Search Results (13)

This study employs density functional theory (DFT) to investigate the electronic and optical properties of molybdenum (Mo) and chalcogen (S, Se, Te) co-doped anatase TiO₂. Two co-doping configurations were examined: Model 1, where the dopants are adjacent, and Model 2, where the dopants are farther apart. The incorporation of Mo into anatase TiO₂ resulted in a significant bandgap reduction, lowering it from 3.22 eV (pure TiO₂) to range of 2.52–0.68 eV, depending on the specific doping model. The introduction of Mo-4d states below the conduction band led to a shift in the Fermi level from the top of the valence band to the bottom of the conduction band, confirming the n-type doping characteristics of Mo in TiO₂. Chalcogen doping introduced isolated electronic states from Te-5p, S-3p, and Se-4p located above the valence band maximum, further reducing the bandgap. Among the examined configurations, Mo–S co-doping in Model 1 exhibited most optimal structural stability structure with the fewer impurity states, enhancing photocatalytic efficiency by reducing charge recombination. With the exception of Mo–Te co-doping, all co-doped systems demonstrated strong oxidation power under visible light, making Mo-S and Mo-Se co-doped TiO₂ promising candidates for oxidation-driven photocatalysis. However, their limited reduction ability suggests they may be less suitable for water-splitting applications. The study also revealed that dopant positioning significantly influences charge transfer and optoelectronic properties. Model 1 favored localized electron density and weaker magnetization, while Model 2 exhibited delocalized charge density and stronger magnetization. These findings underscore the critical role of dopant arrangement in optimizing TiO₂-based photocatalysts for solar energy applications. Full article

Carbon dioxide (CO₂) can be electrochemically, thermally, and photochemically reduced into valuable products such as carbon monoxide (CO), formic acid (HCOOH), methane (CH₄), and methanol (CH₃OH), contributing to carbon footprint mitigation. Extensive research has focused on catalysts, combining experimental approaches with computational quantum mechanics to elucidate reaction mechanisms. Although computational studies face challenges due to a lack of accurate approximations, they offer valuable insights and assist in selecting suitable catalysts for specific applications. This study investigates the electrocatalytic pathways of CO₂ reduction on cuprous oxide (Cu₂O) catalysts, utilizing the computational hydrogen electrode (CHE) model based on density functional theory (DFT). The electrocatalytic performance of flat Cu₂O (100) and hexagonal Cu₂O (111) surfaces was systematically analysed, using the standard hydrogen electrode (SHE) as a reference. Key parameters, including free energy changes (ΔG), adsorption energies (E_ads), reaction mechanisms, and pathways for various intermediates were estimated. The results showed that CO₂ was reduced to CO_(g) on both Cu₂O surfaces at low energies. However, methanol (CH₃OH) production was observed preferentially on Cu₂O (111) at ΔG = −1.61 eV, whereas formic acid (HCOOH) and formaldehyde (HCOH) formation were thermodynamically unfavourable at interfacial sites. The CO₂-to-methanol conversion on Cu₂O (100) exhibited a total ΔG of −3.38 eV, indicating lower feasibility compared to Cu₂O (111) with ΔG = −5.51 eV. These findings, which are entirely based on a computational approach, highlight the superior catalytic efficiency of Cu₂O (111) for methanol synthesis. This approach also holds the potential for assessing the catalytic performance of other transition metal oxides (e.g., nickel oxide, cobalt oxide, zinc oxide, and molybdenum oxide) and their modified forms through doping or alloying with various elements. Full article

Due to its low cost, natural abundance, non-toxicity, and high theoretical capacitance, cobalt oxide (CoO) stands as a promising candidate electrode material for supercapacitors. In this study, binder-less molybdenum doped CoO (Mo@CoO) integrated electrodes were one-step fabricated using a simple electric discharge corrosion (EDC) method. This EDC method enables the direct synthesis of Mo@CoO active materials with oxygen vacancy on cobalt substrates, without any pre-made templates, conductive additives, or chemicals. Most importantly, the EDC method enables precise control over the discharge processing parameter of pulse width, which facilitates tailoring the surface morphologies of the as-prepared Mo@CoO active materials. It was found that the fabricated Mo@CoO based symmetric supercapacitor prepared by a pulse width of 24 μs (Mo@CoO-SCs24) achieved a maximum areal capacitance 36.0 mF cm⁻² (0.15 mA cm⁻²), which is 1.83 and 1.97 times higher than that of Mo@CoO-SCs12 and Mo@CoO-SCs36. Moreover, the Mo@CoO-SCs24 devices could be worked at 10 V s⁻¹, which demonstrates their fast charge/discharge characteristic. These results demonstrated the significant potential of the EDC strategy for efficiency fabricating various metal oxide binder-less integrated electrodes for various applications, like supercapacitors, batteries and sensors. Full article

Climate change and damage to the environment, as well as the limitations of fossil fuels, have pushed governments to explore infinite renewable energy options such as biofuels. Solid Oxide Fuel Cell (SOFC) is a sustainable energy device that transforms biofuels into power and heat. It is now being researched to function at intermediate temperatures (600–700 °C) in order to prevent material deterioration and improve system life span. However, one of the major disadvantages of reducing the temperature is that carbon deposition impairs the electrochemical performance of the cell with a Ni-YSZ traditional anode. Here, molybdenum was doped into La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCFMo) as an innovative anode material with higher coke resistance and better phase stability under reducing conditions. X-ray diffraction (XRD) analysis showed increasing phase stability by increasing the Mo dopant. Electrochemical measurements proved that the LSCFMo anode is an active catalyst towards the methanol oxidation even at low temperatures as 600 °C, with an open circuit voltage (OCV) of 0.55 V, while GDC10 (Ga_0.9Ce_0.1O_1.95) is used as the electrolyte. As an insightful result, no trace of any carbon deposition was found on the anode side after the tests. The combination of phase composition, morphological, and electrochemical studies demonstrate that LSCFMo is a suitable anode material for SOFCs fed by biofuels. Full article

In this study, we report on how to design efficient catalysts for glucose oxidation via the transitional metal doping of nanohybrids of polyoxometalates (POMs) and metal-organic frameworks (MOFs). ZIF-67, a cobalt-based MOF, as well as phosphomolybdic acid (PMo), were used as precursors for the fabrication of pyrolyzed PMo@ZIF-67 (T-PMo@ZIF-67). A different amount of Ni²⁺ was doped into PMo@ZIF-67 to produce Ni_xCo_y@T-PMo@ZIF-67. Among them, Ni₂Co₂@T-PMo@ZIF-67 had the best performance. The power density of the fuel cell that used Ni₂Co₂@T-PMo@ZIF-67 as an anode catalyst was 3.76 times that of the cell that used active carbon as an anode catalyst. SEM and EDS mapping results indicate that Ni₂Co₂@T-PMo@ZIF-67 has a spherical structure and rough surface, and elements such as cobalt, nickel, and molybdenum are evenly distributed. XRD characterization indicates that Co₃O₄, CoMoO₄, CoNiO₄, and MoNiO₄ co-exist in the composites. It is supposed that Co²⁺, Mo⁶⁺, and Ni²⁺ in the composites may have synergistic effects on the catalytic oxidation of glucose. Full article

The cooperative transition of sulfur-containing pollutants of H₂S/CO/H₂ to the high-value chemical methyl mercaptan (CH₃SH) is catalyzed by Mo-based catalysts and has good application prospects. Herein, a series of Al₂O₃-supported molybdenum carbide catalysts with K doping (denoted herein as K-Mo₂C/Al₂O₃) are fabricated by the impregnation method, with the carbonization process occurring under different atmospheres and different temperatures between 400 and 600 °C. The CH₄-K-Mo₂C/Al₂O₃ catalyst carbonized by CH₄/H₂ at 500 °C displays unprecedented performance in the synthesis of CH₃SH from CO/H₂S/H₂, with 66.1% selectivity and a 0.2990 g·g_cat⁻¹·h⁻¹ formation rate of CH₃SH at 325 °C. H₂ temperature-programmed reduction, temperature-programmed desorption, X-ray diffraction and Raman and BET analyses reveal that the CH₄-K-Mo₂C/Al₂O₃ catalyst contains more Mo coordinatively unsaturated surface sites that are responsible for promoting the adsorption of reactants and the desorption of intermediate products, thereby improving the selectivity towards and production of CH₃SH. This study systematically investigates the effects of catalyst carbonization and passivation conditions on catalyst activity, conclusively demonstrating that Mo₂C-based catalyst systems can be highly selective for producing CH₃SH from CO/H₂S/H₂. Full article

Molybdenum carbide (Mo₂C) with a Pt-like d-band electron structure exhibits certain activities for oxygen reduction and evolution reactions (ORR/OER) in alkaline solutions, but it is questioned due to its poor OER stability. Combining Mo₂C with transition metals alloy is a feasible way to stabilize its electrochemical activity. Herein, CoFe-Prussian blue analogues are used as a precursor to compound with graphitic carbon nitride and Mo⁶⁺ to synthesize FeCo alloy and Mo₂C co-encapsulated N-doped carbon (NG-CoFe/Mo₂C). The morphology of NG-CoFe/Mo₂C (800 °C) shows that CoFe/Mo₂C heterojunctions are well wrapped by N-doped graphitic carbon. Carbon coating not only inhibits growth and agglomeration of Mo₂C/CoFe, but also enhances corrosion resistance of NG-CoFe/Mo₂C. NG-CoFe/Mo₂C (800 °C) exhibits an excellent half-wave potential (E_1/2 = 0.880 V) for ORR. It also obtains a lower OER overpotential (325 mV) than RuO₂ due to the formation of active species (CoOOH/β-FeOOH, as indicated by in-situ X-ray diffraction tests). E_1/2 shifts only 6 mV after 5000 ORR cycles, while overpotential for OER increases only 19 mV after 1000 cycles. ORR/OER performances of NG-CoFe/Mo₂C (800 °C) are close to or better than those of many recently reported catalysts. It provides an interfacial engineering strategy to enhance the intrinsic activity and stability of carbides modified by transition-metals alloy for oxygen electrocatalysis. Full article

This paper presents a computational study of the mechanistic models for the laydown of carbon species on nickel surface facets and the burn-off models for their gasification mechanism in methane steam reforming based on density functional theory. Insights into catalyst design strategies for achieving the simultaneous inhibition of the laydown of polymeric carbon and the promotion of its burn-off are obtained by investigating the influence of single atom dopants on nickel surfaces. The effects of single atom dopants on adsorption energies are determined at both low and high carbon coverages on nickel and used to introduce appropriate thermodynamic descriptors of the associated surface reactions. It is found that the critical size of the nucleating polymeric carbon adatom contains three atoms, i.e., C₃. The results show that the burn-off reaction of a polymeric carbon species is thermodynamically limited and hard to promote when the deposited carbon cluster grows beyond a critical size, C₄. The introduction of single atom dopants into nickel surfaces is found to modify the structural stability and adsorption energies of carbon adatom species, as well as the free energy profiles of surface reactions for the burn-off reactions when CH₄, H₂O, H₂, and CO species react to form hydrogen. The results reveal that materials development strategies that modify the sub-surface of the catalyst with potassium, strontium, or barium will inhibit carbon nucleation and promote burn-off, while surface doping with niobium, tungsten, or molybdenum will promote the laydown of polymeric carbon. This study provides underpinning insights into the reaction mechanisms for the coking of a nickel catalyst and the gasification routes that are possible for the recovery of a nickel catalyst during the steam reforming of methane for large-scale production of hydrogen. Full article

Molybdenum carbide (Mo₂C) is a promising and low-cost catalyst for the reverse water−gas shift (RWGS) reaction. Doping the Mo₂C surface with alkali metals can improve the activity of CO₂ conversion, but the effect of these metals on CO₂ conversion to CO remains poorly understood. In this study, the energies of CO₂ dissociation and CO desorption on the Mo₂C surface in the presence of different alkali metals (Na, K, Rb, and Cs) are calculated using density functional theory (DFT). Alkali metal doping results in increasing electron density on the Mo atoms and promotes the adsorption and activation of CO₂ on Mo₂C; the dissociation barrier of CO₂ is decreased from 12.51 on Mo₂C surfaces to 9.51–11.21 Kcal/mol on alkali metal-modified Mo₂C surfaces. Energetic and electronic analyses reveal that although the alkali metals directly bond with oxygen atoms of the oxides, the reduction in the energy of CO₂ dissociation can be attributed to the increased interaction between CO/O fragments and Mo in the transition states. The abilities of four alkali metals (Na, K, Rb, and Cs) to promote CO₂ dissociation increase in the order Na (11.21 Kcal/mol) < Rb (10.54 Kcal/mol) < Cs (10.41 Kcal/mol) < K (9.51 Kcal/mol). Through electronic analysis, it is found that the increased electron density on the Mo atoms is a result of the alkali metal, and a greater negative charge on Mo results in a lower energy barrier for CO₂ dissociation. Full article

In this work, we continued our systematic investigations on synthesis, structural studies, and electrochemical behavior of Ni-rich materials Li[Ni_xCo_yMn_z]O₂ (x + y + z = 1; x ≥ 0.8) for advanced lithium-ion batteries (LIBs). We focused, herein, on LiNi_0.85Co_0.10Mn_0.05O₂ (NCM85) and demonstrated that doping this material with high-charge cation Mo⁶⁺ (1 at. %, by a minor nickel substitution) results in substantially stable cycling performance, increased rate capability, lowering of the voltage hysteresis, and impedance in Li-cells with EC-EMC/LiPF₆ solutions. Incorporation of Mo-dopant into the NCM85 structure was carried out by in-situ approach, upon the synthesis using ammonium molybdate as the precursor. From X-ray diffraction studies and based on our previous investigation of Mo-doped NCM523 and Ni-rich NCM811 materials, it was revealed that Mo⁶⁺ preferably substitutes Ni residing either in 3a or 3b sites. We correlated the improved behavior of the doped NCM85 electrode materials in Li-cells with a partial Mo segregation at the surface and at the grain boundaries, a tendency established previously in our lab for the other members of the Li[Ni_xCo_yMn_z]O₂ family. Full article

Molybdenum oxide (MoO₃) and Fe,Co-codoped MoO₃ thin films obtained by spray pyrolysis have been in-depth investigated to understand the effect of Co and Fe codoping on MoO₃ thin films. The effect of Fe and Co on the structural, morphological and optical properties of MoO₃ thin films have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray analysis (EDAX), optical and photoluminescence (PL) spectroscopy, and electropyroelectric methods. The XRD patterns demonstrated the formation of orthorhombic α-MoO₃ by spray pyrolysis. SEM characterization has shown an increase in roughness of MoO₃ thin films by Fe and Co doping. Optical reflectance and transmittance measurements have shown an increase in optical band gap with the increase in Fe and Co contents. Thermal conductivity and thermal diffusivity of Fe,Co-doped MoO₃ were 24.10–25.86 Wm⁻¹K⁻¹ and 3.80 × 10⁻⁶–5.15 × 10⁻⁶ m²s⁻¹, respectively. MoO₃ thin films have shown PL emission. Doping MoO₃ with Fe and Co increases emission in the visible range due to an increase number of chemisorbed oxygen atoms. The photodegradation of an aqueous solution of methylene blue (MB) depended on the content of the codoping elements (Fe,Co). The results showed that a degradation efficiency of 90% was observed after 60 min for MoO₃: Fe 2%-Co 1%, while the degradation efficiency was about 35% for the undoped MoO₃ thin film. Full article

Various W and Mo co-doped titanium dioxide (TiO₂) materials were obtained through the EISA (Evaporation-Induced Self-Assembly) method and then tested as photocatalysts in the degradation of 4-chlorophenol. The synthesized materials were characterized by thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy (RS), N₂ physisorption, UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results showed that the W-Mo-TiO₂ catalysts have a high surface area of about 191 m²/g, and the presence of an anatase crystalline phase. The co-doped materials exhibited smaller crystallite sizes than those with one dopant, since the crystallinity is inhibited by the presence of both species. In addition, tungsten and molybdenum dopants are distributed and are incorporated into the anatase structure of TiO₂, due to changes in red parameters and lattice expansion. Under our experimental conditions, the co-doped TiO₂ catalyst presented 46% more 4-chlorophenol degradation than Degussa P25. The incorporation of two dopant cations in titania improved its photocatalytic performance, which was attributed to a cooperative effect by decreasing the recombination of photogenerated charges, high radiation absorption capacity, high surface areas, and low crystallinity. When TiO₂ is co-doped with the same amount of both cations (1 wt.%), the highest degradation and mineralization (97% and 74%, respectively) is achieved. Quinones were the main intermediates in the 4-chlorophenol oxidation by W-Mo-TiO₂ and 1,2,4-benzenetriol was incompletely degraded. Full article

A series of LiNbO₃: Mo, Hf crystals with 0.5 mol % fixed MoO₃ and various HfO₂ concentrations (0.0, 2.0, and 3.5 mol %) were grown by the Czochralski technique. The photorefractive properties of the LiNbO₃: Mo, Hf crystals were investigated by two-wave coupling measurements and the beam distortion method was employed to obtain the optical damage resistance ability. The UV-visible and OH⁻ absorption spectra were also studied. The experimental results imply that the photorefractive properties of LiNbO₃: Mo crystals at laser wavelengths of 532, 488, and 442 nm can be greatly enhanced by doping HfO₂ over the threshold concentration. At 442 nm especially, the response time of LN: Mo, Hf_3.5 can be shortened to 0.9 s with a diffraction efficiency of 46.07% and a photorefractive sensitivity reaching 6.28 cm/J. Besides this, the optical damage resistance at 532 nm is 3 orders of magnitude higher than that of the mono-doped LiNbO₃: Mo crystal, which is beneficial for applying it in the field of high-intensity lasers. Full article