Mechanism in chlorine-enhanced Pd catalyst for H2O2 in situ synthesis in electro-Fenton system

Palladium-based catalysts have been widely employed in the electro-Fenton process for in situ generation of H₂O₂. However, the process is still far from being practical on a large scale. In this work, a series of Cl_xFePd/γ-Al₂O₃/Al catalysts were prepared by a three-step-impregnation method. They exhibited excellent activity in H₂O₂ in situ synthesis and high efficiency in phenol degradation. The characterization results showed that Cl could assist in increasing the content of Pd⁰ and reducing the isoelectric point of catalysts, which led to the drastic promotion in the synthesis of H₂O₂. Theoretical calculations further demonstrated that Cl doping could facilitate the main reaction in H₂O₂ synthesis, as well as inhibit side reactions such as dissociation of the O O bond. Furthermore, kinetic models were proposed and fitted. A plausible reaction mechanism as well as degradation pathways were elaborated based on electron spin resonance and gas chromatography–mass spectrometry results. These findings illustrate the value of palladium-based Cl_xFePd/γ-Al₂O₃/Al catalysts for their application in the electro-Fenton process.     

Tailoring surface capacitance of Ti3C2Tx-PANI@CNTs nanoarchitecture for tunable energy storage and high-performance micro-supercapacitor

Transition metal carbide or nitride (MXenes), as a novel family of two-dimensional materials, exhibit huge potential for electrochemical energy storage thanks to their excellent electrical conductivity, fast ion diffusion rate, high electrochemical activity and good hydrophilicity. However, the electrochemical properties of MXenes tend to be deteriorated due to the self-restacking phenomenon. Herein, by self-assembly, a unique three-dimensional (3D) Ti₃C₂T_x-PANI@CNTs (TPCs) nanoarchitecture was constructed. Through optimizing structures, the surface capacitance of TPCs can be tailored to tune energy storage. The optimal specific capacitance up to 431.9 F/g was achieved under 1 A/g. Further, the TPCs nanoarchitectures were prepared into self-standing films with excellent mechanical properties and micro-supercapacitors (MSCs) in various shapes were manufactured based on the film. The MSCs demonstrate competitive energy storage capacities, obtaining an areal capacitance of 78.2 mF/cm² and energy density of up to 2.72 μWh/cm², still maintain excellent performance under harsh bending. The strategy for constructing 3D nanoarchitectures and further manufacturing MSCs can inspire the design of novel electrode materials and devices to advance the development in the field of energy storage.     

Microstructure and mechanical properties of 3D-printed nano-silica reinforced alumina cores

Ceramic cores are an important component in the preparation of hollow turbine blades for aero-engines. Compared with traditional hot injection technology, 3D printing technology overcomes the disadvantages of a long production cycle and the difficulty in producing highly complex ceramic cores. The ceramic cores of hollow turbine blades require a high bending strength at high temperatures, and nano-mineralizers greatly improve their strength. In this study, nano-silica-reinforced alumina-based ceramic cores were prepared, and the effects of nanopowder content on the microstructure and properties of the ceramic cores were investigated. Alumina-based ceramic cores contained with nano-silica were prepared using the vat photopolymerization 3D printing technique and sintered at 1500 °C. The results showed that the linear shrinkage of ceramic cores first increased and then decreased as the nano-silica powder content increased, and the bending strength showed the same trend. The fracture mode changed from intergranular to transgranular. The open porosity and bulk density fluctuated slightly. The weight loss rate was approximately 20%. When the nano-silica content was 3%, the bending strength reached a maximum of 46.2 MPa and 26.1 MPa at 25 °C and 1500 °C, respectively. The precipitation of the glass phase, change in the fracture mode of the material, pinning crack of nanoparticles, and reduction of fracture energy due to the interlocking of cracks, were the main reasons for material strengthening. The successful preparation of 3D printed nano-silica reinforced alumina-based ceramic cores is expected to promote the preparation of high-performance ceramic cores with complex structures of hollow turbine blades.     

Grain orientation evolution and multi-scale interfaces enhanced thermoelectric properties of textured Sr0.9La0.1TiO3 based ceramics

Sr_0.9La_0.1TiO₃ based textured ceramics (SLTT-S3T) with a texture fraction of 0.81 are successfully fabricated by the reactive template grain growth method, in which Sr_0.9La_0.1TiO₃/20 wt%Ti was used as matrix and 10 wt% plate-like Sr₃Ti₂O₇ template seeds were used as templates. The phase transition, microstructure evolution, and the anisotropic thermoelectric properties of SLTT-S3T ceramics were investigated. The results show that the ceramics are mainly composed of Sr_0.9La_0.1TiO₃ and rutile TiO₂ phases. Grains grow with a preferred orientation along (h00). A maximum ZT of 0.26 at 1073 K was achieved in the direction perpendicular to the tape casting direction. The low lattice thermal conductivity of 1.9 W/(m K) at 1073 K was obtained decreased by 34%, 40%, and 38% compared with non-textured, SrTiO₃ and Sr_0.9La_0.1TiO₃ ceramics prepared by the same process, can be attributed to the enhanced phonon scattering by the complex multi-scale boundaries and interfaces. This work provides a strategy of microstructural design for thermoelectric oxides to decrease intrinsic lattice thermal conductivity and further regulate thermoelectric properties via texture engineering.     

Defect-free drying of large fine-particle zirconia compacts prepared by gelcasting method

In this work, drying of bodies prepared by gelcasting fine submicrometre-sized zirconia particles was studied and a drying process for defect-free bodies with large cross-sections was proposed. It was found that the cracking of large bodies could be prevented by reducing the monomer content and using appropriate non-volatile cosolvents. Glycerol and polyethylene glycols with different molecular weights were used as non-volatile cosolvents in aqueous ceramic suspensions. The complex effects of the individual cosolvents on the gelcasting process and, in particular, on the drying step were investigated and explained. The applicability of individual cosolvents for the gelcasting process were discussed and their optimal use was indicated.     

Additive manufacturing,quasi-static and dynamic compressive behaviours of ceramic lattice structures

Ceramic lattice structures (CLSs) are used for construction in common and extreme environments because of the extraordinary properties of ceramics. In this study, we designed and additively manufactured CLSs with distinct structural parameters to explore their quasi-static and dynamic compressive behaviours in detail. It was demonstrated that both the relative density (?ρ) and inclination angle (ω) had a significant impact on the quasi-static and dynamic mechanical properties of the CLSs. Furthermore, the mathematical relationships between the quasi-static compressive properties, including quasi-static compressive strength (QS), quasi-static Young’s modulus (QY), and quasi-static energy absorption (QE), versus ?ρ and ω obeyed the Gibson–Ashby and Deshpande and Fleck models, respectively. It was revealed by experiment and simulation that as the stiffness increased, the quasi-static failure mode of the CLSs changed from a parallel-vertical-inclined mixed mode to a parallel-vertical mode. In addition, the relationship between the dynamic mechanical properties of the CLSs versus ?ρ and ω also followed the Gibson–Ashby and Deshpande and Fleck models. The exceptional dynamic increase factor indicated that CLSs are highly suitable for extreme environments. These findings will aid in the research and development of customised additively manufactured CLSs.     

Hydrogen production with an auto-thermal MSW steam gasification and direct melting system: A process modeling

Municipal solid waste steam gasification and direct melting system is proposed in this study for H₂ production and ash melting simultaneously. Part of the H₂ generated in gasification is extracted for combustion with pure oxygen in the melting zone to provide the energy necessary for auto-thermal operation. A simulation model is developed with Aspen Plus to investigate the performance and optimum conditions of the system. For the feedstock with a lower heating value of 18.91 MJ/kg used in this study, 39.8% of the generated H₂ needs to be extracted to maintain the heat balance of the system at the gasification temperature of 900 °C, melting temperature of 1400 °C, and S/M of 1. The net H₂ yield is ～77.3 kg/t-MSW with a net cold gas efficiency of 49.1% under the same operating condition. An optimum operation condition for T (850–1000 °C) and S/M (0.6–1.0) is determined considering the balance between H₂ production ability and the auto-thermal energy balance.     

Nanoarchitectonics of CdS/ZnSnO3 heterostructures for Z-Scheme mediated directional transfer of photo-generated charges with enhanced photocatalytic performance

The construction of heterostructure is an effective strategy to synergetically couple wide-band-gap with the narrow-band-gap semiconductor with a mediate optical property and charge transfer capability. Herein, the Z-Scheme CdS/ZnSnO₃ (CdS/ZSO) heterostructures were constructed by anchoring CdS nanoparticles on the surface of double-shell hollow cubic ZnSnO₃ via the hydrothermal method. The direct recombination of excited electrons in the conduction band (CB) of ZSO and holes in the valence band (VB) of CdS via d-p conjugation at the interface greatly accelerated the internal electric field (IEF). The transfer mode follows the Z-Scheme mechanism, where CdS/ZSO synergistically facilitates the efficient charges transfer from CdS to ZnSnO₃ through the intimate interface. Here, ZnSnO₃ and CdS serve as an oxidation photocatalyst (OP) and reduction photocatalyst (RP), respectively. Thus, it can promote synergistically the oxidation half-reaction and reduction half-reaction of H₂ evolution. The density-functional theory (DFT) calculation further confirms the charges transfer from CdS to ZnSnO₃. The hydrogen evolution of 5% CdS/ZSO heterostructure reached 1167.3 μmol g^?1, which was about 8 and 3 folds high compared to pristine ZSO (141.9 μmol g^?1) and CdS (315.5 μmol g^?1), during 3 h of reaction respectively. Furthermore, the CdS/ZSO heterostructures could suppress the photo corrosion of CdS, resulting in its high stability. This work is expected to enlighten the rational design of heterostructure for OP and RP to promote the hybrid heterostructures photocatalytic H₂ evolution.     

Fabrication of novel ZnTe-based photocatalyst: Synergistic effect of dye sensitization and bridge engineering for boosting hydrogen evolution over ZnTe

Herein, a novel ZnTe-based photocatalyst is successfully synthesized via a facile combination of water-bath and hydrothermal processes. Morphology characterization and X-ray diffraction analysis reveal that ZnTe presents irregular granular shape and cubic crystal structure. Moreover, Mott-Schottky measurement shows that the conduction band potential of ZnTe is ?0.84 V (vs NHE). With Eosin Y (EY) sensitization, ZnTe exhibits superior photocatalytic hydrogen evolution activity (223.5 μmol g^?1 h^?1). Meanwhile, WC-ZnTe heterojunction is constructed by depositing ZnTe nanoparticles on bulk WC and obtains the optimal H₂ generation rate (559.1 μmol g^?1 h^?1) under EY sensitization. Electrochemical and photoluminescence results further prove that WC as electron bridge could reduce the interfacial resistance and suppress e^?-h⁺ pairs recombination. This study explores the potential application of ZnTe as a newly active photocatalyst in photocatalytic water splitting, and emphasizes the synergistic effect of dye sensitization and bridge engineering.