transfer from Cu(II) to Cu(I), with the regeneration of catalyst and the absence of other intermediate species. Among the reported compounds, [Cu(dmen)₂(NO₃)₂] exhibited the highest catalytic rate (TOF = 1.3 × 10⁴ s⁻¹). The impedance spectroscopy results showed that the resistance charge transfer (R_ct) of the redox pair Cu^II|Cu^I decreased in the presence of O₂ from 36.391 kΩ to 5.54 kΩ. For a better understanding of the effect of aliphatic amines on the ORR, a comparison with the complex [Cu(1,10-phen)₂NO₃]NO₃ is also presented. Full article

Electrochemical CO₂ reduction reaction (CO₂RR) is a key technology for achieving carbon neutrality and efficient utilization of renewable energy, capable of converting CO₂ into high-value-added carbon-based fuels and chemicals. Copper (Cu)-based catalysts have attracted significant attention due to their unique performance in generating multi-carbon (C₂₊) products such as ethylene and ethanol; however, there are still many controversies regarding their complex reaction mechanisms, active sites, and the dynamic evolution of intermediates. In situ Raman spectroscopy, with its high surface sensitivity, applicability in aqueous environments, and precise detection of molecular vibration modes, has become a powerful tool for studying the structural evolution of Cu catalysts and key reaction intermediates during CO₂RR. This article reviews the principles of electrochemical in situ Raman spectroscopy and its latest developments in the study of CO₂RR on Cu-based catalysts, focusing on its applications in monitoring the dynamic structural changes of the catalyst surface (such as Cu⁺, Cu⁰, and Cu²⁺ oxide species) and identifying key reaction intermediates (such as *CO, *OCCO(*O=C-C=O), *COOH, etc.). Numerous studies have shown that Cu-based oxide precursors undergo rapid reduction and surface reconstruction under CO₂RR conditions, resulting in metallic Cu nanoclusters with unique crystal facets and particle size distributions. These oxide-derived active sites are considered crucial for achieving high selectivity toward C₂₊ products. Time-resolved Raman spectroscopy and surface-enhanced Raman scattering (SERS) techniques have further revealed the dynamic characteristics of local pH changes at the electrode/electrolyte interface and the adsorption behavior of intermediates, providing molecular-level insights into the mechanisms of selectivity control in CO₂RR. However, technical challenges such as weak signal intensity, laser-induced damage, and background fluorescence interference, and opportunities such as coupling high-precision confocal Raman technology with in situ X-ray absorption spectroscopy or synchrotron radiation Fourier transform infrared spectroscopy in researching the mechanisms of CO₂RR are also put forward. Full article

Copper and iron species were co-deposited onto a hydroxyapatite surface to produce bimetallic catalysts. Characterization techniques (XRD, XPS, DR-UV spectroscopy and TEM-EDX) helped in unveiling the speciation, nuclearity, and electronic properties of copper and iron in samples with variable total metal loading (1–10 wt.%) and relative Cu-to-Fe ratios. The speciation of Cu was revealed to be not affected by Fe and vice versa. Conversely, the metal loading turned out to be a key factor ruling the aggregation state of Cu and Fe species. The samples were tested as catalysts in the Selective Catalytic Reduction of NO by NH₃ (NH₃-SCR) in dry and wet environments under quasi-real conditions (50,000 ppm O₂; 50,000 ppm H₂O, if present; 120,000 h⁻¹ GHSV) in the 200−500 °C interval. Although the combination of Cu and Fe affords a modest improvement in water resistance compared to their monometallic counterparts, no substantial enhancement in activity was observed for the bimetallic hydroxyapatite-based SCR catalysts. Full article

CuNiAl layered double hydroxide (LDH) catalysts were synthesized and employed for the oxidative destruction of cyanide ion (CN⁻) in wastewater in a plasma–catalyst loop reactor without the addition of any oxidizing agents. It was found that dielectric barrier discharge (DBD) could be used to degrade cyanide water due to the formation of oxidative species such as H₂O₂, ∙OH radicals, and O₃ in the plasma discharge zone. CuNiAl LDH catalysts were employed to destruct cyanide ion using oxidative species generated in situ in the loop reactor. The degradation time required for complete destruction of 100 ppm of CN⁻ was only 60 min, demonstrating the efficiency of the integration of both plasma and heterogeneous catalysts in this plasma–catalyst loop reactor. Full article

Two copper-containing perovskites Ba_0.8Mn_0.7Cu_0.3O₃ and Cu(4 wt%)/Ba_0.7MnO₃ (selected from previous studies) were tested as catalysts for the CO oxidation reaction under conditions similar to the found in the exhaust of last-generation automotive internal combustion engines. The Cu(4 wt%)/Ba_0.7MnO₃ sample has been selected due to its higher tolerance to CO₂. In order to optimize the performance of this sample for the reaction under study, a Cu(2 wt%)Ce(2 wt%)/Ba_0.7MnO₃ formulation was synthesized, characterized and tested. The excellent catalytic performance of the bimetallic formulation, in terms of CO conversion at low temperatures and tolerance to CO₂, is because cerium improves the redox properties and increases the proportion of reduced copper species on the surface compared to the Cu(4 wt%)/Ba_0.7MnO₃ sample. Full article

The selective oxidation of methane to methanol under mild conditions remains a significant challenge due to its stable C-H bond and the propensity for overoxidation of products. Herein, we investigated the Fe- and Cu-modified ZSM-5 catalysts using H₂O₂ as an oxidant for the selective oxidation of methane. It was found that the Fe/Cu ratio had a great impact on methanol yield. The Fe₃Cu₁ displayed the highest methanol yield of 29.7 mmol g_cat⁻¹ h⁻¹ with a selectivity of 80.9% at 70 °C. Further analysis revealed that Fe₃Cu₁ showed the highest Fe³⁺ and Cu⁺ contents. The optimal dual valence cycle not only facilitates the efficient utilization of H₂O₂, promoting the activation of methane to •CH₃ at the Fe site, but also suppresses the deep oxidation caused by the Fenton-like effect of Fe/H₂O₂, thus maintaining the high yield and high selectivity of methanol. Full article

The Ni-Fe coatings modified with AuNPs were deposited on the flexible copper-coated polyimide (Cu/PI) surface using electroless metal plating, while the galvanic displacement technique was applied to modify the surface of NiFe coatings by a small content of AuNPs in the range of 16.5 µg_Au cm⁻². AuNPs of a few nanometers in size were deposited on the NiFe/Cu/PI surface by immersing it in a solution containing AuCl₄⁻ ions. The electrooxidation of sodium borohydride was evaluated in a 1 M NaOH solution containing 0.05 M of sodium borohydride using cyclic voltammetry, chronoamperometry, and chronopotentiometry. In addition, the performance and stability of the NiFe/Cu/PI and AuNPs-NiFe/Cu/PI catalysts were evaluated for potential use in a direct NaBH₄-H₂O₂ fuel cell. The NiFe coating modified with AuNPs demonstrated significantly higher electrocatalytic activity towards the oxidation of sodium borohydride as compared to bare Au or unmodified NiFe/Cu/PI. Furthermore, it exhibited a superior power density of 89.7 mW cm⁻² at room temperature and operational stability under alkaline conditions, while the NiFe anode exhibited 73.1 mW cm⁻². These results suggest that the AuNPs-modified NiFe coating has great potential as a material for use in direct borohydride fuel cells (DBFCs) applications involving the oxidation of sodium borohydride. Full article

This study investigates the influence of pectin and copper incorporation on the catalytic properties of Pd/ZnO catalysts in the liquid-phase hydrogenation of 2-hexyn-1-ol and photocatalytic hydrogen evolution. A series of monometallic Pd/ZnO catalysts with varying pectin contents (0–8.1 wt%) and bimetallic PdCu-Pec/ZnO catalysts with different Pd to Cu mass ratios (3:1, 1:1, 1:3) were synthesized via sequential adsorption of the polymer and metal ions onto ZnO. The catalysts were characterized using TGA, EDX, IR spectroscopy, XRD, TEM, UV–Vis DRS, and XPS. Characterization confirmed successful modification and changes in surface properties. Pectin modification improved the distribution of Pd nanoparticles on the surface of ZnO, resulting in the enhanced catalytic performance of Pd-Pec/ZnO in both hydrogenation and hydrogen evolution reactions compared to unmodified Pd/ZnO. In contrast, copper addition led to a deterioration of catalytic properties in both processes, likely due to the inhibited reduction of Pd caused by Pd–Cu interactions. Among the catalysts studied, Pd-Pec/ZnO with low pectin content (1.8 wt%) exhibited the highest activity in both reactions. The hydrogenation of 2-hexyn-1-ol to cis-2-hexen-1-ol proceeded with high selectivity (96%) at a rate (W_C≡C) of 3.3 × 10⁻⁶ mol/s, and the catalyst retained its activity over 30 consecutive runs. In the photocatalytic hydrogen evolution reaction, the rate reached 1.11 mmol/(h·g_cat) and the catalyst maintained ~94% of its initial activity after three consecutive runs. These findings demonstrate the potential of biopolymer-modified ZnO composites for the design of multifunctional catalysts combining hydrogenation and photocatalytic activity. Full article

The catalytic performance of metal oxide materials is profoundly influenced by both chemical composition and surface morphology, particularly at high dopant loadings where metallic clusters can form. Here, we use density functional theory (DFT) to elucidate how copper incorporation—either as isolated dopants or as surface clusters—modulates the mechanism and activity of ZrO₂ catalysts in the direct carboxylation of phenol to para-hydroxybenzoic acid. Our results reveal that while Cu doping inhibits C–H bond activation, the presence of Cu clusters at the ZrO₂ surface dramatically lowers the barrier for C–C coupling with CO₂, owing to unique interfacial sites that facilitate substrate activation and CO₂ bending. We show that the reaction mechanism shifts from an Eley–Rideal pathway on pure ZrO₂ to a Langmuir–Hinshelwood mechanism on Cu-modified surfaces, with the rate-determining step depending on the Cu morphology. These findings demonstrate that even small amounts of metallic clusters can fundamentally alter catalytic pathways, providing actionable insights for the rational design of heterogeneous catalysts for selective aromatic carboxylation. Full article

In this study, we report, for the first time, the tribo-catalytic degradation of methyl orange (MO) using Cu/Al₂O₃ nanoparticles under mechanical stirring conditions. The hybrid catalyst was synthesized via a wet impregnation method and characterized through different techniques, confirming structural integrity and compositional uniformity. When subjected to friction generated by a PTFE-coated magnetic stir bar, Cu/Al₂O₃ nanoparticles exhibited high tribo-catalytic activity, achieving up to 95% MO degradation within 10 h under dark conditions. The observed activity surpasses that of alumina alone and is attributed to the synergistic effects between copper and alumina, facilitating charge separation and enhancing reactive oxygen species (ROS) formation. Tribo-catalytic efficiency was further influenced by stirring speed and contact area, confirming the key role of mechanical friction. Reusability tests demonstrated stable performance over five cycles, highlighting the material’s durability and potential for practical environmental remediation applications. Full article

Electrocatalytic CO₂ reduction driven by renewable electricity offers a sustainable approach to producing valuable chemicals, though it is often hindered by low activity and selectivity. CuO, an important transition metal oxide, exhibits unique advantages in photoelectrocatalysis due to its high intrinsic catalytic activity and ability to serve as an active site for CO₂ reduction. SiO₂, a widely used substrate, facilitates Cu loading and increases the specific surface area of the catalyst. Meanwhile, g-C₃N₄ provides excellent visible-light responsiveness and efficient charge carrier mobility. Together, CuO, SiO₂, and g-C₃N₄ are earth-abundant, low-cost, and chemically stable, making them ideal for solar-to-fuel applications. Here, a novel ternary heterojunction photocatalyst was constructed using SiO₂, CuO, and g-C₃N₄. The heterostructure significantly improves light-harvesting efficiency, promotes efficient charge separation and transport, and simultaneously mitigates photogenerated carrier recombination and catalyst corrosion. The resulting SiO₂@CuO/g-C₃N₄ catalyst demonstrates outstanding CO₂ conversion performance, achieving a CO yield of 17 mmolg⁻¹h⁻¹ at 1.2 V_RHE with nearly 100% selectivity. Moreover, this work systematically investigates the electrocatalytic CO₂ reduction reaction (CO₂RR) mechanism on Cu-based catalysts, offering insights into the formation of high-value multicarbon products and highlighting the potential of rational heterojunction design in enhancing solar-driven fuel production efficiency. Full article

This study focused on creating a novel material by integrating ZnO and CuO nanoparticles into the structure of halloysite using a hydrothermal method. The formation of the nanocomposite was validated through X-ray diffraction and Raman analysis, which confirmed the presence of ZnO and CuO phases without compromising the structure of halloysite. Microscopic analysis revealed a well-distributed presence of metallic oxide nanoparticles within the nanotubular structure of halloysite, which adhered to both the outer and inner surfaces of the clay mineral. Optical characterization identified a substantial density of defects, which played a key role in improving the performance of the supported semiconductors. Furthermore, the narrow band gap at 3.02 eV promoted the mobility of photogenerated charges. Photocatalytic tests yielded promising results, demonstrating a synergistic effect between photocatalysis and adsorption processes that positively influenced the removal of ciprofloxacin from solutions. The material achieved up to 76% removal of the antibiotic within 120 min, utilizing a catalyst concentration of 0.5 g L⁻¹ with a pollutant concentration of 20 mg L⁻¹. In reuse experiments, the material exhibited high recyclability even after multiple reaction cycles. Halloysite-based nanocomposites represent a strategic advancement in environmental remediation technologies, contributing to the development of clean, effective, and reusable materials. Full article

Ammonium perchlorate (AP), as the most commonly used oxidizer in composite solid propellants, achieving its rapid decomposition at lower temperatures, is one of the key items used to improve propellant performance. Copper-based catalysts, due to their good performance in promoting AP decomposition and improving propellant combustion characteristics, are currently one of the most widely used catalyst types. However, the catalytic performance of copper-based catalysts for the decomposition of ammonium perchlorate, including the decomposition products, changes in the kinetic process during the decomposition, and the combustion process needs further research and clarification in terms of the influencing factors and mechanisms. Based on this question, to further analyze the essence of copper-based catalysts and the decomposition mechanism of CuO-catalyzed ammonium perchlorate, as well as its relationship with particle size, this paper compared and studied the effects of two different particle size CuO catalysts (small-diameter CuO-S and large-diameter CuO-L) on the thermal decomposition and combustion performance of AP. The results indicate that the decomposition of AP catalyzed by CuO mainly includes two stages: the initial low-temperature decomposition stage accelerated by the electron transfer mechanism and the subsequent second stage accelerated by the adsorption and conversion of intermediates by the catalyst. The two stages are controlled by different properties and are related to the particle size of the catalyst. This work provides in-depth research on CuO catalysts for the thermal decomposition of AP. Full article