Catalytic epoxidation of olefin over supramolecular compounds of molybdenum oxide clusters and a copper complex

The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.

Effect of Ni Loading on the Catalytic Properties of Molybdenum Oxides for the Isomerization of Heptane

The catalytic properties of MoOx and incorporation Ni onto the MoOx for the isomerization of heptane have been investigated under atmospheric pressure at different conditions such as different flow rate of H2, different reaction temperature etc.. Compared with MoOx, the Ni addition to the MoOx markedly improved the isomerization activity of heptane by improving the reducibility of MoO3 and activation of H2 in reaction.

Facile solution-processed molybdenum oxide as hole transporting material for efficient organic solar cell

The large energy barrier in hole extraction still remains a great challenge in developing hole transporting layer (HTL) materials for organic solar cells (OSCs).Thus,solution-processed HTL materials with excellent hole collection ability and good compatibility with large-area processing technique are strongly desired for OSCs.Herein,we developed a cost-effective and solution-processed MoO_(3)HTL for efficient OSCs.By adding a small amount of glucose as reducing reagent into the ammonium molybdate precursor solution,a deeply n-doped MoO_(3),namely G:Mo,was prepared through the sol–gel method.Compared to pristine MoO_(3),the conductivity of G:Mo was enhanced by two orders of magnitude,which greatly improved the hole collection ability of the HTL.OSCs with G:Mo can exhibit comparable PCE to the PEDOT:PSS device.Using PBDB-TF:BTP-eC9 as the active layer,a PCE of 17.1%is obtained for the device,which is the highest PCE value for OSC using a solution-processed MoO_(3)HTL.More importantly,G:Mo is well compatible with the blade-coating processing.The OSC using a blade-coated G:Mo showed almost no PCE loss as compared to the device with spin-coated G:Mo HTL.The results from this work indicate that G:Mo is a promising HTL material for the practical production of OSCs.

FORMATION OF MOLYBDENUM OXIDE NANOSTRUCTURES CONTROLLED BY POLY(ETHYLENE OXIDE)

Polymeric systems have played an important role as structure-directing agents and in the control of nucleation and growth of crystals.This article reviews the work of our research group in the field of the polymer-assisted crystallization of inorganic materials,mainly focused on the formation of highly ordered,porous molybdenum oxide nanostructures.Different experimental parameters including the influence of poly(ethylene oxide)-containing polymers on the morphology and structure of the products obtained fr...

PREPARATION OF ELECTRICAL CONDHCTIVE MOLYBDENUM OXIDE BY THERMAL DECOMPOSITION OE HYDRAZINE-CONTAINING MOLYBDENUM SALT

A new method of preparing electrical conductive molybdenum oxide by thermal decomposition from hydrazine-containing molybdenum salt was described.The process of the thermal decomposition of hydrazine- containing molybdemum salt was investigated by thermal analysis(TG and DTA) and the thermally decomposed product was studied by S.E.M.and chemical analysis.The result indicated that the molybdenum oxide obtained in this way was electrical conductive.

Synaptic Transistor Implemented Using Quasi-2D Molybdenum Oxide

Recent years has seen increasing interest in building artificial synaptic devices to emulate the computation performed by biological synapses.Biological synapses are functional links between neurons,through which information is transmitted in the neuron network.The information can be stored and processed simultaneously in the same synapse through tuning synaptic weight,which is defined as the strength of the correlation between

Polysulfides adsorption and catalysis dual-sites on metal-doped molybdenum oxide nanoclusters for Li-S batteries with wide operating temperature

The development of electrocatalysts with high catalytic activity is conducive to enhancing polysulfides adsorption and reducing activation energy of polysulfides conversion, which can effectively reduce polysulfide shuttling in Li-S batteries. Herein, a novel catalyst NiCo-MoO x /rGO (rGO = reduced graphene oxides) with ultra-nanometer scale and high dispersity is derived from the Anderson-type polyoxometalate precursors, which are electrostatically assembled on the multilayer rGO. The catalyst material possesses dual active sites, in which Ni-doped MoO x exhibits strong polysulfide anchoring ability, while Co-doped MoO x facilitates the polysulfides conversion reaction kinetics, thus breaking the Sabatier effect in the conventional electrocatalytic process. In addition, the prepared NiCo-MoO x /rGO modified PP separator (NiCo-MoO x /rGO@PP) can serve as a physical barrier to further inhibit the polysulfide shuttling effect and realize the rapid Li+ migration. The results demonstrate that Li-S coin cell with NiCo-MoO x /rGO@PP separator shows excellent cycling performance with the discharge capacity of 680 mAh·g^(−1) after 600 cycles at 1 C and the capacity fading of 0.064% per cycle. The rate performance is also impressive with the remained capacity of 640 mAh·g^(−1) after 200 cycles even at 4 C. When the sulfur loading is 4.0 mg·cm^(−2) and electrolyte volume/sulfur mass ratio (E/S) ratio is 6.0 μL·mg^(−1), a specific capacity of 830 mAh·g^(−1) is achieved after 200 cycles with a capacity decay of 0.049% per cycle. More importantly, the cell with NiCo-MoO x /rGO@PP separator exhibits cycling performance under wide operating temperature with the reversible capacities of 518, 715, and 915 mAh·g^(−1) after 100 cycles at −20, 0, and 60 °C, respectively. This study provides a new design approach of highly efficient catalysts for sulfur conversion reaction in Li-S batteries.

Investigation of top-emitting OLEDs using molybdenum oxide as anode buffer layer

A high-effective bottom anode is essential for high-performance top-emitting organic light-emitting devices (OLEDs). In this paper, Ag-based top-emitting OLEDs are investigated. Ag has the highest reflectivity for visible light among all metals, yet its hole-injection properties are not ideal for anodes of top-emitting OLED. The performance of the devices is significantly improved using the molybdenum oxide as anode buffer layer at the surface of Ag. By introducing the molybdenum oxide, the hole injection from Ag anodes into top-emitting OLED is largely enhanced with rather high reflectivity retained.

Sub-gap defect density characterization of molybdenum oxide: An annealing study for solar cell applications

The application of molybdenum oxide in the photovoltaic field is gaining traction as this material can be deployed in doping-free heterojunction solar cells in the role of hole selective contact.For modeling-based optimization of such contact,knowledge of the molybdenum oxide defect density of states(DOS)is crucial.In this paper,we report a method to extract the defect density through nondestructive optical measures,including the contribution given by small polaron optical transitions.The presence of defects related to oxygen-vacancy and of polaron is supported by the results of our opto-electrical characterizations along with the evaluation of previous observations.As part of the study,molybdenum oxide samples have been evaluated after post-deposition thermal treatments.Quantitative results are in agreement with the result of density functional theory showing the presence of a defect band fixed at 1.1 eV below the conduction band edge of the oxide.Moreover,the distribution of defects is affected by post-deposition treatment.

H_(2)O_(2) actuated molybdenum oxide nanodots:Multi-enzyme-like activities,leverage of Fenton reaction,and dual-mode sensitive detection of alendronate sodium

Unexpected benefits to the catalytic performance of materials often originate from the presence of surface defects.Here,novel Dpenicillamine modified molybdenum oxide nanodots,with abundant oxygen vacancy defects,were fabrication by a mild,simple,and cost-effective method.Ultraviolet–visible(UV–Vis)absorption spectra analysis showed that the nanodots had peroxidaselike and catalase-like activities.The reactive oxygen species were probed by electronic paramagnetic resonance technique and spectroscopic methods,demonstrating that the nanodots also had oxidase-like activity.Interestingly,the peroxidase-like activity of nanodots was synergistically enhanced in the presence of ferrous ions or ferric ions.Remarkably,less than nanomolar levels of ferrous ions were required to display this phenomenon,meaning Fenton reagent acted as leverage.Based on this,a sensitive colorimetric and fluorescent dual-mode sensor for alendronate sodium was developed.The linear ranges for colorimetric and fluorescence analysis were 0.2–2.5 and 0.2–2.0μM,with detection limits of 31.21 and 71.84 nM,correspondingly.The method has a simple large-scale material preparation process with higher sensitivity and shorter reaction time,which can inspire and enlighten the design of nanozyme sensors.

Confined structure regulations of molybdenum oxides for efficient tumor photothermal therapy

Molybdenum oxide nanoparticles(NPs) with tunable plasmonic resonance in the near-infrared region display superior semiconducting features and photothermal properties, which are highly related to the crystalline and defective structures such as oxygen deficiencies. However,fundamental understanding on the structure-function relationship between crystalline/defective structures and photothermal properties is still unclear. To address this, herein,we have developed an "in-situ confined oxidation-reduction"strategy to regulate the defect features of molybdenum oxide NPs in the dual-mesoporous silica nanoreactor. Especially, the effects of crystalline structure/oxygen defects of molybdenum oxides on the photothermal performances were investigated by facilely tuning the amount of molybdenum resource and the reduction temperature. As a photothermal nanoagent, the optimal defective molybdenum oxide NPs encapsulated in PEGylated porous silica nanoreactor(designated as MoO_(3)@PPSNs) exhibit excellent biological stability and strong localized surface plasmon resonance effect in nearinfrared absorption range with the highest photothermal conversion efficiency up to 78.7% under 808 nm laser irradiation. More importantly, the remarkable photothermal effects of MoO_(3)@PPSNs were comprehensively demonstrated both in vitro and in vivo. Consequently, we envision that the plasmonic MoO_(3)NPs in a biocompatible porous silica nanoreactor could be used as an efficient photothermal therapy agent for photothermal ablation of tumors.

Covalency triggers high catalytic activity of amorphous molybdenum oxides for oxidative desulfurization

Oxidative desulfurization(ODS)is a promising technology to produce clean fuel with requiring superior catalysts to lower kinetic barriers.Although most ODS catalysts are based on crystalline transition-metal oxides(TMOs),extraordinary activity also can be achieved with amorphous TMOs.However,the origin of the remarkable catalytic activity of the amorphous TMOs remains greatly ambiguous.Here,we found the crucial role of Mo–O covalency in ruling the intrinsic catalytic activity of amorphous molybdenum oxides(MoO_(x)).Experimental and theoretical analysis indicated that the nonequivalent connectivity in the amorphous structure strongly enhanced Mo–O covalency,thereby increasing the content of electrophilic oxygen and nucleophilic molybdenum to favor the MoO_(x)–H_(2)O_(2) interaction.With the boosted Mo–O covalency to improve the flexibility of the charge state,the amorphous MoO_(x)-based composite catalyst(PE-MoO_(x)/S-0.05)exhibited outstanding catalytic activity for ODS of fuel oil.The turnover frequency(TOF)value of the catalyst(18.63 h^(-1))was almost an order of magnitude higher than that of most reported crystalline MoO_(x)/molecular sieve composite catalysts.The in-depth understanding of the origin of the amorphous TMOs activity for ODS provides a valuable reference for developing ODS catalysts.

Controllable synthesis and surface modification of molybdenum oxide nanowires: a short review

Transition metal oxides are found to have overwhelming applications in energy,electronics,catalytic,and bio-and micromechanical systems.A recent report emphasized the current advancements in molybdenum oxide(MoO_(x))nanowire synthesis and the corresponding surface-functionalized nanostructured materials based on our previously reported investigations.The preparation of the nanowires and their applications were systematically summarized.MoO_(x) nanowires combined with substrates exhibited remarkable performances for high energy storage and power densities with high stability.In addition,the review concluded the future advancements of MoO_(x) nanowires.

Solution-processed Molybdenum Oxide Hole Transport Layer Stabilizes Organic Solar Cells

The hole transport layer(HTL)affects the device performance and stability of organic solar cells.In this work,a stable molybdenum oxide(MoO_(x))hole transport layer with low cost was prepared by adjusting the state of the precursor solution with an alcoholic solution of molybdenum acetylacetonate through an oxidant.The MoO_(x) transport layer has good transmittance with a work function of 5.07 eV and higher surface energy.The PM6:Y6 devices using MoO_(x) HTL achieve a high efficiency of 16.8%.MoO_(x) HTL exhibits good applicability with excellent performance in both ternary and all-polymer systems.Air storage stability T80 of the all-polymer device using MoO_(x) HTL was over 600 h,much higher than 70 h of the PEDOT:PSS-based device,and its thermal stability at 85℃ and operational stability under light show better stability than that of the PEDOT:PSS hole transport layer.This work provides a facile and low-cost method to fabricate HTL for organic solar cells,which is beneficial to improve their efficiency and stability.

One-step synthesis of carbon-coated monocrystal molybdenum oxides nanocomposite as high-capacity anode materials for lithiumion batteries

Benefitting from higher specific capacities,acceptable cost,nontoxicity and unique crystal structures,the molybdenum oxides have been studied as the anode materials for lithium ion batteries(LIBs).Herein,a direct current(DC)arc-discharge plasma technique has been developed to in-situ synthesize carboncoated monocrystal molybdenum oxides((MoO3NRs/MoO2NPs)@C)nanocomposites,using coarse MoO_(3) bulk as the raw material and methane(CH4)gas as the carbon source.It is indicated that crystallographic traits of MoO_(3) and MoO2 nuclei give rise to an anisotropic growth of monocrystal MoO3 nanorods(NRs)along<100>direction and an isotropic growth of monocrystal MoO_(2) nanoparticles(NPs).The carbon shells on MoO3/MoO2 nanostructures are generated from the absorption of carbon atoms in surrounding atmosphere or the release of supersaturated carbon atoms in MoeOeC solid solution.Unique constitution and pseudo-capacitive behavior of(MoO3NRs/MoO2NPs)@C bring merits to excellent cycling performance and rate capability,i.e.a remarkable specific capacity of 840 mAh·g^(-1) after 100 cycles at a current density of 0.1 Ag^(-1) and a retained capacity of 210 mAh·g^(-1) at 6.4 A g^(-1).This work has offered a simple and efficient approach to fabricate the carbon-coated molybdenum oxides nanostructures for promising anode materials of LIBs。

Millisecond-timescale electrodeposition of platinum atom-doped molybdenum oxide as an efficient electrocatalyst for hydrogen evolution reaction

We present a straightforward method for one-pot electrodeposition of platinum atoms-doped molybdenum oxide(Pt·MoO_(3-x))films and show their superior electrocatalytic activity in the hydrogen evolution reaction(HER).A~15-nm-thick Pt·MoO_(3-x) film was prepared by one-pot electrodeposition at-0.8 V for 1 ms.Due to considerably different solute concentrations,the content of Pt atoms in the electrode-posited composite electrocatalyst is low.No Pt crystals or islands were observed on the flat Pt-MoO_(3-x) films,indicating that Pt atoms were homogeneously dispersed within the MoO_(3-x) thin film.The catalytic performance and physicochemical features of Pt·MoO_(3-x) as a HER electrocatalyst were characterized.The results showed that our Pt·MoO_(3-x) film exhibits 23-and 11-times higher current density than Pt and MoO_(3-x) electrodeposited individually under the same conditions,respectively.It was found that the dramatic enhancement in the HER performance was principally due to the abundant oxygen defects.The use of the developed one-pot electrodeposition and doping method can potentially be extended to various catalytically active metal oxides or hydroxides for enhanced performance in various energy storage and conversion applications.

Near infrared molybdenum oxide quantum dots with high photoluminescence and photothermal performance

The synthesized near infrared molybdenum oxide quantum dots perform excellent red fluorescence imaging performance and photothermal performance,which have 600,650 and 700 nm three unique peaks excited at 540 nm,with a high quantum yield around 20%.Meanwhile,with 808 nm NIR laser excitation,10 mg/mL modified Molybdenum oxide quantum dots can increase temperature up to 72.2℃within 150 s and 77.7℃within 270 s,respectively.

Synergistic tribological effect between polyisobutylene succinimide-modified molybdenum oxide nanoparticle and zinc dialkyldithiophosphate for reducing friction and wear of diamond-like carbon coating under boundary lubrication

Organic molybdenum lubricant additive like molybdenum dialkyl dithiocarbamate(MoDTC)can cause wear acceleration of diamond-like carbon(DLC)coating coupled with steel under boundary lubrication,which hinders its industrial application.Therefore,polyisobutylene succinimide(PIBS),an organo molybdenum amide,was adopted to modify molybdenum oxide affording molybdenum polyisobutylene succinimidemolybdenum oxide nanoparticles(MPIBS-MONPs)with potential to prevent the wear acceleration of DLC coating.The thermal stability of MPIBS-MONPs was evaluated by thermogravimetric analysis.Their tribological properties as the additives in di-isooctyl sebacate(DIOS)were evaluated with MoDTC as a control;and their tribomechanism was investigated in relation to their tribochemical reactions and synergistic tribological effect with zinc dialkyldithiophosphate(ZDDP)as well as worn surface characterizations.Findings indicate that MPIBS-MONPs/ZDDP added in DIOS can significantly reduce the friction and wear of DLC coating,being much superior to MoDTC.This is because MPIBS-MONPs and ZDDP jointly take part in tribochemical reactions to form a composite tribofilm that can increase the wear resistance of DLC coating.Namely,the molybdenum amide on MPIBS-MONPs surface can react with ZDDP to form MoS2 film with excellent friction-reducing ability;and MPIBS-MONPs can release molybdenum oxide nanoparticle to form deposited lubrication layer on worn surfaces.The as-formed composite tribofilm consisting of molybdenum oxide nanocrystal,amorphous polyphosphate,and molybdenum disulfide as well as a small amount of Mo2C accounts for the increase in the wear resistance of DLC coating under boundary lubrication.

The properties of transparent conducting molybdenum-doped ZnO films grown by radio frequency magnetron sputtering

Transparent conducting molybdenum-doped zinc oxide films are prepared by radio frequency（RF） magnetron sputtering at ambient temperature.The MoO3 content in the target varies from 0 to 5 wt%,and each film is polycrystalline with a hexagonal structure and a preferred orientation along the c axis.The resistivity first decreases and then increases with the increase in MoO3 content.The lowest resistivity achieved is 9.2 × 10^-4.cm,with a high Hall mobility of 30 cm^2.V-1.s-1 and a carrier concentration of 2.3×10^20 cm^-3 at an MoO3 content of 2 wt%.The average transmittance in the visible range is reduced from 91% to 80% with the increase in the MoO3 content in the target.

Effects of structures of molybdenum catalysts on selectivity in gas-phase propylene oxidation

Molybdenum-based catalysts for the gas-phase oxidation of propylene with air were investigated. Various types of silica-supported molybdenum oxide and molybdenum-bismuth mixed oxide cata- lysts were prepared from inorganic and organometallic molybdenum precursors using wet impregnation and physical vapor deposition methods. The epoxidation activities of the prepared cata- lysts showed direct correlations with their nanostructures, which were identified using transmission electron microscopy. The appearance of a partly or fully crystalline molybdenum oxide phase, which interacted poorly with the silica support, decreased the selectivity for propylene oxide for- mation to below 10%; non-crystalline octahedrally coordinated molybdenum species anchored on the support gave propylene oxide formations greater than 55%, with 11% propylene conversion. Electrochemical characterization of molybdenum oxides with various morphologies showed the importance of structural defects. Direct promotion by bismuth of the epoxidation reactivities over molybdenum oxides is disputed.