Psychrophilic hydrogen production from petrochemical wastewater via anaerobic sequencing batch reactor: techno-economic assessment and kinetic modelling

Independent hydrogen production from petrochemical wastewater containing mono-ethylene glycol (MEG) via anaerobic sequencing batch reactor (ASBR) was extensively assessed under psychrophilic conditions (15–25 °C). A lab-scale ASBR was operated at pH of 5.50, and different organic loading rates (OLR) of 1.00, 1.67, 2.67, and 4.00 gCOD/L/d. The hydrogen yield (HY) progressed from 134.32 ± 10.79 to 189.09 ± 22.35 mL/gMEG_initial at increasing OLR from 1.00 to 4.00 gCOD/L/d. The maximum hydrogen content of 47.44 ± 3.60% was achieved at OLR of 4.0 gCOD/L/d, while methane content remained low (17.76 ± 1.27% at OLR of 1.0 gCOD/L/d). Kinetic studies using four different mathematical models were conducted to describe the ASBR performance. Furthermore, two batch-mode experiments were performed to optimize the nitrogen supplementation as a nutrient (C/N ratio), and assess the impact of salinity (as gNaCl/L) on hydrogen production. HY substantially dropped from 62.77 ± 4.09 to 6.02 ± 0.39 mL/gMEG_initial when C/N ratio was increased from 28.5 to 114.0. Besides, the results revealed that salinity up to 10.0 gNaCl/L has a relatively low inhibitory impact on hydrogen production. Eventually, the cost/benefit analysis showed that environmental and energy recovery revenues from ASBR were optimized at OLR of 4.0 gCOD/L/d (payback period of 7.13 yrs).     

Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.     

Effect of H2O2 concentration on electrochemical growth and properties of vertically oriented ZnO nanorods electrodeposited from chloride solutions

In this work, ZnO nanostructures are electrodeposited on a transparent conducting glass from chloride baths. The influence of H₂O₂ concentration on the electrochemical characteristics has been studied using cyclic voltammetry (CV) and chronoamperometry (CA) techniques. From the analysis of the current transients on the basis of the Scharifker–Hills model, it is found that nucleation mechanism is progressive with a typical three-dimensional (3D) nucleation and growth process; independently with the concentration of H₂O₂. However, the nucleation rate of the ZnO changes with the increase of H₂O₂ concentration. The Mott–Schottky measurements demonstrate an n-type semiconductor character for all samples with a carrier density varying between 5.14×10¹⁸ cm⁻³ and 1.47×10¹⁸ cm⁻³. Scanning electron microscopy (SEM) observations show arrays of vertically aligned ZnO nanorods (NRs) with good homogeneity. The X-ray diffraction (XRD) patterns show that the ZnO deposited crystallises according to a hexagonal Würtzite-type structure and with the c-axis perpendicular to the electrode surface. The directional growth along (002) crystallographic plane is very important for deposits obtained at 5 and 7 mM of H₂O₂. The high optical properties of the ZnO NRs with a low density of deep defects was checked by UV–vis transmittance analyses, the band gap energy of films varies between 3.23 and 3.31 eV with transparency around 80–90%.     

The effect of growth conditions,point defects and hydrogen on the electronic structure and properties of p-type (Al,N) codoped ZnO: A first principles study

The effects of point defects, hydrogen, and growth conditions on the electronic structure and properties of the (Al,N) codoped p-type ZnO have been investigated using the first principles method. The obtained results showed that the Al_Zn–N_O–V_Zn complex is a shallow acceptor that can play an important role in achieving the p-type conductivity in the (Al,N) codoped ZnO films. Our results showed also that the electrical conductivity type in the (Al,N) codoped ZnO films strongly depends on the donor/acceptor concentrations ratio. The codoped ZnO films prepared under both Zn-rich and O-rich growth conditions with a donors/acceptors ratio of 1:2 have a p-type conductivity, while those prepared with a ratio of 1:1 cannot be p-type unless if they are prepared under O-rich conditions. The achieved p-type quality depends also on the used nitrogen doping source. To prepare p-type ZnO film of high quality using the (Al,N) codoping method, the use of NO or NO₂ is recommended. The presence of donor defects such as oxygen vacancies and hydrogen will significantly affect the electronic properties of the (Al,N) codoped ZnO films, and if the concentration of these defects in the sample is high enough, the material can be easily converted to n-type.     

The effect of baking time,fillet radius,and hardness on the lifecycles of pole fastening screws in an electric motor with hydrogen embrittlement

In order to protect bolts from corrosion, electroplating such as zinc plating is widely used. However, hydrogen can easily penetrate or diffuse into the vacancies and dislocations between the lattices of bolt steel during electroplating. As the diffused hydrogen defects inside the lattice are in gaseous form, small cracks can easily be produced due to high pressure from the hydrogen gas. In this research, in order to determine the root cause of the fracture in pole fastening screws resulting from hydrogen embrittlement in typical electric motors, additional factors that accelerate hydrogen embrittlement fracture were selectively applied, including a small fillet in the head–shank transition and excessive hardness, and parametric study was performed experimentally.     

Occurrence and characterisation of the hydrogen-evolving enzyme in Frankia sp.

An increase in hydrogen evolution from the hydrogen-evolving enzyme in the actinomycete Frankia was recorded in the presence of nickel. Immunogold localisation analysis of the intracellular distribution of hydrogenase proteins indicated that they were evenly distributed in the membranes and cytosol of both hyphae and vesicles. In addition, molecular characterisation of the hydrogen-evolving enzyme at the proteomic level, using two-dimensional gel electrophoresis combined with mass spectrometry, confirmed that the Frankia hydrogen-evolving enzyme is similar to the cyanobacterial bidirectional hydrogenase of Anabena siamensis.     

Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys MI(Ni0.71Co0.15-Al0.06Mn0.08)x (MI=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.     

Inhibition effect of carbon dioxide on the oxidation of hydrogen over a platinum foil catalyst

This paper investigates the catalytic ignition of the H₂/O₂/CO₂ mixture on platinum in a stagnation flow at atmospheric pressure experimentally and numerically. We measure the ignition temperatures of the gas mixtures flowing towards resistively heated platinum with various composition ratios and various diluent gases of N₂, Ar and CO₂. Compared with N₂ or Ar, the CO₂ dilution shows higher ignition temperature by about 50 K, even at the same composition ratio. The ignition temperature increase is proportional to the dilution ratio. Through the numerical simulation, it is illustrated that higher ignition temperature is caused by the adsorption of CO₂ and following dissociation on platinum surface, which was to date considered negligible in catalytic combustion.