Vapor-assisted engineering heterostructure of 1D Mo3N2 nanorod decorated with nitrogen-doped carbon for rapid pH-Universal hydrogen evolution reaction

Reasonable construction of heterostructure is of significance yet a great challenge towards efficient pH-universal catalysts for hydrogen evolution reaction (HER). Herein, a facial strategy coupling gas-phase nitridation with simultaneous heterogenization has been developed to synthesize heterostructure of one-dimensional (1D) Mo₃N₂ nanorod decorated with ultrathin nitrogen-doped carbon layer (Mo₃N₂@NC NR). Thereinto, the collaborative interface of Mo₃N₂ and NC is conducive to accomplish rapid electron transfer for reaction kinetics and weaken the Mo–H_ads bond for boosting the intrinsic activity of catalysts. As expected, Mo₃N₂@NC NR delivers an excellent catalytic activity for HER with low overpotentials of 85, 129, and 162 mV to achieve a current density of 10 mA cm^?2 in alkaline, acidic, and neutral electrolytes, respectively, and favorable long-term stability over a broad pH range. As for practical application in electrocatalytic water splitting (EWS) under alkaline, Mo₃N₂@NC NR || NiFe-LDH-based EWS also exhibits a low cell voltage of 1.55 V and favorable durability at a current density of 10 mA cm^?2, even surpassing the Pt/C || RuO₂-based EWS (1.60 V). Consequently, the proposed suitable methodology here may accelerate the development of Mo-based electrocatalysts in pH-universal non-noble metal materials for energy conversion.     

国产特殊装备用润滑脂的研制

为满足特殊装备使用中的润滑需求,选取聚α-烯烃和酯类油的混配油作为基础油,锂皂作为稠化剂,以纳米MoS_2作为极压抗磨剂,月桂酰胺丙基氧化胺作为助分散剂,月桂酰胺丙基氧化胺与二硫化钼质量比为1∶5,选用酚胺混合型抗氧剂,加入防锈剂C 1%,通过直接皂化的方法制备了一种新型润滑脂,纳米MoS_2和月桂酰胺丙基氧化胺在皂化反应阶段加入。该润滑脂的各项理化性能与现用商品润滑脂相当,且解决了现用润滑脂固体添加剂的团聚和沉降问题,提高了润滑脂的分散稳定性,综合性能优良,可以满足某特殊装备的润滑使用需求。     

New environmental-friendly yellow pigments Y_(4-x)A_xMoO_(9+δ)(A =Ta,Tb)

A series of inorganic yellow pigments with general formula Y_(4-x)A_xMoO_(9+δ)(A = Ta, Tb), where x = 0,0.05,0.1,0.2, 0.4 for Ta and χ = 0, 0.005, 0.01.0.03, 0.05 for Tb,were synthesized by a conventional ceramic method at 1400 ℃ for 6 h in air. The samples were characterized by XRD,EDS,XPS,SEM,TG-DSC,UV-vis-NIR reflectance spectroscopy and CIE L*a*b* color scales. It is found that the substitution of A(A = Ta, Tb) for Y~(3+) in Y_4 MoO_9 decreases the NIR reflectance of the pigment samples, but the developed pigments Y_(4-x)A_xMoO_(9+δ)(A = Ta, Tb) still exhibit impressive NIR solar reflectance. The brighter yellow color of inorganic pigments Y_(4-x)A_xMoO_(9+δ)(A = Ta, Tb) is available when x is about 0.1 for Ta and 0.01 for Tb. The results make them a series of potential candidates as ecological yellow pigments because of their high reflectance, lightness, intense coloration and excellent thermal and chemical stability.     

Studies on influence of hydrogen and carbon monoxide concentration on reduction progression behavior of molybdenum oxide catalyst

Temperature programmed reduction (TPR) analysis was applied to investigate the chemical reduction progression behavior of molybdenum oxide (MoO₃) catalyst. The composition and morphology of the reduced phases were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). The reduction progression of MoO₃ catalyst was attained with different reductant types and concentration (10% H₂/N₂, 10% and 20% CO/N₂ (%, v/v)). Two different modes of reduction process were applied. The first approach of reduction involved non-isothermal mode reduction up to 700 °C, while the second approach of reduction involved the isothermal mode reduction for 60 min at 700 °C. Hydrogen temperature programmed reduction (H₂-TPR) results showed the reduction progression of three-stage reduction of MoO₃ (Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰) with Mo⁵⁺ and Mo⁴⁺. XRD analysis confirmed the formation of Mo₄O₁₁ phase as an intermediate phase followed by MoO₂ phase. After 60 min of isothermal reduction, peaks of metallic molybdenum (Mo) appeared. Whereas, FESEM analysis showed porous crater-like structure on the surface cracks of MoO₂ layer which led to the growth of Mo phase. Meanwhile, the reduction of MoO₃ catalyst in 10% carbon monoxide (CO) showed the formation of unstable intermediate phase of Mo₉O₂₆ at the early stage of reduction. Furthermore, by increasing 20% CO led to the carburization of MoO₂ phase, resulted in the formation of Mo₂C rather than the formation of metallic Mo, as confirmed by XPS analysis. Therefore, the presented study shows that hydrogen gave better reducibility due to smaller molecular size, which contributed to high diffusion rate and achieved deeper penetration into the MoO₃ catalyst compared to carbon monoxide reductant. Hence, the reduction of MoO₃ in carbon monoxide atmosphere promoted the formation of Mo₂C which was in agreement with the thermodynamic assessment.     

Synthesis and photocatalytic performance of MoS2/Polycrystalline black phosphorus heterojunction composite

As a promising catalyst for solar hydrogen production, black phosphorus (BP) has received widespread attention due to variable band gaps, high carrier mobility, and strong light absorption performance. Herein, we use MoS₂ as a cocatalyst to synthesize BP/MoS₂ catalyst with polycrystalline BP to improve photocatalytic performance under visible light irradiation. A small amount of MoS₂ can reduce the recombination of electron-hole pairs in the composite, increase carrier transport efficiency, and then improve photocatalytic performance. As expected, the 10/0.5 ratio of BP/MoS₂ catalyst exhibits the highest photocatalytic hydrogen evolution performance with a hydrogen evolution rate of 575.4 μmol h^?1 g^?1, which is 2.5 times of pure BP. Based on the results above, a simple method is provided to synthesize low-cost black phosphorus-based photocatalysts.     

Copper-doped flower-like molybdenum disulfide/bismuth sulfide photocatalysts for enhanced solar water splitting

A facile synthesis approach to fabricate Cu-doped MoS₂/Bi₂S₃ (Cu-MoS₂/Bi₂S₃) photocatalysts is reported. The photocatalyst samples with varying amounts of Cu are applied in the photocatalytic splitting of water to produce H₂ under the irradiation of simulated solar light. The Cu-MoS₂/Bi₂S₃ photocatalysts with an optimum Cu loading of 20 mol% exhibited high photocatalytic performance, achieving a total H₂ yield of 32.4 μmol/h after 6 h of reaction. The photoactivity of the Cu-doped sample was shown to have risen more than 40% than that of pure MoS₂/Bi₂S₃. The improved performance is attributed to the impurity states generated within Cu-doped MoS₂, which serve as trapping sites for photogenerated electrons. The effective charge transfer mechanism achieved was evidenced by photoelectrochemical measurements. Based on the experimental results obtained, a plausible mechanism for the photocatalytic process associated with Cu-MoS₂/Bi₂S₃ was proposed.     

Facile synthesis of MoS2/N-doped macro-mesoporous carbon hybrid as efficient electrocatalyst for hydrogen evolution reaction

A novel three-dimensional (3D) hybrid consisting of molybdenum disulfide nanosheets (MoS₂) uniformly bound at N-doped macro-mesoporous carbon (N-MMC) surface was fabricated by the solvothermal method. The resulting MoS₂/N-MMC hybrid possesses few-layer MoS₂ nanosheets structure with abundant edges of MoS₂ exposed as active sites for hydrogen evolution reaction (HER), in sharp contrast to large aggregated MoS₂ nanoflowers without N-MMC. The high electric conductivity of N-MMC and an abundance of exposed edges on the MoS₂ nanosheets make the hybrid excellent electrocatalytic performance with a low onset potential of 98 mV, a small Tafel slope of 52 mV/decade, and a current density of 10 mA cm^?2 at the overpotential of 150 mV. Moreover, the MoS₂/N-MMC hybrid exhibits outstanding electrochemical stability and structural integrity owing to the strong bonding between MoS₂ nanosheets and N-MMC.     

Hierarchical MoS2 nanoflowers on carbon cloth as an efficient cathode electrode for hydrogen evolution under all pH values

In this paper, a facile hydrothermal synthetic strategy was developed for MoS₂ nanoflowers with enlarged interlayer spacing on the carbon cloth (CC) as a high efficiency cathode electrode for hydrogen evolution reaction (HER) under wide pH condition. It was observed that the loading amount of MoS₂ has a major impact on the HER performance, where the optimized MoS₂/CC exhibited a low onset potential of 94 mV and a small Tafel slope of 50 mV dec^?1 in strong acid solution (pH = 0). The improved HER performance can be contributed to the enlarged interlayer spacing, abundant defects and more exposed active sites in the small size MoS₂ nanosheets as revealed by XRD and HRTEM. Meanwhile, it also exhibited relatively good performance for HER under basic and neutral conditions with the overpotentials of 188 (pH = 14) and 230 (pH = 7) mV to achieve current density of 10 mA cm^?2 and the Tafel slopes of 52 and 84 mV dec^?1, respectively.     

Efficient overall water splitting over a Mo(IV)-doped Co3O4/NC electrocatalyst

To meet the demand of producing hydrogen at low cost, a molybdenum (Mo)-doped cobalt oxide (Co₃O₄) supported on nitrogen (N)-doped carbon (x%Mo–Co₃O₄/NC, where x% represents Mo/Co molar ratio) is developed as an efficient bifunctional electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This defect engineering strategy is realized by a facile urea oxidation method in nitrogen atmosphere. Through X-ray diffraction (XRD) refinement and other detailed characterizations, molybdenum ion (Mo⁴⁺) is found to be doped into Co₃O₄ by substituting cobalt ion (Co²⁺) at tetrahedron site, while N is doped into carbon matrix simultaneously. 4%Mo–Co₃O₄/NC is the optimized sample to show the lowest overpotentials of 91 and 276 mV to deliver 10 mA cm^?2 for HER and OER in 1 M potassium hydroxide solution (KOH), respectively. The overall water splitting cell 4%Mo–Co₃O₄/NC||4%Mo–Co₃O₄/NC displays a voltage of 1.62 V to deliver 10 mA cm^?2 in 1 M KOH. The Mo⁴⁺ dopant modulates the electronic structure of active cobalt ion (Co³⁺) and boosts the water dissociation process during HER, while the increased amount of lattice oxygen and formation of pyridinic nitrogen due to Mo doping benefits the OER activity. Besides, the smaller grain size owing to Mo doping leads to higher electrochemically active surface area (ECSA) on 4%Mo–Co₃O₄/NC, resulting in its superior bifunctional catalytic activity.     

Interfacing perovskite strontium molybdate to molybdenum disulfide nanoplatelts for boosting HER from water

Due to low hydrogen adsorption free energy at the edges of 2D-MoS₂ layered sheets, nanostructured MoS₂ materials recently are assigned to prospective electrocatalysts for hydrogen evolution reaction (HER) from water. However, the efficiency and stability of HER onto the MoS₂ designed on the conductive substrates are poor. To significantly increase the number of active sites and achieve a long-time working stability, the design of hybrid-type electrodes is crucial. Here, we report the synthesis of a new hybrid material composed of molybdenum disulfide and molybdenum oxides heterostructured with strontium molybdate. For this, a facile one-pot hydrothermal process was developed directly onto the TiO₂ nanotube carpet substrate. The interfacing of strontium molybdate at the electrode substrate verified by X-ray photoelectron spectroscopy and Time of flight secondary ions mass spectrometry (ToF SIMS) techniques. Considerable higher catalytic activity at the surface of this hybrid film, with the onset potential of 190 mV vs RHE and a Tafel slope of 66 mV dec^?1 attaining ~80 mA cm^?2 at 0.35 V overvoltage was ascertained. Exciting HER stability in comparison with the pure synthetic MoS₂ was verified by a prolonged potential cycling from 0.05 to ?0.35 V versus RHE potential and 45 h continuous HER processing at a constant current density.