Periodical Ripening for MOCVD Growth of Large 2D Transition Metal Dichalcogenide Domains

2D semiconductors, especially 2D transition metal dichalcogenides (TMDCs), have attracted ever-growing attention toward extending Moore's law beyond silicon. Metal–organic chemical vapor deposition (MOCVD) has been widely considered as a scalable technique to achieve wafer-scale TMDC films for applications. However, current MOCVD process usually suffers from small domain size with only hundreds of nanometers, in which dense grain boundary defects degrade the crystalline quality of the films. Here, a periodical varying-temperature ripening (PVTR) process is demonstrated to grow wafer-scale high crystalline TMDC films by MOCVD. It is found that the high-temperature ripening significantly reduces the nucleation density and therefore enables single-crystal domain size over 20 µm. In this process, no additives or etchants are involved, which facilitates low impurity concentration in the grown films. Atom-resolved electron microscopy imaging, variable temperature photoluminescence (PL) spectroscopy, and electrical transport results further confirm comparable crystalline quality to those observed in mechanically exfoliated TMDC films. The research provides a scalable route to produce high-quality 2D semiconducting films for applications in electronics and optoelectronics.     

Stainless steel mesh-based CoSe/Ni3Se4 heterostructure for efficient electrocatalytic overall water splitting

The construction of high-efficiency bifunctional electrocatalysts is still a main challenge for hydrogen production from water splitting, in which comprehensive structure regulation plays a key role for synergistically boosting the intrinsic activity and charge collection. Here, we used a two-step hydrothermal method for construction of an interjaculated CoSe/Ni₃Se₄ heterostructure from NiCo LDH nanosheets grown on stainless steel (SS) meshes as bifunctional electrocatalysts for overall water splitting. The SS meshes containing Fe and Ni act as an excellent 3D scaffold for catalyst growth and charge collection. The SS@CoSe/Ni₃Se₄ composite exhibits outstanding electrocatalytic performances with low overpotentials of 97 mV for hydrogen evolution and 230 mV for oxygen evolution to reach a current density of 10 mA cm⁻², respectively. Moreover, by using SS@CoSe/Ni₃Se₄ as both the cathode and anode, the assembled electrolyze only required 1.55 V to reach 10 mA cm⁻² for overall water splitting. The outstanding performance of SS@CoSe/Ni₃Se₄ benefits from the synergy between excellent charge collection capability of SS meshes and the abundant active sites at the CoSe/Ni₃Se₄ heterointerface formed with the in-situ conversion of NiCo LDH nanosheets. Electrochemical active surface area and impedance spectrum indicate that the CoSe/Ni₃Se₄ loaded on SS has the most abundant electrochemically active sites and the smallest electrochemical resistance, thereby exposing more active sites and enhancing the charge transfer to promote the catalytic activity. By integrating the delicate nanoscale heterostructure engineering with the microscale SS mesh scaffold, our work provides a new perspective for the preparation of high-performance and cheap electrocatalysts that are easy to be integrated with industrial applications.     

Hydrogen production via dark fermentation by bacteria colonies on porous PDMS-scaffolds

The development of biofuels and the question of finding renewable energy sources are important issues nowadays, due to the increasing shortage of other supplies. Hydrogen has gained very much attention as biofuel, as it is highly energetic and a clean energy source. A very interesting method to produce hydrogen is dark fermentation. It generates a clean energy from organic wastes with low value and at low energy requirements. The production of hydrogen and bio-hydrogen from waste and wastewaters can have a positive environmental impact in terms of creation of highly effective energy fuel and reduction of waste. Due to their nutrients, organic waste and wastewaters are suitable substrates to obtain bio-hydrogen. In this paper we investigate the behaviour and the stability of porous scaffolds containing iron oxide particles in a dark fermentation environment and explore the possibility of hosting mixed cultures of clostridia on them, aiming to an increase in hydrogen production. We address the effect of embedding hematite particles (in different concentrations) in the scaffolds, to see whether there is an increase in bio-hydrogen-production. This latter can be enhanced, if particles of various metal oxides are present, as they can increase bacterial growth and encourage the bioactivity of species that produce hydrogen. The scaffolds analysed consist of polydimethylsiloxane (PDMS) containing Fe₂O₃ particles and were produced via the sugar template method. X-ray diffraction patterns, SEM images as well as dark fermentation tests in batch procedure are presented and discussed. Bacteria colonies could be detected after long treatment in municipal wastewater and production of biohydrogen was ascertained for all samples investigated.     

The fabrication of Pt–Pb alloy networks with high-density micropores by dealloying for enhanced oxygen reduction activity

Porous Pt-based nanomaterials possess intriguing properties for various important applications due to their abundant exposed active sites and highly accessible surfaces. Importantly, the pore size is a key factor that determines its specific applicability. With the advances of fabrication strategies, Pt-based nanomaterials with a variety of unique pore structure including mesopores and macropores have been extensive reported. However, so far, few effective methods have been reported to prepare the Pt-based nanomaterials with high-density micropores. In this work, we reported a facile method to prepare the high-density microporous Pt–Pb NWs via a chemical etching strategy by using the intermetallic PtPb networks (NWs) as the starting material. After dealloying, a large amount of microporous and defects were successfully introduced into the MP-PtPb NWs. The microporous networks can not only increase the active area both on the exterior and interior surface, but also provide efficient mass transfer and electron mobility for reactant molecules. As a result, the mass activity exhibited by MP-PtPb NWs catalyst is 0.83 A mg⁻¹_Pt, which is 5.8 and 1.9 times than that of commercial Pt/C and IM-PtPb NWs. Besides, even after 10,000 cycles of accelerated durability test, the MP-PtPb NWs and IM-PtPb NWs exhibit comparable drop of ∼10% in mass activity, against a big decrease of 46% for commercial Pt/C. We believe this work provides an efficient strategy to prepare metallic catalysts with high-density microporous nanomaterials for catalysis.     

Effect of mixing metakaolins: Methodological approach to estimate metakaolin reactivity

Geopolymers are obtained from an alkali silicate solution and aluminosilicate sources. The source commonly used geopolymer is metakaolin. The chemical composition, extraction site or calcination process of metakaolin influence its reactivity and thus the properties of the consolidated samples. This work focused on clarifying how the properties of aluminosilicate-based raw materials evolve when different metakaolin sources are mixed. The study involved mixing different metakaolins to evaluate their physico-chemical properties. The different samples were characterized by measuring their granulometry, wettability and zeta potential. Structural data were obtained from X-ray diffraction and ²⁷Al nuclear magnetic resonance spectroscopy. It appears that the properties of the mixtures can be expressed as a function of different parameters. Granulometric properties directly depend on the quantity of each source, wettability is related to the amount of available amorphous aluminum in the sources, and zeta potential is strongly influenced by the source with the highest amount of siliceous-based impurities. This methodological approach can be applied to geopolymer synthesis.     

Confined Tri-Functional FeOx@MnO2@SiO2 Flask Micromotors for Long-Lasting Motion and Catalytic Reactions

H₂O₂-fueled micromotors are state-of-the-art mobile microreactors in environmental remediation. In this work, a magnetic FeO_x@MnO₂@SiO₂ micromotor with multi-functions is designed and demonstrated its catalytic performance in H₂O₂/peroxymonosulfate (PMS) activation for simultaneously sustained motion and organic degradation. Moreover, this work reveals the correlations between catalytic efficiency and motion behavior/mechanism. The inner magnetic FeO_x nanoellipsoids primarily trigger radical species (^•OH and O₂^•−) to attack organics via Fenton-like reactions. The coated MnO₂ layers on FeO_x surface are responsible for decomposing H₂O₂ into O₂ bubbles to provide a propelling torque in the solution and generating SO₄^•− and ^•OH for organic degradation. The outer SiO₂ microcapsules with a hollow head and tail result in an asymmetrical Janus structure for the motion, driven by O₂ bubbles ejecting from the inner cavity via the opening tail. Intriguingly, PMS adjusts the local environment to control over-violent O₂ formation from H₂O₂ decomposition by occupying the Mn sites via inter-sphere interactions and enhances organic removal due to the strengthened contacts and Fenton-like reactions between inner FeO_x and peroxides within the microreactor. The findings will advance the design of functional micromotors and the knowledge of micromotor-based remediation with controlled motion and high-efficiency oxidation using multiple peroxides.     

Photoacoustic dual-gas sensor for simultaneous detection of hydrogen and water vapor

Hydrogen (H₂) is an important energy carrier, however, it can be hazardous owing to the risks involved with boring and explosion with colorless flames. By detecting the concentrations of H₂ and vapor water (H₂O) in real time, such risks can be prevented in advanced. In this study, a sensor system is developed based on photoacoustic spectroscopy using an H-type photoacoustic cell (PAC). Further, the time division multiplexing technique is used in a specific scanning period to realize dual-gas simultaneous detection. The dimensions of the PAC are optimized (inner volume: 1.8 cm³) and N-th characteristic frequencies are simulated through multiphysics simulation in COMSOL software. The optimized PAC is applied in the system and experiments of simultaneous dual gases detection are performed. The detection results show that the sensor's response time is 0.51 s and the recovery time is 0.38 s, and the minimal detection limit of H₂ is 138.69 ppm and H₂O can reach 3.70 ppm.     

Numerical simulation of the interaction and coalescence of inline hydrogen bubbles in biohydrogen production by photofermentation with corncob

The escape rate of hydrogen in photobiological hydrogen production plays an important role in the biochemical reaction process, and the interaction of hydrogen bubbles in bio-hydrogen production material liquid affects the escape rate of hydrogen. In this paper, the Eulerian-Eulerian-Multifluid VOF method is used to simulate the interactions of three types of hydrogen bubbles: coalescence of equal-sized inline hydrogen bubbles, a small leading hydrogen bubble is chased by a large trailing hydrogen bubble and a large leading hydrogen bubble is chased by a small trailing hydrogen bubble. The results show that the interaction strength between hydrogen bubbles is influenced by the initial interval and initial diameter of the hydrogen bubbles and the flow index of the hydrogen-producing material liquid. The hydrogen bubbles exhibit three types of aggregation. In the pre-merger period, the velocity of the trailing hydrogen bubble also shows four stage changes, which are acceleration to the maximum velocity - deceleration - small increase in velocity - deceleration to the merging velocity. There is also a brief acceleration of the leading hydrogen bubble. For the interaction between Type II and Type III hydrogen bubbles of the same size, there is no significant difference in the rise rate of large hydrogen bubbles after the coalescence.     

Effects of geodesic dome trajectories on the specific strength of composite overwrapped pressure vessels: FE modelling

In this study, it was aimed to find out geodesic dome trajectories of composite overwrapped pressure vessels, and investigate the effect of dome profiles on the structural performances. In this context, geodesic paths for 0.2, 0.3, 0.4, 0.5 and 0.6 dimensionless polar opening radii were determined by solving elliptical integrals and filament winding angles were calculated throughout the dome and cylindrical portions. Afterward, finite element analysis was performed to obtain mechanical properties by using the Ansys ACP module. As a result of the current study, it has been concluded that dome profile and filament winding angle are highly dependent on the polar opening radii. When the performance factor was considered, it has been determined that the optimum pressure vessel has 0.6 dimensionless polar opening radii. Moreover, it was observed that minimum equivalent stress, strain, deformation and inverse reverse factors have occurred in the pressure vessel with 0.6 dimensionless polar opening radii. Furthermore, it was showed that effective parameters in the mechanical performance of pressure vessels can be optimized to obtain strengthened and lighter structures.     

Highly active and robust biomimetic ceramic catalyst for oxygen reduction reaction: Inspired by plant leaves

Structural instability under working conditions is critical issue that restricts applications of perovskite O₂ catalysts in the field of solid oxide fuel cells. Inspired by plant leaves, a biomimetic ceramic catalyst with PrBaCo₂O_5+δ ‘mesophyll’ and Gd_0.1Ce_0.9O_1.95 ‘epidermis’ and ‘vein’ was successfully engineered in this work. The ‘epidermis’ reduces the polarization resistance of O₂ reduction reaction on catalyst surface by ∼24%, and the ‘vein’ reduces resistance of O²⁻ transport through cathode layer by ∼65%. Moreover, this biomimetic catalyst increases output power density of the cell by 79% and reverses rapid decay trend of the cell with a 23% increase in power density during first 20 h followed by stabilization at 0.91 W cm⁻² (at 750 °C and 0.7 V). This discovery provides new avenue for the development of high-performance O₂ catalysts with practical applications and enriches the scientific understanding of catalysis.