Lanthanide-organic-frameworks modified ZnIn2S4 for boosting hydrogen generation under UV–Vis and visible light

Novel Ln-MOF with microrods shape were successfully combined with ZnIn₂S₄ (ZIS) microsphere and used for photocatalytic hydrogen generation under UV–Vis and visible light. The Ln-MOFs/ZIS system comprises lanthanide-carboxylate coordination networks (Tm and Gd as metal ions, and 1,3,5-benzenetricarboxylic acid (BTC) as the organic linker) deposited on ZnIn₂S₄ microspheres. Effect of the amount of ((Tm,Gd)-BTC) (1, 5, 10 wt%) on the optical properties and photocatalytic hydrogen evolution performance was investigated. ZIS microsphere shows the marigold flower-like morphology and hexagonal polytopic crystal form. Our results proved that the combination of ZIS microsphere, Ln-MOF and Pt nanoparticles (NPs) caused significant enhancement in hydrogen generation. Amount of formed hydrogen was raised from 196.3 to 7782.1 μmol g^?1 for pristine ZIS and ZIS decorated with 1% (Tm, Gd)-BTC/Pt under UV–Vis light, respectively.     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Fabrication of barium titanate ceramics via digital light processing 3D printing by using high refractive index monomer

A digital light processing (DLP) technology has been developed for 3D printing lead-free barium titanate (BTO) piezoelectric ceramics. By comparing the curing and rheological properties of slurries with different photosensitive monomer, a high refractive index monomer acryloyl morpholine (ACMO) was chosen, and a design and preparation method of BTO slurry with high solid content, low viscosity and high curing ability was proposed. By further selecting the printing parameters, the single-layer exposure time was reduced and the forming efficiency has been greatly improved. Sintered specimens were obtained after a nitrogen-air double-step debinding and furnace sintering process, and the BTO ceramics fabricated with 80 wt% slurry shows the highest relative density (95.32 %) and piezoelectric constant (168.1 pC/N). Furthermore, complex-structured BTO ceramics were prepared, impregnated by epoxy resin and finally assembly made into hydrophones, which has significance for the future design and manufacture of piezoelectric ceramic-based composites that used in functional devices.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

The corrosion of mild and stainless steel in alkaline anaerobic conditions representing the Belgian “supercontainer” concept and the Swiss L/ILW repository

Deep geological repositories for radioactive waste contain metallic materials, either used to construct disposal canisters or as low-/intermediate-level waste (L/ILW). The safety relevance of corrosion is linked to canister lifetime in the former case and gas generation in the latter. More specifically, the Belgian “supercontainer” concept envisages mild steel for the used fuel disposal canister, and in the case of the Swiss L/ILW repository, mild steels are the largest metallic waste component due to the decommissioning of civilian power-generating facilities. For these circumstances, the corrosion environment is dominated by the chemistry of cement, which is used as buffer or backfill material. The corrosion behaviour of mild steel in anoxic environments was studied through the analysis of the hydrogen end-product. Hydrogen analysis was conducted by periodically purging the cell head-space and analysing the gas using a solid-state hydrogen sensor. While this method is limited to providing only uniform corrosion rates averaged over periods of time, ranging from weeks to months, it provides excellent resolution and sensitivity. The test cell environments were matched against the anticipated Belgian high-level waste and Swiss L/ILW repository environments, and also against experiments that have been conducted by other researchers for comparative purposes. Samples were exposed to synthetic cement pore waters, representing fresh and degraded cement. In young cement waters, the formation of initial corrosion products resulted in steel wire corrosion rates of the order of µm/year, which, at 80°C rapidly declined to ∼10 nm/year. In contrast, SA516 grade 70 steel plate corroded much more slowly under similar conditions. In aged cement waters, initial corrosion rates were higher but declined faster towards a longer-term rate of ∼10 nm/year. 316L stainless steel, embedded in cementitious material, corroded at a rate of <1 nm/year at 50°C.     

Increasing the photocatalytic and fungicide activities of Ag3PO4 microcrystals under visible-light irradiation

The present study reports for the first time the performance of silver phosphate (Ag₃PO₄) microcrystals as photocatalyst (degradation of Rodamine B-RhB) and antifungal agent (against Candida albicans–C. albicans) under visible-light irradiation (455 nm). Ag₃PO₄ microcrystals were synthesized by a simple co-precipitation (CP) method at room temperature. The structural and electronic properties of the as-synthetized Ag₃PO₄ have been investigated before and after 4 cycles of RhB degradation under visible light using X-ray diffraction (XRD), micro-Raman spectroscopy, UV–Vis spectrophotometer and field emission scanning electron microscopy (FE-SEM) images. The antifungal activity was analyzed in planktonic cells and 48h-biofilm of C. albicans by colony forming units (CFU) counting, confocal laser and FE-SE microscopies. Statistical analysis was carried out using SPSS software. Morphological and structural modifications of Ag₃PO₄ were observed upon recycling. After 4 recycles, the material maintained its photodegradation property; an eightfold increase in the efficiency of Ag₃PO₄ was observed in planktonic cells and a two fold increase in biofilm when irradiated under visible light. Thus, higher antifungal effectiveness against C. albicans was obtained when associated with visible-light irradiation.     

Effect of spheroidized microstructure on the impact toughness and electrochemical performance of a high-carbon steel

The influence of cementite spheroidization on the impact toughness and electrochemical properties of a high-carbon steel has been thoroughly investigated in this study. Heavy warm rolling, followed by 2 h of annealing, has resulted in near-complete spheroidization, leading to a microstructure consisting of nano-cementite globules dispersed in the ultrafine-grained ferritic matrix. The Charpy impact test exhibited superior impact toughness with increased spheroidization. It is validated by the presence of abundant dimples in the fractographs of spheroidized specimens, in contrast to the as-received one that experienced a brittle failure due to its lamellar pearlitic structure. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) carried out in a 3.5% NaCl solution revealed that the corrosion resistance of the alloy gets improved with the increase in the degree of spheroidization. This is attributed to the lower susceptibility of the spheroidized specimen to microgalvanic corrosion owing to the minimum area of contact between nano-spheroidized cementite and ferrite, as elucidated with the help of EIS results aided by equivalent electrical circuit model.     

Potential influence of microorganisms on the corrosion of carbon steel in the French high- and intermediate-level long-lived radioactive waste disposal context

In the context of the high-level radioactive waste disposal CIGEO, the corrosion rate due to microbially influenced corrosion (MIC) has to be evaluated. In France, it is envisaged to dispose of high- and intermediate-level long-lived radioactive waste at a depth of 500 m in a deep geological disposal, drilled in the Callovo-Oxfordian claystone (Cox) formation. To do so, a carbon steel casing will be inserted inside disposal cells, which are horizontal tunnels drilled in the Cox. A specific cement grout will be injected between the carbon steel casing and the claystone. A study was conducted to evaluate the possibility of MIC on carbon steel in the foreseeable high radioactive waste disposal. The corrosiveness of various environments was investigated at 50°C and 80°C with or without microorganisms enriched from samples of Andra's underground research laboratory. The monitoring of corrosion during the experiments was ensured using gravimetric method and real-time corrosion monitoring using sensors based on the measurements of the electrical resistance. The corrosion data were completed with microbiological analyses including cultural and molecular characterizations.     

Corrosion behavior of T24, T92, VM12, and AISI 304 steels exposed to KCl–NaCl–K2SO4–Na2SO4 salt mixtures

The corrosion mechanisms of T24, T92, VM12, and AISI 304 steels are studied under the influence of NaCl–KCl, NaCl–Na₂SO₄, and KCl–K₂SO₄ salt mixtures in a dry air atmosphere at 650°C for 15 days. NaCl–KCl was the most aggressive deposit and AISI 304 stainless steel exhibited the highest corrosion resistance. There was no relation between the Cr content of the ferritic steels and their corrosion resistance in NaCl–KCl. In contrast, the resistance of high-Cr steels was better when exposed to NaCl–Na₂SO₄ and KCl–K₂SO₄. The high-Cr and the low-Cr steels were more susceptible to NaCl–Na₂SO₄ and to KCl–K₂SO₄, respectively.     

钢管套筒灌浆连接轴向受拉性能模拟试验研究

为研究钢管套筒灌浆连接轴向受拉破坏过程及破坏机理，试验中设计了16组48个钢管套筒灌浆连接试件，试件采用钢板代替圆钢管，并进行静载试验。分析了灌浆料裂缝扩展过程、荷载-相对位移曲线，并对抗剪键高距比、灌浆料厚度、侧向力等因素对破坏过程及承载力的影响进行分析。结果表明：对于不设置抗剪键的套筒灌浆连接试件，斜裂缝随机产生，裂缝分布不均匀；对于设置抗剪键的套筒灌浆连接试件，裂缝首先出现在底部抗剪键位置处，与水平方向夹角约为30°，随后在中部和上部抗剪键位置处分别出现斜裂缝。由于每个抗剪键上荷载分担并不均匀，与抗剪键接触的灌浆料逐渐达到极限压应力，达到极限状态时，承载力全部由抗剪键间的机械咬合力承担，在连接承载力中，可忽略摩擦力和胶结力作用。随着抗剪键高距比h/s增大，各试件初始剪切刚度相差不大，承载力增大，但增幅逐渐减小，建议抗剪键高距比0.06g/s>0.3，同时需要满足灌浆料灌注的施工要求。