Unveiling the Morphology of Carbon-Supported Ru Nanoparticles by Multiscale Modeling.

Simulating the behavior of metal nanoparticles on supports is crucial for boosting their catalytic performance and various nanotechnology applications; however, such simulations are limited by the conflicts between accuracy and efficiency. Herein, we introduce a multiscale modeling strategy to unveil the morphology of Ru supported on pristine and N-doped graphene. Our multiscale modeling started with the electronic structures of a supported Ru single atom, revealing the strong metal-support interaction around pyridinic nitrogen sites. To determine the stable configurations of Ru2-13 clusters on three different graphene supports, global energy minimum searches were performed. The sintering of the global minimum Ru13 clusters on supports was further simulated by ab initio molecular dynamics (AIMD). The AIMD data set was then collected for deep potential molecular dynamics to study the melting of Ru nanoparticles. This study presents comprehensive descriptions of carbon-supported Ru and develops modeling approaches that bridge different scales and can be applied to various supported nanoparticle systems.

Thiacalix[4]arene-Protected Silver Nanoclusters Encapsulating Different Two-Electron Superatom Oligomers.

The subvalent silver kernel represents the nascent state of silver cluster formation, yet the growth mechanism has long been elusive. Herein, two silver nanoclusters (Ag30 and Ag34) coprotected by TC4A4- (H4TC4A = p-tert-butylthiacalix[4]arene) and TBPMT- (TBPMTH = 4-tert-butylbenzenemethanethiol) containing 6e and 4e silver kernels are synthesized and characterized. The trimer of the 2e superatom Ag14 kernel in Ag30 is built from a central Ag6 octahedron sandwiched by two orthogonally oriented Ag5 trigonal bipyramids through sharing vertexes, whereas a double-octahedral Ag10 kernel in Ag34 is a dimer of 2e superatoms. They manifest disparate polyhedron fusion growth patterns at the beginning of the silver cluster formation. Their excellent solution stabilities are contributed by the multisite and multidentate coordination fashion of TC4A4- and the special valence electron structures. This work demonstrates the precise control of silver kernel growth by the solvent strategy and lays a foundation for silver nanocluster application in photothermal conversion.

In silico analysis of potential inhibitors for breast cancer targeting 17beta-hydroxysteroid dehydrogenase type 1 (17beta-HSD1) catalyses.

Breast cancer (BC) is still one of the major issues in world health, especially for women, which necessitates innovative therapeutic strategies. In this study, we investigated the efficacy of retinoic acid derivatives as inhibitors of 17beta-hydroxysteroid dehydrogenase type 1 (17beta-HSD1), which plays a crucial role in the biosynthesis and metabolism of oestrogen and thereby influences the progression of BC and, the main objective of this investigation is to identify the possible drug candidate against BC through computational drug design approach including PASS prediction, molecular docking, ADMET profiling, molecular dynamics simulations (MD) and density functional theory (DFT) calculations. The result has reported that total eight derivatives with high binding affinity and promising pharmacokinetic properties among 115 derivatives. In particular, ligands 04 and 07 exhibited a higher binding affinity with values of -9.9 kcal/mol and -9.1 kcal/mol, respectively, than the standard drug epirubicin hydrochloride, which had a binding affinity of -8.2 kcal/mol. The stability of the ligand-protein complexes was further confirmed by MD simulations over a 100-ns trajectory, which included assessments of hydrogen bonds, root mean square deviation (RMSD), root mean square Fluctuation (RMSF), dynamic cross-correlation matric (DCCM) and principal component analysis. The study emphasizes the need for experimental validation to confirm the therapeutic utility of these compounds. This study enhances the computational search for new BC drugs and establishes a solid foundation for subsequent experimental and clinical research.

DFT Guided Design and Preparation of Quasi-Nanocrystalline Hf-La2O3 Cathode with Unprecedented Thermal Emission Performance.

With the guidance of density functional theory (DFT), a high-performance hafnium (Hf) cathode for an air/water vapor plasma torch is designed and the concepts and principles for high performance are elucidated. A quasi-nanocrystalline hexagonal close-packed (HCP) Hf-La2O3 cathode based on these design principles is successfully fabricated via a powder metallurgy route. Under identical voltage and temperature conditions, the thermal emission current density of this quasi-nanocrystalline Hf-La2O3 cathode is ≈20 times greater than that of conventional Hf cathodes. Additionally, its cathodic lifespan is significantly extended. Quasi-nanocrystalline Hf-La2O3 products are manufactured into cathode devices with standard dimensions. This fabrication process is straightforward, requires minimal doped oxides, and is cost-effective. Consequently, the approach offers substantial performance enhancements over traditional Hf melting methods without incurring significantly additional costs.

3D Fast Sodium Transport Network of MoS2 Endowed by Coupling of Sulfur Vacancies and Sn Doping for Outstanding Sodium Storage.

A sulfur vacancy-rich, Sn-doped as well as carbon-coated MoS2 composite (Vs-SMS@C) is rationally synthesized via a simple hydrothermal method combined with ball-milling reduction, which enhances the sodium storage performance. Benefiting from the 3D fast Na+ transport network composed of the defective carbon coating, Mo─S─C bonds, enlarged interlayer spacing, S-vacancies, and lattice distortion in the composite, the Na+ storage kinetics is significantly accelerated. As expected, Vs-SMS@C releases an ultrahigh reversible capacity of 1089 mAh g-1 at 0.1 A g-1, higher than the theoretical capacity. It delivers a satisfactory capacity of 463 mAh g-1 at a high current density of 10 A g-1, which is the state-of-the-art rate capability compared to other MoS2 based sodium ion battery anodes to the knowledge. Moreover, a super long-term cycle stability is achieved by Vs-SMS@C, which keeps 91.6% of the initial capacity after 3000 cycles under the current density of 5 A g-1 in the voltage of 0.3-3.0 V. The sodium storage mechanism of Vs-SMS@C is investigated by employing electrochemical methods and ex situ techniques. The synergistic effect between S-vacancies and doped-Sn is evidenced by DFT calculations. This work opens new ideas for seeking excellent metal sulfide anodes.

Designing a Novel C3-Fe-N Interface Local Coordination Microenvironment for Efficient Electrocatalytic Water Splitting.

Developing single-atomic electrocatalysts (SACs) with high activity and stability for electrocatalytic water-splitting has been challenging. Moreover, the practical utilization of SACs is still far from meeting the the theoretical prediction. Herein a facile and easy scale-up fabrication method is proposed for designing a novel carbon-iron-nitrogen (C-Fe-N) electrocatalyst with a single atom electron bridge (C-Fe-N SAEBs), which exhibits lower overpotential and impedance than previously reported electrocatalysts. 0.8-C-Fe-N SAEBs exhibits significant activity and excellent stability in the bi-functional decomposition of water. The excellent performance of the C-Fe-N SAEBs electrocatalyst can be attributed to the strong coupling effect at the interface owing to the formation of a single atom C3-Fe-N local coordination microenvironment at the interface, which enhance the exposure of active sites and charge transfer, and reduced the adsorption energy barrier of intermediates. Theoretical calculation and synchrotron radiation analysis are performed to understand the mechanistic insights behind the experimental results. The results reveal that the active C3-Fe-N local coordination microenvironment at the interface not only improves water-splitting behavior but also provides a deeper understanding of local-interface geometry/electronic structure for improving the electrocatalytic activity. Thus, the proposed electrocatalyst, as well as the mechanistic insights into its properties, presents a significant stride toward practical application.

Bimetallic Sulfide Hollow Nanocubes Heterostructure Promotes Dual Coupling of Conversion and Alloying/Dealloying Reactions to Achieve Durable Potassium-Ion Battery Anode.

Conversion and alloying-type transitional metal sulfides have attracted significant interests as anodes for Potassium-ion batteries (PIBs) and Sodium-ion batteries (SIBs) due to their high theoretical capacities and low cost. However, the poor conductivity, structural pulverization, and high-volume expansions greatly limit the performance. Herein, Co1-xS/ZnS hollow nanocube-like heterostructure decorated on reduced graphene oxide (Co1-xS/ZnS@rGO) composite is fabricated through convenient hydrothermal and post-heat vulcanization techniques. This unique composite can provide a more stable conductive network and shorten the diffusion length of ions, which exhibits a remarkable initial charge capacity of 638.5 mA h g-1 at 0.1 A g-1 for SIBs and 606 mA h g-1 at 0.1 A g-1 for PIBs, respectively; It is worth noting that the composite presents remarkable long stable cycle performance in PIBs, which initially delivered 274 mA h g-1 and sustained the charge capacity up to 245 mA h g-1 at high current density of 1 A g-1 after 2000 cycles. A series of in situ/ex situ detections and first principle calculations further validate the high potassium ions adsorption ability of Co1-xS/ZnS anode materials with high diffusion kinetics. This work will accelerate the fundamental construction of bimetallic sulfide hollow nanocubes heterostructure electrodes for energy storage applications.

DFT Predirected Molecular Engineering Design of Donor-Acceptor Structured g-C3N4 for Efficient Photocatalytic Tetracycline Abatement.

The photocatalytic environmental decontamination ability of carbon nitride (g-C3N4, CN) typically suffers from their inherent structural defects, causing rapid recombination of photogenerated carriers. Conjugating CN with tailored donor-acceptor (D-A) units to counteract this problem through electronic restructuring becomes a feasible strategy, where confirmation by density functional theory (DFT) calculations becomes indispensable. Herein, DFT is employed to predirect the copolymerization modification of CN by benzene derivatives, screening benzaldehyde as the optimal electron-donating candidate for the construction of reoriented intramolecular charge transfer path. Experimental characterization and testing corroborate the formation of a narrowed bandgap as well as high photoinduced carrier separation. Consequently, the optimal BzCN-2 exhibited superior photocatalytic capacity in application for tetracycline hydrochloride degradation, with 3.73 times higher than that of CN. Besides, the BzCN-2-based photocatalytic system is determined to have a toxicity-mitigating effect on TC removal via T.E.S.T and prefers the removal of dissociable TC2- species under partial alkalinity. This work provides insight into DFT guidance for the design of D-A conjugated polymer and its application scenarios in photocatalytic decontamination.

FeNiCo|MnGaOx Heterostructure Nanoparticles as Bifunctional Electrocatalyst for Zn-Air Batteries.

Driven by the pressing demand for stable energy systems, zinc-air batteries (ZABs) have emerged as crucial energy storage solutions. However, the quest for cost-effective catalysts to enhance vital oxygen evolution and reduction reactions remains challenging. FeNiCo|MnGaOx heterostructure nanoparticles on carbon nanotubes (CNTs) are synthesized using liquid-phase reduction and H2 calcination approach. Compared to its component, such FeNiCo|MnGaOx/CNT shows a high synergistic effect, low impedance, and modulated electronic structure, leading to a superior bifunctional catalytic performance with an overpotential of 255 mV at 10 mA cm-2 and half-wave potential of 0.824 V (ω = 1600 rpm and 0.1 m KOH electrolyte). Moreover, ZABs based on FeNiCo|MnGaOx/CNT demonstrate notable features, including a peak power density of 136.1 mW cm-2, a high specific capacity of 808.3 mAh gZn -1, and outstanding stability throughout >158 h of uninterrupted charge-discharge cycling. Theoretical calculations reveal that the non-homogeneous interface can introduce more carriers and altered electronic structures to refine intermediate adsorption reactions, especially promoting O* formation, thereby enhancing electrocatalytic performance. This work demonstrates the importance of heterostructure interfacial modulation of electronic structure and enhancement of adsorption capacity in promoting the implementation of OER/ORR, ZABs, and related applications.

Biomass-Derived Carbon Quantum Dots Chemical Bonding with Sn-Doped Bi2O2CO3 Endowed Fast Carriers' Dynamics and Stabilized Oxygen Vacancies for Efficient Decontamination of Combined Pollutants.

Surface defects on photocatalysts could promote carrier separation and generate unsaturated sites for chemisorption and reactant activation. Nevertheless, the inactivation of oxygen vacancies (OVs) would deteriorate catalytic activity and limit the durability of defective materials. Herein, bagasse-derived carbon quantum dots (CQDs) are loaded on the Sn-doped Bi2O2CO3 (BOC) via hydrothermal procedure to create Bi─O─C chemical bonding at the interface, which not only provides efficient atomic-level interfacial electron channels for accelerating carriers transfer, but also enhances durability. The optimized Sn-BOC/CQDs-2 achieves the highest photocatalytic removal efficiencies for levofloxacin (LEV) (88.7%) and Cr (VI) (99.3%). The elimination efficiency for LEV and Cr (VI) from the Sn-BOC/CQDs-2 is maintained at 55.1% and 77.0% while the Sn-BOC is completely deactivated after four cycle tests. Furthermore, the key role of CQDs in stabilization of OVs is to replace OVs as the active center of H2O and O2 adsorption and activation, thereby preventing reactant molecules from occupying OVs. Based on theoretical calculations of the Fukui index and intermediates identification, three possible degradation pathways of LEV are inferred. This work provides new insight into improving the stability of defective photocatalysts.

Decoding Upconversion-Emitting Phase in Complex Composites Through Single-Particle-Level Upconversion Imaging and Density Functional Theory Calculations.

The crystal structure and phase stability of a host lattice plays an important role in efficient upconversion phenomena. In stable hosts, lanthanides doping should not generally change the crystal structure of the host itself. But when phase of a system drastically changes after lanthanide doping resulting in multiple phases, accurate identification of upconverting phase remains a challenge. Herein, an attempt to synthesize lanthanide-doped NiMoO4 by microwave hydrothermal method produced MoO3/Yb2Mo4O15/NiMoO4 micro-nano composite upconversion phosphor. A combined approach of density functional theory (DFT) calculations and single-particle-level upconversion imaging has been employed to elucidate the phase stability of different phases and upconversion properties within the composite. Through single-particle-level imaging under 980 nm excitation, an unprecedented resolution in visualizing individual emitting and non-emitting regions within the composite has been achieved, thereby allowing to accurately assign the Yb2Mo4O15 as a sole upconversion emitting phase in the composite. Result of the DFT calculation further shows that the Yb2Mo4O15 phase is the most thermodynamically preferred over other lanthanide-doped phases in the composite. This comprehensive understanding not only advances the knowledge of upconversion emission from composite materials but also holds promise for tailoring optical properties of materials for various applications, including bioimaging, sensing, and photonics, where controlled light emission is crucial.

Antibacterial Photodynamic Therapy by Zn(II)-Curcumin Complex: Synthesis, Characterization, DFT Calculation, Antibacterial Activity, and Molecular Docking.

The increase in antibacterial drug resistance is threatening global health conditions. Recently, antibacterial photodynamic therapy (aPDT) has emerged as an effective antibacterial treatment with high cure gain. In this work, three Zn(II) complexes viz., [Zn(en)(acac)Cl] (1), [Zn(bpy)(acac)Cl] (2), [Zn(en)(cur)Cl] (3), where en=ethylenediamine (1 and 3), bpy=2,2'-bipyridine (2), acac=acetylacetonate (1 and 2), cur=curcumin monoanionic (3) were developed as aPDT agents. Complexes 1-3 were synthesized and fully characterized using NMR, HRMS, FTIR, UV-Vis. and fluorescence spectroscopy. The HOMO-LUMO energy gap (Eg), and adiabatic splittings (ΔS1-T1 and ΔS0-T1 ) obtained from DFT calculation indicated the photosensivity of the complexes. These complexes have not shown any potent antibacterial activity under dark conditions but the antibacterial activity of these complexes was significantly enhanced upon light exposure (MIC value up to 0.025 µg/mL) due to their light-mediated 1 O2 generation abilities. The molecular docking study suggested that complexes 1-3 interact efficiently with DNA gyrase B (PDB ID: 4uro). Importantly, 1-3 did not show any toxicity toward normal HEK-293 cells. Overall, in this work, we have demonstrated the promising potential of Zn(II) complexes as effective antibacterial agents under the influence of visible light.

Chiral Sulfoximine Mediated Cobalt-Catalyzed Atropselective C-H Annulation of Ynamides.

An achiral Cp*Co(III)-catalyzed enantioselective C-H activation/annulation of chiral sulfoximine-enabled thioamides with ynamides is presented herein. This method successfully synthesizes axially chiral five-membered 2-amidoindenones with good enantiocontrol. Interestingly, the annulation with chiral oxazolidone-containing ynamides could provide a separable mixture of diastereomers (up to ~10 : 1 dr). Moreover, enantiopure sulfoximines could be recovered with ~99 % purity, making this method practical. DFT studies show valuable insight into the mechanism and origin of asymmetric induction.

Structure and Chiroptical Properties of Anthra[1,2-a]anthracene-1-yl Dimers as New Biaryls.

Dimers of anthra[1,2-a]anthracene-1-yl units and its mesityl derivative were synthesized by Ni(0)-mediated coupling of the corresponding chloro derivatives as new biaryls. The X-ray analysis and DFT calculations revealed that two polycyclic aromatic units with nonplanar deformations took a twisted conformation about the single bond as a chiral axis. Enantiomers of the nonsubstituted compound were resolved by chiral HPLC, and the enantiopure samples showed intense Cotton effects at 321 nm in the circular dichroism (CD) spectra and emission bands at 449 nm in the circularly polarized luminescence (CPL) spectra with dissymmetry factor of |glum| 3.6×10-3. The absolute stereochemistry of this biaryl was determined by the theoretical calculation of CD spectrum by the time-dependent DFT method. The barrier to enantiomerization was determined to be 108 kJ mol-1 at 298 K. The dynamic process proceeded via a stepwise mechanism involving the helical inversion of each aromatic unit and the rotation about the biaryl axis as analyzed by the DFT calculations.

Axial Coordination Engineering on Fe‒N‒C Materials for Oxygen Reduction: Insights from Theory.

Axial coordination engineering has emerged as an effective strategy to regulate the catalytic performance of metal‒N‒C materials for oxygen reduction reaction (ORR). However, the ORR mechanism and activity changes of their active centers modified by axial ligands are still unclear. Here, a comprehensive investigation of the ORR on a series of FeN4‒L moieties (L stands for an axial ligand) is performed using advanced density functional theory (DFT) calculations. The axial ligand has a substantial effect on the electronic structure and catalytic activity of the FeN4 center. Specially, FeN4‒C6H5 is screened as a promising active moiety with superior ORR activity, as further revealed by constant-potential calculations and kinetic analysis. The enhanced activity is attributed to the weakened *OH adsorption caused by the altered electronic structure. Moreover, microkinetic modeling shows that at pH = 1, FeN4‒C6H5 possesses an impressive theoretical half-wave potential of ~1.01 V, superior to the pristine Fe‒N‒C catalysts (~0.88 V) calculated at the same level. These findings advance the understanding of the ORR mechanism of FeN4‒L and provide guidance for optimizing the ORR performance of single-metal-atom catalysts.

Synthesis, Structure and (Photo)Catalytic Behavior of Ce-MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights.

Cerium-based Metal-Organic frameworks (Ce-MOFs) are attracting increasing interest due to their similar structural features to zirconium MOFs. The redox behavior of Ce(III/IV) adds a range of properties to the compounds. Recently, perfluorinated linkers have been used in the synthesis of MOFs to introduce new characteristic into the structure. We report the synthesis and structural characterization of Ce(IV)-based MOFs constructed using two perfluorinated alkyl linkers. Their structure, based on hexanuclear Ce6O4(OH)4 12+ clusters linked to each other by the dicarboxylate ions, has been solved ab-initio from X-ray powder diffraction data and refined by the Rietveld method. The crystallization kinetics and the MOF formation mechanism was also invesitigated by Synchrotron radiation with XAS spectroscopies (EXAFS and XANES). The MOFs present the same fcu cubic topology as observed in MOF-801 and UiO-66, and they showed good stability in water at different pH conditions. The electronic structure of these MOFs has been studied by DFT calculations in order to obtain insights into the density of states structure of the reported compounds, resulting in band gaps in the range of 2.8-3.1 eV. Their catalytic properties were tested both thermally and under visible light irradiation for the degradation of methyl orange (MO) dye.

Synthesis and Spectroscopic Properties of Diarylethene-Subporphyrinoid Hybrids.

Two novel diarylethene-fused subporphyrinoids were prepared and characterized. A mono diarylethene derivative was obtained via a statistical condensation reaction with 2 eq. of 1,2-dicyanobenzene and 1 eq. of thiophene-disubstituted butenedinitrile. The symmetric triply diarylethene-fused subporphyrazine was synthesized via a cyclotrimerization reaction of the thiophene-disubstituted butenedinitrile derivative. These compounds were characterized by NMR spectroscopy and high-resolution mass spectrometry. The spectroscopic properties have been measured in hexane and in chloroform. The mono diarylethene-fused-type compound showed photochromism at 580 nm and >700 nm wavelength, accompanied by degradation. According to DFT calculations, photoreactivity likely depends on the contribution of aromatic feature of pyrrole ring bonded to two thiophene rings.

Bimetallic synergistic catalysts based on two-dimensional carbon-rich conjugated frameworks for nitrate electrocatalytic reduction to ammonia: catalyst screening and mechanism insights.

The discovery of the 'two birds, one stone' electrochemical nitrate reduction reaction (NO3RR) allows for the removal of harmful NO3-pollutants as well as the production of economically beneficial ammonia (NH3). However, current understanding of the catalytic mechanism of NO3RR is not enough, and this research is still challenging. To determine the mechanism needed to create efficient electrocatalysts, we thoroughly examined the catalytic activity of molybdenum-based diatomic catalysts (DACs) anchored on two-dimensional carbon-rich conjugated frameworks (2D CCFs) for NO3RR. Among the 23 candidate materials, after a four-step screening method and detailed mechanism studies, we discovered that NO3RR can efficiently generate NH3by following the N-end pathway on the MoTi-Pc, MoMn-Pc, and MoNb-Pc, with limiting potential of -0.33 V, -0.13 V, and -0.38 V, respectively. The activity of NO3RR can be attributed to the synergistic effect of the TM1-TM2dimer d orbital coupling to the anti-bonding orbital of NO3-. Additionally, high hybridization between the Mo-4d, TM-3d(4d), and NO3--2p orbitals on the MoTMs-Pc DACs can speed up the flow of electrons from the Mo-TM dual-site to NO3-. The research presented here paves the way for the reasonable design of effective NO3RR catalysts and offers a theoretical basis for experimental research.

Recovering Valuable Chemicals from Polypropylene Waste via a Mild Catalyst-Free Hydrothermal Process.

Waste polypropylene (PP) presents a significant environmental challenge, owing to its refractory nature and inert C-C backbone. In this study, we introduce a practical chemical recovery strategy from PP waste using a mild catalyst-free hydrothermal treatment (HT). The treatment converts 64.1% of the processed PP into dissolved organic products within 2 h in an air atmosphere at 160 °C. Higher temperatures increase the PP conversion efficiency. Distinct electron absorption and emission characteristics of the products are identified by spectral analysis. Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) reveals the oxidative cracking of PP into shorter-chain homologues (10-50 carbon atoms) containing carboxylic and carbonyl groups. Density functional theory (DFT) calculations support a reaction pathway involving thermal C-H oxidation at the tertiary carbon sites in the polymer chain. The addition of 1% H2O2 further enhances the oxidation reaction to produce valuable short-chain acetic acids, enabling gram-scale recycling of both pure PP and disposable surgical masks from the real world. Techno-economic analysis (TEA) and environmental life cycle costing (E-LCC) analysis suggest that this hydrothermal oxidation recovery technology is financially viable, which shows significant potential in tackling the ongoing plastic pollution crisis and advancing plastic treatment methodologies toward a circular economy paradigm.

Unexpected Promotion Effect of H2O on the Selective Catalytic Reduction of NOx with NH3 over Cu-SSZ-39 Catalysts.

Water molecules commonly inhibit the selective catalytic reduction (SCR) of NOx with NH3 on most catalysts, and water resistance is a long-standing challenge for SCR technology. Herein, by combining experimental measurements and density functional theory (DFT) calculations, we found that water molecules do not inhibit and even promote the NOx conversion to some extent over the Cu-SSZ-39 zeolites, a promising SCR catalyst. Water acting as a ligand on active Cu sites and as a reactant in the SCR reaction significantly improves the O2 activation performance and reduces the overall energy barrier of the catalytic cycle. This work unveils the mechanism of the unexpected promotion effect of water on the NH3-SCR reaction over Cu-SSZ-39 and provides fundamental insight into the development of zeolite-based SCR catalysts with excellent activity and water resistance.