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Nanocomposites are gaining high demand for the development of next-generation energy storage devices because of their eco-friendly and cost-effective natures. However, their short-term energy retainability and marginal stability are regarded as hindrances to overcome. In this work, we demonstrate a high-performance supercapacitor fabricated by biocarbon-based MoSsub2/sub(Bio-C/MoSsub2/sub) nanoparticles synthesized by a facile hydrothermal approach using date fruits. Here, we report the high specific capacitance for a carbon-based nanocomposite employing the pyrolysis technique of converting agricultural biowaste into a highly affordable energy resource. The biocompatible Bio-C/MoSsub2/subnanospheres exhibited a high capacitance of 945 F gsup-1/supat a current density of 0.5 A gsup-1/supand an excellent reproducing stability of 92% after 10000 charge/discharge cycles. In addition, the Bio-C/MoSsub2/subNS showed an exceptional power density of 3800-8000 W kgsup-1/supand an energy density of 74.9-157 Wh kgsup-1/sup. The results would pave a new strategy for design of eco-friendly materials toward the high-performance energy storage technology.

The injection of oxygenated water into anoxic aquifers during managed aquifer recharge (MAR) can cause the mobilization of metal(loid)s. Here, we study the processes controlling MAR-induced molybdenum (Mo) release in dolomitic aquifers. Sequential chemical extractions and energy dispersive X-ray spectroscopy combined with scanning electron microscopy point to an association of Mo with easily soluble sulfurized organic matter present in intercrystalline spaces of dolomites or directly incorporated within dolomite crystals. The easily soluble character was confirmed by a batch experiment that demonstrated the rapid mobilization of Mo, dissolved organic carbon, and sulfur. The type and time of batch solution contact with the sulfurized organic matter impacted the release of Mo, as demonstrated by a 36% increase in Mo concentrations when shaking was intensified. Based on the experimental results, a conceptual model for the release of Mo was formulated, where (i) the injection of oxygenated water causes the oxidation of pyrite in the aquifer matrix, and (ii) the associated release of protons (H

Real-time thermal sensing on flexible substrates could enable a plethora of new applications. However, achieving fast, sub-millisecond response times even in a single sensor is difficult, due to the thermal mass of the sensor and encapsulation. Here, we fabricate flexible monolayer molybdenum disulfide (MoS

International audience; Benzene-1,2,4,5-tetrathiolate (btt) has been used as a bridging ligand to prepare a redox active (molybdenocene dithiolene)-based bimetallic complex Cp2Mo(btt)MoCp2, which exhibits four successive electron transfers up to the tetracation. Spectro-electrochemical investigations together with DFT and TD-DFT calculations evidence that the two electroactive MoS2C2 metallacycles are electronically coupled in the monocationic as in the dicationic state. Two salts of the dication [Cp2Mo(btt)MoCp2]2+ have been structurally characterized with PF6- and HSO4- counterions, showing different chair or boat conformations associated with variable folding angles of the two MoS2C2 metallacycles along the S---S hinge. The bis-oxidized dicationic complex exhibits a diradical character, with both radicals essentially localized on the metallacycles and with antiferromagnetic coupling evidenced from magnetic susceptibility measurements.

The synthesis of enantioenriched molybdenum precatalysts for the asymmetric hydrogenation of substituted quinolines and naphthalenes is described. Three classes of pincer ligands with chiral substituents were evaluated as supporting ligands in the molybdenum-catalyzed hydrogenation reactions, where oxazoline imino(pyridine) chelates were identified as optimal. A series of 2,6-disubstituted quinolines was hydrogenated to enantioenriched decahydroquinolines with high diastereo- and enantioselectivities. For quinoline derivatives, selective hydrogenation of both the carbocycle and heterocycle was observed depending on the ring substitution. Spectroscopic and mechanistic studies established molybdenum η

Photothermal therapy (PTT) in the second near-infrared (NIR-II) window has emerged as a better candidate for deep-tissue tumor elimination. More interestingly, the photothermal ablated tumor cells also manifest somewhat immunostimulation potency to elicit antitumor immunity, although most dying cells are undergoing apoptosis that is commonly considered as immunologically silent. Here, a NIR-II responsive nanosystem is established for tumor photoimmunotherapy using molybdenum dioxide (MoO

Thorough investigations of the environmental fate and risks are necessary for the safe application of engineered nanomaterials. Nevertheless, the current understanding of potential transformations of MoS

Two relatively simple synthetic procedures were developed for the synthesis of Pt–HxMoO3 composites. The obtained materials may be of interest as CO-tolerant catalysts for hydrogen-air fuel cells with proton-exchange membranes (PEMFCs). The first step of both syntheses was to prepare hydrogen molybdenum bronzes (HxMoO3) through the addition of Zn powder to acidic solutions containing Mo(VI) species. Two types of hydrogen-containing molybdenum bronzes were synthesized, namely, red bronze (x≈1.55) and green bronze (x≈2.0). The next step was the Pt deposition in a redox reaction between HxMoO3 and potassium tetrachloroplatinate (K2PtCl4) under open-circuit conditions that resulted in composite materials defined by aPt⋅b(HxMoO3). Numerous physical methods, including XRD, STEM, SEM, and XPS, were used to determine both the composition and structure of the catalysts. Platinum clusters were distributed over the surface of catalytically active support (HxMoO3) in both cases; however, the type of molybdenum bronze used for synthesis affects the size of Pt particles. Linear sweep voltammetry (LSV) was used to determine the regularities of both adsorbed carbon monoxide electrodesorption and dissolved CO electrooxidation. CO-tolerance of prepared composites was estimated using H2/100 ppm CO mixture under conditions of both an electrochemical cell and a membrane electrode assembly (MEA). The results of this work are promising, as they provide a relatively simple method for the synthesis of CO-tolerant catalysts. The understanding of the origin of the CO-tolerance is essential for the development of electrode materials that could be used in the real fuel cells.

The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo2C decorated carbon nanosheets, α-Mo2C nanoparticles, θ-Fe3C nanoparticles, and χ-Fe5C2 nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NOx impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.

Supported bimetallic molybdenum and tungsten carbides are viable replacements for noble metal catalysts and are suitable for the decarboxylation/decarbonylation and (hydro-)deoxygenation of renewable triglyceride‑based feedstocks. Here, we show that the Mo:W ratio in bimetallic carbide can steer the product yield towards either aldehydes, alcohols, alkenes or alkanes. The mixed carbides with a higher Mo/W ratio (3:1) reached higher yields of aldehydes and alcohols, while the carbides with a lower Mo/W (1:3) ratio yielded high concentrations of alkenes. Interestingly, a physical mixture of two monometallic (1 +1) carbides had a similar catalytic performance to the 1:1 mixed carbides. The intrinsic activity (turnover frequency (TOF)) of the catalysts was assessed based on both H2 and CO chemisorption. The TOFH2 related linearly with the Mo/W ratio, while the TOFCO did not show a relevant relationship. Therefore H2 chemisorption is suggested as the preferred way to assess the intrinsic activities of these catalysts.

The leaching and non-recoverability of mental ions have always limited the practical application of Fenton-like processes. For the first time, we synthesized molybdenum phosphide (MoP) with dual active sites for the degradation of diclofenac (DCF) in the Fenton-like process. The DCF degradation rate constant (k) of MoP + H2O2 process was calculated to be 0.13 min-1 within 40 min, indicating a highly efficient catalytic ability of MoP. In addition, this catalyst exhibits a stable structure and good activity, which could apply in a broad pH range, different ions solution and real wastewater condition. Accordingly, this efficient catalytic capability may be attributed to the presence of the metal sites Moδ+ and the electron-rich sites Pδ− in MoP, which could induce the generation of hydroxyl radical (•OH) and superoxide radical (•O2−) through electron transfer, resulting in the effective removal of DCF. This study provides an idea for the optimization of Fenton-like technologies and environmental remediation.

Molecular metal chalcogenides have attracted great attention as electrocatalysts for the hydrogen evolution reaction (HER). However, efficient utilisation of the active sites and catalytic performance modulation has been challenging. Here we explore the design of immobilized molecular molybdenum polyselenides [Mo2O2S2(Se2)(Sex)]2– that exhibit efficient hydrogen evolution at low overpotential and stability over 1000 cycles. Density functional calculations provide evidence of a unimolecular mechanism in the HER process via the exploration of viable reaction pathways. The discussed findings are of a broad interest in the development of efficient molecular electrocatalytic materials.

Cellulose nanocrystals (CNCs) and molybdenum disulphide (MoS2) incorporated into ZnO nanorods (NRs) were synthesized via a chemical precipitation route at room temperature. All concerned samples were characterized to examine their optical properties, elemental composition, phase formation, surface morphology and functional group presence. The aim of this research was to enhance the catalytic properties of ZnO by co-doping with various concentrations of CNCs and MoS2 NRs. It was renowned that doped ZnO NRs showed superior catalytic activity compared to bare ZnO NRs. Statistically significant (p < 0.05) inhibition zones for samples were recorded for E. coli and S. aureus at low and high concentrations, respectively. The in vitro bactericidal potential of ZnO-CNC and ZnO-CNC-MoS2 nanocomposites was further confirmed through in silico molecular docking predictions against the DHFR and DHPS enzymes of E. coli and S. aureus. Molecular docking studies suggested the inhibition of these enzyme targets by CNC nanocomposites as a possible mechanism governing their bactericidal activity.

Incomplete tumor ablation and subsequent tumor metastasis usually occur during photothermal anti-tumor processes. The combination of photothermal and immunotherapy has proven to be a promising method to conquer technical challenges. Inhibiting the programmed death ligand-1 (PD-L1)/programmed cell death protein 1 (PD-1) immune pathway represents one of the most successful immunotherapy strategies. Whereas, the PD-L1 expression level significantly differs, leading to a relatively low response rate to the immune checkpoint blockade (ICB) approaches. Therefore, improving the expression level of PD-L1 becomes one potential method to enhance the response rate. Herein, NIH 3T3 cells were educated to steadily express PD-1 protein. Furthermore, the synthesized molybdenum nitride was then coated with PD-1 protein-modified cytomembrane, which endows it with immune checkpoint blocking capability. Moreover, under the irradiation of near-infrared light, the local mild heat released from the molybdenum nitride causes the apoptosis of tumor cells. More importantly, the elevated temperature simultaneously helps elevate the expression level of PD-L1, further enhancing the response rate of ICB. Finally, the PD-1 cytomembrane coatings interact with the upregulated PD-L1, leading to the activation of the immune system. In summary, we confirmed that the PD-1 protein-coated molybdenum nitride could synergistically ablate tumors and avoid metastasis.

Nano drug delivery systems are a research hotspot in the field of tumor therapy. In this work, molybdenum disulfide (MoS

Polymeric biocomposites display some advantages over metal or ceramic biomaterials, and are regarded as a promising candidate for artificial joint application. Herein, molybdenum disulfide (MD) nanosheets were prepared and incorporated into polyimide (PI) to form MD/PI composites with a MD content of 20 wt% (PM20) and 40 wt% (PM40). The results revealed that incorporation of MD nanosheets obviously improved the tribological performances, surface properties (

X-Ray-induced photodynamic therapy represents a suitable modality for the treatment of various malignancies. It is based on the production of reactive oxygen species by radiosensitizing nanoparticles activated by X-rays. Hence, it allows overcoming the depth-penetration limitations of conventional photodynamic therapy and, at the same time, reducing the dose needed to eradicate cancer in the frame of radiotherapy treatment. The direct production of singlet oxygen by octahedral molybdenum cluster complexes upon X-ray irradiation is a promising avenue in order to simplify the architecture of radiosensitizing systems. One such complex was utilized to prepare water-stable nanoparticles using the solvent displacement method. The nanoparticles displayed intense red luminescence in aqueous media, efficiently quenched by oxygen to produce singlet oxygen, resulting in a substantial photodynamic effect under blue light irradiation. A robust radiosensitizing effect of the nanoparticles was demonstrated

On the basis of the higher order perturbation formulas of g-factors for a 4d1 group in tetragonally compressed octahedra, the g-factors, optical absorption, local structure and their concentration dependences of pentavalent molybdenum in 40PbO-(10-x)Y2 O3 -50P2 O5 :xMoO3 (1 ≤ x ≤ 5 mol%) glass are uniformly investigated. The experimental optical absorption spectra and g factors for Mo5+ at various concentrations x are reasonably regenerated by using the reasonable exponential concentration functions of the cubic field parameter Dq, covalent factor N and relative tetragonal compression ratio ρ. The tetragonal compression ratio ρ due to the Jahn-Teller effect was found in the range of 3.8-4.2%. The decreasing trend of Dq and N and the increasing trend of ρ with concentration can be interpreted as the fact that the variations of MoO3 and Y2 O3 concentrations lead to the modulations of local structure and electron cloud distribution around Mo5+ , associated with the adjustment of the glass network. The concentration dependence of optical basicity is also analyzed for the above glass systems.

Two-phase titanium-based alloys are widely used in aerospace and biomedical applications, and they are obtained through phase transformations between a low-temperature hexagonal closed-packed α-phase and a high-temperature body-centred cubic β-phase. Understanding how a new phase evolves from its parent phase is critical to controlling the transforming microstructures and thus material properties. Here, we report time-resolved experimental evidence, at sub-angstrom resolution, of a non-classically nucleated metastable phase that bridges the α-phase and the β-phase, in a technologically important titanium–molybdenum alloy. We observed a nanosized and chemically ordered superstructure in the α-phase matrix; its composition, chemical order and crystal structure are all found to be different from both the parent and the product phases, but instigating a vanishingly low energy barrier for the transformation into the β-phase. This latter phase transition can proceed instantly via vibrational switching when the molybdenum concentration in the superstructure exceeds a critical value. We expect that such a non-classical phase evolution mechanism is much more common than previously believed for solid-state transformations. A full kinetic pathway of a non-classical nucleation-induced phase transformation through metastable states is elucidated at sub-angstrom resolution in a technologically important titanium alloy.

During the reduction of molybdenum trioxide (MoO3 ) to metallic molybdenum, the first reduction step yielding molybdenum dioxide as an intermediary product is of crucial importance. In this study, we examined the impact of the parameters reduction temperature, water influx, and potassium content on the hydrogen reduction of this first reaction step. Beginning from the same starting material, the chemical vapor transport mechanism was utilized to yield the phase pure MoO2 . Analyses including powder X-ray diffraction, inductively coupled plasma-mass spectrometry, scanning electron microscopy, and high performance optical microscopy were performed on the product phases. Modulations of the specific surface areas of molybdenum dioxide ranging from 2.28 to 0.41 m2 /g were possible. Furthermore, a distinct shift from small plate-like grains to cuboid-like forms was achieved.

Scalable synthesis of one-dimensional molybdenum chalcogenides with tunable electronic properties may be critical for the development of nanoscale electronic device components as well as functional...

A new [PCCP]-coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η2 -alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N2 -complex, which is converted to a dinuclear μ-(η1 :η1 )-N2 -bridged intermediate prior to N-N bond cleavage. Protonation, alkylation and acylation of the resulting molybdenum nitrido complex led to the corresponding N-functionalized imido complexes. Upon oxidation of the N-acylated imido derivative in MeCN, a fumaronitrile fragment was built up via C-C coupling of MeCN to afford a dinuclear molybdenum complex. The key finding that the strong N≡N bond may be cleaved in the presence of a weaker, but spatially constrained C≡C bond contradicts the widespread paradigm that coordinated alkynes are in general more reactive than gaseous N2 .

Reversing the thermal induced sintering phenomenon and forming high temperature stable fine dispersed metallic centers with unique structural and electronic properties is one of the ever-lasting targets of heterogeneous catalysis. Here we report that the dispersion of metallic Ni particles into under-coordinated two-dimensional Ni clusters over γ-Mo2N is a thermodynamically favorable process based on the AIMD simulation. A Ni-4nm/γ-Mo2N model catalyst is synthesized and used to further study the reverse sintering effect by the combination of multiple in-situ characterization methods, including in-situ quick XANES and EXAFS, ambient pressure XPS and environmental SE/STEM etc. The under-coordinated two-dimensional layered Ni clusters on molybdenum nitride support generated from the Ni-4nm/γ-Mo2N has been demonstrated to be a thermally stable catalyst in 50 h stability test in CO2 hydrogenation, and exhibits a remarkable catalytic selectivity reverse compared with traditional Ni particles-based catalyst, leading to a chemo-specific CO2 hydrogenation to CO., Reversing the thermal induced sintering phenomenon and forming high temperature stable fine dispersed metallic centers is one of the ever-lasting targets in heterogeneous catalysis. Here the authors report the dispersion of metallic Ni particles into under-coordinated two-dimensional Ni clusters over γ-Mo2N.

The reaction chemistry of both silanes and hydrogen at para-terphenyl diphosphine-supported molybdenum complexes was explored within the context of carbon dioxide (CO₂) reduction. CO₂ hydrosilylation commonly affords reduction products via silyl acetals. However, while silyl hydride complexes were characterized in the present system, synthetic, spectroscopic, and kinetic studies suggest C–O cleavage of CO₂ occurs independently of silanes. In their presence, a putative molybdenum oxo intermediate is hypothesized to undergo O-atom transfer, yielding silanol. In contrast, hydrogenation chemistry does occur through an intermediate molybdenum dihydride capable of inserting CO₂ to yield a formate hydride complex. This process is reversible; slow deinsertion under dinitrogen affords a mixture of molybdenum dihydride, η²-CO₂, and N₂ complexes. The molybdenum hydride formate species is a competent precatalyst for both CO₂ hydrogenation to formate (in the presence of lithium cations and base) and formic acid dehydrogenation to CO₂ and hydrogen (in the presence of base). Mechanistic studies of both catalytic processes are presented.

Upon addition of 5-15% PhNMe2H+X- (X = B(3,5-(CF3)2C6H3)4 or B(C6F5)4) to Mo(NAr)(styrene)(OSiPh3)2 (Ar = N-2,6-i-Pr2C6H3) in C6D6 an equilibrium mixture of Mo(NAr)(styrene)(OSiPh3)2 and Mo(NAr)(CMePh)(OSiPh3)2 is formed over 36 h at 45 °C (Keq = 0.36). A plausible intermediate in the interconversion of the styrene and 1-phenethylidene complexes is the 1-phenethyl cation, [Mo(NAr)(CHMePh)(OSiPh3)2]+, which can be generated using [(Et2O)2H][B(C6F5)4] as the acid. The interconversion can be modeled as two equilibria involving protonation of Mo(NAr)(styrene)(OSiPh3)2 or Mo(NAr)(CMePh)(OSiPh3)2 and deprotonation of the α or β phenethyl carbon atom in [Mo(NAr)(CHMePh)(OSiPh3)2]+. The ratio of the rate of deprotonation of [Mo(NAr)(CHMePh)(OSiPh3)2]+ by PhNMe2 in the α position versus the β position is ∼10, or ∼30 per Hβ. The slow step is protonation of Mo(NAr)(styrene)(OSiPh3)2 (k1 = 0.158(4) L/(mol·min)). Proton sources such as (CF3)3COH or Ph3SiOH do not catalyze the interconversion of Mo(NAr)(styrene)(OSiPh3)2 and Mo(NAr)(CMePh)(OSiPh3)2, while the reaction of Mo(NAr)(styrene)(OSiPh3)2 with pyridinium salts generates only a trace (∼2%) of Mo(NAr)(CMePh)(OSiPh3)2 and forms a monopyridine adduct, [Mo(NAr)(CHMePh)(OSiPh3)2(py)]+ (two diastereomers). The structure of [Mo(NAr)(CHMePh)(OSiPh3)2]+ has been confirmed in an X-ray study; there is no structural indication that a β proton is activated through a CHβ interaction with the metal. W(NAr)(CMePh)(OSiPh3)2 is also converted into a mixture of W(NAr)(CMePh)(OSiPh3)2 and W(NAr)(styrene)(OSiPh3)2 (Keq = 0.47 at 45 °C in favor of the styrene complex) with 10% [PhNMe2H][B(C6F5)4] as the catalyst; the time required to reach equilibrium is approximately the same as in the Mo system.

Molybdenum nitrogenase catalyses the reduction of N2 to NH3 at its cofactor, an [(R-homocitrate)MoFe7S9C] cluster synthesized via the formation of a [Fe8S9C] L-cluster prior to the insertion of molybdenum and homocitrate. We have previously identified a [Fe8S8C] L*-cluster, which is homologous to the core structure of the L-cluster but lacks the 'ninth sulfur' in the belt region. However, direct evidence and mechanistic details of the L*- to L-cluster conversion upon 'ninth sulfur' insertion remain elusive. Here we trace the 'ninth sulfur' insertion using SeO32- and TeO32- as 'labelled' SO32-. Biochemical, electron paramagnetic resonance and X-ray absorption spectroscopy/extended X-ray absorption fine structure studies suggest a role of the 'ninth sulfur' in cluster transfer during cofactor biosynthesis while revealing the incorporation of Se2-- and Te2--like species into the L-cluster. Density functional theory calculations further point to a plausible mechanism involving in situ reduction of SO32- to S2-, thereby suggesting the utility of this reaction to label the catalytically important belt region for mechanistic investigations of nitrogenase.

We have studied for the first time the role of hydrophobicity of the mesoporous silicate SBA-15 on the activity and the service life of a catalyst in the peroxide oxidation of sulfur-containing compounds. Immobilization of the molybdate anion on the SBA-15 support via ionic bonding with triethylammonium groups allows us not only to decrease the reaction temperature to a relatively low value of 60 °C without a drop in the dibenzothiophene conversion degree but also to increase the service life of the catalyst to many times that of the known analogs. The support and catalyst structures were investigated by low-temperature nitrogen adsorption/desorption, Fourier-transform infrared spectroscopy, X-ray fluorescence analysis, and transmission electron microscopy. Immobilization of the molybdate anion on the SBA-15 support, modified with ammonium species, prevents the leaching of active sites. However, only alkyl-substituted ammonium species minimize DBT sulfone adsorption, which significantly increases the catalyst’s service life. The synthesized catalyst Mo/Et3N-SBA-15 with hydrophobic properties is not sensitive to the initial sulfur content and hydrogen peroxide amount and retains its activity for at least six cycles of oxidation without regeneration. These catalysts can be efficiently used for clean fuel production.

The paper investigates the sulfidation of the precursor of a dispersed molybdenum catalyst consisting of 190–500 nm particles in the hydroconversion of crude oil vacuum residue. The experiments were carried out in a flow-through autoclave reactor system at a hydrogen pressure of 2.5 MPa, in the temperature range of 380–440°C, and with a reaction time of 50–150 min. The catalyst sulfidation was demonstrated to result from a reaction with H2S, which is formed from the thermal decomposition of petroleum feedstock. The sulfidation at 380–400°C is a fairly slow process. At higher hydroconversion temperatures (420–440°C), the H2S concentration in the gas phase grows. However, the formation of compaction products creates a diffusion barrier for H2S transportation to the surface of the catalyst particles and, thus, prevents the precursor from being converted completely to the sulfide form. To enhance the degree of sulfidation, it is preferable to use sulfiding agents that ensure that hydrogen sulfide is formed under the hydroconversion conditions of heavy petroleum feedstock.

Nanoparticles of MoS3 were synthesized from (NH4)2MoS4 in acid media using water-soluble starch as a capping agent. X-Ray Diffraction patterns confirmed the formation of MoS3 while Transmission Electron Microscopy results showed the presence of nanoparticles with sizes of about 30−40 nm that were covered by the polymer. X-Ray Photoelectron spectroscopy analysis confirmed the formation of molybdenum sulfides. The MoS3 nanoparticles were thermally treated in CS2/H2 and converted to MoS2 nanoparticles which showed very low or no stacking of the slabs. The activity of the latter was assessed in the hydrodesulfurization of Vacuum Gas Oil (VGO) and upgrading of Athabasca bitumen. The solids that were prepared using starch exhibited better catalytic activity when compared to commercial MoS2 nanoparticles (Hydrotreating of Vacuum Gasoil) and a NiMo/Al2O3 supported catalyst (upgrading of bitumen), and the stacking of the layers did not increase after reaction. This opens up the possibility of using the facile method of preparation here developed for the application of nanoparticles in a slurry process for heavy crude oil upgrading.

The synthesis of ammonia from atmospheric dinitrogen, nitrogen fixation, is one of the essential reactions for human beings. Because the current industrial nitrogen fixation depends on dihydrogen produced from fossil fuels as raw material, the development of a nitrogen fixation reaction that relies on the energy provided by renewable energy, such as visible light, is an important research goal from the viewpoint of sustainable chemistry. Herein, we establish an iridium- and molybdenum-catalysed process for synthesizing ammonia from dinitrogen under ambient reaction conditions and visible light irradiation. In this reaction system, iridium complexes and molybdenum triiodide complexes bearing N-heterocyclic carbene-based pincer ligands act as cooperative catalysts to activate 9,10-dihydroacridine and dinitrogen, respectively. The reaction of dinitrogen with 9,10-dihydroacridine is not thermodynamically favoured, and it only takes place under visible light irradiation. Therefore, the described reaction system is one that affords visible light energy–driven ammonia formation from dinitrogen catalytically.

MoO

In the iron-based advanced oxidation processes (AOPs), direct use of Fe

International audience; Whereas the olefin metathesis is recognized as a powerful tool to produce alkene, the use of fluoroalkenes in metathesis-catalyzed reactions still remains a major current challenge. Herein, we presented the main developments in that field both in ring-closing metathesis and cross-metathesis, highlighting the major improvements of these past years.

The MoS2 thin film has attracted a lot of attention due to its potential applications in flexible electronics, sensors, catalysis, and heterostructures. Understanding the effect of long-term ambient exposure on the electrical properties of the thin film is important for achieving many overreaching goals of this material. Here, we report for the first time a systematic study of electrical property variation and stability of MoS2 thin films under ambient exposure of up to a year. The MoS2 thin films were grown via the sulfurization of 6 nm thick molybdenum films. We found that the resistance of the samples increases by 114% just in 4 weeks and 430% in 4 months and they become fully insulated in a year of ambient exposure. The dual-sweep current-voltage (I-V) characteristic shows hysteretic behavior for a 4-month-old sample which further exhibits pronounced nonlinear I-V curves and hysteretic behavior after 8 months. The X-ray photoelectron spectroscopy measurements show that the MoS2 thin film gradually oxidizes and 13.1% of MoO3 and 11.8% oxide of sulfur were formed in 4 months, which further increased to 23.1 and 12.7% in a year, respectively. The oxide of the sulfur peak was not reported in any previous stability studies of exfoliated and chemical vapor deposition-grown MoS2, suggesting that the origin of this peak is related to the distinct crystallinity of the MoS2 thin film due to its smaller grain sizes, abundant grain boundaries, and exposed edges. Raman studies show the broadening of E2g1 and A1g peaks with increasing exposure time, suggesting an increase in the disorder in MoS2. It is also found that coating the MoS2 thin film with polymethylmethacrylate can effectively prevent the electrical property degradation, showing only a 6% increase in resistance in 4 months and 40% over a year of ambient exposure.

For entropic reasons, the synthesis of macrocycles via olefin ring-closing metathesis (RCM) is impeded by competing acyclic diene metathesis (ADMET) oligomerization. With cationic molybdenum imido ...