Feeble Single-Atom Pd Catalysts for H2 Production from Formic Acid.

Single-atom catalysts are thought to be the pinnacle of catalysis. However, for many reactions, their suitability has yet to be unequivocally proven. Here, we demonstrate why single Pd atoms (PdSA) are not catalytically ideal for generating H2 from formic acid as a H2 carrier. We loaded PdSA on three silica substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate functional groups. The Pd catalytic activity on amino-functionalized silica (SiO2-NH2/PdSA) was far higher than that of the thiol-based catalysts (SiO2-S-PdSA and SiO2-NHCS2-PdSA), while the single-atom stability of SiO2-NH2/PdSA against aggregation after the first catalytic cycle was the weakest. In this case, Pd aggregation boosted the reaction yield. Our experiments and calculations demonstrate that PdSA in SiO2-NH2/PdSA loosely binds with amine groups. This leads to a limited charge transfer from Pd to the amine groups and causes high aggregability and catalytic activity. According to the density functional calculations, the loose binding between Pd and N causes most of Pd's 4d electrons in amino-functionalized SiO2 to remain close to the Fermi level and labile for catalysis. However, PdSA chemically binds to the thiol group, resulting in strong hybridization between Pd and S, pulling Pd's 4d states deeper into the conduction band and away from the Fermi level. Consequently, fewer 4d electrons were available for catalysis.

Templated Synthesis of Exfoliated Porous Carbon with Dominant Graphitic Nitrogen.

We present here a new approach for the synthesis of nitrogen-doped porous graphitic carbon (g-NC) with a stoichiometry of C6.3H3.6N1.0O1.2, using layered silicate as a hard sacrificial template. Autogenous exfoliation is achieved due to the heterostacking of 2D silicate and nitrogen-doped carbon layers. Micro- and meso-porosity is induced by melamine and cetyltrimethylammonium (C16TMA). Our density functional calculations and X-ray photoelectron spectroscopy (XPS) observations confirm that the most dominant nitrogen configuration in g-CN is graphitic, while pyridinic and pyrrolic nitrogens are thermodynamically less favored. Our large-scale lattice dynamics calculations show that surface termination with H and OH groups at pores accounts for the observed H and O in the composition of the synthesized g-NC. We further evaluate the electrocatalytic and the supercapacitance activities of g-NC. Interestingly, this material exhibits a specific capacitance of ca. 202 F g-1 at 1 A g-1, retaining 90% of its initial capacitance after 10,000 cycles.

Transforming Cl-Containing Waste Plastics into Carbon Resource for Steelmaking: Theoretical Insight.

The accumulation of waste plastics poses a significant environmental challenge, leading to persistent pollution in terrestrial and aquatic ecosystems. A practical approach to address this issue involves the transformation of postconsumer waste plastics into industrially valuable products. This study focuses on an example of harnessing the carbon content in these polymers for carbon-demanding industrial processes, thereby reducing waste plastics from the environment and alleviating the demand for mined carbon resources. Employing quantum simulations, we examine the viability of polychloroprene as a carburizing agent in the steelmaking process. Our simulations reveal that polychloroprene exhibits excellent carbon diffusivity in molten iron, with a theoretical diffusion coefficient of 8.983 × 10-5cm2 s-1. This value competes favorably with that of metallurgical coke and surpasses the carbon diffusivity of other polymers, such as polycarbonate, polyurethane, and polysulfide. Additionally, our findings demonstrate that the chlorine content in polychloroprene does not permeate into molten iron but instead remains confined to the molten iron and slag interface.

Ultrasonically-assisted synthesis of CeO2 within WS2 interlayers forming type II heterojunction for a VOC photocatalytic oxidation.

Here, we investigate the band structure, density of states, photocatalytic activity, and heterojunction mechanism of WS2 with CeO2 (CeO2@WS2) as a photoactive heterostructure. In this heterostructure, CeO2's growth within WS2 layers is achieved through ultrasonicating WS2 and intercalating CeO2's precursor within the WS2 interlayers, followed by hydrothermal treatment. Through a set of density functional calculations, we demonstrate that CeO2 and WS2 form an interface through a covalent bonding that can be highly stable. The electrochemical impedance spectroscopy (EIS) found that the CeO2@WS2 heterostructure exhibits a remarkably higher conductivity (22.23 mS cm-2) compared to either WS2 and CeO2, assignable to the interface in CeO2@WS2. Furthermore, in a physically mixed CeO2-WS2 where the interaction between particles is noncovalent, the resistance was significantly higher (0.67 mS cm-2), confirming that the heterostructure in the interface is covalently bonded. In addition, Mott-Schottky and the bandgap measurements through Tauc plots demonstrate that the heterojunction in CeO2 and WS2 is type II. Eventually, the CeO2@WS2 heterostructure indicated 446.7 µmol g -1 CO2 generation from photocatalytic oxidation of a volatile organic compound (VOC), formic acid, compared to WS2 and CeO2 alone.

Interface-Driven Multiferroicity in Cubic BaTiO3-SrTiO3 Nanocomposites.

Perovskite multiferroics have drawn significant attention in the development of next-generation multifunctional electronic devices. However, the majority of existing multiferroics exhibit ferroelectric and ferromagnetic orderings only at low temperatures. Although interface engineering in complex oxide thin films has triggered many exotic room-temperature functionalities, the desired coupling of charge, spin, orbital and lattice degrees of freedom often imposes stringent requirements on deposition conditions, layer thickness and crystal orientation, greatly hindering their cost-effective large-scale applications. Herein, we report an interface-driven multiferroicity in low-cost and environmentally friendly bulk polycrystalline material, namely cubic BaTiO3-SrTiO3 nanocomposites which were fabricated through a simple, high-throughput solid-state reaction route. Interface reconstruction in the nanocomposites can be readily controlled by the processing conditions. Coexistence of room-temperature ferromagnetism and ferroelectricity, accompanying a robust magnetoelectric coupling in the nanocomposites, was confirmed both experimentally and theoretically. Our study explores the 'hidden treasure at the interface' by creating a playground in bulk perovskite oxides, enabling a broad range of applications that are challenging with thin films, such as low-power-consumption large-volume memory and magneto-optic spatial light modulator.

MOF-derived nanocrystalline ZnO with controlled orientation and photocatalytic activity.

We show here that MOF-5, a sample Zn-based MOF, can uniquely transform into distinct zinc oxide nanostructures. Inspired by the interconversion synthesis of zeolites, we converted MOF-5 into nanocrystalline ZnO. We found the conversion of MOF-5 into ZnO to be tunable and straightforward simply by controlling the treatment temperature and choosing an appropriate structure-directing agent (SDA). Refined X-ray diffraction (XRD) patterns showed that a synthesis temperature of 180 °C (sample ZnO-180) was optimal for achieving high crystallinity. We examined ZnO-180 with high-resolution transmission electron microscopy (HRTEM), which confirmed that the samples were made of individual crystallites grown along the c-axis, or the (001) direction, thus exposing lower energy surfaces and corroborating the XRD pattern and the molecular dynamics calculations. Further investigations revealed that the obtained ZnO at 180 °C has a superior photocatalytic activity in degrading methylene blue to other ZnO nanostructures obtained at lower temperatures.

Exceptionally high saturation magnetisation in Eu-doped magnetite stabilised by spin-orbit interaction.

The significance of the spin-orbit interaction is very well known in compounds containing heavier elements such as the rare-earth Eu ion. Here, through density functional calculations, we investigated the effect of the spin-orbit interaction on the magnetic ground state of Eu doped magnetite (Fe3O4:EuFe). By examining all possible spin alignments between Eu and magnetite's Fe, we demonstrate that Eu, which is most stable when doped at the tetrahedral site, adapts a spin almost opposite the substituted Fe. Consequently, because of smaller spin cancellation between the cations on the tetrahedral site (FeTet and EuTet) and the cations on the octahedral sites (FeOct), Fe3O4:EuFe exhibits a maximum saturation magnetisation of 9.451 µB per f.u. which is significantly larger than that of undoped magnetite (calculated to be 3.929 µB per f.u.). We further show that this large magnetisation persists through additional electron doping. However, additional hole doping, which may unintentionally occur in Fe deficient magnetite, can reduce the magnetisation to values smaller than that of the undoped magnetite. The results presented here can aid in designing highly efficient magnetically recoverable catalysts for which both magnetite and rare earth dopants are common materials.

Bispropylurea bridged polysilsesquioxane: A microporous MOF-like material for molecular recognition.

Microporous organosilicas assembled from polysilsesquioxane (POSS) building blocks are promising materials that are yet to be explored in-depth. Here, we investigate the processing and molecular structure of bispropylurea bridged POSS (POSS-urea), synthesised through the acidic condensation of 1,3-bis(3-(triethoxysilyl)propyl)urea (BTPU). Experimentally, we show that POSS-urea has excellent functionality for molecular recognition toward acetonitrile with an adsorption level of 74 mmol/g, which compares favourably to MOFs and zeolites, with applications in volatile organic compounds (VOC). The acetonitrile adsorption capacity was 132-fold higher relative to adsorption capacity for toluene, which shows the pores are highly selective towards acetonitrile adsorption due to their size and arrangement. Theoretically, our tight-binding density functional and molecular dynamics calculations demonstrated that this BTPU based POSS is microporous with an irregular placement of the pores. Structural studies confirm maximal pore sizes of ∼1 nm, with POSS cages possessing an approximate edge length of ∼3.16 Å.

Hard-templated metal-organic frameworks for advanced applications.

Template-directing strategies for synthesising metal-organic frameworks (MOFs) have brought about new frontiers in materials chemistry due to the possibility of applying control over crystal growth, morphology and secondarily generated pores. In particular, hard templates have resulted in performance breakthroughs in catalysis, secondary ion batteries, supercapacitance, drug delivery and molecular sieving by offering facile routes for maximising the surface areas of shape-directed MOFs. In this tutorial review, a variety of hard templates employed to direct MOFs' growth into superior nano-architectures with enhanced functionalities are discussed. Hard templates discussed here include polymers, silica nanostructures, metal oxides, layered metal hydroxides, noble metals, graphene, zeolites and MOFs themselves. These templates can be divided into three broad categories: sacrificial, semi-sacrificial and non-sacrificial templates. We elaborate on the rationale behind the choice of nanomaterials as hard templates, how hard templates direct the synthesis of MOFs, how sacrificial hard templates can be removed from the final product and what the enhanced functionalities of hard-templated MOFs are. In the case of non-sacrificial hard-templates, synergistic effects arising from the coexistence of the MOF and the hard template will also be reviewed.

Carbamate-Isocyanurate-Bridged Periodic Mesoporous Organosilica for van der Waals CO2 Capture.

We synthesized a new organosiloxane bridge on the basis of an isocyanurate derivative through a simple melt-fusion approach by the reaction of 3-isocyanatopropyltriethoxysilane (IPTES) with 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6(1H,3H,5H)-trione (THEIC). The obtained carbamate-isocyanurate-based organosiloxane bridge precursor was used for the preparation of chemo- and thermostable periodic mesoporous organosilica (PMO-THEIC) on condensation with tetrathoxysilane silicon precursor through a soft-template approach. Furthermore, the synthesized PMO-THEIC with unique surface functionality was investigated for CO2 capture. The results show that the PMO-THEIC has higher activity than pure SBA-15 for CO2 capture due to the high affinity of carbamate functionalities embedded within the pore walls toward CO2 molecules. The affinity of organosiloxane bridge for CO2 molecules is mainly facilitated via the van der Waals force with carbamate functional groups rather than the isocyanurate ring, according to the density functional calculations.

Imaging of the muscle and bone from benchtop to bedside.

Studies have begun to show that muscles and bones play a role in the regulation of biological functions through a combination of biomechanical and biochemical signals. In vivo and ex vivo imaging techniques are crucial in the understanding of the morphology and architecture of muscle and bone for further understanding of musculoskeletal physiology and pathophysiology. This systematic review of the literature summarizes current knowledge and outlines new insights into the functions of muscle and bone elucidated by imaging techniques, with a focus on the recent advances in the musculoskeletal system enabled by novel technologies, such as CLARITY, Fast Free-of-Acrylamide Clearing Tissue (FACT), computed tomography (CT), and positron emission tomography (PET). This may serve as guidance for the development of new strategies to prevent and diagnose motor or metabolism disorders related to the malfunction of muscle and bone.

Coordination Polymer to Atomically Thin, Holey, Metal-Oxide Nanosheets for Tuning Band Alignment.

Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal-based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two-unit cells. The process involves rapid exfoliation of bulk-layered, MCPs (Ce-, Ti-, Zr-based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high-yield, room-temperature, and template-free approach to synthesize ultrathin holey nanosheets with high-level functionalities.

Template-oriented synthesis of hydroxyapatite nanoplates for 3D bone printing.

The design of hydroxyapatite (HA) nanoarchitecture is critical for fabricating artificial bone tissues as it dictates the biochemical and the mechanical properties of the final product. Herein, we incorporated a simple hard-template approach to synthesise single crystal nanoplates of HA. We used the 2D graphitic nitride (g-C3N4) material to prepare an HA sol-gel under hydrothermal conditions. A new HA nanostructure was then formed during the calcination and removal of g-C3N4 at a higher temperature, which finally led to the production of nanoplates (thickness of ∼100 nm) while in lateral dimension the average size was in the micrometre scale. We characterised the synthesised HA nanoplates with XRD, TEM, and HRTEM. The theoretically predicted nanostructure construction based on Wulff's method is in full agreement with the experimental observations. We then prepared different weight ratios of HA and polylactic acid (PLA) composites for artificial 3D bone fabrication. The strong interaction between PLA and HA's (110) facet, which was the second most prevalent, resulted in the composite's mechanical robustness. After mechanical testing, an optimum ratio was selected for biological studies and 3D printing. Biological experiments demonstrated that the synthesised composite had excellent viability in vitro.

Effect of pulsed electromagnetic field on mandibular fracture healing: A randomized control trial, (RCT).

INTRODUCTION: Currently, the pulsed electromagnetic field (PEMF) method is utilized for the treatment of nonunion long bone fractures. Considering the established effect of the PEMF on the acceleration of the bone healing process, we conducted this study to evaluate the effect of PEMF on the healing process in mandibular bone fractures. MATERIAL AND METHODS: This research was a randomized control trial (RCT) study. The sample consisted of patients with a mandibular fracture who were hospitalized in order to receive closed reduction treatment. The participants were randomly selected and then sequentially divided into two groups of 16 participants each (controls = 16, cases = 16). The patients in the control group received conventional therapy without any extra treatment, while the patients in the case group received PEMF therapy in addition to conventional therapy. For the PEMF therapy, patients in the case group received immediate post-surgery PEMF therapy for 6 h. Next, they received 3 h of exposure for the next 6 d, and finally, the same process was repeated for 1.5 h for post-surgery days 8-13. The maxillomandibular fixation (MMF) device was removed at post-surgery week 4. The patients in the control group, however, did not receive any extra treatment. The efficiency of the treatment modalities was evaluated clinically and radiographically. For the radiographical assessment, we employed a direct digital panoramic machine to calculate the computerized density of the bone, and those measurements were used for comparison of the results between the control group and the study patients. RESULTS: There was no significant difference in the mean bone density values between the two groups (P > 0.05). However, the percentage of changes in bone density of the two groups revealed that the case group had insignificant decreases at post-surgery day 14 and a significant increase at post-surgery day 28 compared with the control group (P < 0.05). After releasing the MMF, a bimanual mobility test of the fractured segments showed the stability of the segments in all patients. In the case group, the mouth opening was significantly more stable than that of the control group (P < 0.05). CONCLUSION: PEMF therapy postoperatively leads to increased bone density, faster recovery, increased formation of new bone, a further opening of the mouth, and decreased pain.

Au quantum dots engineered room temperature crystallization and magnetic anisotropy in CoFe2O4 thin films.

For the first time, this work presents a novel room temperature time-effective concept to manipulate the crystallization kinetics and magnetic responses of thin films grown on amorphous substrates. Conventionally, metal-induced crystallization is adopted to minimize the crystallization temperature of the upper-layer thin film. However, due to the limited surface area of the continuous metal under-layer, the degree of crystallization is insufficient and post-annealing is required. To expose a large surface area of the metal under-layer, we propose a simple and novel approach of using an Au nanodots array instead of a continuous metallic under-layer to obtain crystallization of upper-layer thin films. Spinel cobalt ferrite (CFO) thin film as a 'model' was deposited on an Au nano-dots array to realize this methodology. Our findings revealed that the addition of quantum-sized Au nano-dots as a metal under-layer dramatically enhanced the crystallization of the cobalt ferrite upper layer at room temperature. The appearance of major X-ray diffraction peaks with high intensity and well-defined crystallized lattice planes observed via transmission electron microscopy confirmed the crystallization of the CFO thin film deposited at room temperature on 4 nm-sized Au nano-dots. This crystallized CFO thin film exhibits 18-fold higher coercivity (Hc = 4150 Oe) and 4-fold higher saturation magnetization (Ms = 262 emu cm-3) compared to CFO deposited without the Au under-layer. The development of this novel concept of room-temperature crystallization without the aid of additives and solvents represents a crucial breakthrough that is highly significant for exploring the green and energy-efficient synthesis of a variety of oxide and metal thin films.

Ab Initio Investigation of Water Adsorption and Hydrogen Evolution on Co9S8 and Co3S4 Low-Index Surfaces.

We used density functional theory approach, with the inclusion of a semiempirical dispersion potential to take into account van der Waals interactions, to investigate the water adsorption and dissociation on cobalt sulfide Co9S8 and Co3S4(100) surfaces. We first determined the nanocrystal shape and selected representative surfaces to analyze. We then calculated water adsorption and dissociation energies, as well as hydrogen and oxygen adsorption energies, and we found that sulfur vacancies on Co9S8(100) surface enhance the catalytic activity toward water dissociation by raising the energy level of unhybridized Co 3d states closer to the Fermi level. Sulfur vacancies, however, do not have a significant impact on the energetics of Co3S4(100) surface.

The effect of octahedral distortions on the electronic properties and magnetic interactions in O3 NaTMO2 compounds (TM = Ti-Ni & Zr-Pd).

The interplay between the coordination environment and magnetic properties in O3 layered sodium transition metal oxides (NaTMO2) is a fascinating and complex problem. Through detailed and comprehensive density functional investigations on O3 NaTMO2 compounds, we demonstrate that the TM ions in O3 NaMnO2, NaFeO2 and NaCoO2 adopt a high spin state. Structurally, NaMnO2 and NaPdO2 undergo Jahn-Teller distortions while NaNbO2 undergoes puckering distortion. Furthermore, in addition to Jahn-Teller distortion, NaPdO2 exhibits charge disproportionation as it contains Pd2+, Pd3+ and Pd4+ species. These distortions stabilize the inter-plane ferromagnetism. Additionally, the inter-plane ferromagnetic coupling is stabilized by kinetic p-d exchange mechanism in undistorted NaCoO2, NaNiO2 and NaTcO2. The intra-plane coupling in this family of compounds on the other hand was found to be generally weak. Only NaMnO2, NaNiO2 and NaTcO2 are predicted to show bulk ferromagnetism with estimated Curie temperatures below ∼50 K.

Magnetism and spin entropy in Ru doped Na0.5CoO2.

The effect of Ru doping on the magnetic coupling among Co ions and on the Seebeck effect in Na0.5CoO2 was systematically studied using density functional theory. It was found that the Ru dopant takes the 4+ oxidation state and replaces a Co4+ ion. In addition, the remaining Co4+ ions in Na0.5CoO2:Ru were stabilized in a low spin state. Magnetically, the Ru dopants couple in a ferrimagnetic manner with Co ions in the host lattice. Due to the higher electronic degeneracy of Ru4+ dopants, the Seebeck coefficient in Na0.5CoO2 is predicted to be higher than that of the pristine compound.

Bioremediation of soil contaminated crude oil by Agaricomycetes.

BACKGROUND: One of the most important environmental problems is the decontamination of petroleum hydrocarbons polluted soil, particularly in the oil-rich country. Bioremediation is the most effective way to remove these pollutants in the soil. Spent mushroom compost has great ability to decompose lignin-like pollution. The purpose of this study was the bioremediation of soil contaminated with crude oil by an Agaricomycetes. METHODS: Soil sample amended with spent mushroom compost into 3%, 5% and 10% (w/w) with or without fertilizer. Ecotoxicity germination test was conducted with Lipidium sativa. RESULTS: The amplified fragment (18 s rDNA) sequence of this mushroom confirmed that the strain belonged to Pleurotus ostreatus species with complete homology (100% identity). All tests experiment sets were effective at supporting the degradation of petroleum hydrocarbons contaminated soil after three months. Petroleum contaminated soil amended with Spent mushroom compost 10% and fertilizer removed 64.7% of total petroleum hydrocarbons compared control. The germination index (%) in ecotoxicity tests ranged from 60.4 to 93.8%. CONCLUSIONS: This showed that the petroleum hydrocarbons contaminated soil amended with 10% Spent mushroom compost had higher bioremediation ability and reduced soil toxicity in less than three months.

Dopant incorporation site in sodium cobaltate's host lattice: a critical factor for thermoelectric performance.

NaxCoO2 that comprises alternating Na and CoO layers has exotic magnetic and thermoelectric properties that could favorably be manipulated by adding dopants or varying Na concentration. In this work, we investigated the structural and electronic properties of Sr and Sb doped NaxCoO2 (x = 0.50, 0.625, 0.75 and 0.875) through comprehensive density functional calculations. We found that Sr dopants always occupy a site in the Na layer while Sb dopants always substitute a Co ion in the host lattice regardless of Na concentration. This conclusion withstood when either generalized gradient approximation (GGA) or GGA + U method was used. By residing on the Na layer, Sr dopants create charge and mass inertia against the liquid-like Na layer and, therefore, improve the crystallinity and decrease the electrical resistivity through better carrier mobility. On the other hand, by substituting Co ions, Sb dopants reduce the electrical conductivity and therefore decrease the Seebeck coefficient.