Hydrogen gas sensing of nano-confined Pt/g-C3N4 composite at room temperature

In this study, we report the hydrogen sensing properties of the Pt dispersed graphitic carbon nitride (g-C₃N₄) nanocomposite at room temperature and inert atmosphere. The nanocomposite was synthesized by a wet-chemical approach, where melamine and chloroplatinic acid hexahydrate were used as precursors. The fabrication of the sensor was done by jet nebulizer-based spray pyrolysis setup. Various characterizations were performed for the analysis of the synthesized nanocomposite. Electrical resistance in the presence and absence of the analyte gas was drastically different. The results at different concentrations and film thickness show Pt/g-C₃N₄ to possess good sensitivity towards the hydrogen gas, suggesting that it could be used for reliable hydrogen gas sensing.     

Pt=Pd separation modified Ti3C2TX MXene for hydrogen detection at room temperature

Hydrogen sensing with a fast response at room temperature is still a challenge. In this study, a novel Pt=Pd/Ti₃C₂T_X hydrogen sensor was prepared by a straightforward hydrothermal chemical reduction method. The Pt=Pd/Ti₃C₂T_X was characterized by X-ray diffraction, transmission electron microscope, and X-ray photoelectron spectroscopy. The experimental results showed that the response of the Pt=Pd/Ti₃C₂T_X sensor was 24.6% and the response/recovery time was 6/8 s in the case of 200 ppm hydrogen at room temperature. The Pt=Pd/Ti₃C₂T_X sensor could detect the hydrogen concentration as low as 1 ppm. Besides, the Pt=Pd/Ti₃C₂T_X sensor exhibited good linearity, long-term stability, good repeatability, and high selectivity. The Pt=Pd/Ti₃C₂T_X sensor has great potential in the field of hydrogen energy.     

Effect of Nb2O5 on MgH2 properties during mechanical milling

Recently, it was shown that hydrogen absorption–desorption kinetics in magnesium were improved by milling magnesium hydride (MgH₂) with transition metal oxides. Herein, we investigate the role of the most effective of these oxides, Nb₂O₅ when added in larger volume fraction. The effect of Nb₂O₅ on magnesium crystalline structure, particle size and (ab)desorption properties has been characterised. Moreover, we report that pure MgH₂ can also show fast hydrogen sorption kinetics after a long milling time. The effects of Nb₂O₅ on MgH₂ sorption properties are rationalised in a new approach considering Nb₂O₅ as a dispersing agent, which helps reduce MgH₂ particle size during milling.     

Cu0.6Ni0.4Co2O4 nanowires,a novel noble-metal-free catalyst with ultrahigh catalytic activity towards the hydrolysis of ammonia borane for hydrogen production

In this work, we have prepared a series of Cu_xNi_1-xCo₂O₄ (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1) nanowires with a diameter of approximately 30 nm, which were characterized by X-ray powder diffractometry, scanning and transmission electron microscopy, and X-ray photoelectron spectrometry. For the first time, the catalytic activity of these Cu_xNi_1-xCo₂O₄ nanowires in ammonia borane (AB) hydrolysis was investigated, and it was found that a significant synergistic effect exists between NiCo₂O₄ and CuCo₂O₄ in the hydrolytic reaction. Among these Cu_xNi_1-xCo₂O₄ samples, the Cu_0.6Ni_0.4Co₂O₄ nanowires showed the highest turnover frequency (TOF) of 119.5 mol_hydrogen min^?1 mol_cat^?1. This value is 1.66 times as high as that for CoP nanoparticles, which is the most active noble-metal-free catalyst towards AB hydrolysis ever reported in the literature. Because of the low cost and high catalytic performance, the Cu_0.6Ni_0.4Co₂O₄ nanowires can be a robust catalyst towards AB hydrolysis in practical applications.     

Structural, morphological and electrochromic properties of Nb2O5 films deposited by reactive sputtering

Nb₂O₅ films were prepared successfully by DC reactive sputtering process. The relationships among structural, morphological and electrochromic properties were studied using XRD, AFM, AES and cyclic voltammograms. Results show that the films deposited on heated substrates are composed of columnar TT-Nb₂O₅ microcrystalline with many grain-to-grain boundaries. These structural characteristics provide films strong electrochemical stability, high Li⁺ insertion/extraction reversibility and good electrochromic properties. DC reactive sputtered Nb₂O₅ films are colorless in bleached state and brownish gray in colored state and may be a promising candidate for the application in electrochromic devices.     

Effect of TiO2 mixtures on the optical, structural and electrochromic properties of Nb2O5 thin films

Metal oxide films are important for various optical devices and especially for solar energy materials. TiO₂-mixed Nb₂O₅ thin films have been produced by sol–gel dip-coating method. Several parameters such as heat treatment, thickness, and mixture percentages are studied for the effect of the optical, structural and electrochromic properties of the materials. Optical parameters of the films were calculated through transmission and reflection measurement by a refractive index, extinction coefficient and thickness analyzer. Structural, electrochromic and surface analyses of the films were done by X-ray diffractometer, potentiostat/galvanostat and atomic force microscope systems.     

Electrochromic behaviour of Nb2O5 thin films with different morphologies obtained by spray pyrolysis

Two different procedures to stabilize the precursor NbCl₅ have been applied to obtain Nb₂O₅ thin films by spray pyrolysis. Depending on the procedure used, determined by the way in which the precursor solution was injected into the air stream of the spray nozzle, niobium oxide thin films with different surface morphologies can be obtained. The structural properties of the Nb₂O₅ thin films depend on the post-annealing temperature because as-deposited films are amorphous, independently of the synthesis procedure used. The electrochromic behaviour has been estimated for all films, where monochromatic colouration efficiency (at 660 nm) of 25.5 cm²/C and a cathodic charge density close to 24 mC/cm² were found to give the best results to date for niobium oxide thin films obtained by spray pyrolysis.     

Influence of multiple oxide (Cr2O3/Nb2O5) addition on the sorption kinetics of MgH2

The influence of multiple additions of two oxides, Cr₂O₃ and Nb₂O₅, as additives on the hydrogen sorption kinetics of MgH₂ after milling was investigated. We found that the desorption kinetics of MgH₂ were improved more by multiple oxide addition than by single addition. Even for the milled MgH₂ micrometric size powders, the high hydrogen capacity with fast kinetics were achieved for the powders after addition of 0.2 mol% Cr₂O₃ + 1 mol% Nb₂O₅. For this composition, the hydride desorbed about 5 wt.% hydrogen within 20 min and absorbed about 6 wt.% in 5 min at 300 °C. Furthermore, the desorption temperature was decreased by 100 °C, compared to MgH₂ without any oxide addition, and the activation energy for the hydrogen desorption was estimated to be about 185 kJ mol⁻¹, while that for MgH₂ without oxide was about 206 kJ mol⁻¹.     

In situ preparation of N doped orthorhombic Nb2O5 nanoplates /rGO composites for photocatalytic hydrogen generation under sunlight

The synthesis of nitrogen doped orthorhombic niobium oxide nanoplates/reduced graphene oxide composites (NNb₂O₅/rGO) and their photocatalytic activity towards hydrogen generation from water and H₂S under natural sunlight has been demonstrated, uniquely. Nanostructured NNb₂O₅/rGO is synthesized by in situ wet chemical method using urea as a source of nitrogen and optimized by varying percentage of graphene oxide (GO). X?ray diffraction (XRD) study reveals that NNb₂O₅ have orthorhombic crystal structure with crystalline size, 35 nm. Further, X?ray photoelectron spectroscopy (XPS) confirm the presence of nitrogen and rGO in NNb₂O₅/rGO nanocomposite. Morphological features of (NNb₂O₅/rGO) were examined by FE?SEM and FE?TEM showed Nb₂O₅ nanoplates of diameter 25–40 nm anchored on 2D rGO. Diffuse reflectance spectra depicts the extended absorbance in the visible region with band gap of 2.2 eV. Considering the band gap in the visible region, the photocatalytic hydrogen generation from water and H₂S has been performed. The 1 wt % rGO hybridized NNb₂O₅ (S2) exhibited superior photocatalytic hydrogen generation (537 μmol/h) from water and (1385 μmol/h) from H₂S under sunlight. The improved photocatalytic activity is attributed due to an extended absorbance in the visible region, modified electronic structure upon doping and formation of well defined NNb₂O₅/rGO interface, provides large surface area, accelerates the supression of electron and hole pairs recombination rate. In our opinion, this works may provides facile route for energy efficient and economic approach for fabrication of NNb₂O₅/rGO nanocomposites as a visible light active photocatalyst.     

Numerical approach to evaluate performance of porous SiC5/4O3/2 as potential high temperature hydrogen gas sensor

Porous silicon oxycarbide (SiCO) is a novel class of nano-porous material with superior gas sensing performance. In this work, the amorphous porous structure of SiC_5/4O_3/2 is successfully reproduced by simulating the experimental etching process, and the gas sensing performance of porous SiCO at high temperature is investigated. The calculation results show porous SiC_5/4O_3/2 exhibits a much higher sensitivity towards H₂ than CO, NO₂ and acetone at 773 K. Compared with the other three gases, H₂ absorbed system show shorter adsorption distance and more obvious increasing in density of states around Fermi level. Therefore, porous SiC_5/4O_3/2 shows a highly selective sensitivity toward H₂ at high temperature. Moreover, our results show the Si–C/O units are the major sensing sites of H₂ at high temperature, and the large diffusion coefficient of H₂ in SiC_5/4O_3/2 is related to the fast response of porous SiCO gas sensor.     

Room temperature sensing properties of networked GaN nanowire sensors to hydrogen enhanced by the Ga2Pd5 nanodot functionalization

Multiple-networked GaN nanowires with excellent sensing properties to hydrogen were realized by functionalizing their surfaces with Ga₂Pd₅-related nanodots. Compared to the bare-GaN nanowire sensors, functionalization improved the relative resistance responses by a factor of >50 at H₂ concentrations ranging from 100 to 2000 ppm. At room temperature, the nanodot-functionalized GaN nanowire sensors exhibited a relative resistance response of 34.1% at 100 ppm H₂. Interestingly, a shell layer was transformed mostly into Ga₂Pd₅-phased nanodots, which was confirmed by X-ray diffraction and transmission electron microscopy. The mechanisms responsible for the improvement induced by nanodot functionalization are proposed in terms of the hydrogen spillover effect.     

One-step synthesis of Ni3S2 nanowires at low temperature as efficient electrocatalyst for hydrogen evolution reaction

Ni₃S₂ is an emerging cost-effective catalyst for hydrogen generation. However, a large amount of reported Ni₃S₂ was synthesized via multi-step approaches and few were fabricated based on the one-step strategies. Herein, we report a facile one-step low-temperature synthesis of Ni₃S₂ nanowires (NWs). In this strategy, a resin containing sulfur element is recommended as a sulfur resource to form Ni₃S₂ NWs. It presents a plausible explanation on the vapor–solid–solid (VSS) growth mechanism according to the results of this experiment and reported in literature that has been published. The Ni₃S₂ NW exhibits a potential ∼199 mV at 10 mA cm⁻² and the long-term durability over 30 h at 20 mA cm⁻² HER operation, better than other reported Ni₃S₂. More importantly, according to replace transition metal foam as the initial metal, other transition metal sulfide can be readily synthesized via this original approach.     

Effect of additive distribution in H2 absorption and desorption kinetics in MgH2 milled with NbH0.9 or NbF5

This paper presents a comparative study of H₂ absorption and desorption in MgH₂ milled with NbF₅ or NbH_0.9. The addition of NbF₅ or NbH_0.9 greatly improves hydriding and dehydriding kinetics. After 80 h of milling the mixture of MgH₂ with 7 mol.% of NbF₅ absorbs 60% of its hydrogen capacity at 250 °C in 30 s, whereas the mixture with 7 mol.% of NbH_0.9 takes up 48%, and MgH₂ milled without additive only absorbs 2%. At the same temperature, hydrogen desorption in the mixture with NbF₅ finishes in 10 min, whereas the mixture with NbH_0.9 only desorbs 50% of its hydrogen content, and MgH₂ without additive practically does not releases hydrogen. The kinetic improvement is attributed to NbH_0.9, a phase observed in the hydrogen cycled MgH₂ + NbF₅ and MgH₂ + NbH_0.9 materials, either hydrided or dehydrided. The better kinetic performance of the NbF₅-added material is attributed to the combination of smaller size and enhanced distribution of NbH_0.9 with more favorable microstructural characteristics. The addition of NbF₅ also produces the formation of Mg(H_xF_1-x)₂ solid solutions that limit the practically achievable hydrogen storage capacity of the material. These undesired effects are discussed.     

Enhancement of photoelectrochemical activity of Fe2O3 nanowires decorated with carbon quantum dots

Owing to its up-conversion photoluminescence, photo-induced electron transfer property, and excellent conductivity, carbon quantum dots (CQDs) have been established as effective sensitizers in combination with Fe₂O₃ nanowires for enhancing the catalytic activity of photoelectrochemical water oxidation. In comparison to pristine Fe₂O₃ nanowires, Fe₂O₃ nanowires decorated with CQDs demonstrate 27 orders of magnitude increase in photocurrent density at 0.23 V vs. Ag/AgCl. The mechanism of enhanced photoelectrochemical activity of CQDs/Fe₂O₃ composite was also investigated. Thereby, it is confirmed that the enhanced optical absorption, accelerated interfacial charge carrier transfer and effective separation of photogenerated electron-hole pairs induced by CQDs decoration account for the enhancement of CQDs/Fe₂O₃ nanowire arrays in photoelectrochemical application.     

Reactions over Cu/Nb2O5 catalysts promoted with Pd and Ru during hydrogen production from ethanol

Hydrogen production from reactions between ethanol and steam at 300 °C was evaluated under low conversion conditions for the Cu/Nb₂O₅ system promoted with Pd and Ru. Parallel reactions occurred on the surface of all samples as it was verified from the production of H₂, CO₂, CH₄, CO, C₂H₄, C₂H₆, C₂H₄O and (C₂H₅)₂O. Hydrogen production occurs mainly from ethanol dehydrogenation and secondly, from steam reforming and ethanol decomposition. Dehydration reactions were also identified and analyzed among others. Addition of Pd and Ru to the catalyst improves product selectivity and it was verified that Pd-Ru-Cu/Nb₂O₅ tri-metallic catalyst is the most promising for H₂ production due to its selectivity and lower deactivation, among all samples tested.     

Cesium tungsten bronze nanostructures and their highly enhanced hydrogen gas sensing properties at room temperature

In this study, cesium tungsten bronze (Cs_xWO₃) a well-known metal oxide semiconductor and excellent photocatalyst and active photothermal material was used as a sensing material toward hydrogen for the first time. The Cs_xWO₃ nanorods were synthesized using a new hydrothermal method and examined through systematic material investigations. The synthesized Cs_xWO₃ nanorods were coated on SiO₂/Si substrates and subsequently fabricated laterally with multi-finger platinum (Pt)-based electrodes to test their gas detecting properties. The gas detecting property of the prepared material was studied toward very toxic hydrogen gas (10–500 ppm concentration). The gas sensing results demonstrate that the synthesized Cs_xWO₃ material has excellent gas sensing properties toward hydrogen (31.3%), which is overwhelmingly superior to as-prepared WO₃ (4.7%) due to its suitable electrical and optical properties at room temperature (RT). The selectivity results also indicate that the material has outstanding selectivity toward hydrogen compared with different gases such as ammonia and carbon dioxide. The critical features of this material are its high reliability, simple synthesis method, low humidity susceptibility, and high selectivity, making it viable for use in hydrogen sensors. Compared with the as-prepared WO₃, the adsorption capability and conductance of the Cs_xWO₃ surface induces active O₂ functional groups, significantly enhancing the gas sensing properties.     

Dehydrogenation of methylcyclohexane over Pt/V2O5 and Pt/Y2O3 for hydrogen delivery applications

Dehydrogenation of methylcyclohexane (MCH) for hydrogen transportation and delivery application was carried out over 3 wt% Pt/V₂O₅ and 3 wt% Pt/Y₂O₃ catalyst. The catalytic activity was tested using a spray-pulse mode of reactor. Effective dehydrogenation of MCH under spray-pulse mode of reactant injection was observed. In terms of hydrogen evolution rate at 60 min from start of reaction the activity of 958 mmol/g/min was obtained at temperature of 350 °C. Nearly 100% selectivity toward hydrogen was obtained. A relatively high conversion of 98% was observed with 3 wt% Pt/Y₂O₃ at 60 min using an advanced spray-pulse reactor system. The catalysts were characterized using x-ray diffraction pattern (XRD), CO-chemisorption metal analysis, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis.     

Catalytic mechanism of Nb2O5 and NbF5 on the dehydriding property of Mg95Ni5 prepared by hydriding combustion synthesis and mechanical milling

The catalytic mechanism of Nb₂O₅ and NbF₅ on the dehydriding property of Mg₉₅Ni₅ prepared by hydriding combustion synthesis and mechanical milling (HCS + MM) was studied. It was shown that NbF₅ was more efficient than Nb₂O₅ in improving the dehydriding property. In particular, the dehydriding temperature onset decreases from 460 K for Mg₉₅Ni₅ to 450 K for Mg₉₅Ni₅with 2.0 at.% Nb₂O₅, whereas it decreases to 410 K for that with 2.0 at.% NbF₅. By means of X-ray diffraction and X-ray photoelectron spectroscopy, it was confirmed that the interaction between the Nb ions and the H atoms and that between the anions (O²⁻ or F⁻) and Mg²⁺ existed in Mg₉₅Ni₅ doped with Nb₂O₅ or NbF_5. Further, the pressure–concentration-isotherms analysis clarified that these interactions destabilized the Mg–H bonding, and that NbF₅ had a better effect on the destabilization of the Mg–H bonding than Nb₂O₅ contributing to the better dehydriding property of (Mg₉₅Ni₅)2.0−NbF₅.     

Synergetic effect of Ni and Nb2O5 on dehydrogenation properties of nanostructured MgH2 synthesized by high-energy mechanical alloying

Nanostructured MgH₂-Ni/Nb₂O₅ nanocomposite was synthesized by high-energy mechanical alloying. The effect of MgH₂ structure, i.e. crystallite size and lattice strain, and the presence of 0.5 mol% Ni and Nb₂O₅ on the hydrogen-desorption kinetics was investigated. It is shown that the dehydrogenation temperature of MgH₂ decreases from 426 °C to 327 °C after 4 h mechanical alloying. Here, the average crystallite size and accumulated lattice strain are 20 nm and 0.9%, respectively. Further improvement in the hydrogen desorption is attained in the presence of Ni and Nb₂O₅, i.e. the dehydrogenation temperature of MgH₂/Ni and MgH₂/Nb₂O₅ is measured to be 230 °C and 220 °C, respectively. Meanwhile, the dehydrogenation starts at 200 °C in MgH₂–Ni/Nb₂O₅ system, revealing synergetic effect of Ni and Nb₂O₅. The mechanism of the catalytic effect is presented.