Search Results (112)

Using density functional theory (M06-2X-D3/def2-TZVP), we investigated the 1,2-addition reactions of NH₃ with a series of heavy imine analogues, G13=P-Rea (where G13 denotes a Group 13 element; Rea = reactant), featuring a mixed G13–P–Ga backbone. Theoretical analyses revealed that the bonding nature of the G13=P moiety in G13=P-Rea molecules varies with the identity of the Group 13 center. For G13=B, Al, Ga, and In, the bonding is best described as a donor–acceptor (singlet–singlet) interaction, whereas for G13=Tl, it is characterized by an electron-sharing (triplet–triplet) interaction. According to our theoretical studies, all G13=P-Rea species—except the Tl=P analogue—undergo 1,2-addition with NH₃ under favorable energetic conditions. Energy decomposition analysis combined with natural orbitals for chemical valence (EDA–NOCV), along with frontier molecular orbital (FMO) theory, reveals that the primary bonding interaction in these reactions originates from electron donation by the lone pair on the nitrogen atom of NH₃ into the vacant p-π* orbital on the G13 center. In contrast, a secondary, weaker interaction involves electron donation from the phosphorus lone pair of the G13=P-Rea species into the empty σ* orbital of the N–H bond in NH₃. The calculated activation barriers are primarily governed by the deformation energy of ammonia. Specifically, as the atomic weight of the G13 element increases, the atomic radius and G13–P bond length also increase, requiring a greater distortion of the H₂N–H bond to reach the transition state. This leads to a higher geometrical deformation energy of NH₃, thereby increasing the activation barrier for the 1,2-addition reaction involving these Lewis base-stabilized, heavy imine-like G13=P-Rea molecules and ammonia. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) into value-added multi-carbon C₂₊ products holds significant promise for sustainable chemical synthesis and carbon-neutral energy cycles. Among the various strategies developed to enhance CO₂RR, the use of ionic liquids (ILs) has emerged as a powerful approach for modulating the local microenvironment and electronic structure of Cu-based metal catalysts. In this study, to unravel the molecular-level mechanisms underlying these enhancements, density functional theory calculations (DFTs) were employed to systematically explore how ILs with different terminal groups modulate the electronic reconstruction of the Cu surface, further affecting the *CO–*CO coupling and product selectivity. Electronic structure analyses reveal that ILs bearing polar moieties (–SH, –COOH) can synergistically enhance the interfacial electron accumulation and induce an upshift of the Cu d-band center, thereby strengthening *CO adsorption. In contrast, nonpolar IL (CH₃) exhibits negligible effects, underscoring the pivotal role of ILs’ polarity in catalyst surface-state engineering. The free energy diagrams and transition state analyses reveal that ILs with polar groups significantly lower both the reaction-free energy and activation barrier associated with the *CO–*CO coupling step. This energetic favorability selectively inhibits the C₁ product pathways and hydrogen evolution reaction (HER), further improving the selectivity of C₂ products. These theoretical insights not only unveil the mechanistic origins of IL-induced performance enhancement but also offer predictive guidance for the rational design of advanced IL–catalyst systems for efficient CO₂ electroreduction. Full article

A “thermal-annealing vacancy-filling” synthesis strategy was developed to engineer cobalt single-atom catalysts (Co-MoS₂/RGO) for exceptional hydrogen evolution reaction (HER) performance. By anchoring atomic Co onto Frenkel defect-engineered MoS₂ nanosheets supported by reduced graphene oxide (RGO), we achieved simultaneous optimization of catalytic stability, electrical conductivity, and active site accessibility. The optimized Co₃-MoS₂/RGO hybrid demonstrates remarkable alkaline HER activity, requiring only 94.0 mV overpotential to achieve 10 mA cm⁻² current density while maintaining excellent durability over extended operation. The atomically dispersed Co promoted HER kinetics through electronic structure modulation of MoS₂ basal planes, creation of catalytic active centers, and defect-mediated synergies. The RGO further contributed to performance enhancement by preventing nanosheet aggregation, facilitating charge transfer, and exposing active sites. This defect engineering strategy provides a facile method for developing cost-effective, stable, and high-performance electrocatalysts for sustainable hydrogen production. 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 design of efficient hydrogen evolution reaction (HER) catalysts to minimize reaction overpotentials plays a pivotal role in advancing water electrolysis and clean energy solutions. Ru-based catalysts, regarded as potential replacements for Pt-based catalysts, face stability challenges during catalytic process. The precise regulation of metal–support interactions effectively prevents Ru nanoparticle degradation while optimizing interfacial electronic properties, enabling the simultaneous enhancement of catalytic activity and stability. Herein, we design an amorphous/crystalline support and employ in situ replacement to develop a Ru-NiP_x-Ni structure. The crystalline Ni phase with ordered atomic arrangement ensures efficient charge transport, while the amorphous phase with unsaturated dangling bonds provides abundant anchoring sites for Ru nanoclusters. This synergistic structure significantly enhances HER performance, which attains overpotentials of 19 mV at 10 mA cm⁻² and 70 mV at 100 mA cm⁻² in 1 m KOH, with sustained operation exceeding 55 h at 100 mA cm⁻². Electrochemical impedance spectroscopy analysis confirms that the Ru-NiP_x-Ni structure not only has a high density of active centers for HER, but also reduces the charge transfer resistance at the electrode–electrolyte interface, which effectively enhances HER kinetics. This study presents new directions for designing high-efficiency HER catalysts. Full article

The reasonable design of low-cost, high-activity single-atom catalysts (SACs) is crucial for achieving highly efficient electrochemical CO₂RR. In this study, we systematically explore, using density functional theory (DFT), the performance of transition metal (TM = Mn, Fe, Co, Ni, Cu, Zn)-doped defect-type hexagonal boron nitride (h-BN) SACs TM@B₋₁N (B vacancy) and TM@BN₋₁ (N vacancy) in both CO₂RR and the hydrogen evolution reaction (HER). Integrated crystal orbital Hamiltonian population (ICOHP) analysis reveals that these catalysts weaken the sp orbital hybridization of CO₂, which promotes the formation of radical-state intermediates and significantly reduces the energy barrier for the hydrogenation reaction. Therefore, these theoretical calculations indicate that the Mn, Fe, Co@B₋₁N, and Co@BN₋₁ systems demonstrate excellent CO₂ chemical adsorption properties. In the CO₂RR pathway, Mn@B₋₁N exhibits the lowest limiting potential (U_L = −0.524 V), and its higher d-band center (−0.334 eV), which aligns optimally with the adsorbate orbitals, highlights its excellent catalytic activity. Notably, Co@BN₋₁ exhibits the highest activity in HER, while U_L is −0.217 V. Furthermore, comparative analysis reveals that Mn@B₋₁N shows 16.4 times higher selectivity for CO₂RR than for HER. This study provides a theoretical framework for designing bifunctional SACs with selective reaction pathways. Mn@B₋₁N shows considerable potential for selective CO₂ conversion, while Co@BN₋₁ demonstrates promising prospects for efficient hydrogen production. Full article

Catalysts with anionic metal centers have recently been proposed to enhance the performance of various chemical processes. Here, we focus on the reactivity of ${\mathrm{Co}\left(\mathrm{CO}\right)}_4^{-}$ for the polymerization of aziridine and carbon monoxide to form polypeptoids, motivated by earlier experimental studies. We used multi-reference and density functional theory methods to investigate possible reaction mechanisms and provide insights into the role of the negatively charged cobalt center. Two different reaction paths were identified. In the first path, ${\mathrm{Co}}^{-}$ acts as a nucleophile, donating an electron pair to the reaction substrate, while in the second path, it performs a single electron transfer to the substrate, initiating radical polymerization. The difference in the activation barriers for the two key steps is small and falls within the accuracy of our calculations. As suggested in the literature, solvent effects can play a primary role in determining the outcomes of such reactions. Future investigations will involve different metals or ligands and will investigate the effects of these two reaction paths on other chemical transformations. Full article

Identifying efficient and physically meaningful descriptors is crucial for the rational design of hydrogen evolution reaction (HER) catalysts. In this study, we systematically investigate the HER activity of transition metal dichalcogenide (TMD) monolayers by combining density functional theory (DFT) calculations and machine learning techniques. By exploring the relationship between key electronic properties, including the conduction band minimum (CBM), p_z band center, and hydrogen adsorption free energy (ΔG_*H), we establish a strong linear correlation between the CBM and ΔG_*H, identifying the CBM as a reliable and physically meaningful descriptor for HER activity. Furthermore, this correlation is validated in vacancy-defected TMD systems, demonstrating that the CBM remains an effective descriptor even in the presence of structural defects. To enable the rapid and accurate prediction of the CBM, we develop an interpretable three-dimensional model using the Sure Independence Screening and Sparsifying Operator (SISSO) algorithm. The SISSO model achieves a high predictive accuracy, with correlation coefficients (r) and coefficients of determination (R²) reaching 0.98 and 0.97 in the training and 0.99 and 0.99 in the validation tests, respectively. This study provides an efficient computational framework that combines first-principles calculations and machine learning to accelerate the screening and design of high-performance TMD-based HER catalysts. Full article

The success of establishing new trees in cities and their subsequent growth depend, among others, on the proper selection of tree species which can easily tolerate the post-planting stress. In the spring of 2023, young Italian alder (Alnus cordata (Loisel.) Duby) and common lime (Tilia × europaea L. ‘Pallida’) trees were planted in a street of heavy traffic in Warsaw. In the summer of 2023, leaf samples were collected during the growing season for chlorophyll a fluorescence measurements and chemical analyses. Additionally, the autumn phenological phases were monitored. Chlorophyll a fluorescence measurements revealed higher values of F_v/F_m, density of reaction centers per cross-section, and electron transport chain efficiency between photosystems II and I, as well as lower energy dissipation rate per active reaction center of photosystem II in A. cordata. Moreover, A. cordata revealed higher chlorophyll a, chlorophyll b, and carotenoid content. The flavonoid and proline content in both species was the highest by the end of July and then decreased. In T. × europea ‘Pallida’, the contents of these stress biomarkers increased in the late growing season. Our results showed that T. × europaea ‘Pallida’ is less resistant to post-planting stress in urban conditions, while A. cordata showed higher resistance to variable weather conditions, high photosynthetic efficiency, and long foliage lifespan. Full article

Electrochemical water splitting provides a sustainable method for hydrogen production. However, the primary challenge for electrochemical hydrogen generation is the high cost and limited availability of platinum-based noble-metal catalysts. Transition-metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction (HER) in alkaline electrolytes. Nonetheless, the identification of active sites and the underlying catalytic mechanism remain elusive. In this study, phosphorus-doped nickel sulfide has been successfully synthesized, demonstrating enhanced activity for alkaline HER. Investigating surface chemistry through X-ray photoelectron spectroscopy (XPS), depth profiling revealed that surface restructuring occurs during the HER process. The presence of phosphorus significantly influences this transformation, promoting the formation of a novel active Ni-O layer. This Ni-O layer is responsible for enhanced catalytic activity by upshifting the d-band center and increasing the density of states near the Fermi level, along with expanding the electrochemical surface area. This study reveals that the surface restructuring of transition-metal sulfides is highly tied to the electronic structure of the parent catalysts. Gaining a comprehensive understanding of this surface restructuring is essential for predicting and exploring more efficient non-precious transition-metal sulfide electrocatalysts. Full article

Fe₂B is a potentially promising electrocatalyst for the oxygen evolution reaction (OER) due to its excellent electronic conductivity, which is superior to that of traditional oxide catalysts. However, the activity of Fe₂B is still not satisfactory. In this study, meta-stable microstructure stacking faults (SFs) were incorporated into Fe₂B through a one-step high-pressure and high-temperature (HPHT) method. Pressure suppressed atomic diffusion but formed SFs when the grain grew. Fe₂B with SFs exhibited remarkable OER activity, with low overpotential values of only 269 and 344 mV required to reach current densities of 10 and 100 mA cm⁻², respectively; because of the presence of SFs, the overpotential for the OER was reduced to only 67.7% of that of Fe₂B without SFs at 10 mA cm⁻². Theoretical and experimental investigations confirmed that these SFs regulate the d-band center of Fe₂B toward the Fermi level, optimizing the catalytic site activity. Furthermore, SFs reduced the charge transfer between Fe atoms and boron (B) atoms, increasing the number of free electrons in the structure and thereby increasing conductivity. Finally, this study suggests a strategy to construct microstructures in crystals, providing new insights into designing excellent catalysts via microstructure engineering. Full article

Hydrogenation and dehydrogenation reactions are fundamental in chemistry and essential for all living organisms. We employ density functional theory (DFT) to understand the reaction mechanism of the oxidative dehydrogenation (ODH) of the pyridyl-amine complex [Fe^IIIL³]³⁺ (L³, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanonane) to the mono-imine complex [Fe^IIL⁴]²⁺ (L⁴, 1,9-bis(2′-pyridyl)-5-[(ethoxy-2″-pyridyl)methyl]-2,5,8-triazanon-1-ene) in the presence of dioxygen. The nitrogen radical [Fe^IIL³_N8•]²⁺, formed by deprotonation of [Fe^IIIL³]³⁺, plays a crucial role in the reaction mechanism derived from kinetic studies. O₂ acts as an oxidant and is converted to H₂O. Experiments with the deuterated ligand L³ reveal a primary C-H kinetic isotope effect, k^CH/k^CD = 2.30, suggesting C-H bond cleavage as the rate-determining step. The DFT calculations show that (i) ³O₂ abstracts a hydrogen atom from the α-pyridine aliphatic C-H moiety, introducing a double bond regio-selectively at the C₇N₈ position, via the hydrogen atom transfer (HAT) mechanism, (ii) O₂ does not coordinate to the iron center to generate a high-valent Fe oxo species observed in enzymes and biomimetic complexes, and (iii) the experimental activation parameters (ΔH^≠ = 20.38 kcal mol⁻¹, ΔS^≠ = −0.018 kcal mol⁻¹ K⁻¹) fall within in the range of values reported for HAT reactions and align well with the computational results for the activated complex [Fe^IIL³_N8•]²⁺···³O₂. Full article

The systematic design of ruthenium-based electrocatalysts for the hydrogen evolution reaction (HER) is crucial for sustainable hydrogen production via electrocatalytic water splitting in an alkaline medium. However, the mismatch between water dissociation and hydrogen adsorption kinetics limits its HER activity. Herein, we present a phase engineering-modulated strategy to develop an ultrasmall ZnRu bimetallic metal–organic framework electrocatalyst (ZnRu₃₀-ZIF) for catalyzing alkaline HER. Experimental results and density functional theory calculations indicate that the incorporation of Ru atoms modifies the crystal structure of the ZIF-8 phase, resulting in enlarged facet spacing and smaller nanocrystals (45 ± 3 nm). This optimization of the crystal structure regulates the electronic properties of the ZnRu₃₀-ZIF, forming a higher d-band center (−5.91 eV), which reduces the water dissociation energy (0.19 eV) and facilitates hydrogen desorption (ΔG_H* = 1.09 eV). The prepared ZnRu₃₀-ZIF exhibits a low overpotential of 48 mV at 10 mA cm⁻² and an excellent mass activity of 2.9 A mg_Ru⁻¹ at 0.1 V (vs. RHE). This work establishes a phase-engineering strategy for the preparation of high-performance Ru-based MOF electrocatalysts for HER. Full article

This work presents the results of a study on the influence of fillers on the neutron absorption capacity of materials made from ultra-high molecular weight polyethylene (UHMWPE). Composite materials based on UHMWPE were obtained using gas-flame technology with the addition of powdered UHMWPE fillers (H₃BO₃, WC, and PbO). A radiation cassette has been developed and constructed for conducting studies on the neutron absorption capacity of the material, allowing for the placement of a sample with activation indicators. Samples of UHMWPE with fillers were irradiated at different doses on the unique research reactor IVG-1M, located at the National Nuclear Center of the Republic of Kazakhstan in the city of Kurchatov. The reaction rate of ⁶³Cu (n, g), ⁶⁴Cu and ⁵⁸Ni (n, p)⁵⁸Co on activation indicators and neutron flux density at the sample location were determined. Neutron-physical and thermal-physical calculations were performed in order to determine their characteristics. The structure and phase state of UHMWPE with fillers were studied before and after irradiation. Full article

Coating conductive nanoparticles onto the surface of hollow glass microspheres (HGMs) is essential for broadening their applications. However, the low density and high specific surface area of HGM powders, along with the thin walls of the cavity shells and poor surface adhesion, pose challenges for the uniform attachment of functional particles. In this study, we developed a novel integrated process that combines flotation, hydroxylation, and amination pretreatment for HGMs with in situ surface polymerization to achieve a uniform coating of polypyrrole (PPy) on the surface of HGMs. We explored the corresponding growth process and coating mechanism. Our findings indicate that the amount of coating, particle size, and uniformity of PPy on the surface of HGMs are significantly influenced by the pretreatment and the in situ polymerization time, as well as the microspheres/pyrrole feedstock ratio. The in situ polymerization on the surface of HGMs resulted in a uniform encapsulation of spherical PPy, with the average particle size of PPy-coated HGMs (PPy@HGMs) increasing by 14.60% compared to the original HGMs. The elemental nitrogen in the PPy@HGMs primarily exists in the form of C-N and N-H bonds. This study demonstrates that the surface functional groups of HGMs engage in chemical bonding and interactions with PPy molecules. Mechanistic analysis reveals that the hydroxyl and amino groups enriched on the surface of the pretreated HGMs serve as activation centers, facilitating the uniform enrichment of pyrrole monomers and promoting chain growth polymerization of the conjugated chain through nucleophilic and electrophilic interactions with the subamino groups in the pyrrole ring. Additionally, the reaction between the Lewis acid properties of PPy and the Lewis-type electron-donating amino groups in KH550 fosters strong bonding and the formation of a robust interface. Full article