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.     

Zeolite-templated sub-nanometer carbon nanotube arrays and membranes for hydrogen storage and separation

Adsorbents and membranes consisting of carbon nanotube (CNT) pores with diameters of molecular dimensions are highly desirable for hydrogen storage and selective, high-flux membrane separation. However, fabrication of such materials with precise pore sizes and monodispersity as well as evaluation of the mechanisms associated to adsorption and molecular transport are challenging. Herein, we grew aluminophsphate zeolites (CoAPO-5, AFI crystal structure) consisting of one-dimensional, monodisperse parallel pores with diameter of ～7 Å, and utilized them as templates to grow singe-walled CNTs (SWNTs) inside the pores. The resulting materials were examined as adsorbents and membranes for hydrogen storage and separation, respectively, using single-gas and real mixture feeds. Detailed mechanistic analysis and fundamental investigation of permeance and adsorption behavior of the resulting CNT-in-zeolite systems via combined adsorption, equilibrium, and kinetic studies were carried out. A superior gravimetric hydrogen uptake of 1.2 wt% at 35 °C and 1 bar was achieved in the case of the SWNTs grown in the cobalt-richer AFI host. Permeability measurements were performed on the respective Co(x)APO@SWNT membranes with the Co-richAPO@SWNT membrane exhibiting the highest permeance for all studied gases as a consequence of larger and more densely packed AFI crystals along with higher number of SWNT-filled pores, assets attributed to the higher Co catalyst content. Notably, the produced composite membranes exhibited gas permeability values that were two orders of magnitude higher than what predicted by the Knudsen mechanism.     

Dynamic simulation of hydrogen-based off-grid zero energy buildings with hydrogen storage considering Fanger model thermal comfort

In this study, some locations with different climates, off-grid zero energy buildings with hydrogen energy storage systems are designed, and transient analysis is conducted. These considered buildings supply their electricity consumption without using the electrical grid and PV panels or wind turbines. Also, they supply thermal comfort to occupants by using a vapor compression chiller and humidifier. Domestic hot water of occupants is supplied using solar collectors. For analyzing building's performance and objectives achievement, TRNSYS software is used. Also, for evaluating occupant thermal comfort, the Fanger model is used. The considered building is a one-story building with a 150 m² area. Four occupants are considered. Both of them are seated at rest, and another is seated with light working such as typing. Using the Fanger model equation and MATLAB software, the thermal comfort of occupants is determined. For domestic hot water consumption, verified profiles that vary during 24 h of the day are considered. Achieved results show that for humid and cold cities, PV panels with an area of 73 and 76 m² can be supplied the required electricity of considered building with four occupants and battery state of charge is higher than 50% and 10%, respectively. Moreover, with a suitable air conditioner system, the predicted percentage of dissatisfied (PPD) can be lower than 12% and 8% for humid and cold cities. Therefore, the building can be converted to a zero-energy building using its rooftop area.     

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.     

Enhancing the dehydrogenation properties of LiAlH4 using K2NiF6 as additive

Lithium alanate (LiAlH₄) is a material that can be potentially used for solid-state hydrogen storage due to its high hydrogen content (10.5 wt%). Nevertheless, a high desorption temperature, slow desorption kinetic, and irreversibility have restricted the application of LiAlH₄ as a solid-state hydrogen storage material. Hence, to lower the decomposition temperature and to boost the dehydrogenation kinetic, in this study, we applied K₂NiF₆ as an additive to LiAlH₄. The addition of K₂NiF₆ showed an excellent improvement of the LiAlH₄ dehydrogenation properties. After adding 10 wt% K₂NiF₆, the initial decomposition temperature of LiAlH₄ within the first two dehydrogenation steps was lowered to 90 °C and 156 °C, respectively, that is 50 °C and 27 °C lower than that of the аs-milled LiAlH₄. In terms of dehydrogenation kinetics, the dehydrogenation rate of K₂NiF₆-doped LiAlH₄ sample was significantly higher as compared to аs-milled LiAlH₄. The K₂NiF₆-doped LiAlH₄ sample can release 3.07 wt% hydrogen within 90 min, while the milled LiAlH₄ merely release 0.19 wt% hydrogen during the same period. According to the Arrhenius plot, the apparent activation energies for the desorption process of K₂NiF₆-doped LiAlH₄ are 75.0 kJ/mol for the first stage and 88.0 kJ/mol for the second stage. These activation energies are lower compared to the undoped LiAlH₄. The morphology study showed that the LiAlH₄ particles become smaller and less agglomerated when K₂NiF₆ is added. The in situ formation of new phases of AlNi and LiF during the dehydrogenation process, as well as a reduction in particle size, is believed to be essential contributors in improving the LiAlH₄ dehydrogenation characteristics.     

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.     

Societal acceptance of hydrogen for domestic and export applications in Australia

With the urgent need to decarbonise the world's energy system, clean hydrogen is emerging as a potential technological solution. As with any new technology, understanding the public's response to hydrogen is critical to its success. Most studies examining public attitudes towards hydrogen have focused on refuelling stations and transport options. As a first of its kind, using a national survey (N = 2785) we evaluate the Australian public's response towards hydrogen for domestic and export use. In Australia, acceptance of hydrogen in domestic applications was influenced by its relative cost, ability to reduce air pollution and associated health benefits. Further, support for a hydrogen export industry was influenced by levels of trust in the government to manage the associated risks and the industry's commitment to climate protection. The paper concludes that effective, nuanced communication and engagement along with supporting financial policies will be critical in facilitating societal acceptance of hydrogen in Australia.     

Effects of different metal corrosion inhibitors on hydrogen suppression and film formation with Mg–Zn alloy dust in NaCl solutions

To improve the safety of wet dust removal systems for processing magnesium-based alloys, a new method is proposed for preventing hydrogen generation. In this paper, hydrogen generation by Mg–Zn alloy dust was inhibited with six common metal corrosion inhibitors. The results showed that sodium dodecylbenzene sulfonate was the best hydrogen inhibitor, while CeCl₃ enhanced hydrogen precipitation. The film-forming stability of sodium dodecylbenzene sulfonate was tested with different contents, temperatures, Cl^? concentrations and perturbation rates. The results showed that this inhibitor formed stable protective films on the surfaces of Mg–Zn alloy particles, and adsorption followed the Langmuir adsorption model.     

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.     

Heterofullerene C48B12-impregnated MOF-5 and IRMOF-10 for hydrogen storage: A combined DFT and GCMC simulations study

The H₂ storage properties of isoreticular metal-organic framework materials (IRMOFs), MOF-5 and IRMOF-10, impregnated with different numbers and types of heterogeneous C₄₈B₁₂ molecules were investigated using density functional theory and grand canonical Monte Carlo (GCMC) calculations. The excess hydrogen adsorption isotherms of IRMOFs at 77 K within 20 bar indicate that suitable number and type of C₄₈B₁₂ molecules play a crucial role in improving the H₂ storage properties of IRMOFs. Among the studied pure and nC₄₈B₁₂ (n = 1, 2, 4, 8) in Ci symmetry impregnating into MOF-5, at 77 K under 6 bar, MOF-5-4C₄₈B₁₂ with a 3.5 wt% and 29.9 g/L hydrogen storage density, and at 77 K under 12 bar, the pure MOF-5 with a 4.9 wt% and 31.0 g/L hydrogen storage density has the best hydrogen storage properties. Whereas, among the studied pure and nC₄₈B₁₂ (n = 1, 2, 4, 8) in S6 symmetry impregnating into IRMOF-10, IRMOF-10-8C₄₈B₁₂ always shows the best hydrogen storage properties among the pure and C₄₈B₁₂-impregnated IRMOF-10 at 77 K within 20 bar. IRMOF-10-8C₄₈B₁₂ has a 6.0 wt% and 34.6 g/L hydrogen storage density at 77 K under 6 bar, and has a 7.1 wt% and 41.4 g/L hydrogen storage density at 77 K under 12 bar. The confinement effect of IRMOFs on C₄₈B₁₂ molecules, and steric hindrance effect of C₄₈B₁₂ molecules on IRMOFs mainly affects the H₂ uptake capacity by comparing the absolute H₂ molecules in individual IRMOFs units, C₄₈B₁₂ molecules, and IRMOFs-nC₄₈B₁₂ compounds. The absolute hydrogen adsorption profiles show that eight C₄₈B₁₂ molecules impregnating into MOF-5 can exert obvious steric effects for H₂ adsorption. The saturated gravimetric and volumetric H₂ densities of IRMOF-10-8C₄₈B₁₂ higher than those of MOF-5-8C₄₈B₁₂ due to with larger free volume.