Search Results (565)

A facile and versatile strategy to obtain NPs@ZnAlO nanocomposite materials, comprising controlled-size nanoparticles (NPs) within a ZnAlO matrix is reported. The mono-(Au, Ni) and bimetallic (Ni-Au) NPs serving as an active phase were prepared by the polyol-alkaline method, while the ZnAlO support was obtained via the thermal decomposition of its corresponding layered double hydroxide (LDH) precursors. X-ray diffraction (XRD) patterns confirmed the successful fabrication of the nanocomposites, including the synthesis of the metallic NPs, the formation of LDH-like structure, and the subsequent transformation to ZnO phase upon LDH calcination. The obtained nanostructures confirmed the nanoplate-like morphology inherited from the original LDH precursors, which tended to aggregate after the addition of gold NPs. According to the UV-Vis spectroscopy, loading NPs onto the ZnAlO support enhanced the light absorption and reduced the band gap energy. ATR-DRIFT spectroscopy, H₂-TPR measurements, and XPS analysis provided information about the functional groups, surface composition, and reducibility of the materials. The catalytic performance of the developed nanostructures was evaluated by the photodegradation of bisphenol A (BPA), under simulated solar irradiation. The conversion of BPA over the bimetallic Ni-Au@ZnAlO reached up to 95% after 180 min of irradiation, exceeding the monometallic Ni@ZnAlO and Au@ZnAlO catalysts. Its enhanced activity was correlated with good dispersion of the bimetals, narrower band gap, and efficient charge carrier separation of the photo-induced e⁻/h⁺ pairs. Full article

A simple and inexpensive thermal oxidation process is used to grow β-Ga₂O₃ oxide (β-Ga₂O₃) thin films/nanorods on a c-plane (0001) sapphire substrate using Ag/Au catalysts. The effect of these catalysts on the growth mechanism of Ga₂O₃ was studied by different characterization techniques, including X-ray diffraction analysis (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray analysis (EDX). The XRD results of the grown Ga₂O₃ on a sapphire substrate show three sharp diffraction peaks located at 19.31°, 38.70° and 59.38° corresponding to the $\left(\overline{2}01\right), \left(\overline{4}02\right)$ and $\left(\overline{6}03\right)$ planes of β-Ga₂O₃. Field Emission Scanning Electron Microscope (FESEM) analysis showed the formation of longer and denser Ga₂O₃ nanowires at higher temperatures, especially in the presence of silver nanoparticles as catalysts. Full article

The development of non-noble metal catalysts for gas-phase propylene epoxidation with H₂/O₂ remains challenging due to their inadequate activity and stability. Herein, we report a Cs⁺-modified Ni/TS-1 catalyst (9%Ni-Cs/TS-1), which exhibits unprecedented catalytic performance, giving a state-of-the-art PO formation rate of 382.9 g_PO·kg_cat⁻¹·h⁻¹ with 87.8% selectivity at 200 °C. The catalyst stability was sustainable for 150 h, far surpassing reported Ni-based catalysts. Ni/TS-1 exhibited low catalytic activity. However, the Cs modification significantly enhanced the performance of Ni/TS-1. Furthermore, the intrinsic reason for the enhanced performance was elucidated by multiple techniques such as XPS, N₂ physisorption, TEM, ²⁹Si NMR, NH₃-TPD-MS, UV–vis, and so on. The findings indicated that the incorporation of Cs⁺ markedly boosted the reduction of Ni, enhanced Ni⁰ formation, strengthened Ni-Ti interactions, reduced acid sites to inhibit PO isomerization, improved the dispersion of Ni nanoparticles, reduced particle size, and improved the hydrophobicity of Ni/TS-1 to facilitate propylene adsorption/PO desorption. The 9%Ni-Cs/TS-1 catalyst demonstrated exceptional performance characterized by a low cost, high activity, and long-term stability, offering a viable alternative to Au-based systems. Full article

Mechanochemical and transition-metal-catalyzed reactions of alkynes, exhibiting significant advantages like short reaction time, solvent-free, high yield and good selectivity, were considered to be green and sustainable pathways to access functionalized molecules and obtained increasing attention due to the superiorities of mechanochemical processes and the reactivities of alkynes. The ball milling and CuI-catalyzed Sonogashira coupling of alkyne and aryl iodide avoided the use of common palladium catalysts. The mechanochemical Rh(III)- and Au(I)-catalyzed C–H alkynylations of indoles formed the 2-alkynylated and 3-alkynylated indoles selectively. The mechanochemical and copper-catalyzed azide-alkyne cycloaddition (CuAAC) between alkynes and azides were developed to synthesize 1,2,3-triazoles. Isoxazole could be formed through ball-milling-enabled and Ru-promoted cycloaddition of alkyne and hydroxyimidel chloride. In this review, the generation of mechanochemical and transition-metal-catalyzed reactions of alkynes was highlighted. Firstly, the superiority and application of transition-metal-catalyzed reactions of alkynes were briefly introduced. After presenting the usefulness of green chemistry and mechanochemical reactions, mechanochemical and transition-metal-catalyzed reactions of alkynes were classified and demonstrated in detail. Based on different kinds of reactions of alkynes, mechanochemical and transition-metal-catalyzed coupling, cycloaddition and alkenylation reactions were summarized and the proposed reaction mechanisms were disclosed if available. Full article

Epoxide deoxygenation by photocatalysis was explored using Au-Co alloy nanoparticles supported on ZrO₂ under visible light irradiation. The active metals were deposited on commercial monoclinic ZrO₂ by chemical impregnation to achieve controlled mass ratios of gold and cobalt in the alloy nanoparticles. The characterisation of the alloy nanoparticles confirmed the technique produced an average particle size of 4.50 ± 0.29 nm. Catalysts containing pure 3% Au and different Au-Co metal ratios attached to the ZrO₂ induced the deoxygenation of styrene oxide in an isopropanol solvent medium. Only 20 mg of pure Au/ZrO₂ catalyst gave a 99% yield of styrene at an 80 °C temperature within 16 h under visible light irradiation (400–800 nm). Au-Co/ZrO₂ catalysts generally induced conversion to styrene under the same conditions below 60 °C. Above 60 °C, a new reaction pathway was observed to favour a different product over Au-Co/ZrO₂, which was identified as styrene glycol. This study developed a new approach to the synthesis of styrene glycol, a molecule that has many useful applications in the chemical and polymer industries. Surface-enhanced Raman spectroscopic (SERS) studies and electron paramagnetic resonance spectroscopic (EPR) studies identified changes in the reaction mechanism and pathway upon increasing the cobalt molar ratio in the Au-Co alloy catalysts. Full article

Extensive research has been conducted on the catalytic properties of molybdenum disulfide (MoS₂) materials in the context of the hydrogen evolution reaction (HER). This study focuses on exploring hybrid MoS₂/Au structures as a catalyst for HER, utilizing linear sweep voltammetry as the experimental methodology. Firstly, 2D-MoS₂ flakes were synthesized by the chemical vapor deposition (CVD) approach and directly added to gold nanoparticles during or after their preparation process. The prepared nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy with energy-dispersive X-ray analysis (SEM/EDX). The HER performance was tested for the two resulting samples to show that the preparation of gold nanoparticles with the coexistence of CVD-MoS₂ flakes produces a superior electrocatalytic performance of the sample in a neutral medium. Notably, the onset potential was measured as −0.152 V (versus reversible hydrogen electrode (RHE)) with an exchange current density (j₀) of 0.22 mA/cm². Chronoamperometric data show that all composites retained initial current densities for 15 hours, confirming stable, efficient HER performance post-decay. Full article

Hydrogen peroxide (H₂O₂) is an important industrial chemical that is widely applied in many areas. The direct synthesis of H₂O₂ from H₂ and O₂ has proved to be a green and economic pathway. Pd-based bimetallic catalysts, due to their superior catalytic performances in this reaction, have attracted intensive attention. Herein, Tetrakis(hydroxymethyl)phosphonium chloride (THPC) was adopted as the protective ligand to immobilize Pd-Au alloy nanoparticles onto activated carbon (AC). The varied Pd/Au molar ratios demonstrated homogeneously distributed Pd-Au nanoalloys with average particle sizes ranging from 3.51 to 5.75 nm. The optimal ratio was observed over the Pd₃Au₁/AC-THPC catalyst with a maximum H₂O₂ productivity of 165 mol/(kg_Pd·h) and selectivity of 82.3% under ambient pressure. The relationship between the electronic structure and catalytic activity indicated Pd⁰ was the active site, while the presence of Au inhibited H₂O₂ degradation rate. This research could help in the design efficient bimetallic catalysts for the direct synthesis of H₂O₂. Full article

Adsorbate-induced surface segregation significantly influences the catalytic and electrochemical performance of bimetallic alloys. Using density functional theory (DFT), we investigated Rh segregation in Au–Rh(111) alloys under the influence of adsorbed NO, CO, or O₂. The computational results reveal that these adsorbates can markedly alter Rh segregation trends on the Au–Rh(111) surface. Under vacuum conditions, the Rh atom remains preferentially in the bulk of the alloy; whereas, in the presence of adsorption, it segregates to the topmost layer, where NO has the greatest influence, followed by CO and O₂. Electronic structure analysis and adsorption energy evaluations further reveal that the strength of the surface–adsorbate interactions critically governs the Rh segregation behavior under reactive conditions. These findings establish a theoretical framework for designing Au–Rh alloys as efficient catalysts for CO oxidation. Full article

Electrochemical nitrogen reduction reaction (NRR) has emerged as a promising approach for sustainable ammonia synthesis under ambient conditions, offering a low-energy alternative to the traditional Haber–Bosch process. However, the development of efficient and sustainable electrocatalysts for NRR remains a significant challenge. Noble metals, known for their exceptional chemical stability under electrocatalytic conditions, have garnered considerable attention in this field. In this study, we report the successful synthesis of nanoporous CuAuPtPd quasi-high-entropy alloy (quasi-HEA) prism arrays through “melt quenching” and “dealloying” techniques. The as-obtained alloy demonstrates remarkable performance as an NRR electrocatalyst, achieving an impressive ammonia synthesis rate of 17.5 μg h⁻¹ mg⁻¹ at a potential of −0.2 V vs. RHE, surpassing many previously reported NRR catalysts. This work not only highlights the potential of quasi-HEAs as advanced NRR electrocatalysts but also provides valuable insights into the design of nanoporous multicomponent materials for sustainable energy and catalytic applications. Full article

The rational development of single-atom catalysts (SACs) for selective formic acid dehydrogenation (FAD) requires an atomic-scale understanding of metal–support interactions and electronic modulation. In this study, spin-polarized density functional theory (DFT) calculations were performed to systematically examine platinum-group SACs anchored on graphitic carbon nitride (g-C₃N₄). The findings reveal that Pd and Au SACs exhibit superior selectivity toward the dehydrogenation pathway, lowering the free energy barrier by 1.42 eV and 1.39 eV, respectively, compared to the competing dehydration route. Conversely, Rh SACs demonstrate limited selectivity due to nearly equivalent energy barriers for both reaction pathways. Stability assessments indicate robust metal–support interactions driven by d–p orbital hybridization, while a linear correlation is established between the d-band center position relative to the Fermi level and catalytic selectivity. Additionally, charge transfer (ranging from 0.029 to 0.467 e) substantially modulates the electronic structure of the active sites. These insights define a key electronic descriptor for SAC design and offer a mechanistic framework for optimizing selective hydrogen production. Full article

The synthesis and characterization of MgO-ZrO₂ heterostructures are examined in this work. To promote the creation of nanowires, the Si substrate is first covered with a catalyst layer of various Au thicknesses. Sputtering is used to achieve this deposition. After that, chemical vapor deposition (CVD) with a Au catalyst layer is used to create MgO nanowire arrays on the silicon substrate. Second, MgO/ZrO₂ Core–shell Nanowire Arrays are created by applying ZrO₂ layers to the surface of MgO nanowires of different diameters using chemical vapor deposition (CVD) procedures. The presence of both magnesium oxide (MgO) and zirconium dioxide (ZrO₂) in their oxidized forms was shown by the detailed characterization of the MgO-ZrO₂ core–shell nanowire samples utilizing a variety of methods. Phase formation, mechanical homogeneity, optical characteristics, and topographical structure and roughness were all thoroughly examined at various stresses. MgO hardness values ranged from 1.4 to 3.2 GPa, whereas MgO-ZrO₂ ranged from 0.38 to 1.2 GPa. The I–V parameter study was a further step in the examination of the heterostructure’s electrical properties. The structural, morphological, optical, mechanical, and electrical properties of the MgO-ZrO₂ heterostructure were all thoroughly described using these techniques. Full article

Transition metal dichalcogenides (TMDs) are recognized for their exceptional energy storage capabilities and electrochemical potential, stemming from their unique electronic structures and physicochemical properties. In this study, we focus on chromium disulfide (CrS₂) as the primary research subject and employ a combination of density functional theory (DFT) and first-principle calculations to investigate the effects of incorporating transition metal elements onto the surface of CrS₂. This approach aims to develop a class of bifunctional single-atom catalysts with high efficiency and to analyze their catalytic performance in detail. Theoretical calculations reveal that the Au@CrS₂ single-atom catalyst demonstrates outstanding catalytic activity, with a low overpotential of 0.34 V for the oxygen evolution reaction (OER) and 0.37 V for the oxygen reduction reaction (ORR). These results establish Au@CrS₂ as a highly effective bifunctional catalyst. Moreover, the catalytic performance of Au@CrS₂ surpasses that of traditional commercial catalysts, such as Pt (0.45 V) and IrO₂ (0.56 V), suggesting its potential to replace these materials in fuel cells and other energy applications. This study provides a novel approach to the design and development of advanced transition metal-based catalytic materials. Full article

The rational design of high-performance catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is essential for the development of clean and renewable energy technologies, particularly in fuel cells and metal-air batteries. Two-dimensional (2D) covalent organic frameworks (COFs) possess numerous hollow sites, which contribute to the stable anchoring of transition metal (TM) atoms and become promising supports for single atom catalysts (SACs). Herein, the OER and ORR catalytic performance of a series of SACs based on TQBQ-COFs were systematically investigated through density functional theory (DFT) calculations, with particular emphasis on the role of the coordination environment in modulating catalytic activity. The results reveal that Rh/TQBQ exhibits the most effective OER catalytic performance, with an overpotential of 0.34 V, while Au/TQBQ demonstrates superior ORR catalytic performance with an overpotential of 0.50 V. A critical mechanistic insight lies in the distinct role of boundary oxygen atoms in TQBQ, which perturb the adsorption energetics of reaction intermediates, thereby circumventing conventional scaling relationships governing OER and ORR pathways. Furthermore, we established the adsorption energy of TM atoms (Ead) as a robust descriptor for predicting catalytic activity, enabling a streamlined screening strategy for SAC design. This study emphasizes the significance of the coordination environment in determining the performance of catalysts and offers a new perspective on the design of novel and effective OER/ORR COFs-based SACs. Full article

Anion exchange membrane fuel cells (AEMFCs) are versatile power generation devices that can be fed by both gaseous (H₂) and liquid fuels. The development of sustainable, efficient, and stable catalysts for the oxidation of hydrogen (HOR) and oxygen reduction (ORR) under alkaline conditions remains a challenge currently facing AEMFC technology. Reducing the loading of PGMs is essential for reducing the overall cost of AEMFCs. One strategy involves exploiting the synergistic effects of two metals in bimetallic nanoparticles (NPs). Here, we report that the activity for the HOR and the ORR can be finely tuned through surface engineering of carbon-supported PdAu-PVA NPs. The activity for both ORR and HOR can be adjusted by subjecting the material to heat treatment. Specifically, heat treatment at 500 °C under an inert atmosphere increases the crystallinity and oxophilicity of the nanoparticles, thereby enhancing anodic HOR performance. On the contrary, heat treatment significantly lowers ORR activity, highlighting how reduced surface oxophilicity plays a major role in increasing active sites for ORR. The tailored activity in these catalysts translates into high power densities when employed in AEMFCs (up to 1.1 W cm⁻²). Full article

As the energy crisis and environmental pollution continue to intensify, the demand for clean energy has increased. Using two-dimensional materials to catalyze overall water splitting is an important pathway for clean energy production. This study investigated the catalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) of tri-atomic clusters supported on a two-dimensional material, graphenylene (GPN). The structural stability of GPN was thoroughly investigated, and materials were employed as substrates to support a series of 28 distinct trimer clusters composed of 3d, 4d, and 5d transition metals. Ideal combinations of these systems were screened and designed. The loading configurations of TM₃@GPN in two different systems were systematically studied. The stability of the catalyst was assessed by calculating the binding and cohesive energies and by performing molecular dynamics simulations, to confirm the catalyst stability. The optimal bifunctional catalysts for overall water splitting were identified as Au₃@GPN, Pt₃@GPN, and Pd₃@GPN, all of which demonstrated superior overall water splitting performance. As a novel two-dimensional material, biphenylene-based materials, when used to support metal clusters as bifunctional catalysts for water splitting, represent an efficient and innovative approach. Full article