Search Results (57)

The activation and dissociation of O₂ molecules play a key role in the oxidation of toxic gas molecules and the oxygen reduction reaction (ORR) in hydrogen–oxygen fuel cells. The interactions between O₂ molecules and the surfaces of Fe-doped γ-graphyne were systematically explored, mainly adopting the combined method of the density functional theory with dispersion correction (DFT-D3) and the climbing image nudged elastic band (CI-NEB) method. The order of the formation energy values of these defective systems is E_f(Fe_C2) < E_f(Fe_C1) < E_f(Fe_D1) < E_f(V_C1) < E_f(V_D1) < E_f(V_C2) < E_f(Fe_D2) < E_f(V_D2), which indicates that the process of Fe dopant atoms substituting single-carbon atoms/double-carbon atoms is relatively easier than the formation of vacancy-like defects. The results of ab initio molecular dynamics (AIMD) simulations confirm that the doped systems can maintain structural stability at room temperature conditions. Fe-doped atoms transfer a certain amount of electrons to the adsorbed O₂ molecules, thereby causing an increase in the O-O bond length of the adsorbed O₂ molecules. The electrons obtained by the anti-bonding 2π* orbitals of the adsorbed O₂ molecules are mainly derived from the 3d orbitals of Fe atoms. There is a competitive relationship between the substrate’s carbon atoms and the adsorbed O₂ molecules for the charges transferred from Fe atoms. In the C1 and C2 systems, O₂ molecules have a greater advantage in electron accepting ability compared to the substrate’s carbon atoms. The elongation of O-O bonds and the amount of charge transfer exhibit a positive relationship. More electrons are transferred from Fe-3d orbitals to adsorbed O₂ molecules, occupying the 2π* orbitals of adsorbed O₂ molecules, further elongating the O-O chemical bond until it breaks. The dissociation process of adsorbed O₂ molecules on the surfaces of GY-Fe systems (C2 and D2 sites) involves very low energy barriers (0.016 eV for C2 and 0.12 eV for D2). Thus, our studies may provide useful insights for designing catalyst materials for oxidation reactions and the oxygen reduction reaction. 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

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

Contact electrification (CE) spans from atomic to macroscopic scales, facilitating charge transfer between materials upon contact. This interfacial charge exchange, occurring in solid–solid (S–S) or solid–liquid (S–L) systems, initiates radical generation and chemical reactions, collectively termed contact-electro-chemistry (CE-Chemistry). As an emerging platform for green chemistry, CE-Chemistry facilitates redox, luminescent, synthetic, and catalytic reactions without the need for external power sources as in traditional electrochemistry with noble metal catalysts, significantly reducing energy consumption and environmental impact. Despite its broad applicability, the mechanistic understanding of CE-Chemistry remains incomplete. In S–S systems, CE-Chemistry is primarily driven by surface charges, whether electrons, ions, or radicals, on charged solid interfaces. However, a comprehensive theoretical framework is yet to be established. While S–S CE offers a promising platform for exploring the interplay between chemical reactions and triboelectric charge via surface charge modulation, it faces significant challenges in achieving scalability and optimizing chemical efficiency. In contrast, S–L CE-Chemistry focuses on interfacial electron transfer as a critical step in radical generation and subsequent reactions. This approach is notably versatile, enabling bulk-phase reactions in solutions and offering the flexibility to choose various solvents and/or dielectrics to optimize reaction pathways, such as the degradation of organic pollutants and polymerization, etc. The formation of an interfacial electrical double layer (EDL), driven by surface ion adsorption following electron transfer, plays a pivotal role in CE-Chemical processes within aqueous S–L systems. However, the EDL can exert a screening effect on further electron transfer, thereby inhibiting reaction progress. A comprehensive understanding and optimization of charge transfer mechanisms are pivotal for elucidating reaction pathways and enabling precise control over CE-Chemical processes. As the foundation of CE-Chemistry, charge transfer underpins the development of energy-efficient and environmentally sustainable methodologies, holding transformative potential for advancing green innovation. This review consolidates recent advancements, systematically classifying progress based on interfacial configurations in S–S and S–L systems and the underlying charge transfer dynamics. To unlock the full potential of CE-Chemistry, future research should prioritize the strategic tuning of material electronegativity, the engineering of sophisticated surface architectures, and the enhancement of charge transport mechanisms, paving the way for sustainable chemical innovations. Full article

The current paradigm of low-T combustion and autoignition of hydrocarbons is based on the sequential two-step oxygenation of fuel radicals. The key chain-branching occurs when the second oxygenation adduct (OOQOOH) is isomerized releasing an OH radical and a key ketohydroperoxide (KHP) intermediate. The subsequent homolytic dissociation of relatively weak O–O bonds in KHP generates two more radicals in the oxidation chain leading to ignition. Based on the recently introduced intramolecular “catalytic hydrogen atom transfer” mechanism (J. Phys. Chem. 2024, 128, 2169), abbreviated here as I-CHAT, we have identified a novel unimolecular decomposition channel for KHPs to form their classical isomers—enol hydroperoxides (EHP). The uncertainty in the contribution of enols is typically due to the high computed barriers for conventional (“direct”) keto–enol tautomerization. Remarkably, the I-CHAT dramatically reduces such barriers. The novel mechanism can be regarded as an intramolecular version of the intermolecular relay transfer of H-atoms mediated by an external molecule following the general classification of such processes (Catal. Rev.-Sci. Eng. 2014, 56, 403). Here, we present a detailed mechanistic and kinetic analysis of the I-CHAT-facilitated pathways applied to n-hexane, n-heptane, and n-pentane models as prototype molecules for gasoline, diesel, and hybrid rocket fuels. We particularly examined the formation kinetics and subsequent dissociation of the γ-enol-hydroperoxide isomer of the most abundant pentane-derived isomer γ-C5-KHP observed experimentally. To gain molecular-level insight into the I-CHAT catalysis, we have also explored the role of the internal catalyst moieties using truncated models. All applied models demonstrated a significant reduction in the isomerization barriers, primarily due to the decreased ring strain in transition states. In addition, the longer-range and sequential H-migration processes were also identified and illustrated via a combined double keto–enol conversion of heptane-2,6-diketo-4-hydroperoxide as a potential chain-branching model. To assess the possible impact of the I-CHAT channels on global fuel combustion characteristics, we performed a detailed kinetic analysis of the isomerization and decomposition of γ-C5-KHP comparing I-CHAT with key alternative reactions—direct dissociation and Korcek channels. Calculated rate parameters were implemented into a modified version of the n-pentane kinetic model developed earlier using RMG automated model generation tools (ACS Omega, 2023, 8, 4908). Simulations of ignition delay times revealed the significant effect of the new pathways, suggesting an important role of the I-CHAT pathways in the low-T combustion of large alkanes. Full article

An electrocatalytic nitrogen reduction reaction (eNRR) presents an appealing strategy for ammonia (NH₃) production at ambient conditions. Through systematic density functional theory (DFT) calculations, the eNRR performance of 23 double-atom catalysts has been investigated. These catalysts are composed of a Mo atom and a transition metal atom anchored on the graphdiyne (GDY), and they are named MoM-GDYs. Among the 23 MoM-GDYs studied, 14 MoM-GDYs highlighted catalytic selectivity by inhibiting a competitive hydrogen evolution reaction (HER) and demonstrated commendable eNRR catalytic performance. MoRu-GDY, MoMo-GDY, MoFe-GDY and MoY-GDY exhibited excellent eNRR catalytic activity with limiting potentials of −0.05 V, −0.13 V, −0.21 V and −0.24 V, respectively. These 14 catalysts favor N₂ adsorption compared to H and exhibit less negative U_L than the −0.98 V benchmark of the stepped Ru(0001) surface. Among them, MoRu-GDY has the best catalytic activity with an U_L of −0.05 V. The excellent catalytic performance originates from the synergistic effect of the dual catalytic sites, where the alternation of the consecutive and enzymatic paths effectively reduces the limiting potentials. In addition, the catalytic activity can be evaluated using ΔG*_NH3 − ΔG*_NH2 as a theoretical descriptor, while U_L and the ΔG*_NH3 − ΔG*_NH2 fit coefficient R² reached 0.99. These findings not only contribute to the development of dual-atom electrocatalysts for eNRR but also offer a valuable pathway for identifying new eNRR catalysts with high activity and selectivity. Full article

The industrial application of polymer electrolyte membrane fuel cells is limited by the high cost of platinum catalysts. In this study, we developed a one−step synthesis strategy for low−platinum alloy catalysts based on crystal−structure predictions. Using this method, we successfully prepared a low−platinum alloy catalyst, i.e., CaPt₂, which exhibits the same structure as its theoretically predicted counterpart in a single step via arc melting. There was no hazardous waste emission during the preparation of the alloy catalyst. Electrons were successfully enriched on the surfaces of platinum atoms, and the electronic structures of the platinum atoms were adjusted. The migration of oxygen intermediates during oxygen reduction was determined via an extensive oxygen−intermediate adsorption site test. The reaction path for the oxygen reduction process was determined. Electronic−structure analysis revealed the interaction mechanism between the oxygen intermediate and the platinum atom on the catalyst surface. The incorporation of calcium atoms into the alloy catalyst effectively improved the adsorption/dissociation state of the oxygen intermediates on the catalyst surface. Meanwhile, the molar fraction of platinum atoms in the CaPt₂ alloy catalyst reduced by 33%, thus decreasing the feedstock cost of the catalyst. The double reduction in raw materials and manufacturing costs is conducive to the popularization and application of alloy catalysts. This study provides a reference for the design and production of other functional catalysts. Full article

Fullerene C₆₀ is by far the most studied of all allotropic modifications of carbon. Chemical modification of the double bond over the years has led to the emergence of a variety of fullerene derivatives. These derivatives have now found numerous applications in medicine, materials and supramolecular chemistry, and as efficient electron acceptors in organic photovoltaic devices. The main method for the functionalization of C₆₀ fullerenes, which makes it possible to obtain its derivatives in a preparative volume, is the Bingel–Hirsch reaction. But this method makes it possible to obtain fullerocyclopropanes containing only carboxyl substituents at the bridging carbon atom. Therefore, in order to obtain new materials, we began to study the interaction with organic carbonates in combination with Grignard reagents in the presence of Ti-containing complex catalysts. We hope that replacing the olefin in the Kulinkovich reaction with a C₆₀ fullerene molecule will lead to new and hard-to-find functionalization products of the latter. Organic carbonates were chosen as the object of study due to the fact that they are used in the industry as solvents for natural and synthetic resins, cellulose ethers, dispersants, blowing agents, emulsifiers, absorbents of hydrogen sulfide and carbon dioxide, starting materials for the industrial synthesis of fibers and plastics, as well as plasticizers, pharmaceuticals and plant protection products. Full article

Seawater electrolysis represents a promising green energy technology with significant potential for efficient energy conversion. This study provides an in-depth examination of the key scientific challenges inherent in the seawater-electrolysis process and their potential solutions. Initially, it analyzes the potential issues of precipitation and aggregation at the cathode during hydrogen evolution, proposing strategies such as self-cleaning cathodes and precipitate removal to ensure cathode stability in seawater electrolysis. Subsequently, it addresses the corrosion challenges faced by anode catalysts in seawater, introducing several anti-corrosion strategies to enhance anode stability, including substrate treatments such as sulfidation, phosphidation, selenidation, and LDH (layered double hydroxide) anion intercalation. Additionally, this study explores the role of regulating the electrode surface microenvironment and forming unique coordination environments for active atoms to enhance seawater electrolysis performance. Regulating the surface microenvironment provides a novel approach to mitigating seawater corrosion. Contrary to the traditional understanding that chloride ions accelerate anode corrosion, certain catalysts benefit from the unique coordination environment of chloride ions on the catalyst surface, potentially enhancing oxygen evolution reaction (OER) performance. Lastly, this study presents the latest advancements in the industrialization of seawater electrolysis, including the in situ electrolysis of undiluted seawater and the implementation of three-chamber dual anion membranes coupled with circulating electrolyte systems. The prospects of seawater electrolysis are also explored. Full article

Anodic TiO₂ nanotube arrays decorated with Ni, Cu, and NiCu alloy thin films were investigated for the first time for the photocatalytic degradation of paracetamol in water solution under UV irradiation. Metallic co-catalysts were deposited on TiO₂ nanotubes using magnetron sputtering. The influence of the metal layer composition and thickness on the photocatalytic activity was systematically studied. Photocatalytic experiments showed that only Cu-rich co-catalysts provide enhanced paracetamol degradation rates, whereas Ni-modified photocatalysts exhibit no improvement compared with unmodified TiO₂. The best-performing material was obtained by sputtering a 20 nm thick film of 1:1 atomic ratio NiCu alloy: this material exhibits a reaction rate more than doubled compared with pristine TiO₂, enabling the complete degradation of 10 mg L⁻¹ of paracetamol in 8 h. The superior performance of NiCu-modified systems over pure Cu-based ones is ascribed to a Ni and Cu synergistic effect. Kinetic tests using selective holes and radical scavengers unveiled, unlike prior findings in the literature, that paracetamol undergoes direct oxidation at the photocatalyst surface via valence band holes. Finally, Chemical Oxygen Demand (COD) tests and High-Resolution Mass Spectrometry (HR-MS) analysis were conducted to assess the degree of mineralization and identify intermediates. In contrast with the existing literature, we demonstrated that the mechanistic pathway involves direct oxidation by valence band holes. Full article

A series of M(x)CoCeMgAlO mixed oxides with different transition metals (M = Cu, Fe, Mn, and Ni) with an M content x = 3 at. %, and another series of Fe(x)CoCeMgAlO mixed oxides with Fe contents x ranging from 1 to 9 at. % with respect to cations, while keeping constant in both cases 40 at. % Co, 10 at. % Ce and Mg/Al atomic ratio of 3 were prepared via thermal decomposition at 750 °C in air of their corresponding layered double hydroxide (LDH) precursors obtained by coprecipitation. They were tested in a fixed bed reactor for complete methane oxidation with a gas feed of 1 vol.% methane in air to evaluate their catalytic performance. The physico-structural properties of the mixed oxide samples were investigated with several techniques, such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), elemental mappings, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction under hydrogen (H₂-TPR) and nitrogen adsorption–desorption at −196 °C. XRD analysis revealed in all the samples the presence of Co₃O₄ crystallites together with periclase-like and CeO₂ phases, with no separate M-based oxide phase. All the cations were distributed homogeneously, as suggested by EDX measurements and elemental mappings of the samples. The metal contents, determined by EDX and ICP-OES, were in accordance with the theoretical values set for the catalysts’ preparation. The redox properties studied by H₂-TPR, along with the surface composition determined by XPS, provided information to elucidate the catalytic combustion properties of the studied mixed oxide materials. The methane combustion tests showed that all the M-promoted CoCeMgAlO mixed oxides were more active than the M-free counterpart, the highest promoting effect being observed for Fe as the doping transition metal. The Fe(x)CoCeMgAlO mixed oxide sample, with x = 3 at. % Fe displayed the highest catalytic activity for methane combustion with a temperature corresponding to 50% methane conversion, T₅₀, of 489 °C, which is ca. 40 °C lower than that of the unpromoted catalyst. This was attributed to its superior redox properties and lowest activation energy among the studied catalysts, likely due to a Fe–Co–Ce synergistic interaction. In addition, long-term tests of Fe(3)CoCeMgAlO mixed oxide were performed, showing good stability over 60 h on-stream. On the other hand, the addition of water vapors in the feed led to textural and structural changes in the Fe(3)CoCeMgAlO system, affecting its catalytic performance in methane complete oxidation. At the same time, the catalyst showed relatively good recovery of its catalytic activity as soon as the water vapors were removed from the feed. Full article

X-ray absorption fine structure (XAFS) spectroscopy, temperature-programmed reduction (TPR), and temperature-programmed hydride decomposition (TPHD) were employed to elucidate the structures of a series of PdRe/Al₂O₃ bimetallic catalysts for the selective hydrogenation of furfural. TPR evidenced low-temperature Re reduction in the bimetallic catalysts consistent of the migration of [ReO₄]⁻ (perrhenate) species to hydrogen-covered Pd nanoparticles on highly hydroxylated γ-Al₂O₃. TPHD revealed a strong suppression of β-PdH_x formation in the reduced catalysts prepared by (i) co-impregnation and (ii) [HReO₄] impregnation of the reduced Pd/Al₂O₃, indicating the formation of Pd-rich alloy nanoparticles; however, reduced catalysts prepared by (iii) [Pd(NH₃)₄]²⁺ impregnation of calcined Re/Al₂O₃ and subsequent re-calcination did not. Re L_III X-ray absorption edge shifts were used to determine the average Re oxidation states after reduction at 400 °C. XAFS spectroscopy and high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM) revealed that a reduced 5 wt.% Re/Al₂O₃ catalyst contained small Re clusters and nanoparticles comprising Re atoms in low positive oxidation states (~1.5+) and incompletely reduced Re species (primarily Re⁴⁺). XAFS spectroscopy of the bimetallic catalysts evidenced Pd-Re bonding consistent with Pd-rich alloy formation. The Pd and Re total first-shell coordination numbers suggest that either Re is segregated to the surface (and Pd to the core) of alloy nanoparticles and/or segregated Pd nanoparticles are larger than Re nanoparticles (or clusters). The Cowley short-range order parameters are strongly positive indicating a high degree of heterogeneity (clustering or segregation of metal atoms) in these bimetallic catalysts. Catalysts prepared using the Pd(NH₃)₄[ReO₄]₂ double complex salt (DCS) exhibit greater Pd-Re intermixing but remain heterogeneous on the atomic scale. Full article

Global warming, driven by greenhouse gases like CH₄ and CO₂, necessitates efficient catalytic conversion to syngas. Herein, Ni containing different molecular sieve nanomaterials are investigated for dry reforming of methane (DRM). The reduced catalysts are characterized by surface area porosity, X-ray diffraction, Raman infrared spectroscopy, CO₂ temperature-programmed desorption techniques, and transmission electron microscopy. The active sites over each molecular sieve remain stable under oxidizing gas CO₂ during DRM. The reduced 5Ni/CBV10A catalyst, characterized by the lowest silica–alumina ratio, smallest surface area and pore volume, and narrow 8-ring connecting channels, generated the maximum number of active sites on its outer surface. In contrast, the reduced-5Ni/CBV3024E catalyst, with the highest silica–alumina ratio, more than double the surface area and pore volume, 12-ring sinusoidal porous channels, and smallest Ni crystallite, produced the highest H₂ output (44%) after 300 min of operation at 700 °C, with a CH₄:CO₂ = 1:1, P = 1 atom, gas hour space velocity (GHSV) = 42 L gcat⁻¹ h⁻¹. This performance was achieved despite having 25% fewer initial active sites, suggesting that a larger fraction of these sites is stabilized within the pore channels, leading to sustained catalytic activity. Using central composite design and response surface methodology, we successfully optimized the process conditions for the 5Ni/CBV3024E catalyst. The optimized conditions yielded a desirable H₂ to CO ratio of 1.00, with a H₂ yield of 91.92% and a CO yield of 89.16%, indicating high efficiency in gas production. The experimental results closely aligned with the predicted values, demonstrating the effectiveness of the optimization approach. Full article

Studies have shown that the incorporation of fluorine into materials can improve their properties, but C–F bonds are not readily formed in nature. Although some researchers have studied the reaction of fluorinating alkenes catalyzed by hypervalent iodine, far too little attention has been paid to its reaction mechanism. This study aimed to explore the mechanism of the hypervalent iodine-catalyzed 1,4-difluorination of dienes. We found that the catalyst is favorable for the activation of C1=C2 double bonds through halogen bonds, and then two HFs interact with one F atom in the catalyst via hydrogen bonds, resulting in the cleavage of I–F bonds and the formation of [F–H∙∙∙F]⁻. Subsequently, the catalyst interacts with C1, and the roaming [F–H···F]⁻ attacks C4 from the opposite side of the catalyst. After the fluorination step is completed, the nucleophile F⁻ substitutes the catalyst via the S_N2 mechanism. Our calculations demonstrated that the interaction between HF and F⁻ is favorable for the stabilization of the transition state within the fluorination process for which the presence of two HFs in the reaction is the best. We also observed that [F–H∙∙∙F]⁻ attacking C4 from the opposite side of the catalyst is more advantageous than attacking from the same side. This study therefore offers a novel perspective on the mechanism of the hypervalent iodine-catalyzed fluoridation of dienes. Full article

Due to the very efficient relaxation of elastic stress on strain-free sidewalls, III–V nanowires offer almost unlimited possibilities for bandgap engineering in nanowire heterostructures by using material combinations that are attainable in epilayers. However, axial nanowire heterostructures grown using the vapor–liquid–solid method often suffer from the reservoir effect in a catalyst droplet. Control over the interfacial abruptness in nanowire heterostructures based on the group V interchange is more difficult than for group-III-based materials, because the low concentrations of highly volatile group V atoms cannot be measured after or during growth. Here, we develop a self-consistent model for calculations of the coordinate-dependent compositional profiles in the solid and liquid phases during the vapor–liquid–solid growth of the axial nanowire heterostructure ${\mathrm{A}}_{{\mathrm{x}}_0}{\mathrm{B}}_{1-{\mathrm{x}}_0}\mathrm{C}/{\mathrm{A}}_{{\mathrm{x}}_1}{\mathrm{B}}_{1-{\mathrm{x}}_1}\mathrm{C}$ with any stationary compositions ${\mathrm{x}}_0$ and ${\mathrm{x}}_1$. The only assumption of the model is that the growth rates of both binaries AC and BC are proportional to the concentrations of group V atoms A and B in a catalyst droplet, requiring high enough supersaturations in liquid phase. The model contains a minimum number of parameters and fits quite well the data on the interfacial abruptness across double heterostructures in GaP/GaAs_xP_1−x/GaP nanowires. It can be used for any axial III–V nanowire heterostructures obtained through the vapor–liquid–solid method. It forms a basis for further developments in modeling the complex growth process and suppression of the interfacial broadening caused by the reservoir effect. Full article