Thermal and photon effects on the reaction of H2 and O2 to water over Ag–Pd/TiO2

The reaction of H₂ and O₂ to water are studied over a Ag–Pd/TiO₂ anatase catalyst, under dark and photo-irradiation conditions in the gas and liquid phases. The catalyst consisted of metal particles of mean size of ca.1 nm dispersed over 10–15 nm TiO₂ particles. Kinetic parameters including order of reaction (n), rate constant (k), and activation energy (E_a), were evaluated. E_a for the thermal reaction was found to be 49-47 kJ mol^?1. The oxidation reaction rate constant was found to be ca. 3 times higher in the presence of photons when compared to dark reaction at room temperature. The overall quantum yield of the reaction in the slurry phase was found to be 0.09. Considering the number of metal particles on TiO₂, the photon yield per metal particle was found to be 0.16. A possible explanation of the changes in kinetics with respect to experimental conditions is given.     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

Micron-sized silica mesh for enhancing the performance of quantum dot sensitized solar cells

Three dimensional silica mesh structures are prepared through a new and simple method for enhancing the quantum dot sensitized solar cells performance and stability.Silica patterns are made on the top of the TiO₂ photoanodes and a marked improvement in light scattering properties of meshed structures is confirmed by diffuse reflectance spectroscopy measurements. This improvement enhances the current density and consequently the cells ‘efficiency. Parameters of electron transport in cells are explored by electrochemical impedance spectroscopy (EIS). According to the EIS results, silica mesh declines the recombination rate in cells in a clear way. Here more than 50% efficiency improvement is obtained in meshed structures in comparison to cells with normal TiO₂ photoanode structures. The insulated silica mesh, reduces the electrolyte's deleterious effect on the semiconductor layers and the cells’ stability is improved.     

Hollow In2O3 nanotubes decorated with Cd0.67Mo0.33Se QDs for enhanced photocatalytic hydrogen production performance

Novel Cd_0.67Mo_0.33Se/In₂O₃ hollow nanotubes were prepared for photocatalytic hydrogen production application. Under visible light irradiation, Cd_0.67Mo_0.33Se/In₂O₃ hollow nanotubes showed enhanced photocatalytic performance. And the apparent quantum efficiency of 34.86% was obtained when irradiated with 420 nm monochromatic light. The modification of Cd_0.67Mo_0.33Se QDs on the surface of In₂O₃ hollow nanotubes effectively improved the utilization rate of light absorption, increased the separation and migration rate of electrons, inhibited the recombination of photo-generated electron and hole pairs, thus enhancing the photocatalytic activity of water splitting to produce hydrogen. It would be an efficient photocatalyst for hydrogen production application in future.     

Moment quantization of inhomogeneous spin ensembles

Robust excitation of a large spin ensemble is a long-standing problem in the field of quantum information science and engineering and presents a grand challenge in quantum control. A formal theoretical treatment of this task is to formulate it as an ensemble control problem defined on an infinite-dimensional space. In this paper, we present a distinct perspective to understand and control quantum ensemble systems. Instead of directly analyzing spin ensemble systems defined on a Hilbert space, we transform them to a space where the systems have reduced dimensions with distinctive network structures through the introduction of moment representations. In particular, we illustrate the idea of moment quantization for a spin ensemble and illuminate how this technique leads to a dynamically equivalent control system of moments. This equivalence enables the control of spin ensembles through the control of their moment systems, which in turn creates a new control analysis and design paradigm for quantum ensemble systems based on the use of truncated moment systems.     

Photocatalytic hydrogen production from water-methanol and -glycerol mixtures using Pd/TiO2(-WO3) catalysts and validation in a solar pilot plant

This paper is focused on the photocatalytic hydrogen production on Pd/TiO₂(-WO₃) catalysts from water-methanol and water-glycerol mixtures under UVA and solar irradiation. The photodeposition method for Pd was studied varying conditions such as Pd amount, catalyst concentration and methanol concentration. The catalysts were tested at lab scale under simulated solar light and UVA radiation and also at large scale (25 L) under solar energy using a pilot-scale solar Compound Parabolic Collector (CPC). The catalysts characterization was performed by means of ICP-OES, N₂ adsorption–desorption isotherms, XRD, HR-TEM, XPS and DR–UV–Vis spectroscopy. Hydrogen evolution was monitored by on-line gas chromatography.From results it was found the Pd photodeposition method plays a key role to increase the hydrogen evolution, affecting parameters like the Pd amount deposited, the Pd nanoparticles size and dispersion. The highest quantum efficiency (ϕ) obtained in this study was 11.8% and 41.2% under simulated solar and UVA irradiation, respectively, using Pd(0.24 wt%)/P25 in an aqueous solution of methanol (50 vol%). In the pilot-scale solar CPC, for Pd(0.24 wt%)//P25 catalysts in 5 vol% of methanol or glycerol as sacrificial agents, the quantum yield were 2.1 and 2.2%, respectively. When the concentration of the sacrificial agents decreased to 0.37 vol%, the quantum yields were 1.3 and 2.4% for methanol and glycerol, respectively. Compared to literature, the low noble metal content of these catalysts (0.25 wt%) seems to be a competitive factor considering their high price.     

A subtle review on the challenges of photocatalytic fuel cell for sustainable power production

The revolution in the arena of functional materials for the development of well advanced engineered photocatalyst can efficiently harness photon energy from a wide spectrum of electromagnetic radiation. These next-generation smart materials would be a spectacular approach in designing devices such as photovoltaic cells, photoelectrochemical cells, and photocatalytic fuel cells. Photocatalytic oxidation of water or wastewater for concurrent production of hydrogen and electric current has turned out as a principal concept for the construction of modern photocatalytic fuel cells (PFCs). Such PFCs mimics reverse photosynthesis process where electrical energy is generated from organic pollutants. In recent years many reviews on focusing the design, fabrication, and theoretical efficiency of the PFCs have been published. Hence the present review is aimed to unveil the wall-to-wall information starting from fundamentals spanning to working principles, structural configuration, electrochemical degradation of pollutants and photoelectrochemical properties, electron transport, thermodynamic behavior and columbic efficiency of studied PFCs.     

Morphological engineering of carbon-based materials: in the quest of efficient catalysts for overall water splitting

This work attempts to optimize the catalytic activity of the carbon-based materials by engineering their morphological structure. Several flake-like quantum dots with different shapes such as triangulene, elliptical, rhomboid, and square, as well as hydrocarbons having sunflower, kekulene, and snow-like structures, are considered and their electrocatalytic activities toward the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are theoretically evaluated. The activity analysis indicates that the OER overpotentials for the examined carbon materials vary in the range between 0.56 and 1.22 V. Benefiting from the improved electronic properties due to the proper morphology, remarkable catalytic activity was achieved for the snow-like morphology affording overpotentials of 0.56 V for OER and ?0.05 V for HER. In addition to snow-like, other morphologies such as triangulene and square can effectively promote acidic hydrogen evolution via Volmer-Heyrovsky mechanism. On contrary, the high values of free energies for H₂O dissociation step reveal that, under the alkaline condition, the examined carbon materials cannot be considered as efficient HER catalysts.     

Evaluation of Scale and Corrosion Inhibition of Modified Polyaspartic Acid

Amino acid modified polyaspartic acids were evaluated as calcium-scale inhibitors. Feasibility of scale inhibition experiments was analyzed by molecular dynamics simulation and Gaussian optimization, and the scale inhibition mechanism was theoretically analyzed. Scale inhibition performance was studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, static scale inhibition experiments, and electrochemical performance testing, which provided an experimental basis for the molecular dynamics simulation. The experimental results showed that Arg-SA-PASP has better scale inhibition and corrosion inhibition performance than His-SA-PASP. The scale inhibition effect increased with increasing concentration. Electrochemical tests indicated that Arg-SA-PASP is an excellent scale and corrosion inhibitor.     

Effects of annealing on bandgap and surface plasmon resonance enhancement in Au/SnO2 quantum dots

Au/SnO₂ quantum dots (AuSQDs) were synthesized, and the effects of annealing on their structural and optical properties were examined. Significant changes were observed in the bandgap and surface plasmon resonance (SPR) of the AuSQDs after thermal treatment at different temperatures (400, 500, and 600 °C). The properties of the as-prepared and annealed samples were characterized via X-ray diffraction analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy, and diffuse reflectance spectroscopy. Annealing reduced the bandgap from 3.03 to 2.33 eV and increased the crystallinity while maintaining an average crystallite size below 10 nm. XPS valence band (VB) profiles provided information regarding the VB edge potentials, which helped to determine the conduction band edge potentials. An enhancement in the SPR of the Au nanoparticles was observed for AuSQD-500, which had the smallest bandgap among the samples investigated.