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Metal carbides are promising materials for electrocatalytic reactions such as water electrolysis. However, for application in catalysis for the oxygen evolution reaction (OER), protection against oxidative corrosion, a high surface area with facile electrolyte access, and control over the exposed active surface sites are highly desirable. This study concerns a new method for the synthesis of porous tungsten carbide films with template‐controlled porosity that are surface‐modified with thin layers of nickel oxide (NiO) to obtain active and stable OER catalysts. The method relies on the synthesis of soft‐templated mesoporous tungsten oxide (mp. WOx) films, a pseudomorphic transformation into mesoporous tungsten carbide (mp. WCx), and a subsequent shape‐conformal deposition of finely dispersed NiO species by atomic layer deposition (ALD). As theoretically predicted by density functional theory (DFT) calculations, the highly conductive carbide support promotes the conversion of Ni2+ into Ni3+, leading to remarkably improved utilization of OER‐active sites in alkaline medium. The obtained Ni mass‐specific activity is about 280 times that of mesoporous NiOx (mp. NiOx) films. The NiO‐coated WCx catalyst achieves an outstanding mass‐specific activity of 1989 A gNi−1 in a rotating‐disc electrode (RDE) setup at 25 °C using 0.1 m KOH as the electrolyte. [ABSTRACT FROM AUTHOR]

SnO2 is one of the most employed n‐type semiconducting metal oxide in chemo‐resistive gas‐sensing although it presents serious limitations due to a low selectivity. Herein, the authors introduce 1D SnO2‐SiO2 core‐shell nanowires (CSNWs). The amorphous SiO2‐shell layer with varying thicknesses (1.8–10.5 nm) is grown onto the SnO2 nanowires (NWs) by atomic layer deposition (ALD). SiO2‐coated SnO2 CSNWs show a dramatic improvement of the selectivity towards hydrogen. Moreover, the sensing‐response is strongly correlated to the thickness of the SiO2‐shell and the working temperature. The SnO2‐SiO2 CSNWs sensor with a 4.8‐nm SiO2 shell thickness exhibits the best selectivity and sensitivity, having ca. 7‐fold higher response toward hydrogen compared to bare‐SnO2 NWs. The selectivity and enhanced sensing‐response are related to the masking effect of the SiO2 shell and an increase in the width of the electron‐depletion‐layer due to a strong electronic coupling between the SnO2 core and SiO2 coating, respectively. [ABSTRACT FROM AUTHOR]

Nanocomposites of TiO2 and carbon nanotubes (CNTs) have been extensively studied in photocatalysis, sensing, and energy conversion and storage over the last decade. The unique properties of these nanocomposites are greatly dependent on the morphology, crystallinity, and homogeneity of the TiO2 coating. However, a fine control of the film microstructure is still challenging due to limited understanding of early stages of the TiO2 growth. The presence of an intermediate buffer layer can induce remarkable changes in the morphological and structural characteristics of the coatings. Here, TiO2 films deposited by atomic layer deposition (ALD) on CNTs without and with different intermediate layers (Al2O3 and ZnO) have been systematically investigated. Compared to bare CNTs, it is suggested that these two intermediate layers with higher surface energy can lead to a delay of the TiO2 crystallization, ultimately resulting in the growth of conformal and crystalline TiO2 films. This study demonstrates a strategy to tailor the microstructure and the properties of thin films via ALD by applying intermediate layers and provides information about the role of surface energy of the substrate in crystallization and growth behavior of ALD thin films. [ABSTRACT FROM AUTHOR]

We report CNT/Al2O3 core–shell nanostructures for the electrochemical detection of dihydroxybenzene (DHB) isomers. Amorphous films of Al2O3 (1.2–15.4 nm in thickness) are uniformly deposited onto the inner and outer walls of CNTs by atomic layer deposition. The effect of the Al2O3 shell thickness on the electrochemical detection of dihydroxybenzene isomers was explored using cyclic and square-wave voltammetry. The best sensing properties are found at a shell thickness of approx. 2.4 nm (CNT/Al2O3(9) sensor), where the oxidation peak currents (sensor-signal) increased ca. 10 times as compared to a sensor fabricated with non-coated CNTs. All of the three DHB isomers (hydroquinone, catechol and resorcinol) are independently detected in the concentration ranges of 2–1000 μmol L−1, 0.5–700 μmol L−1 and 3.5–500 μmol L−1, respectively. The sensors show reliable repeatability, reproducibility, long-term stability, and applicability in the analysis of real samples. Based on these findings, a plausible mechanism is proposed highlighting the role of the Al2O3–shell. [ABSTRACT FROM AUTHOR]

Coordination polymers (CPs) and metal–organic frameworks (MOFs) have emerged as versatile precursors for transition-metal phosphides catalysts. However, the controlled synthesis of CPs-derived bimetallic phosphides remains a challenge, as mixtures of various phosphide phases are often formed. Here, it is shown that controlling the formation of pure CoMoP and CoMoP2 nanoparticles requires a careful choice of the ligands used to construct the precursors based on the chemical properties of the metals. In particular, the nature and number of the coordination moieties of the ligand play key roles. CoMoP and CoMoP2 particles coated with N-doped carbon were derived from phosphonate-based CPs and compared as hydrogen evolution reaction (HER) electrocatalysts in acidic medium. CoMoP2 is more active and shows a turnover frequency (TOF) of 0.9 s–1 compared to 0.4 s–1 for CoMoP. The higher intrinsic activity of the CoMoP2 catalytic sites correlates with the differences in the electronic structure of the materials, with a larger charge transfer from the molybdenum to the phosphorus found for CoMoP2. [ABSTRACT FROM AUTHOR]

Van der Waals p–n junctions of 2D materials present great potential for electronic devices due to the fascinating properties at the junction interface. In this work, an efficient gas sensor based on planar 2D van der Waals junctions is reported by stacking n‐type and p‐type atomically thin MoS2 films, which are synthesized by chemical vapor deposition (CVD) and soft‐chemistry route, respectively. The electrical conductivity of the van der Waals p–n junctions is found to be strongly affected by the exposure to NO2 at room temperature (RT). The MoS2 p–n junction sensor exhibits an outstanding sensitivity and selectivity to NO2 at RT, which are unavailable in sensors based on individual n‐type or p‐type MoS2. The sensitivity of 20 ppm NO2 is improved by 60 times compared to a p‐type MoS2 sensor, and an extremely low limit of detection of 8 ppb is obtained under ultraviolet irradiation. Complete and very fast sensor recovery is achieved within 30 s. These results are superior to most of the previous reports related to NO2 detection. This work establishes an entirely new sensing platform and proves the feasibility of using such materials for the high‐performance detection of gaseous molecules at RT. [ABSTRACT FROM AUTHOR]

Lithium and sodium thiophosphates (and related compounds) have recently attracted attention because of their potential use as solid electrolytes in solid‐state batteries. These compounds, however, exhibit only limited stability in practice as they react with the electrodes. The decomposition products partially remain redox active hence leading to excess capacity. The redox activity of thiophosphates is explicitly used to act as electrode for sodium‐ion batteries. Copper thiophosphate (Cu3PS4) is used as a model system. The storage behavior between 0.01 and 2.5 V versus Na+/Na is studied in half cells using different electrolytes with 1 m NaPF6 in diglyme showing the best result. Cu3PS4 shows highly reversible charge storage with capacities of about 580 mAh g−1 for more than 200 cycles @120 mA g−1 and about 450 mAh g−1 for 1400 cycles @1 A g−1. The redox behavior is studied by operando X‐ray diffraction and X‐ray photoelectron spectroscopy. During initial sodiation, Cu3PS4 undergoes a conversion reaction including the formation of Cu and Na2S. During cycling, the redox activity seems dominated by sulfur. Interestingly, the capacity of Cu3PS4 for lithium storage is smaller, leading to about 170 mAh g−1 after 200 cycles. The results demonstrate that thiophosphates can lead to reversible charge storage over several hundred cycles without any notable capacity decay. [ABSTRACT FROM AUTHOR]

Two‐dimensional (2D) reduced graphene oxide (rGO) is often combined with metal oxides for energy‐storage applications, owing to its unique properties. Here, we compare the electrochemical performance of Nb2O5‐rGO and amorphous carbon‐coated‐Nb2O5 composites, synthesized in similar conditions. The composite made of Nb2O5 and amorphous carbon (using 1,3,5‐triphenylbenzene as carbon source) outperforms the Nb2O5‐rGO counterpart as a high rate anode electrode material in Li‐ion and Na‐ion half‐cells and hybrid supercapacitors, delivering specific capacities of 134 mAh g−1 at 25 C against 98 mAh g−1 for the rGO‐based composite (in Li electrolyte) and 125 mAh g−1 at 20 C against 98 mAh g−1 (in Na electrolyte). The organic molecules, which are the precursor of the amorphous carbon, control the size and coat the metal oxide particles more efficiently, leading to more extensive carbon‐oxide contacts, which benefits the energy‐storage performance. [ABSTRACT FROM AUTHOR]

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al2O3 dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al2O3–SCCNT, Al2O3–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region. [ABSTRACT FROM AUTHOR]