Exploration of the Photocatalytic Cycle for Sacrificial Hydrogen Evolution by Conjugated Polymers Containing Heteroatoms

We analyze the photocatalytic activity of heteroatom containing linear conjugated polymers for sacrificial hydrogen evolution using a recently proposed photocatalytic cycle. We find that the thermodynamic barrier to electron transfer, relevant both in the presence and absence of noble metal co-catalysts, changes with polymer composition, reducing upon going from electron-rich to electron-poor polymers, and disappearing completely for the most electron-poor polymers in a water rich environment. We discuss how the latter is probably the reason why electron-poor polymers are generally more active for sacrificial hydrogen evolution than their electron-rich counterparts. We also study the barrier to hydrogen-hydrogen bond formation on the polymer rather than the co-catalyst and find that it too changes with composition but is always, at least for the polymer studied here, much larger than that experimentally reported for platinum. Therefore, it is expected that in the presence of any noble metal particles these will act as the site of hydrogen evolution.

Review on the Use of Heavy Metal Deposits from Water Treatment Waste towards Catalytic Chemical Syntheses

The toxicity and persistence of heavy metals has become a serious problem for humans. These heavy metals accumulate mainly in wastewater from various industries’ discharged effluents. The recent trends in research are now focused not only on the removal efficiency of toxic metal particles, but also on their effective reuse as catalysts. This review discusses the types of heavy metals obtained from wastewater and their recovery through commonly practiced physico-chemical pathways. In addition, it covers the advantages of the new system for capturing heavy metals from wastewater, as compared to older conventional technologies. The discussion also includes the various structural aspects of trapping systems and their hypothesized mechanistic approaches to immobilization and further rejuvenation of catalysts. Finally, it concludes with the challenges and future prospects of this research to help protect the ecosystem.

Unveiling the key factor for the phase reconstruction and exsolved metallic particle distribution in perovskites

To significantly increase the amount of exsolved particles, the complete phase reconstruction from simple perovskite to Ruddlesden-Popper (R-P) perovskite is greatly desirable. However, a comprehensive understanding of key parameters affecting the phase reconstruction to R-P perovskite is still unexplored. Herein, we propose the Gibbs free energy for oxygen vacancy formation in Pr0.5(Ba/Sr)0.5TO3-δ (T = Mn, Fe, Co, and Ni) as the important factor in determining the type of phase reconstruction. Furthermore, using in-situ temperature & environment-controlled X-ray diffraction measurements, we report the phase diagram and optimum ‘x’ range required for the complete phase reconstruction to R-P perovskite in Pr0.5Ba0.5-xSrxFeO3-δ system. Among the Pr0.5Ba0.5-xSrxFeO3-δ, (Pr0.5Ba0.2Sr0.3)2FeO4+δ – Fe metal demonstrates the smallest size of exsolved Fe metal particles when the phase reconstruction occurs under reducing condition. The exsolved nano-Fe metal particles exhibit high particle density and are well-distributed on the perovskite surface, showing great catalytic activity in fuel cell and syngas production.

Metal (Mo, W, Ti) Carbide Catalysts: Synthesis and Application as Alternative Catalysts for Dry Reforming of Hydrocarbons—A Review

Dry reforming of hydrocarbons (DRH) is a pro-environmental method for syngas production. It owes its pro-environmental character to the use of carbon dioxide, which is one of the main greenhouse gases. Currently used nickel catalysts on oxide supports suffer from rapid deactivation due to sintering of active metal particles or the deposition of carbon deposits blocking the flow of gases through the reaction tube. In this view, new alternative catalysts are highly sought after. Transition metal carbides (TMCs) can potentially replace traditional nickel catalysts due to their stability and activity in DR processes. The catalytic activity of carbides results from the synthesis-dependent structural properties of carbides. In this respect, this review presents the most important methods of titanium, molybdenum, and tungsten carbide synthesis and the influence of their properties on activity in catalyzing the reaction of methane with carbon dioxide.

Effect of Implant Surface Roughness and Macro- and Micro-Structural Composition on Wear and Metal Particles Released

Background: Considerations about implant surface wear and metal particles released during implant placement have been reported. However, little is known about implant surface macro- and microstructural components, which can influence these events. The aim of this research was to investigate accurately the surface morphology and chemical composition of commercially available dental implants, by means of multivariate and multidimensional statistical analysis, in order to predict their effect on wear onset and particle release during implant placement. Methods: The implant surface characterization (roughness, texture) was carried out through Confocal Microscopy and SEM-EDS analysis; the quantitative surface quality variables (amplitude and hybrid roughness parameters) were statistically analyzed through post hoc Bonferroni’s test for pair comparisons. Results: The parameters used by discriminant analysis evidenced several differences in terms of implant surface roughness between the examined fixtures. In relation to the observed surface quality, some of the investigated implants showed the presence of residuals due to the industrial surface treatments. Conclusions: Many structural components of the dental implant surface can influence the wear onset and particles released during the implant placement.

Mechanical Properties and Corrosion Behavior of Ti6Al4V Particles Obtained by Implantoplasty: An In Vitro Study. Part II

In the field of implant dentistry there are several mechanisms by which metal particles can be released into the peri-implant tissues, such as implant insertion, corrosion, wear, or surface decontamination techniques. The aim of this study was to evaluate the corrosion behavior of Ti6Al4V particles released during implantoplasty of dental implants treated due to periimplantitis. A standardized protocol was used to obtain metal particles produced during polishing the surface of Ti6Al4V dental implants. Physicochemical and biological characterization of the particles were described in Part I, while the mechanical properties and corrosion behavior have been studied in this study. Mechanical properties were determined by means of nanoindentation and X-ray diffraction. Corrosion resistance was evaluated by electrochemical testing in an artificial saliva medium. Corrosion parameters such as critical current density (icr), corrosion potential (ECORR), and passive current density (iCORR) have been determined. The samples for electrochemical behavior were discs of Ti6Al4V as-received and discs with the same mechanical properties and internal stresses than the particles from implantoplasty. The discs were cold-worked at 12.5% in order to achieve the same properties (hardness, strength, plastic strain, and residual stresses). The implantoplasty particles showed a higher hardness, strength, elastic modulus, and lower strain to fracture and a compressive residual stress. Resistance to corrosion of the implantoplasty particles decreased, and surface pitting was observed. This fact is due to the increase of the residual stress on the surfaces which favor the electrochemical reactions. The values of corrosion potential can be achieved in normal conditions and produce corroded debris which could be cytotoxic and cause tattooing in the soft tissues.