CNT-interconnected iron-doped NiP2/Ni2P heterostructural nanoflowers as high-efficiency electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) plays a decisive role in electrolytic water splitting. However, it is still challengeable to develop low-cost and efficient OER electrocatalysts. Herein, we present a combination strategy via heteroatom doping, hetero-interface engineering and introducing conductive skeleton to synthesize a hybrid OER catalyst of CNT-interconnected iron-doped NiP₂/Ni₂P (Fe-(NiP₂/Ni₂P)@CNT) heterostructural nanoflowers by a simple hydrothermal reaction and subsequent phosphorization process. The optimized Fe-(NiP₂/Ni₂P)@CNT catalyst delivers an ultralow Tafel slope of 46.1 mV dec^?1 and overpotential of 254 mV to obtain 10 mA cm^?2, which are even better than those of commercial OER catalyst RuO₂. The excellent OER performance is mainly attributed to its unique nanoarchitecture and the synergistic effects: the nanoflowers constructed by a 2D-like nanosheets guarantee large specific area and abundant active sites; the highly conductive CNT skeleton and the electronic modulation by the heterostructural NiP₂/Ni₂P interface and the hetero-atom doping can improve the catalytic activity; porous nanostructure benefits electrolyte penetration and gas release; most importantly, the rough surface and rich defects caused by phosphorization process can further enhance the OER performance. This work provides a deep insight to boost catalytic performance by heteroatom doping and interface engineering for water splitting.     

Understanding on the hydrogen detection of plasma sprayed tin oxide/tungsten oxide (SnO2/WO3) sensor

The plasma spray technique was well proven in producing metal oxide based gas sensors in the last two decades using different powder feedstocks. However, limited research was made to fabricate hydrogen gas sensor from tin oxide layer coated over tungsten oxide layer. This paper attempts to interpret the hydrogen gas sensing performances of plasma sprayed coating derived by depositing tin oxide layer over tungsten oxide (SnO₂/WO₃) layer. Plasma sprayed SnO₂/WO₃ sensor showed maximum response of 90% at 150 °C in contrast to stand-alone WO₃ (89% at 350 °C) and stand-alone SnO₂ (89% at 250 °C). The lower operating temperature of SnO₂/WO₃ sensor without compromising gas response was attributed to the WO₃–SnO₂ hetero-junction. SnO₂/WO₃ sensor showed selective sensing towards hydrogen with respect to carbon monoxide and methane gases. This sensor also possessed repeatable characteristics after 39 days from the initial measurement. In a nut-shell, plasma spayed SnO₂/WO₃ sensor showed stability of base resistance, repeatability after successive response and recovery cycles, selective sensing towards 500 ppm H₂ with significant magnitude of gas response of 90%, response time of 35 s and recovery time of 269 s at a temperature of 150 °C.     

FeCo alloys in-situ formed in Co/Co2P/N-doped carbon as a durable catalyst for boosting bio-electrons-driven oxygen reduction in microbial fuel cells

Non-noble metal catalyst with high catalytic activity and stability towards oxygen reduction reaction (ORR) is critical for durable bioelectricity generation in air-cathode microbial fuel cells (MFCs). Herein, nitrogen-doped (iron-cobalt alloy)/cobalt/cobalt phosphide/partly-graphitized carbon ((FeCo)/Co/Co₂P/NPGC) catalysts are prepared by using cornstalks via a facile method. Carbonization temperature exerts a great effect on catalyst structure and ORR activity. FeCo alloys are in-situ formed in the catalysts above 900 °C, which are considered as the highly-active component in catalyzing ORR. AC-MFC with FeCo/Co/Co₂P/NPGC (950 °C) cathode shows the highest power density of 997.74 ± 5 mW m^?2, which only declines 8.65% after 90 d operation. The highest Coulombic efficiency (23.3%) and the lowest charge transfer resistance (22.89 Ω) are obtained by FeCo/Co/Co₂P/NPGC (950 °C) cathode, indicating that it has a high bio-electrons recycling rate. Highly porous structure (539.50 m² g^?1) can provide the interconnected channels to facilitate the transport of O₂. FeCo alloys promote charge transfer and catalytic decomposition of H₂O₂ to ?OH and ?O₂^?, which inhibits cathodic biofilm growth to improve ORR durability. Synergies between metallic components (FeCo/Co/Co₂P) and N-doped carbon energetically improve the ORR catalytic activity of (FeCo)/Co/Co₂P/NPGC catalysts, which have the potential to be widely used as catalysts in MFCs.     

钨中空位及其团簇的能量学和动力学性质参数

在总结前人钨中空位及其团簇的能量学和动力学行为的研究成果基础上，采用第一性原理方法系统计算了钨中空位及其团簇的结合能和扩散能垒。研究发现，交换关联泛函PW91和PBE较PBEsol、AM05和LDA更适合用于计算钨空位的能量学性质。基于第一性原理计算结果对文献中单空位形成能、双空位作用性质等争议性问题进行了讨论，并对钨经验势进行了评估。研究结果表明，钨中孤立单空位间总是相互排斥，而空位团簇（V_n>3）对单空位具有很强的吸引作用，其结合能随着所含空位个数增多呈现波动性增大的趋势。空位团簇稳定结构可通过最小化Wigner-Seitz表面积来确定，其结合能与V_n与V_n-1之间的Wigner-Seitz面积之差呈正比。     

Novel energy-saving window coating based on F doped TiO2 nanocrystals with enhanced NIR shielding performance

To reduce the energy consumption of cooling in the hot summer days, searching for novel NIR shielding materials for buildings is of great value. In this report, monodispersed F doped TiO₂ nanocrystals with an average size of 8.6 nm were synthesized as novel solar shielding materials for energy-saving windows. All the products adopted an anatase TiO₂ structure. After doping of F ions, the morphology of TiO₂ was transformed from an irregular shape to a pseudospherical shape. The Raman shift and XPS depth analysis confirmed the successful doping of F⁻ ions into the lattice oxygen sites in the TiO₂ structure. The introduction of F⁻ ions generated free electrons and bulk Ti³⁺ in TiO₂ crystals, which activated a localized surface plasmon resonance (LSPR) absorption in the NIR region. Correspondingly, the NIR shielding performance of the TiO₂ films improved with increasing F doping amounts. The NIR shielding value of the films increased from 1.3% to 43.2% when the molar ratio of F to Ti increased from 0 to 0.3. The reason can be attributed to the enhanced NIR absorption induced by the increased electron concentration after doping of fluorine ions. The F–TiO₂ films showed superior visible transmittance (90.1–96.7%). Moreover, the F–TiO₂ films lowered the indoor temperature of the heat box by 5.3 °C in the thermal tests. Overall, the prepared F–TiO₂ nanocrystals show a great potential to be used for energy-saving windows.     

High performance H2 sensor based on rGO-wrapped SnO2–Pd porous hollow spheres

Hydrogen (H₂) sensors based on metal oxide semiconductors (MOS) are promising for many applications such as a rocket propellant, industrial gas and the safety of storage. However, poor selectivity at low analyte concentrations, and independent response on high humidity limit the practical applications. Herein, we designed rGO-wrapped SnO₂–Pd porous hollow spheres composite (SnO₂–Pd@rGO) for high performance H₂ sensor. The porous hollow structure was from the carbon sphere template. The rGO wrapping was via self-assembly of GO on SnO₂-based spheres with subsequent thermal reduction in H₂ ambient. This sensor exhibited excellently selective H₂ sensing performances at 390 °C, linear response over a broad concentration range (0.1–1000 ppm) with recovery time of only 3 s, a high response of ～8 to 0.1 ppm H₂ in a minute, and acceptable stability under high humidity conditions (e. g. 80%). The calculated detection limit of 16.5 ppb opened up the possibility of trace H₂ monitoring. Furthermore, this sensor demonstrated certain response to H₂ at the minimum concentration of 50 ppm at 130 °C. These performances mainly benefited from the special hollow porous structure with abundant heterojunctions, the catalysis of the doped-PdO_x, the relative hydrophobic surface from rGO, and the deoxygenation after H₂ reduction.     

One-dimensional ZnO nanorods doped with neodymium for enhanced resorcinol degradation under sunlight irradiation

Neodymium-doped ZnO nanorods (Nd/ZNRs) were prepared for the first time by a simple and surfactant-free solvothermal route. The synthesized samples were characterized using different instrumental techniques. The photoluminescence results showed that the Nd(2.0 at%)/ZNRs exhibited the highest separation rate of charge carriers and the highest formation rate of hydroxyl radicals. The photocatalytic activities of synthesized samples were investigated toward the degradation of endocrine disrupting chemical resorcinol under natural sunlight irradiation. Among the samples, Nd(2.0 at%)/ZNRs showed considerable improvement in the photocatalytic activity for the resorcinol degradation as compared to ZNRs and commercial TiO₂. Kinetic studies revealed that the photocatalytic degradation of resorcinol obeyed pseudo-first-order kinetic. The high-performance liquid chromatography and total organic carbon analyses also demonstrated the progressive mineralization of resorcinol into carbon dioxide and water. Furthermore, high stability of Nd/ZNRs in photocatalytic reaction also demonstrated promising potential toward practical applications in purifying environmental pollutants.     

Chemical looping glycerol reforming for hydrogen production by Ni@ZrO2 nanocomposite oxygen carriers

The research describes the synthesis of nanocomposite Ni@ZrO₂ oxygen carriers (OCs) and lanthanide doping effect on maintaining the platelet-structure of the nanocomposite OCs. The prepared OCs were tested in chemical looping reforming of glycerol (CLR) process and sorption enhanced chemical looping reforming of glycerol (SE-CLR) process. A series of characterization techniques including N₂ adsorption-desorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution transmission electron microscopy (HRTEM), H₂ temperature-programmed reduction (H₂-TPR), H₂ pulse chemisorption and O₂ temperature-programmed desorption (O₂-TPD) were used to investigate the physical properties of the fresh and used OCs. The results show that the platelet-stack structure of nanocomposite OCs could significantly improve the metal support interaction (MSI), thus enhancing the sintering resistance. The effect of lanthanide promotion on maintaining this platelet-stack structure increased with the lanthanide radius, namely, La³⁺ > Ce³⁺ > Pr³⁺ > Yb³⁺. Additionally, the oxygen mobility was also enhanced because of the coordination of oxygen transfer channel size by doping small radius lanthanide ions. The CeNi@ZrO₂ showed a moderate ‘dead time’ of 220 s, a high H₂ selectivity of 94% and a nearly complete glycerol conversion throughout a 50-cycle CLR test. In a 50-cycle SE-CLR stability test, the CeNi@ZrO₂CaO showed high H₂ purity of 96.3%, and an average CaCO₃ decomposition percentage of 53% without external heating was achieved.     

Development of the method of production of the ultrafine macrohomogeneous composite powder

ABSTRACT

A method of ultrafine macro-homogeneous composite powder – B₄C–ZrO₂ production using a planetary mill was developed. From the macro-homogeneous composite high-density ceramics, B₄C–ZrB₂ was produced by the method of reactive sintering (in situ) at 2000°C under the pressure of 41–42?MPa. The effect of ZrO₂ grain size and of its distribution in the matrix on the consolidation parameters, and the microstructure of the obtained ceramics was studied.