Photocatalytic hydrogen evolution performance of metal ferrites /polypyrrole nanocomposites

The combination of inorganic (e.g., ferrite nanoparticles) and organic (e.g., conducting polymers) materials in the fabrication of heterojunctions or composites is an attractive scheme in the field of photocatalysis. We took the advantage of this phenomenon by fabricating MFerrite (M = Co, Ni, and Zn) @polypyrrole (MFerrite@Ppy) nanocomposites with a varying weight percentage of Ppy for the hydrogen production through photocatalytic water splitting under visible light irradiation. The structural, spectral, morphological, compositional, and optical features of the as-prepared nanocomposites were analyzed in full depth. The average crystallite sizes were estimated to be 30–40 nm from the XRD patterns which were further validated by TEM images from which a core-shell structure of the composites can be inferred. Likewise, the SEM images revealed spherical Ppy particles with a diameter in the range of 100–300 nm. From a photocatalytic viewpoint, CoFerrite@30Ppy is endowed with some peculiar characteristics including but not limited to strong light-harvesting ability (ranging between 300 and 650 nm), narrow optical band gap (as low as 1.6 eV), and higher photoluminescence (PL) lifetime (6.41 ns) which justify why it stands out among all composites in terms of photocatalysis. Under 8 h illumination of simulated visible light and using triethanolamine (TEOA) as a hole scavenger and Eosin-Y (EY) as a dye sensitizer, the photocatalytic hydrogen evolution (HER) amount for CoFerrite@30Ppy was found to be 10.44 mmol g^?1, far greater than any other composite catalysts in this study. From the PL spectra, it can be pointed out that sensitization of CoFerrite with 30 wt % Ppy conduces to simultaneous deceleration of the electron-hole recombination process and acceleration of the transference of excitons within the system.     

Natural hydrogen emanations in Namibia: Field acquisition and vegetation indexes from multispectral satellite image analysis

Natural hydrogen exploration is now active in various places of the world. Onshore, correlation between natural H₂ generation and the presence of iron rich rocks especially from Archean and Neoproterozoic cratons have been observed. Emanations and accumulations of H₂ have already been confirmed in such geological settings in Australia, South Africa and Brazil. The geological similitude and the presence of numerous sub circular depressions that are a good proxy for hydrogen emanations suggest that hydrogen resources may also exist in Namibia. We present here the results of a data acquisition campaign which allowed us to confirm the presence of natural hydrogen in this country in the vicinity of Neoproterozoic Banded Iron Formation. The H₂ content in the soil, as in Brazil, is variable within the depressions in time and space and is particularly time sensitive across the day. Comparison of the H₂ signal versus time within these two regions shows a similar behavior of the soils with an increase of the H₂ flow at the middle of the day. In addition, these new data allow us to better constrain the morphological characteristics of such H₂-emiting depressions. By using satellite images and digital elevation model we propose a new proxy to differentiate potentially H₂-emiting features from other type of depressions such as Salt Pan. The Landsat multispectral images and their processing through NDVI and SAVI indexes, that highlight a ring of healthy vegetation around the sub circular area with scarce vegetation already observed appear able to discriminate between H₂ emitting structures and other soft depressions.     

Ni2P(O)–Fe2P(O)/CeOx as high effective bifunctional catalyst for overall water splitting

The development of cost-effective bifunctional catalysts with excellent performance and good stability is of great significance for overall water splitting. In this work, NiFe layered double hydroxides (LDHs) nanosheets are prepared on nickel foam by hydrothermal method, and then Ni₂P(O)–Fe₂P(O)/CeO_x nanosheets are in situ synthesized by electrodeposition and phosphating on NiFe LDHs. The obtained self-supporting Ni₂P(O)–Fe₂P(O)/CeO_x exhibit excellent catalytic performances in alkaline solution due to more active sites and fast electron transport. When the current density is 10 mA cm^?2, the overpotential of hydrogen evolution reaction and oxygen evolution reaction are 75 mV and 268 mV, respectively. In addition, driven by two Ni₂P(O)–Fe₂P(O)/CeO_x electrodes, the alkaline battery can reach 1.45 V at 10 mA cm^?2.     

Swapping catalytic active sites from cationic Ni to anionic F in Fe–F–Ni3S2 enables more efficient alkaline oxygen evolution reaction and urea oxidation reaction

Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni₃S₂ nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni₃S₂ material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.     

Highly stable γ-NiOOH/ZnCdS photocatalyst for efficient hydrogen evolution

It is extremely desirable to develop high hydrogen evolution activity and stable visible-light-driven photocatalysts. The sluggish oxidation process and holes accumulation are the main obstacles to high catalysis activity and photo-stability. An efficient γ-NiOOH/ZnCdS photocatalyst was prepared by in-situ hydrothermal method. The γ-NiOOH nanosheets distribute on ZnCdS nanospheres surface and accelerate holes transfer. The hydrogen evolution rate is up to 48.60 mmol g^?1 h^?1 under visible-light illumination (λ = 400–780 nm), about 10.8 times of pure ZnCdS (4.50 mmol g^?1 h^?1) and 1.8 times of general β-NiOOH modified ZnCdS (27.40 mmol g^?1 h^?1). And apparent quantum yield of γ-NiOOH/ZCS-100 is up to 18.23% (400 nm). The carrier lifetime extends from 5.50 ns (ZnCdS) to 6.10 ns (γ-NiOOH/ZCS), examined by steady photoluminescence and time-resolved photoluminescence. Moreover, the γ-NiOOH/ZCS photocatalyst has exhibited excellent photo-stability even after one-year of storage. The γ-NiOOH nanosheets can be an excellent co-catalyst on accelerating both holes transfer and oxidation process for high photo-stability and photo-activity.     

Enhanced oxygen evolution reaction kinetics through biochar-based nickel-iron phosphides nanocages in water electrolysis for hydrogen production

Highly-efficient and stable non-noble metal electrocatalysts for overcoming the sluggish kinetics of oxygen evolution reaction (OER) is urgent for water electrolysis. Biomass-derived biochar has been considered as promising carbon material because of its advantages such as low-cost, renewable, simple preparation, rich structure, and easy to obtain heteroatom by in-situ doping. Herein, Ni₂P–Fe₂P bimetallic phosphide spherical nanocages encapsulated in N/P-doped pine needles biochar is prepared via a simple two-step pyrolysis method. Benefiting from the maximum synergistic effects of bimetallic phosphide and biochar, high conductivity of biochar encapsulation, highly exposed active sites of Ni₂P–Fe₂P spherical nanocages, rapid mass transfer in porous channels with large specific surface area, and the promotion in adsorption of reaction intermediates by high-level heteroatom doping, the (Ni_0.75Fe_0.25)₂P@NP/C demonstrates excellent OER activity with an overpotential of 250 mV and a Tafel slope of 48 mV/dec at 10 mA/cm² in 1 M KOH. Also it exhibits a long-term durability in 10 h electrolysis and its activity even improves during the electrocatalytic process. The present work provides a favorable strategy for the inexpensive synthesis of biochar-based transition metal electrocatalysts toward OER, and improves the water electrolysis for hydrogen production.     

Constitutive model for gas hydrate-bearing soils considering different types of hydrate morphology and prediction of strength-band

The present study proposes a new elasto-plastic constitutive model that considers different types of hydrates in pore spaces. Many triaxial compression tests on both methane hydrate-bearing soils and carbon dioxide hydrate-bearing soils have been carried out over the last few decades. It has been revealed that methane hydrate-bearing soils and carbon dioxide hydrate-bearing soils have different strength and dilatancy properties even though they have the same hydrate contents. The reason for this might be due to the different types of hydrate morphology. In this study, therefore, the effect of the hydrate morphology on the mechanical response of gas-hydrate-bearing sediments is investigated through a model analysis by taking into account the different hardening rules corresponding to each type of hydrate morphology. In order to evaluate the capability of the proposed model, it is applied to the results of past triaxial compression tests on both methane hydrate-containing and carbon dioxide hydrate-containing sand specimens. The model is found to successfully reproduce the different stress–strain relations and dilatancy behaviors, by only giving consideration to the different morphology distributions and not changing the fitting parameters. The model is then used to predict a possible range in which the maximum deviator stress can move for various hydrate morphology ratios; the range is defined as the strength-band. The predicted curve of the maximum deviator stress obtained by the constitutive model matches the empirical equations obtained from past experiments. It supports the fact that the hydrate morphology ratio changes with the total hydrate saturation. These findings will contribute to a better understanding of the relation between the microscopic structures and macro-mechanical behaviors of gas-hydrate-bearing sediments.     

Phase composition and property evolution of (Yb1−xHox)2Si2O7 solid solution as environmental/thermal barrier coating candidates

RE disilicates are good candidates as environmental/thermal barrier coating for SiC_f/SiC composite in harsh gas turbine engines. We designed (Yb_1?xHo_x)₂Si₂O₇ solid solutions and studied mechanical properties, thermal properties, and water vapor resistance. Powders with different compositions were synthesized by pressureless sintering, and bulk samples were prepared by Spark Plasma Sintering (SPS). Polymorphic changes with temperature and composition of the solid solutions were examined. Through doping Ho into Yb₂Si₂O₇, water vapor corrosion resistance is significantly promoted, and thermal expansion coefficient is maintained close to that of Si-based ceramics. Compared with host disilicates, thermal conductivity of solid solutions are decreased, and mechanical properties, including Vickers hardness and fracture toughness, are increased. A two-phase domain is found at (Yb_1/2Ho_1/2)₂Si₂O₇, and the γ to δ phase transition of Ho₂Si₂O₇ is observed during SPS. Among all samples, γ-(Yb_1/3Ho_2/3)₂Si₂O₇ possesses superior high temperature stability, and excellent water vapor resistance, indicating its performance as environmental/thermal barrier coating.     

Fabrication and properties of diatomite ceramics with hierarchical pores based on direct stereolithography

Porous diatomite ceramics with hierarchical pores and high apparent porosity (50.29–56%) were successfully fabricated via direct stereolithography. The pre-ball-milling time, dispersant type and dispersant concentration were systematically investigated to prepare diatomite pastes with high solid loading, low viscosity and a self-supporting effect. The results showed that a pre-ball-milling time of 24 h was more suitable to prepare diatomite pastes with high solid loading, and Span80 at 2 wt% was the optimal dispersant to obtain 40 vol% diatomite paste with a low viscosity and a self-supporting effect. To restrain the formation of defects, a heating rate as low as 0.2 °C/min was allowed to control the pyrolysis rate in the multistage debinding process. At sintering temperatures ranging from 900 °C to 1000 °C, porous diatomite ceramics exhibited a typical bimodal porosity, high apparent porosity and great flexural strength.     

Preparation of self-healing Cf/SiBCN(O) composite using a novel polyborosilazane

In this study, novel polyborosilazane-derived SiBCN(O) ceramic was used as self-healing component in self-healing C_f/SiBCN(O) composite, which was prepared by polymer infiltration and pyrolysis (PIP) process. Molecular-level structure design of boron-containing ceramic precursors was utilized to achieve uniform dispersion of boron-containing self-healing components in prepared composites. No elemental diffusion was observed at the interface of ceramic matrix and carbon fibers, which resulted in stable SiBCN(O) structure. In addition, boron was uniformly distributed in C_f/SiBCN(O) composite ceramic matrix, which was beneficial for self-healing of cracks. Cracks and indentations were able to heal at high temperatures in air. The best crack-healing behavior occurred in air atmosphere at 1000 °C, with nearly complete crack healing. This excellent self-healing behavior was achieved because silicon and boron atoms in SiBCN(O) ceramic reacted with available oxygen at high temperatures to form SiO₂(l), B₂O₃(l), and B₂O₃·xSiO₂ liquid phases, which effectively filled cracks. In general, as-prepared C_f/SiBCN(O) composite exhibited excellent self-healing properties and shows great application potential in high-temperature environment applications such as aviation, aerospace, and nuclear power.