Hydrogen and deuterium isotope effects beyond the electromagnetic force

A mechanism is presented concerning electrolysis of deuteriated water with a palladium cathode that is infused with deuterium (palladium deuteride) resulting in the formation of small amounts of radioactive tritium, excess energy (more than allowed by EMF chemistry alone) and the concomitant liberation of ⁴He. These net electron catalyzed nuclear chemical reactions (²H + ²H + e^? $\to$ ⁴He + e^? + heat) and (²H + ¹H + e^? $\to$ ³H + e^?) appear to be a result of respectively four and three isotope effects acting in combination with each other in a non-linear (chaotic) fashion to produce a metastable nuclear isomer of hydrogen-4 or hydrogen-3. The four isotope effects begin with the influx of electrons into the –PdDPdD Bravais lattice conduction band and consequent preferred rupture of individual weak Pd-D bonds (over those of PdH) in the cathode liberating D₂. This is followed by the newly freed deuterium capturing an electron yielding a di-neutron (_on_on). The _on_on then reacts with a deuterium or hydrogen (from protic impurity in the lattice) via phonon enforced quantum tunneling resulting in ^4mH or ³H respectively. The ^4mH quickly undergoes nuclear internal conversion to form ⁴He. These reactions involve the weak force (Feynman Diagrams are shown), but they take place in simple electrochemical systems that are normally thought of in terms of the electromagnetic forces only. The combined influence of the four isotope effects explains thousands of, what were considered, anomalous observations by top electrochemical researchers. The newly described mechanistic effects involve a very important and almost forgotten intermediate (the di-neutron) and may even involve unique safety concerns.     

In-situ synthesis of palladium-base binary metal oxide nanoparticles with enhanced electrocatalytic activity for ethylene glycol and glycerol oxidation

To achieve the better electrocatalytic activity and stability of Pd-base catalysts for ethylene glycol and glycerol oxidation reactions, a novel Pd-base binary PdCo oxides nanoparticles (PdPdO-CoO_x) was synthesized by in-situ oxidation of PdCo precursor. The strategy was simple, mild, green and efficient. The prepared nanoparticles exhibited a mutually connected, fused irregular nanoparticles in TEM. The as-synthesized PdPdO-CoO_x (1:4) nanoparticles displayed prominent catalytic activity (5.82 A $\mathrm{m}{\mathrm{g}}_{\mathrm{Pd}}^{\mathrm{?}1}$ for ethylene glycol and 5.16 A $\mathrm{m}{\mathrm{g}}_{\mathrm{Pd}}^{\mathrm{?}1}$ for glycerol) for ethylene glycol and glycerol oxidation reactions in alkaline solution compared to the commercial Pt/C (1.64 A $\mathrm{m}{\mathrm{g}}_{\mathrm{Pt}}^{\mathrm{?}1}$ for ethylene glycol and 1.48 A $\mathrm{m}{\mathrm{g}}_{\mathrm{Pt}}^{\mathrm{?}1}$ for glycerol) catalyst. The improved electrocatalytic activity of PdPdO-CoO_x catalyst mainly ascribes to the producing Strong Metal-Support Interactions (SMSI) between PdO-CoO_x and Pd nanoparticles, the synergistic effect between PdO and CoO_x and the presence of CoO_x promoved hydroxyl adsorption at lower potentials. Combined with the simple synthetic method, lower cost and good performance, PdPdO-CoO_x is a promising catalyst for direct fuel cells.     

Performance of CoNiO spinel oxide coating on AISI 430 stainless steel as interconnect for intermediate temperature solid oxide fuel cell

In order to decrease oxide growth kinetics, maintain suitable conductivity and prevent Cr-volatilization of AISI 430 stainless steels (430 SS) as the interconnect for intermediate temperature solid oxide fuel cells (SOFCs), a CoNiO spinel oxide protective coating has been successfully fabricated on the 430 SS specimen using a simple and cheap process with two steps: 1) electroplation of CoNi alloy layer and 2) pre-oxidation treatment to convert the CoNi alloy into spinel oxide. The CoNiO spinel layer on the 430 SS (CoNiO 430 SS) is dense and uniform with 8–10 μm thickness. And the CoNiO spinel oxide protective coating consists of a main face-centered-cubic (fcc) NiCo₂O₄ spinel phase and a minor fcc NiO phase. Compared with bare 430 SS, the oxidation resistance and the conductivity of the CoNiO 430 SS have been improved remarkably under simulated typical SOFC operating cathode conditions (at 800 °C in air). After an isothermal oxidation test at 800 °C, the area specific resistance (ASR) of CoNiO 430 SS is much lower and stable (0.1 Ω cm² for 100 h and 0.9 Ω cm² for 600 h) than that of bare 430 SS (1.2 Ω cm² for 100 h and 2.4 Ω cm² for 600 h). These performances of CoNiO 430 SS imply that it can be a promising candidate interconnect for solid oxide fuel cell.     

Effective excitons separation on graphene supported ZrO2TiO2 heterojunction for enhanced H2 production under solar light

A novel photocatalyst comprises of ZrO₂TiO₂ immobilized on reduced graphene oxide (rGO) – a ternary heterojunction (ZrO₂TiO₂/rGO) was synthesized by using facile chemical method. The nanocomposite was prepared with a strategy to achieve better utilization of excitons for catalytic reactions by channelizing from metal oxide surfaces to rGO support. TEM and XRD analysis results revealed the heterojunction formed between ZrO₂ and single crystalline anatase TiO₂. The mesoporous structure of ZrO₂TiO₂ was confirmed using BET analysis. The red shift in absorption edge position of ZrO₂TiO₂/rGO photocatalyst was characterized by using diffuse reflectance UV–Visible spectra. ZrO₂TiO₂/rGO showed greater interfacial charge transfer efficiency than ZrO₂TiO₂, which was evidenced by well suppressed PL intensity and high photocurrent of ZrO₂TiO₂/rGO. The suitable band gap of 1.0 wt% ZrO₂TiO₂/rGO facilitated the utilization of solar light in a wide range by responding to the light of energy equal to as well as greater than 2.95 eV by the additional formation of excited high-energy electrons (HEEs). ZrO₂TiO₂/rGO showed the enhanced H₂ production than TiO₂/rGO, which revealed the role of ZrO₂ for the effective charge separation at the heterojunction and the solar light response. The optimum loading of 1.0 wt% of ZrO₂ and rGO on TiO₂ showed the highest photocatalytic performance (7773 μmolh^?1$g_{cat}^{?1}$) for hydrogen (H₂) production under direct solar light irradiation.     

In situ preparation of N doped orthorhombic Nb2O5 nanoplates /rGO composites for photocatalytic hydrogen generation under sunlight

The synthesis of nitrogen doped orthorhombic niobium oxide nanoplates/reduced graphene oxide composites (NNb₂O₅/rGO) and their photocatalytic activity towards hydrogen generation from water and H₂S under natural sunlight has been demonstrated, uniquely. Nanostructured NNb₂O₅/rGO is synthesized by in situ wet chemical method using urea as a source of nitrogen and optimized by varying percentage of graphene oxide (GO). X?ray diffraction (XRD) study reveals that NNb₂O₅ have orthorhombic crystal structure with crystalline size, 35 nm. Further, X?ray photoelectron spectroscopy (XPS) confirm the presence of nitrogen and rGO in NNb₂O₅/rGO nanocomposite. Morphological features of (NNb₂O₅/rGO) were examined by FE?SEM and FE?TEM showed Nb₂O₅ nanoplates of diameter 25–40 nm anchored on 2D rGO. Diffuse reflectance spectra depicts the extended absorbance in the visible region with band gap of 2.2 eV. Considering the band gap in the visible region, the photocatalytic hydrogen generation from water and H₂S has been performed. The 1 wt % rGO hybridized NNb₂O₅ (S2) exhibited superior photocatalytic hydrogen generation (537 μmol/h) from water and (1385 μmol/h) from H₂S under sunlight. The improved photocatalytic activity is attributed due to an extended absorbance in the visible region, modified electronic structure upon doping and formation of well defined NNb₂O₅/rGO interface, provides large surface area, accelerates the supression of electron and hole pairs recombination rate. In our opinion, this works may provides facile route for energy efficient and economic approach for fabrication of NNb₂O₅/rGO nanocomposites as a visible light active photocatalyst.     

Alloy design of V-based hydrogen permeable membrane under given temperature and pressure condition

For alloy design of hydrogen permeable membrane, it is important to control pressure–composition–isotherm (PCT curve) in an appropriate manner in order to obtain high hydrogen permeability with strong resistance to hydrogen embrittlement. Based on this concept, V-based alloy membranes are designed under some given pressure conditions at a temperature in view of the partial molar enthalpy change, $\Delta {\overline{H}}_{0.2}$, and entropy change, $\Delta {\overline{S}}_{0.2}$, of hydrogen for hydrogen dissolution. It is demonstrated that the PCT curve can be controlled very precisely in view of $\Delta {\overline{H}}_{0.2}$ and $\Delta {\overline{S}}_{0.2}$. Also, the required membrane area to obtain 300 Nm³ h^?1 of hydrogen flow is estimated. It is found that, in view of the membrane area, it is favorable to apply at least 400 kPa of hydrogen pressure at feed side.     

Effects of silicon concentration in SOFC alloy interconnects on the formation of oxide scales in hydrocarbon fuels

Oxide scale formations on FeCr alloy interconnects were investigated in anode gas (mixtures of CH₄ and H₂O) atmospheres for solid oxide fuel cells. The silicon concentration in FeCr alloy changed the microstructures of oxide scales, elemental distribution and oxide scale growth rates. Oxide scale is composed of the following phases from surface to inner oxides: FeMn spinel, Cr₂O₃, oxide scale/alloy interface and internal oxides of Si and Al. With decreasing the Si concentration from 0.4 to 0.01 mass%, formation of thin Si and Mn layer was observed inside the FeCr alloy. Oxide scale growth rate constants decreased by lowering the Si concentration in FeCr alloy from 4.2 × 10⁻¹⁸ to 2.1 × 10⁻¹⁸ m² s⁻¹ at 1073 K. Diffusivity of Fe and Cr was changed by the concentration of Si in FeCr alloy, which affects the growth rates of oxide scale. The electrical conductivity of oxidized FeCr alloy shows almost same level regardless the Si concentration (in the orders of 10 S cm⁻² at 1073 K).     

Kinetics of collisional ionization of alkali metal atoms and recombination of electrons with alkali metal ions in flames

The rate constant k₂ has been measured in flames of H₂ + O₂ + N₂ for the ionization of alkali metal atoms M in collisions with flame species X in

$M+X\to M^{+}+e^{?}+X$

. Results are compared with every previously reported measurement of k₂ in similar flames for each alkali metal. It is concluded that

$k_2=(9.9\pm 2.7)\times {10}^{?9}{T}^{1/2}exp?(?V/RT)$

, ml molecule ^?1 sec^?1, where V is the ionization potential of the alkali metal atom and T the temperature. k₂ does not depend on flame composition and is the same for each alkali to a good approximation.The third-order recombination rate constant k_?2 for the reverse of (II) can be written as

$k_{?2}=(4.1\pm 1.1)\times {10}^{?24}{T}^{?1}$

, ml² molecule^?2 sec^?1. There is no significant dependence of k_?2 on flame composition or on which alkali metal is considered. These facts enable the rates of the forward and reverse processes in (II) to be estimated in flames generally.     

Role of lattice strain and texture in hydrogen embrittlement of 18Ni (300) maraging steel

Hydrogen embrittlement causes engineering components to fail unexpectedly. Maraging 300 steel was hydrogen charged and subjected to slow strain rate tensile test until fracture. Electron backscatter diffraction analysis of fractured specimen revealed that cracks initially propagated intergranulary along prior-austenite grain boundaries. When cracks faced martensitic $\left\{111\right\}\alpha$ planes parallel to normal direction (ND) they were deflected and continued to propagate transgranulary through $\left\{001\right\}\alpha //\text{ND}$ planes. Finally, cracks were arrested by $\left\{111\right\}\alpha //\text{ND}$ planes. Crystallographic planes on which cracks propagate/are arrested, correlate well with planes that exhibit highest/lowest magnitude of lattice strain determined during tensile loading using in situ synchrotron X-ray diffraction.     

Hydrogen production from steam and autothermal reforming of LPG over high surface area ceria

Steam and autothermal reforming reactions of LPG (propane/butane) over high surface area CeO₂ (CeO₂ (HSA)) synthesized by a surfactant-assisted approach were studied under solid oxide fuel cell (SOFC) operating conditions. The catalyst provides significantly higher reforming reactivity and excellent resistance toward carbon deposition compared to the conventional Ni/Al₂O₃. These benefits of CeO₂ are due to the redox property of this material. During the reforming process, the gas–solid reactions between the hydrocarbons present in the system (i.e. C₄H₁₀, C₃H₈, C₂H₆, C₂H₄, and CH₄) and the lattice oxygen (O_O^x) take place on the ceria surface. The reactions of these adsorbed surface hydrocarbons with the lattice oxygen (C_nH_m + O_O^x → nCO + m/2(H₂) + V_O + 2e′) can produce synthesis gas (CO and H₂) and also prevent the formation of carbon species from hydrocarbons decomposition reactions (C_nH_m ⇔ nC + 2mH₂). Afterwards, the lattice oxygen (O_O^x) can be regenerated by reaction with the steam present in the system (H₂O + V_O + 2e′ ⇔ O_O^x + H₂). It should be noted that V_O denotes as an oxygen vacancy with an effective charge 2⁺.At 900 °C, the main products from steam reforming over CeO₂ (HSA) were H₂, CO, CO₂, and CH₄ with a small amount of C₂H₄. The addition of oxygen in autothermal reforming was found to reduce the degree of carbon deposition and improve product selectivities by completely eliminating C₂H₄ formation. The major consideration in the autothermal reforming operation is the O₂/LPG (O/C molar ratio) ratio, as the presence of a too high oxygen concentration could oxidize the hydrogen and carbon monoxide produced from the steam reforming. A suitable O/C molar ratio for autothermal reforming of CeO₂ (HSA) was 0.6.     

Thin-film rechargeable lithium batteries

Thin-film rechargeable batteries with a lithium metal anode, an amorphous inorganic electrolyte, and cathodes of amorphous V₂O₅ and crystalline and amorphous Li_xMn₂O₄ have been fabricated and characterized. The performance of the thin-film cells was evaluated at different current densities and, in the case of LiV₅, at several temperatures. Electrical measurements show that the current density of the thin-film cells is limited by the lithium-ion mobility in the cathodes. The resistance of LiLi_xMn₂O₄ cells with crystalline cathodes is about two orders of magnitude lower than that of LiV₅ cells with amorphous cathodes.