Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.     

Understanding the Structural Evolution and Redox Mechanism of a NaFeO2–NaCoO2 Solid Solution for Sodium‐Ion Batteries

Na‐ion batteries have become promising candidates for large‐scale energy‐storage systems because of the abundant Na resources and they have attracted considerable academic interest because of their unique behavior, such as their electrochemical activity for the Fe³⁺/Fe⁴⁺ redox couple. The high‐rate performance derived from the low Lewis‐acidity of the Na⁺ ions is another advantage of Na‐ion batteries and has been demonstrated in NaFe_1/2Co_1/2O₂ solutions. Here, a solid solution of NaFeO₂‐NaCoO₂ is synthesized and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of operando X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and density functional theory (DFT) calculations for Na_{1– x} Fe_1/2Co_1/2O₂ reveals that the O3‐type phase transforms into a P3‐type phase coupled with Na⁺/vacancy ordering, which has not been observed in O3‐type NaFeO₂. The substitution of Co for Fe stabilizes the P3‐type phase formed by sodium extraction and could suppress the irreversible structural change that is usually observed in O3‐type NaFeO₂, resulting in a better cycle retention and higher rate performance. Although no ordering of the transition metal ions is seen in the neutron diffraction experiments, as supported by Monte‐Carlo simulations, the formation of a superlattice originating from the Na⁺/vacancy ordering is found by synchrotron X‐ray diffraction for Na_0.5Fe_1/2Co_1/2O₂, which may involve a potential step in the charge/discharge profiles.     

Low temperature (< 100 °C) deposited P-type cuprous oxide thin films: Importance of controlled oxygen and deposition energy

With the emergence of transparent electronics, there has been considerable advancement in n-type transparent semiconducting oxide (TSO) materials, such as ZnO, InGaZnO, and InSnO. Comparatively, the availability of p-type TSO materials is more scarce and the available materials are less mature. The development of p-type semiconductors is one of the key technologies needed to push transparent electronics and systems to the next frontier, particularly for implementing p-n junctions for solar cells and p-type transistors for complementary logic/circuits applications. Cuprous oxide (Cu₂O) is one of the most promising candidates for p-type TSO materials. This paper reports the deposition of Cu₂O thin films without substrate heating using a high deposition rate reactive sputtering technique, called high target utilisation sputtering (HiTUS). This technique allows independent control of the remote plasma density and the ion energy, thus providing finer control of the film properties and microstructure as well as reducing film stress. The effect of deposition parameters, including oxygen flow rate, plasma power and target power, on the properties of Cu₂O films are reported. It is known from previously published work that the formation of pure Cu₂O film is often difficult, due to the more ready formation or co-formation of cupric oxide (CuO). From our investigation, we established two key concurrent criteria needed for attaining Cu₂O thin films (as opposed to CuO or mixed phase CuO/Cu₂O films). First, the oxygen flow rate must be kept low to avoid over-oxidation of Cu₂O to CuO and to ensure a non-oxidised/non-poisoned metallic copper target in the reactive sputtering environment. Secondly, the energy of the sputtered copper species must be kept low as higher reaction energy tends to favour the formation of CuO. The unique design of the HiTUS system enables the provision of a high density of low energy sputtered copper radicals/ions, and when combined with a controlled amount of oxygen, can produce good quality p-type transparent Cu₂O films with electrical resistivity ranging from 10² to 10⁴ Ω-cm, hole mobility of 1-10 cm²/V-s, and optical band-gap of 2.0-2.6 eV. These material properties make this low temperature deposited HiTUS Cu₂O film suitable for fabrication of p-type metal oxide thin film transistors. Furthermore, the capability to deposit Cu₂O films with low film stress at low temperatures on plastic substrates renders this approach favourable for fabrication of flexible p-n junction solar cells.     

Self-organized Ce(1-x)Gd(x)O(2-y) nanowire networks with very fast coarsening driven by attractive elastic interactions

Assembling arrays of ordered nanowires is a key objective for many of their potential applications. However, a lack of understanding and control of the nanowires' growth mechanisms limits their thorough development. In this work, an appealing new path towards self-organized epitaxial nanowire networks produced by high-throughput solution methods is reported. Two requisites are identified to generate the nanowires: a thermodynamic driving force for an unrestricted elongated equilibrium island shape, and a very fast effective coarsening rate. These requirements are met in anisotropically strained Ce(1-x)Gd(x)O(2-y) nanowires with the (011) orientation grown on the (001) surface of LaAlO(3) substrates. Nanowires with aspect ratios above ≈100 oriented along two mutually orthogonal axes are obtained leading to labyrinthine networks. A very fast effective nanowire growth rate (≈60 nm min(-1)) for ex-situ thermally annealed nanostructures derives from simultaneous kinetic processes occurring in a branched network. Ostwald ripening and anisotropic dynamic coalescence, both promoted by strain-driven attractive nanowire interaction, and rapid recrystallization, enabled by fast atomic diffusion associated with a high concentration of oxygen vacancies, contribute to such an effective growth rate. This bottom-up approach to self-organized nanowire growth has a wide potential for many materials and functionalities.     

Cu2O-WO3复合物的制备及其光催化性质研究

采用室温液相还原法制备了Cu2O微米立方块和Cu2O-WO3复合物,利用XRD和FESEM对产物进行了表征。研究了太阳光照下氧化亚铜微米立方块对不同染料的光催化降解性能,结果表明合成产物对阴离子染料有较好的降解效果,对阳离子染料降解效果不明显。Cu2O-WO3复合物对阳离子染料亚甲基蓝的光催化活性明显高于纯的Cu2O,其中10%Cu2O-WO3复合物的光催化效果最好。借助荧光光谱分析了复合物提高阳离子染料亚甲基蓝的光催化效果的原因。     

Understanding the Role of (W,Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques

Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H₂) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H₂ production. Here, a scalable strategy to prepare doped cobalt oxide (Co₃O₄) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co₃O₄ electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm⁻² for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g⁻¹ at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co₃O₄ as a low-cost material for green hydrogen electrocatalysis at large scales.     

Amorphous Vanadium Oxide Nanosheets with Alterable Polyhedron Configuration for Fast-Charging Lithium-Ion Batteries

Transition metal oxides with high theoretical capacities are promising anode materials for lithium-ion batteries (LIBs). However, the sluggish reaction kinetics remain a bottleneck for fast-charging applications due to its slow Li⁺ migration rate. Herein, a strategy is reported of significantly reducing the Li⁺ diffusion barrier of amorphous vanadium oxide by constructing a specific ratio of the V O local polyhedron configuration in amorphous nanosheets. The optimized amorphous vanadium oxide nanosheets with a ratio ≈1:4 for octahedron sites (O_h) to pyramidal sites (C_4v) revealed by Raman spectroscopy and X-ray absorption spectroscopy (XAS) demonstrate the highest rate capability (356.7 mA h g⁻¹ at 10.0 A g⁻¹) and long-term cycling life (455.6 mA h g⁻¹ at 2.0 A g⁻¹ over 1200 cycles). Density functional theory (DFT)calculations further verify that the local structure (O_h:C_4v = 1:4) intrinsically changes the degree of orbital hybridization between V and O atoms and contributes to a higher intensity of electron occupied states near the Fermi level, thus resulting in a low Li⁺ diffusion barrier for favorable Li⁺ transport kinetics. Moreover, the amorphous vanadium oxide nanosheets possess a reversible V O vibration mode and volume expansion rate close to 0.3%, as determined through in situ Raman and in situ transmission electron microscopy.     

Lignin Impact on Fibre Degradation: 1—Quinone Methide Intermediates Formedfrom Lignin DuringIn VitroFermentation ofCorn Stover*

Experiments were conducted to determine whether formation of quinone methide intermediates from lignin occurs during ruminal fermentation of corn stover, as indicated by nucleophilic addition reaction with sulphur-containing reducing agents. Corn stover leaf and stem fractions harvested at full maturity were incubated in buffered ruminal fluid without reducing agents or with (NH₄)₂SO₄ (S-control), Na₂S.9H₂O, cysteine-HCl (cysHCl), or cysHCl plus Na₂S.9H₂O; and in only buffer with or without cysHCl plus Na₂S.9H₂O. Mixed reducing agents (cysHCl plus Na₂S.9H₂O) enhanced ( P< 0.001) in vitro fibre degradation after 48 h, tended to increase solubilisation of fibre ( P =0.07) and dry matter ( P =0.06) in buffer alone, and elevated ( P< 0.001) S-content of residual fibre. In vitro incorporation of S into the undegraded fibre was determined for corn stover fractions of varying lignin compositions that were harvested at two maturities (early dent and full maturity) in 2 years. Extent of fibre degradation was correlated with extent of S-incorporation ( r =-0.54, P< 0.001), and with lignin methoxyl content ( r =-0.84, P< 0.001). The negative association of lignin methoxyl content with digestibility is explained by the relative likelihood of quinone methide intermediate formation from guaiacyl and syringyl units in lignin.     

ESTIMATION OF VOLATILE SULPHUR COMPOUNDS IN BEER

A method has been developed for the quantitative estimation of volatile sulphur compounds in beer at levels below 0.1 μg litre^?1. The method relies on the concentration of beer headspace volatiles onto a porous polymer followed by injection into a capillary gas chromatographic column using a thermal desorption cold trap injector. The volatile components are separated using temperature programming and detected by a flame photometric detector specific for sulphur compounds. The mean concentrations and the estimates of r₉₅ (μg litre^?1) for volatile sulphur compounds measured in a commercial lager were respectively: methanethiol (0.33, 0.30); dimethyl sulphide (19.3, 5.3); carbon disulphide (0.42, 0.32); ethylene sulphide (0.37, 0.05); 1-propanethiol (0.11, 0.02); methyl thioacetate (11.7; 2.7); methyl disulphide (0.34, 0.42). The method is a significant improvement over previous techniques for the quantification of sulphur-containing volatiles in beer .