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.     

Role of functionalized graphene quantum dots in hydrogen evolution reaction: A density functional theory study

Rapid advances in the field of catalysis require a microscopic understanding of the catalytic mechanisms. However, in recent times, experimental insights in this field have fallen short of expectations. Furthermore, experimental searches of novel catalytic materials are expensive and time-consuming, with no guarantees of success. As a result, density functional theory (DFT) can be quite advantageous in advancing this field because of the microscopic insights it provides and thus can guide experimental searches of novel catalysts. Several recent works have demonstrated that low-dimensional materials can be very efficient catalysts. Graphene quantum dots (GQDs) have gained much attention in past years due to their unique properties like low toxicity, chemical inertness, biocompatibility, crystallinity, etc. These properties of GQDs which are due to quantum confinement and edge effects facilitate their applications in various fields like sensing, photoelectronics, catalysis, and many more. Furthermore, the properties of GQDs can be enhanced by doping and functionalization. In order to understand the effects of functionalization by oxygen and boron based groups on the catalytic properties relevant to the hydrogen-evolution reaction (HER), we perform a systematic study of GQDs functionalized with the oxygen (O), borinic acid (BC₂O), and boronic acid (BCO₂). All calculations that included geometry optimization, electronic and adsorption mechanism, were carried out using the Gaussian16 package, employing the hybrid functional B3LYP, and the basis set 6-31G(d,p). With the variation in functionalization groups in GQDs, we observe significant changes in their electronic properties. The adsorption energy E_ads of hydrogen over O-GQD, BC₂O-GQD, and BCO₂-GQD is ?0.059 eV, ?0.031 eV and ?0.032 eV respectively. Accordingly, Gibbs free energy (ΔG) of hydrogen adsorption is extraordinarily near the ideal value (0 eV) for all the three types of functionalized GQDs. Thus, the present work suggests pathways for experimental realization of low-cost and multifunctional GQDs based catalysts for clean and renewable hydrogen energy production.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

Effect of SnO–P2O5–MgO glass addition on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

NASICON-type structured compounds Li_1+xM_xTi_2-x(PO₄)₃ (M = Al, Fe, Y, etc.) have captured much attention due to their air stability, wide electrochemical window and high lithium ion conductivity. Especially, Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) is a potential solid electrolyte due to its high ionic conductivity. However, its actual density usually has a certain gap with the theoretical density, leading the poor ionic conductivity of LATP. Herein, LATP solid electrolyte with series of SnO–P₂O₅–MgO (SPM, 0.4 wt%, 0.7 wt%, 1.0 wt%, 1.3 wt%) glass addition was successfully synthesized to improve the density and ionic conductivity. The SPM addition change Al/Ti–O bond and P–O bond distances, leading to gradual shrinkage of octahedral AlO₆ and tetrahedral PO₄. The bulk conductivity of the samples increases gradually with SPM glass addition from 0.4 wt% to 1.3 wt%. Both SPM and the second-phase LiTiPO₅, caused by glass addition, are conducive to the improvement of compactness. The relative density of LATP samples increases first from 0 wt% to 0.7 wt%, and then decreases from 0.7 wt% to 1.3 wt% with SPM glass addition. The grain boundary conductivity also changes accordingly. Especially, the highest ionic conductivity of 2.45 × 10^?4 S cm^?1, and a relative density of 96.72% with a low activation energy of 0.34 eV is obtained in LATP with 0.7 wt% SPM. Increasing the density of LATP solid electrolyte is crucial to improve the ionic conductivity of electrolytes and SPM glass addition can promote the development of dense oxide ceramic electrolytes.     

The control of paracetamol particle size and surface morphology through crystallisation in a spray dryer

The parameters governing the crystallisation of paracetamol using various conventional techniques has been extensively studied, however the factors influencing the drug crystallisation using spray drying is not as well understood. The aim of this work was to investigate the crystallisation of an active pharmaceutical ingredient through evaporative crystallisation using a spray dryer to study the physicochemical properties of the drug and to use semi-empirical equations to gain insight into the morphology and particle size of the dried powder. Paracetamol solutions were spray dried at various inlet temperatures ranging from 60 °C to 120 °C and also from a series of inlet feed solvent compositions ranging from 50/50% v/v ethanol/water to 100% ethanol and solid-state characterisation was done. The size and morphology of the dried materials were altered with a change in spray drying parameters, with an increase in inlet temperature leading to an increase in particle Sauter mean diameter (from 3.0 to 4.4 µm) and a decrease in the particle size with an increase in ethanol concentration in the feed (from 4.6 to 4.4 µm) as a result of changes in particle density and atomised droplet size. The morphology of the dried particles consisted of agglomerates of individual crystallites bound together into larger semi-spherical agglomerates with a higher tendency for particles having crystalline ridges to form at higher ethanol concentrations of the feed.     

Lewis acid-oxygen vacancy interfacial synergistic catalysis over SO42−/Ce0.84Zr0.16O2–WO3–ZrO2 for N,N-diethylation of aniline with ethanol

Herein, a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis for aniline N,N-diethylation with ethanol was proposed, and the SO₄²⁻/Ce_0.84Zr_0.16O₂–WO₃–ZrO₂ catalyst (SCWZ) with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method, which shows better catalytic activity than the reported solid acidic catalysts. Besides, the SO₄²⁻/ZrO₂ (SZ) and SO₄²⁻/WO₃–ZrO₂ (SWZ) catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component. The SO₄²⁻ and WO₃ mainly generate Lewis acid by bonding with ZrO₂, which is beneficial for the fracture of the N–H bond in aniline. The Ce_0.84Zr_0.16O₂ solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species, which can participate in stripping –OH from ethanol, then the carbocation will also be released, which only needs 1.3805 kcal/mol energy, calculated by density functional theory (DFT), to be input. In comparison, the traditional reaction mechanism needs the Brønsted acidic sites to promote the protonation of ethanol, then dehydration and subsequent formation of carbocation followed, and 108.6846 kcal/mol energy needs to be input, which is far higher than that of the new mechanism. The apparent activation energy (E_a) over SCWZ was measured by experiment to be 34.09 kJ/mol, which is much lower than that of SWZ (47.10 kJ/mol) and SZ (54.37 kJ/mol), illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ. Besides, the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100% and 73%, respectively. The SCWZ can be renewed for 4 times without rapid deactivation, and the longevity of SCWZ is longer than that of SWZ and SZ, as the loaded SO₄²⁻ and tetragonal ZrO₂ are stabilized by Ce_0.84Zr_0.16O₂ and WO₃, respectively.     

Quantitative structure-properties relationship,molecular dynamic simulations and designs of some novel lubricant additives

Quantitative structure-properties relationship (QSPR) method was used to design some novel antioxidant lubricant additives, while molecular dynamics simulations were used to calculate their dynamic binding energies on steel and to hydrogen-containing DLC (a-C: H) crystal surfaces. 29 synthesized antioxidant lubricant additives were collected from literature and geometrically optimized by Spartan’14 version 1.1.2 software while Genetic Function Algorithm (GFA) method of the material studio version 8.0 software was used to build the predictive QSPR model. Four novel antioxidant lubricant additives were successfully designed out of which E)-3-(4-((3-amino-4-methylphenyl)diazenyl)-5-hydroxy-4H-pyrazol-3-yl)-2-argio-6,7-difluoroquinazolin-4(3H)-one with excellent property of 3.531295 (KOH/g) was found to be better than the one reported by other researchers. The dynamic binding energy results revealed that one of the designed additives was excellently bound to steel (?1120.11 kcal/mol) and to hydrogen-containing DLC (a-C: H) crystals surface (7814.156 kcal/mol) surfaces than its co-additives. This investigation shows that the entire studied antioxidant lubricant additive was found to be better bound to the steel surface than hydrogen-containing DLC (a-C: H) crystals surface. This study will help in synthesizing novel anti-oxidant lubricant additives with better additive properties that will slow the tendency of oil to oxidize and will not possess a threat to the environment as the structures do not contain zinc and phosphorus that could limit the operation of the catalytic converter in the exhaust pipe.     

Fluoride-mediately solvothermal synthesis and tunable photocatalytic selectivity of urchin-like ZrO2 hollow microspheres

Photocatalysts often show excellent performances on the basis of their surface state of exposed faces with high reactivity, but unfortunately surfaces of this type are usually concealed into the interior of crystals for their high surface energy. We report here a possibility that for fluorine-terminated surfaces of monoclinic ZrO₂, these higher-energy surfaces could be retained and exposed. Urchin-like ZrO₂ hollow microspheres (UZHS) composed of nanoribbons with exposed (010) facets are obtained through a fluoride mediately solvothermal method. We prove the stabilization effect of fluorine adsorption on (010) facets by density functional theory calculations. More interestingly, UZHS exhibit tunable photocatalytic selectivity in dye degradation. The fluorinated UZHS exhibit good performances both on decomposing Congo red (CR) and methylene blue, while the surface-modified UZHS by calcination only favor decomposition of CR.     

Facile synthesis of Ni doped CoWO4 nanoarrays grown on nickel foam substrates for efficient urea oxidation

Urea electrolysis is a promising technology for hydrogen production, which can alleviate environmental pollution of urea-rich wastewater. It's worth noting that electrochemistry activity can be significantly improved by reasonably regulating the electron configuration around the active site for the doped materials. In this work, a series of well-tuned Ni doped CoWO₄ nanoarrays on Ni foam supports have been prepared through a typical hydrothermal approach for the first time. Moreover, the resulting Ni–CoWO₄-2 material significantly promotes urea oxidation performance with an applied potential of 1.35 V at 50 mA cm^?2, which is lower than that of water oxidation reaction (1.60 V). Density functional theory results suggest that the Ni doped CoWO₄ has larger urea adsorption energy compared with CoWO₄ and the CO(NH₂)₂ molecule is strongly adsorbed on surface of Ni doped CoWO₄, which is beneficial to accelerate the kinetics of the reaction and improve the electrocatalytic activity of the urea electrolysis.     

Evaluation of particle recovery from microalgae

Coccoliths are micro-structured biomineral particles found in cell protective covering layers of coccolithophore species. They are mainly composed of CaCO₃ and their individual crystal entities are arranged in such a way that they construct complex and unique structures. This complexity is found down to the individual particle level and appears to have promising properties to offer. This study focuses on the essential step prior to any kind of implementation, which is the recovery of the material. It summarizes cleaning protocols found in literature, compares them for the first time for the same freshly cultivated material and addresses challenges that still need to be overcome. Further, it highlight the advantages and disadvantages of the best cleaning protocols, suggests optimizations with promising results and uses size distribution measurements to analyse the recovery efficiency. To that end, further characterization techniques, new for coccoliths, are introduced and used to improve our current knowledge of the particles behaviour.