Molybdenum Oxide Research Articles

Mitochondria‐Targeted Photoredox Catalysis Activates Pyroptosis for Effective Tumor Therapy

AbstractThe development of biocompatible and efficient photocatalytic redox systems to mimic bio‐photoreactors in living cells holds great potential for manipulating intracellular biochemical reaction processes and thus advancing tumor therapy. In this study, a mitochondria‐targeted photoredox catalyst, 2D vacancy‐rich molybdenum oxide nanosheets (Mt‐VR‐MoO3) is presented. These nanosheets possess a high density of oxygen vacancies (19.2%) and exhibit strong photocatalytic redox activity under near‐infrared (NIR) light. Following a two‐step functionalization, Mt‐VR‐MoO3 effectively disrupts mitochondrial electron flow in an oxygen‐independent manner upon irradiation with second near‐infrared (NIR‐II) light. This targeted disruption leads to on‐demand induction of substantial damage to tumor cell mitochondria, characterized by increased production of mitochondrial reactive oxygen species (mtROS) and the release of cytochrome c (Cyt c), which collectively trigger the pyroptosis of cancer cells. The approach achieved tumor‐targeted photocatalytic eradication with high efficacy (tumor growth inhibition rate of 86.9%) in an orthotopic breast 4T1 murine tumor model, with no observable harm to normal organs. These findings provide inspiration for manipulating intracellular biochemical reactions using artificial photocatalytic materials, paving the way for pyroptosis activation as a promising approach in tumor therapy.

A Single-Atom Mn/MoO3- x Nanoagonist for Cascade cGAS/STING Activation in Tumor-Specific Catalytic Metalloimmunotherapy.

The cyclic GMP-AMP synthase (cGAS)/stimulator of interferon genes (STING) pathway plays a crucial role in initiating anti-tumor immunity. Despite the development of various STING agonists, their effectiveness is often limited by suboptimal activation efficiency and poor sustainability. To address this, a Mn/MoO3- x nanoagonist featuring Mn single-atom sites is presented, designed for cascade cGAS/STING activation in tumor-specific catalytic metalloimmunotherapy. The single-atom nanoagonist (SANA) is meticulously crafted by doping Mn atoms into defective molybdenum oxide (MoO3- x), enabling robust peroxidase-mimicking catalysis and inducing severe double-stranded DNA (dsDNA) damage in tumors. Of note, Mn2+ and MoO4 2- can be responsively released from Mn/MoO3- x SANA and enhance the sensitivity of cGAS to dsDNA. Importantly, MoO4 2- with a relatively slow-release profile and facile cellular accumulation compensates for Mn2+ that has poor cellular accumulation due to continuous efflux, thus continuatively triggering the secretion of type I interferon for beyond 72 h. Remarkably, Mn/MoO3- x SANA significantly inhibits tumor growth and metastasis without supplementary STING agonists or external stimulation. This study offers a promising cascade cGAS/STING activation approach to enhance the efficacy and sustainability of catalytic metalloimmunotherapy.

Gamma Radiation Shielding and Interaction Properties of MoO3-Doped Cadmium Zinc Lithium-Borate Glasses

This study, theoretically examined the impact of MoO3 addition on gamma radiation shielding properties of cadmium zinc lithium-borate (BCZLMx) glasses to find the optimal quantity of molybdenum oxide (MoO3) needed for a stable glass matrix with excellent gamma shielding capabilities. Gamma radiation transmission parameters that include Mass attenuation coefficient, Mass energy absorption coefficient, Equivalent atomic number, Effective electron density, Dose rate, Exposure buildup factors and Energy absorption buildup factor were evaluated using FLUKA and XCOM computer programs. Results showed that 60B2O3-20CdO-10ZnO-8Li2O-2MoO3 (BCZLM5) was the most stable and efficient glass sample for X-rays and gamma radiation shielding across all photon energy ranges. Hence, BCZLM5 should be deployed for X-rays and gamma radiation shielding to provide maximum protection and exceptional safety for workers in hospital X-ray rooms and nuclear installations against ionizing radiation.

Porous molybdenum oxides prepared from hydrothermal precursor

Porous molybdenum oxides prepared from hydrothermal precursor

Zn2Mo3O8/ZnMo8O10/Mo8O23 nanocomposites; structural properties, synthesis and its emerging application in electrochemical hydrogen storage

Electrode materials based on zinc molybdenum oxides were designed by the saccharide-assisted sol-gel procedure for electrochemical hydrogen storage (EHS). By using different characterization methods to observe the formation of nanostructures, it was possible to determine that carbon texture was present on the nanostructured surfaces of zinc molybdenum oxides. The effects of employing various saccharides (mono, di, and poly saccharides) as carbon sources and fuel on the microstructure, electrochemical behaviors, and purity of synthesized samples were compared. The growth of nanocomposites including Zn2Mo3O8, ZnMo8O10, and Mo8O23 phases was facilitated by the saccharide. A charge-discharge method was used to build three-electrode cells and expose them to galvanostatic cycling. To ascertain the stability of electrode architectures, cycling performance at various rates was carried out. The samples' hydrogen storage capabilities were examined, and the sample generated with glucose showed an optimum capacity about 1017 mAhg−1 after 15th cycle.

Defect-engineered thermal diffusivity modifications of molybdenum oxide: A photopyroelectric study

Defect-engineered thermal diffusivity modifications of molybdenum oxide: A photopyroelectric study

Praseodymium-Cerium Oxide-Infiltrated Perovskite Cathode with Superior Electrochemical Performance for Solid Oxide Fuel Cells.

This study presents a high-performance solid oxide fuel cell employing a perovskite cathode, strontium iron molybdenum oxide [Sr2Fe1.5Mo0.5O6-δ (SFM)], infiltrated with praseodymium-cerium oxide [Pr0.2Ce0.8O2-δ (PCO)], a fluorite. This infiltration notably enhances the oxygen reduction reaction kinetics and long-term stability. Evidence of enhanced stability is seen through minimized impedance degradation over 50 h. Furthermore, PCO infiltration improves the cathode's resistance to chromium poisoning by suppressing strontium degradation. Compared to the bare SFM cathode, the PCO-infiltrated SFM composite cathode doubles the cell's power density at 800 °C.

Disassembling one-dimensional chains in molybdenum oxides

Abstract The dimensionality of quantum materials strongly affects their physical properties. Although many emergent phenomena, such as charge-density wave and Luttinger liquid behavior, are well understood in one-dimensional (1D) systems, the generalization to explore them in higher dimensional systems is still a challenging task. In this study, we aim to bridge this gap by systematically investigating the crystal and electronic structures of molybdenum-oxide family compounds, where the contexture of 1D chains facilitates rich emergent properties. While the quasi-1D chains in these materials share general similarities, such as the motifs made up of MoO6 octahedrons, they exhibit vast complexity and remarkable tunability. We disassemble the 1D chains in molybdenum oxides with different dimensions and construct effective models to excellently fit their low-energy electronic structures obtained by ab initio calculations. Furthermore, we discuss the implications of such chains on other physical properties of the materials and the practical significance of the effective models. Our work establishes the molybdenum oxides as simple and tunable model systems for studying and manipulating the dimensionality in quantum systems.

The Synergic Effect of h-MoO3, α-MoO3, and β-MoO3 Phase Mixture as a Solid Catalyst to Obtain Methyl Oleate.

Extensive research in the last few decades has conclusively demonstrated the significant influence of experimental conditions, surfactants, and synthesis methods on semiconductors' properties in technological applications. Therefore, in this study, the synthesis of molybdenum oxide (MoO3) was reported by the addition of 2.5 (MoO3_2.5), 5 (MoO3_5), 7.5 (MoO3_7.5), and 10 mL (MoO3_10) of nitric acid, obtaining the respective concentrations of 0.6, 1.10, 1.6, and 0.6 mol L-1. In this study, all samples were synthesized by the hydrothermal method at 160 °C for 6 h. The materials obtained were structurally characterized by X-ray diffraction (XRD) and structural Rietveld refinement, Raman spectroscopy, and infrared spectroscopy (FTIR), confirming the presence of all crystallographic planes and bands associated with active modes for the pure hexagonal phase (h-MoO3) when the solution's concentration was 0.6 mol L-1 of nitric acid. For concentrations of 1.10, 1.60, and 2.10 mol L-1, the presence of crystallographic planes and active modes associated with the formation of mixtures of molybdenum oxide polymorphs was confirmed, in this case, the orthorhombic, monoclinic, and hexagonal phases. X-ray photoelectron spectroscopy reveals the occurrence of the states Mo4+, Mo5+, and Mo6+, which confirm the predominance of the acid Lewis sites, corroborating the analysis by adsorption of pyridine followed by characterization by infrared spectroscopy. The images collected by scanning electron microscopy confirmed the information presented in the structural characterization, where microcrystals with hexagonal morphology were obtained for the MoO3_2.5 sample. In contrast, the MoO3_5, MoO3_7.5, and MoO3_10 samples exhibited hexagonal and rod-shaped microcrystals, where the latter morphology is characteristic of the orthorhombic phase. The catalytic tests carried out in the conversion of oleic acid into methyl oleate, using the synthesized samples as a heterogeneous catalyst, resulted in conversion percentages of 52.5, 58.6, 69.1, and 97.2% applying the samples MoO3_2.5, MoO3_5, MoO3_7.5, and MoO3_10, respectively. The optimization of the catalytic tests with the MoO3_10 sample revealed that the conversion of oleic acid into methyl oleate is a thermodynamically favorable process, with a variation in the Gibbs free energy between -67.3 kJ mol-1 and 83.4 kJ mol-1 as also, the energy value of activation of 24.6 kJ mol-1, for the temperature range from 80 to 140 °C, that is, from 353.15 to 413.15 K, respectively. Meanwhile, the catalyst reuse tests resulted in percentages greater than 85%, even after the ninth catalytic cycle. Therefore, the expressive catalytic performance of the mixture of h-MoO3 and α-MoO3 (MoO3_10) phases is confirmed, associated with the synergistic effect, mainly due to the increase in the surface area and available Lewis sites of these phases.

Molybdenum-Oxide-Modified PEDOT:PSS as Efficient Hole Transport Layer in Perovskite Solar Cells.

Over the last ten years, there has been a remarkable enhancement in the power conversion efficiency (PCE) of perovskite solar cells (PSCs), with poly (3,4-ethylenedioxythiohene):poly (styrenesulfonate) (PEDOT:PSS) emerging as a prevalent choice for the hole transport layer (HTL). Nevertheless, the evolution of the widely utilized PEDOT:PSS HTL has not kept pace with the swift advancements in PSC technology, attributed to its suboptimal electrical conductivity, acidic nature, and inadequate electron-blocking performance. This study presents a novel approach to enhance the HTL by introducing molybdenum oxide (MoO3) into the PEDOT:PSS, leveraging the conductivity and solution processing compatibility of MoO3. Two methods for MoO3 integration were explored: an ammonium molybdate tetrahydrate (AMT) precursor and the direct addition of MoO3 nanoparticles. The carrier dynamics of PSCs modified by MoO3 are significantly optimized. Therefore, the PCE of the device modified by AMT and molybdenum oxide is increased to 18.23 and 19.64%, respectively, and the stability of the device is also improved. This study emphasizes the potential of MoO3 in contributing to the development of more efficient and stable PSCs.

Enhanced Energy Storage Capacity of TiO2 Atomic Layered Molybdenum Oxide–Sulfide Negatrode for an Aqueous Ammonium Ion Supercapacitor

Enhanced Energy Storage Capacity of TiO2 Atomic Layered Molybdenum Oxide–Sulfide Negatrode for an Aqueous Ammonium Ion Supercapacitor

Metal-to-insulator phase transition of molybdenum oxide for reversible writing and erasing information encryption

Abstract We have reported a theoretical device design for reversible writing and erasing information encryption using a simple two layered structure, which consists of a MoOx layer and a SiO2 space layer on a silver substrate. The MoOx layer can be switched between two phases, i.e., metallic MoO2 and insulating MoO3. The phase transition of MoOx possesses very complicated processes, which makes it advantageous for information decryption. Generally, in the proposed structure with metallic MoO2, various colors can be generated due to the F-P enhanced absorption at wavelengths where construction interference occurs. However, owing to the low loss of insulating MoO3 in visible region, the absorption is low though out the whole visible region, thus all colors can be erased to white. Therefore, the color image information can be written and erased with our proposed structure by switching MoOx between phases of metallic MoO2 and insulating MoO3. The proposed image encryption device can be acquired easily by masking and coating processes. We believe our results provides a new way in designing encryption devices.

A Comparative Study of the Impact of La2O3 and La2Zr2O7 Dispersions on Molybdenum Microstructure, Mechanical Properties, and Fracture

AbstractWe report, for the first time, the effect of lanthanum zirconate (La2Zr2O7) particles on the microstructure and mechanical behavior of an experimental molybdenum oxide dispersion-strengthened alloy. The focus was on the preparation of the novel Mo–La2Zr2O7 composite using high-energy ball milling and spark plasma sintering and on the comparison of its microstructural and mechanical properties with pure Mo and Mo–La2O3 ODS alloy counterparts. Mechanical properties were assessed using a Vickers hardness test at room temperature and a three-point flexural test in the temperature range from − 150 to 150 °C. The microstructure of the studied materials and their fracture behavior were evaluated using x-ray diffraction, energy-dispersive x-ray spectroscopy, and scanning electron and transmission electron microscopy. The strengthening effect of La2Zr2O7 particles was found to be lower than that of La2O3 particles, resulting in a 30-35% lower yield stress and flexural strength of the Mo–La2Zr2O7 alloy compared to the Mo–La2O3 alloy. The experimental Mo–La2Zr2O7 alloy exhibited low plasticity and no distinct ductile-to-brittle transition temperature (DBTT) in the tested temperature range, unlike pure Mo and the Mo–La2O3 alloy, which had the DBTT of 63 and 1 °C, respectively. Fracture occurred mainly in a brittle intergranular manner in the entire testing temperature range, while the counterpart materials showed localized plastic stretching at grain boundaries and within grains at and above the transition region. The observed behavior was primarily related to lower strengthening and brittleness as well as less effective grain boundary purification.

In‐Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water‐Gas Shift Reaction

AbstractIn situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water‐gas shift (RWGS) reaction. Surface oxygen atoms in various Mo‐based catalysts are removed in H2‐containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt‐dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal−1 ⋅ h−1 at 600 °C has been achieved over in situ carbonized H‐intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.

In-Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water-Gas Shift Reaction.

In situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water-gas shift (RWGS) reaction. Surface oxygen atoms in various Mo-based catalysts are removed in H2-containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt-dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal -1 ⋅ h-1 at 600 °C has been achieved over in situ carbonized H-intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.

Synthesis and assessment of the Mo/MoO3/CZTS/Ag diode fabricated by one-pot hydrothermal route: impact of temperature

A facile one-step hydrothermal method was utilized to prepare Cu2ZnSnS4 film employing EDTA as a complexing agent. An effective Molybdenum oxide layer was also formed in the same approach for forming the Cu2ZnSnS4 film. The influence of preparation temperature on structural, morphology, and optical characteristics was studied. The formation of crystalline kesterite phase Cu2ZnSnS4 films with preferred orientation along the (112) plane was confirmed by X-ray diffraction and Raman spectroscopy, and it was also demonstrated that structure property changes with preparation temperatures: kesterite phase Cu2ZnSnS4 is formed at lower preparation temperatures and kesterite phase Cu2ZnSnS4 and Cu2S are formed with increasing preparation temperature. Also, Raman analysis confirmed the formation of a Molybdenum oxide layer on the Mo substrate. Field emission scanning electron microscopy revealed that surface morphology changes from leaves of trees to flake-flowers. According to UV-visible analysis, Cu2ZnSnS4 films exhibited high and wide absorbance spectra in the visible and infrared regions and a band gap between (1.67-1.9) eV. Photoluminescence analysis revealed emission peaks at (1.569, 1.55, and 1.56) eV for samples prepared at (160, 200, and 230)0C, respectively, which is very close to the band's gap of Cu2ZnSnS4. Finally, the electrical study of Mo/MoO3/CZTS/Ag junctions was performed by using current-voltage (I-V) measurement.

Mo-modified Pt/C electrocatalyst prepared by the catalytic decomposition of molybdenum peroxo-complexes for the hydrogen oxidation reaction with enhanced CO tolerance

Commercial 20 % Pt/C catalyst was modified by molybdenum via catalytic decomposition of peroxocomplexes of molybdenum with the subsequent reduction of the Pt2Mo1/C precursor in H2 flow at 600 °C. The detailed HRTEM, EDX, XRD and XPS studies showed that amorphous molybdenum oxide was deposited on Pt particles surface and partially on carbon support. After reduction of the Pt2Mo1/C precursor, the substantial Mo fraction merges the structure of Pt particles thus forming PtMo alloy with reduced lattice parameter, while the rest of molybdenum covers the surface of PtMo particles as MoO3. The presented method of Mo-modification of Pt-based catalysts provides rather simple way to vary Pt:Mo molar ratio. Electrochemical study revealed that the amount of the surface MoO3 plays a key role in the CO tolerance of the PtMo/C catalyst. As prepared Pt2Mo1/C precursor is 15 times superior to the Pt/C catalyst in the CO-tolerance. After reduction, the Pt2Mo1/C electrocatalyst exhibits extremely high CO-tolerance, more than 100 times higher than that of the pristine commercial platinum catalyst.

Reduction and structural modification of MoOx/γ-Al2O3 catalysts through acetic acid treatment for green diesel production from corn distiller’s oil

Enabling new environmentally-friendly resources for fuels and platform chemicals is crucial to fulfill our future energy demands while enhancing circularity. Corn distiller’s Oil (CDO) − as a coproduct of the ethanol industry, serves as a sustainable supply of carbon that may be converted into energy, fuels and specialty chemicals. A current challenge in using renewable oxygenated feedstocks is the high amount of coking and catalyst fouling that occurs. This study examined the hydrothermal deoxygenation of CDO into green diesel using molybdenum oxide (MoOx) catalysts in a continuous process without using any external hydrogen. The possibility of reduction and developing oxygen-deficient surfaces on molybdenum oxide (MoOx) catalysts through acetic acid treatment or adding ceria (CeO2) was investigated in order to enhance the acidity of catalysts as well as catalytic activity and stability required for the production of green diesel from CDO. Results showed that the acidity of these catalysts as measured by NH3 temperature programmed desorption (NH3-TPD) had a strong correlation between the degree of deoxygenation and catalyst stability. Acetic acid treatment of the 7.5 wt% MoO3/γ-Al2O3 catalyst reduced MoO3 to MoO3-x, increased the Mo5+ species from 8.7 % to 22 %, created Mo4+ species and increased the catalyst surface acidity in the range of low to moderate strength by approximately 17 %. The use of acetic acid-treated molybdenum oxide (Hac-7.5 wt% MoO3/γ-Al2O3) catalyst enabled nearly complete (99.9 %) deoxygenation of CDO and heavy hydrocarbons cracking to produce diesel-like fuels. A moderate increase in catalyst surface acidity by acetic acid treatment also increased the selectivity of diesel-like fuel through hydrocracking of long-chain hydrocarbons. This low-cost modification step of catalyst improvement is promising for industrial application. However, cracking of hydrocarbons generated amorphous coke (no graphitic coke was observed) on the catalyst surface, which required periodic removal by controlled calcination of the catalyst in presence of air for further use.

Hydrothermally synthesized nitrogen-doped hydrochar from sawdust biomass for supercapacitor electrodes

Porous carbon generated from biomass is among the most promising electrode materials for supercapacitor applications. In this research work, sawdust was used as a carbon source to synthesize N-doped hydrochars via the hydrothermal method in the presence of nitrogen-containing compounds including ammonium chloride, urea agar, ammonium molybdate tetrahydrate, and mammalian urine, followed by chemical activation by potassium hydroxide. Using the hydrothermal technique, it was possible to dope 7.06 wt% of nitrogen into the hydrochar. The as synthesized materials were characterized by TGA/DTA, FTIR, BET, XRD, SEM/EDS, XPS, and proximate analysis. Furthermore, EIS, CV, and GCD were used to assess electrochemical performance. All the N-doped hydrochars synthesized samples possess crystalline and mesoporous structures with hydroxyl and amide functional groups. The KOH activation improved the specific surface area and pore volume by 8.5 % and 21 %, respectively. The maximum specific surface area and pore volume were found to be 560.72 m2/g and 0.2246 cc/g, respectively. The CV findings demonstrate the battery-like characteristics of the electrocatalysts made with molybdenum (VI) oxide (MoO3) embedded in these N-doped hydrochars, yielding 35.16 F/g specific capacitance at 10 mV/s. In contrast, the GCD's specific capacitance displays 80 F/g at 0.5 Ag−1.

Valence-engineered catalysis-selectivity regulation of molybdenum oxide nanozyme for acute kidney injury therapy and post-cure assessment.

The optimization of the enzyme-like catalytic selectivity of nanozymes for specific reactive oxygen species (ROS)-related applications is significant, and meanwhile the real-time monitoring of ROS is really crucial for tracking the therapeutic process. Herein, we present a mild oxidation valence-engineering strategy to modulate the valence states of Mo in Pluronic F127-coated MoO3-x nanozymes (denoted as MF-x, x: oxidation time) in a controlled manner aiming to improve their specificity of H2O2-associated catalytic reactions for specific therapy and monitoring of ROS-related diseases. Experimentally, MF-0 (Mo average valence 4.64) and MF-10 (Mo average valence 5.68) exhibit exclusively optimal catalase (CAT)- or peroxidase (POD)-like activity, respectively. Density functional theory (DFT) calculations verify the most favorable reaction path for both MF-0- and MF-10-catalyzed reaction processes based on free energy diagram and electronic structure analysis, disclosing the mechanism of the H2O2 activation pathway on the Mo-based nanozymes. Furthermore, MF-0 poses a strong potential in acute kidney injury (AKI) treatment, achieving excellent therapeutic outcomes in vitro and in vivo. Notably, the ROS-responsive photoacoustic imaging (PAI) signal of MF-0 during treatment guarantees real-time monitoring of the therapeutic effect and post-cure assessment in vivo, providing a highly desirable non-invasive diagnostic approach for ROS-related diseases.