Search Results (371)

Ammonia is indispensable to the fertilizer and chemical industries, yet its manufacture still relies predominantly on the energy-intensive Haber–Bosch process operated at 400–500 °C and 150–250 bar, with a substantial carbon footprint. Single-atom catalysts (SACs) and sub-nanometric clusters have recently emerged as promising alternatives for thermocatalytic ammonia synthesis under milder conditions because they maximize metal utilization and enable precise control of the active site environment. This review first summarizes how the transition from conventional Fe and Ru nanoparticles to isolated or few-atom sites fundamentally alters the kinetic landscape, favoring associative N₂ activation pathways that lower apparent activation energies and alleviate H₂ poisoning. We then discuss Ru-based SACs and SAAs supported on zeolites, carbons, ceria, and MXenes, highlighting how strong metal–support and promoter interactions, tandem single-atom/nanoparticle motifs, and alloying strategies tune N₂ and H₂ binding to deliver high NH₃ productivities at 200–400 °C and ≤30 bar. In parallel, we review emerging non-noble systems based on Fe and Co, including high-loading Fe–N₄ sites prepared via MOF-derived post-metal-replacement routes and Co single atoms or Co₂ clusters on N-doped carbons, which already rival or surpass Ru benchmarks under similar conditions. Collectively, these studies show that tailoring the number of atom metal sites, coordination, and support polarity around isolated metal sites provides a useful tool to mitigate some aspects of volcano and scaling-relation limitations, indicating that SACs could contribute to low-temperature ammonia synthesis when combined with appropriate process design. Full article

We report the synthesis of Fe/N/C ORR electrocatalysts by an original collinear CO₂ laser pyrolysis of liquid aerosol droplets in various configurations and compared them to a catalyst synthesized in the classical perpendicular one. While the precursors were always injected at the bottom side of the reactor, two collinear configurations of the laser entry into the reactor are considered: by the Top Side (T.S.) or by the Bottom Side (B.S.). The two corresponding catalysts sets show significant different ORR performances. An in-depth XPS analysis and fitting of the N1s spectra allowed for drawing the ORR performance as a function of FeN_x sites components. An original approach considering the energy delivered to a quantity of precursors in J.g⁻¹, linked to the flame temperature feature, evidenced very different conditions for perpendicular CO₂ laser pyrolysis and each of the two collinear configurations. This mass-weighted energy delivered in the classical perpendicular configuration is too low to allow for the formation of FeN_x sites and the resulting ORR performance is extremely poor, suggesting a marginal role of nitrogen species without interaction with iron atoms. In contrast, the delivered mass-weighted energies are sufficient in both collinear configurations to produce FeN_x sites. The ORR performance for catalysts produced in these both configurations is positively correlated with the amount of energy deposited on the precursors. The ORR performance in the T.S. laser configuration is positively correlated to the amount of FeN_x sites. The best performing catalysts obtained in the B.S. configuration show an opposite variation. These trends, and the ORR performance degradation of B.S. catalysts under prolonged chronoamperometry are discussed in light of the effect of temperature on the formation of the various kind of FeN_x sites. A tentative explanation is given, considering that N1s XPS fitting with a single FeN_x component may hinder the fact that Pyridinic sites components may contain a part of FeN_x sites, as suggested by theoretical calculation from the literature. The best catalysts obtained in this work by collinear configuration show similar performances to those obtained by double stage perpendicular pyrolysis previously reported with an ORR onset potential of ~860 mV. Full article

Single-atom nanozymes (SANs) with atomically dispersed metal sites show great potential in small biomolecule detection. This review first summarizes SAN synthesis (wet chemistry, atomic layer deposition, etc.), structural features (tunable coordination, metal-carrier interactions), and catalytic mechanisms (synergistic effects, d-band modulation). Afterwards, this review focuses on the applications of SANs in detecting small biomolecules, including glucose, glutathione, uric acid, ascorbic acid, hydrogen peroxide, and dopamine via colorimetry, fluorescence, and electrochemistry. Challenges such as matrix interference and stability, along with future directions in flexible electronics and clinical translation, are discussed, aiming to advance SAN-based detection technologies. Full article

Metal-chalcogenide compounds with perovskite-type compositions have drawn increasing attention for their optical properties for solar energy conversion. Herein, a new α-type polymorph of the ternary sulfide SrHfS₃ is described, crystallizing in the NH₄CdCl₃ structure type. The yellow-colored plate-shaped crystals were synthesized at 1173 K using an elemental tin flux in an evacuated sealed tube. Its crystal structure was characterized at room temperature using single crystal X-ray diffraction to form in the orthorhombic Pnma space group, with the refined cell parameters of a = 8.5041(4) Å, b = 3.8004(2) Å, c = 13.8935(6) Å, and V = 449.02(4) ų. The structure comprises five independent crystallographic sites, having one Sr, one Hf, and three S sites. The structure can be described as containing one-dimensional chains of distorted HfS₆ octahedra extending down the b-axis to form ${\displaystyle \genfrac{}{}{0pt}{}{1}{\infty }}[$HfS₃]²⁻ strips of edge-sharing octahedra. The Sr atoms act as charge-balancing space fillers in the structure. High-purity bulk samples of α-SrHfS₃ could be prepared for measurement of its bandgap by optical diffuse-reflectance spectroscopy, showing a direct bandgap of 2.1(1) eV. Results of electronic structure calculations are consistent with this bandgap and type. The conduction and valence band edges stem from the respective empty Hf d-orbitals and the filled S p-orbital states. In summary, crystal growth of the α-type polymorph of SrHfS₃ has been demonstrated using a Sn flux approach, which can facilitate future broader synthetic explorations at lower temperatures. Full article

Catalytic ozonation often suffers from a low ozone utilization rate and incomplete mineralization of organic pollutants. To address these challenges, we designed and prepared a novel catalyst via a one-step thermal polymerization method, anchoring single-atom manganese on a glucose-derived carbon network-modified C₃N₅ framework (Mn/C-C₃N₅). Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) on an FEI Titan Themis Z microscope confirmed the atomic dispersion of Mn sites, while Raman spectroscopy using a Renishaw inVia Reflex laser micro-Raman spectrometer verified the successful incorporation of a graphitic carbon network within the C₃N₅ matrix. Moreover, electrochemical analyses, including electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) performed on a Bio-Logic SP-150 electrochemical workstation, demonstrated that the integration of the conductive carbon matrix substantially enhanced the interfacial charge transfer capability. The optimized Mn/C-C₃N₅ catalyst demonstrated exceptional performance in phenol mineralization, achieving a 97% total organic carbon (TOC) removal within 60 min, a remarkable improvement compared to pristine C₃N₅ (30%). Furthermore, the catalyst exhibited excellent operational stability, preserving more than 95% of its original activity over five repeated runs. Mechanistic investigations, including electron paramagnetic resonance (EPR) spectroscopy and radical quenching experiments, revealed that the Mn/C-C₃N₅ system accelerated the generation of multiple oxidizing radicals (•O₂⁻, ¹O₂, and •OH), with •OH identified as the predominant reactive species responsible for complete mineralization. This work establishes an integrated catalytic platform and provides fundamental insights into electronic structure modulation for designing advanced oxidation catalysts. Full article

Eight H-bonded salts of arsenic acid and nitrogen bases (2,4,6-trimethylpyridine, pyridine-2,6-diamine, pyridin-4-ol, 4-methoxypyridine, 4-methoxyaniline, 1,3,5-triazine-2,4,6-triamine, diethylamine and N¹,N¹,N²,N²-tetraethylethane-1,2-diamine) were studied in the solid state by single crystal X-ray diffraction technique and DFT calculations. In all cases quite short (≤2.65 Å) OHO bonds were found in the self-assembled supramolecular ribbons or 2D networks of dihydrogen arsenates, constituting a repertoire of five different H-bonding patterns (motifs). The electron localization function maps revealed the spots of the nucleophilic sites on oxygen atoms that determine the preferable directions for H-bonding of H₂AsO₄⁻ anions observed in the crystal packing. Analysis of the electrostatic potential maps for isolated species has demonstrated that upon H-bonding between H₂AsO₄⁻ anions and protonated nitrogen bases, NH⁺⋯⁻OAsO(OH)₂, the redistribution of electron density within the anion provides otherwise virtually non-existent electrophilic sites on hydrogen atoms, which balances the Coulomb repulsion and allows for the anion⋯anion pairing within the crystal. The topological analysis of the calculated crystalline electron density after relaxation of the hydrogen atoms’ positions was used to classify the OHO bonds as moderately strong ones (with an interaction energy up to 65 kJ/mol) and revealed a high degree of ionicity of molecular moieties within ion pairs (with an absolute charge up to 0.87 e). For the strongest OHO and NHO bonds, the noticeable covalent character was shown by using the crystal orbital Hamiltonian population analysis. Full article

Atomic oxygen in low Earth orbit erodes polyimide, increasing surface roughness and degrading performance. The reactive species scission polymer chains and remove surface material, exposing fresh sites that accelerate further attack and disrupt thermal, electrical, and mechanical functions. In this paper, we evaluate nanoscale reinforcements of polyimide with graphene and metal oxides under controlled atomic oxygen exposure equivalent to 145 days at a 550 km orbit. Graphene with a thickness of few nanometers and particle size less than 2 µm, and metal oxides zirconia, zinc oxide, and titania with particle size less than 100 nm were investigated. Hybrids containing graphene plus metal oxide at a 1:1 ratio and a total loading of 0.75 wt% increased roughness relative to neat polyimide, with graphene-zirconia showing a rise of +121 percent, graphene-zinc oxide +10 percent, and graphene–titania +20 percent. The behavior is consistent with agglomeration, incomplete dispersion, and interfacial mismatch that hinder uniform blocking of atomic oxygen and limit formation of protective oxygenated groups. In contrast, single-filler composites at 0.75 wt% reduced average roughness, with graphene lowering S_a by about 59 percent, zirconia by about 51%, titania by about 47%, and zinc oxide by about 47%. Varying graphene loading from 0.25 to 0.75 wt% diminished erosive features at the higher end, but atomic force microscopy revealed isolated tall peaks at 0.75 wt%, indicating localized restacking or agglomeration. Mechanical testing of graphene-reinforced coatings on fiberglass showed a similar trade-off, with tensile strength around 23 MPa and peak load greater than 50 N at 0.5 wt% compared to about 21 MPa and 40 N at 0.75 wt%, while strain at break remained comparable. These results define practical limits for nanoparticle reinforcement in polyimide, linking filler identity, loading, and dispersion quality to atomic oxygen response and sustained function in LEO. Full article

This paper investigates the different relaxation channels of a single symmetric top NH₃ and a spherical top CH₄ molecule trapped at low temperature in a clathrate hydrate nano-cage in the infrared absorption domain of their vibrational degrees of freedom. The approach utilizes the Born–Oppenheimer approximation and the extended site inclusion model applied to CO₂ in a previous work, which was based on pairwise atom–atom effective interaction potentials. The calculations show that trapping the methane or ammonia molecule is energetically more favorable in a type sI clathrate structure than in an sII one, and entropic considerations show that methane can be released much more easily than ammonia from clathrate hydrate nano-cages. In the small (s) and large (l) nano-cages with the sI structure, the CH₄ molecule exhibits a more or less perturbed rotational motion, while the NH₃ molecule shows a strongly hindered orientational motion that tends to a three-dimension librational motion (oscillation motion) around its orientational equilibrium configuration. The calculated orientational energy level schemes are quite different from those of the molecular free rotation. In the static field inside the cage, degenerate ${\nu }_3$ and ${\nu }_4$ vibrational modes of methane and ammonia molecules are shifted and split. Moreover, for ammonia molecules, the ${\nu }_1$ and ${\nu }_2$ modes are shifted, and the inversion motion is no longer allowed. The non-radiative and radiative relaxation channels of CH₄, NH₃ and CO₂ in clathrate nano-cages are discussed with reference to the matrix isolation spectroscopic results. Upon laser excitation, then, from the energy levels calculated for the different degrees of freedom, NH₃ and CO₂ are expected to fluoresce, while for CH₄, non-radiative relaxation should lead to evaporation at the surface of clathrates. Experimental setups are suggested to localize and study these species underneath ice surfaces on distant planets or planetesimals from mobile detectors such as drones or CubeSats equipped with appropriate laser sources and telescopes with 2D imaging detectors. Full article

For Co-N-C materials prepared under high-temperature calcination conditions, the formation of Co nanoparticles occurs when the metal loading exceeds 2%. Typically, CoNx is regarded as the primary active site of the catalyst, while Co nanoparticles are considered to possess limited catalytic activity. Consequently, within Co-N-C materials, Co nanoparticles are often likened to ‘ballast stone’ in a catalyst. In the model reaction of formic acid dehydrogenation, we incorporated boron into the precursor, thereby enhancing the electronic metal-support interactions (EMSI) between Co nanoparticles and carbon carriers. Consequently, this modification resulted in a catalytic performance of Co nanoparticles that was comparable to that of Co single-atom catalysts (SACs). Full article

Heteroatom functionalization of graphene is an effective strategy for designing more sustainable lithium-ion battery electrodes, as it can tune both interfacial adhesion and the electronic features of the carbon lattice. In this work, we investigated the interfacial compatibility between three graphene sheets—pristine graphene, graphene doped with one nitrogen atom (Graphene–N), and graphene doped with one sulfur atom (Graphene–S)—and three lignocellulosic binders (carboxymethylcellulose (CMC); coniferyl alcohol (LcnA); and sinapyl alcohol (LsiA)) using density functional theory (DFT). Geometries were optimized using CAM-B3LYP and M06-2X in combination with the LANL2DZ basis set, while ωB97X-D/LANL2DZ was employed for dispersion-consistent single-point refinements. The computed adsorption energies indicate that all binder–surface combinations are thermodynamically favorable within the present finite-model framework (ΔE_int ≈ −22.6 to −31.1 kcal·mol⁻¹), with LSiA consistently showing the strongest stabilization across surfaces. Nitrogen doping produces a modest but systematic strengthening of adsorption relative to pristine graphene for all binders and is accompanied by electronic signatures consistent with localized donor/basic sites while preserving the delocalized π framework. In contrast, sulfur doping yields a more binder-dependent response: it maintains strong stabilization for LSiA but weakens LCnA relative to pristine/N-doped sheets, consistent with an S-induced local distortion/polarizability pattern that can alter optimal π–π registry depending on the adsorption geometry. A combined interpretation of adsorption energies, electronic descriptors (including ΔE_gap as a model-dependent HOMO–LUMO separation), and topological analyses (AIM, ELF, LOL, and MEP) supports that Graphene–N provides the best overall balance between electronic continuity and chemically active interfacial sites, whereas Graphene–S can enhance localized anchoring but introduces more heterogeneous, lone-pair–dominated domains that may partially perturb electronic connectivity. Full article

The widespread occurrence of pharmaceutical contaminants in aquatic environments poses significant risks to ecosystems and public health, necessitating the development of efficient and sustainable treatment technologies. Herein, a visible-light (VL)–active zinc single-atom catalyst supported on biochar (SAZn@BC) was synthesized via pyrolysis and applied for the degradation of ibuprofen (IBP), sulfamethoxazole (SMX), trimethoprim (TMP), and carbamazepine (CBZ) in water. Structural characterization confirmed the presence of g-C₃N₄ domains, abundant oxygen-containing functional groups, and atomically dispersed Zn sites with a Zn–N₄ coordination environment. Under VL irradiation, SAZn@BC achieved degradation efficiencies of 43.9%, 64.4%, and 61.9% for IBP, SMX, and TMP, respectively, within 30 min, while CBZ exhibited limited removal. Mechanistic investigations combining quenching experiments, electrochemical analyses, and X-ray photoelectron spectroscopy revealed that superoxide and hydroperoxyl radicals were the dominant reactive oxygen species, with hydroxyl radicals and singlet oxygen contributing to a lesser extent. In addition, a nonradical pathway involving direct interfacial electron transfer between oxygen functional groups on the biochar support and pharmaceutical molecules played a critical role, mediated by single-atom Zn sites and enhanced under VL irradiation. These findings demonstrate that SAZn@BC enables synergistic radical and nonradical pathways for pharmaceutical degradation and represents a promising strategy for water treatment applications. Full article

Solar-driven hydrogen production via photocatalytic water splitting represents a promising route toward sustainable and low-carbon energy systems. Among emerging photocatalysts, porphyrin-based framework materials, specifically porphyrinic metal–organic frameworks (PMOFs) and porphyrinic covalent organic frameworks (PCOFs), have attracted increasing attention owing to their strong visible-light absorption, tunable electronic structures, permanent porosity, and well-defined catalytic architectures. In these systems, porphyrins function as versatile photosensitizers whose photophysical properties can be precisely tailored through metalation, peripheral functionalization, and integration into ordered frameworks. This review provides a comprehensive, design-oriented overview of recent advances in PMOFs, PCOFs, and hybrid porphyrinic architectures for photocatalytic H₂ evolution. We discuss key structure–activity relationships governing light harvesting, charge separation, and hydrogen evolution kinetics, with particular emphasis on the roles of porphyrin metal centers, secondary building units, linker functionalization, framework morphology, and cocatalyst integration. Furthermore, we highlight how heterojunction engineering through coupling porphyrinic frameworks with inorganic semiconductors, metal sulfides, or single-atom catalytic sites can overcome intrinsic limitations related to charge recombination and limited spectral response. Current challenges, including long-term stability, reliance on noble metals, and scalability, are critically assessed. Finally, future perspectives are outlined, emphasizing rational molecular design, earth-abundant catalytic motifs, advanced hybrid architectures, and data-driven approaches as key directions for translating porphyrinic frameworks into practical photocatalytic hydrogen-generation technologies. Full article

Metallaphotoredox catalysis merges the powerful bond-forming abilities of transition metal catalysis with unique electron or energy transfer pathways accessible in photoexcited states, injecting new vitality into organic synthesis. However, most transition metal catalysts cannot be excited by visible light. Thus, prevalent metallaphotoredox catalytic systems require dual catalysts: a transition metal catalyst and a separate photosensitizer. This leads to inefficient electron transfer between these two low-concentration catalytic species, which often limits overall photocatalytic performance. Single-atom site catalysts (SASCs) offer a promising solution, wherein isolated and quasi-homogeneous transition metal sites are anchored on heterogeneous supports. When semiconductors are employed as the support, the photosensitive unit and transition metal catalytic site can be integrated into one system. This integration switches the electron transfer mode from intermolecular to intramolecular, thereby significantly enhancing photocatalytic efficiency. Furthermore, such heterogeneous catalysts are easier to separate and reuse. This review summarizes recent advances in the application of SASCs for photocatalytic organic synthesis, with a particular focus on elucidating structure–activity relationships of the single-atom sites. Full article

Electrochemical CO₂ reduction (CO₂RR) is a promising route to transform a major greenhouse gas into value-added fuels and chemicals. However, its deployment is still hindered by the sluggish activation of CO₂, poor selectivity toward multielectron products, and competition with the hydrogen evolution reaction (HER). Single-atom catalysts (SACs) have emerged as powerful materials to address these challenges because they combine maximal metal utilization with well-defined coordination environments whose electronic structure can be precisely tuned through metal–support interactions. This minireview summarizes current understanding of how structural, electronic, and chemical features of SAC supports (e.g., porosity, heteroatom doping, vacancies, and surface functionalization) govern the adsorption and conversion of key CO₂RR intermediates and thus control product distributions from CO to CH₄, CH₃OH and C₂⁺ species. Particular emphasis is placed on selectivity descriptors (e.g., coordination number, d-band position, binding energies of *COOH and *OCHO) and on rational design strategies that exploit curvature, microenvironment engineering, and electronic metal–support interactions to direct the reaction along desired pathways. Representative SAC systems based primarily on N-doped carbons, complemented by selected examples on oxides and MXenes are discussed in terms of Faradaic efficiency (FE), current density and operational stability under practically relevant conditions. Finally, the review highlights remaining bottlenecks and outlines future directions, including operando spectroscopy and data-driven analysis of dynamic single-site ensembles, machine-learning-assisted DFT screening, scalable mechanochemical synthesis, and integration of SACs into industrially viable electrolyzers for carbon-neutral chemical production. Full article

The thermodynamic instability and relatively low mechanical strength of γ/γ′ phase boundaries in Ni-based single-crystal superalloys compromise the service safety of these materials. The interfacial segregation behavior of alloying elements is expected to enhance the thermodynamic stability and mechanical strength of γ/γ′ phase boundaries. In the present research, first-principles computations grounded in density functional theory were performed to examine the unclarified cosegregation characteristics of W-Re/Cr solutes at the γ-Ni/γ′-Ni₃Al phase boundary, as well as the impacts of such cosegregation on interfacial formation heat and Griffith fracture work. The results indicated that Re and Cr atoms tend to segregate preferentially at the γ-L₁-3.52-cp site within the W-alloyed phase boundary. This phenomenon can be attributed to the attractive interactions between W and Re/Cr, along with the fact that this site exhibits the most negative segregation energy. The thermodynamic stability of W-Re and W-Cr cosegregated phase boundaries is significantly enhanced, being much higher than that of clean or W-segregated phase boundaries, which is ascribed to deeper pseudogaps at the Fermi level. Notably, the preferred fracture path remains in region-1 after cosegregation, as directly evidenced by its lower Griffith fracture work compared to region-2. This disparity is rationalized by charge density analysis, which reveals a pronounced charge accumulation and consequently stronger bonding in region-2. Our results may provide atomistic insights into the solute cosegregation behaviors and their interfacial strengthening and stabilizing effects, and also the interfacial composition manipulation of Ni-based single-crystal superalloys. Full article