H2 production with ultra-low CO selectivity via photocatalytic reforming of methanol on Au/TiO2 catalyst

_H2${\mathrm{H}}_2$ with ultra-low CO concentration was produced via photocatalytic reforming of methanol on Au/_TiO2$\mathrm{Au}/{\mathrm{TiO}}_2$ catalyst. The rate of _H2${\mathrm{H}}_2$ production is greatly increased when the gold particle size is reduced from 10 to smaller than 3 nm. The concentration of CO in _H2${\mathrm{H}}_2$ decreases with reducing the gold particle size of the catalyst. It is suggested that the by-product CO is mostly produced via decomposition of the intermediate formic acid species derived from methanol. The smaller gold particles possibly switch the HCOOH decomposition reaction mainly to _H2${\mathrm{H}}_2$ and _CO2${\mathrm{CO}}_2$ products while suppress the CO and _H2${\mathrm{H}}_2$O products. In addition, some CO may be oxidized to _CO2${\mathrm{CO}}_2$ by photogenerated oxidizing species at the perimeter interface between the small gold particles and _TiO2${\mathrm{TiO}}_2$ under photocatalytic condition.     

Evaluation of conversion efficiency of light to hydrogen energy by Anabaena variabilis

Cyanobacteria provide an efficient system for producing _H2${\mathrm{H}}_2$ from water using solar energy. The energy conversion efficiency can be defined by the ratio of _H2${\mathrm{H}}_2$ produced to the light energy absorbed. An IR and opalescent plate method was used to measure the light energy absorbed. Since cyanobacteria absorb light in the visible range but not in the infrared range, the net amount of light energy absorbed by the cells can be estimated by measuring the IR and visible light intensities transmitted through the biochamber. A rectangular biochamber was used for measuring the conversion efficiency from light energy to _H2${\mathrm{H}}_2$ energy. A quantum meter and radiometer were used to measure the light intensity transmitted through the chamber. Anabaena variabilis was cultured in a BG11 medium with 3.6 mM NaNO₃${}_3$ and the light intensity was 40–50 μmol/m²/s$\mathrm{\mu }\mathrm{mol}/{\mathrm{m}}^2/\mathrm{s}$ in the growth phase and 120–140 μmol/m²/s$\mathrm{\mu }\mathrm{mol}/{\mathrm{m}}^2/\mathrm{s}$ in the _H2${\mathrm{H}}_2$ production phase. The maximum _H2${\mathrm{H}}_2$ production was 50 ml for 40 h and cell density was 1.2 g/l. The _H2${\mathrm{H}}_2$ production rate was 4.1 ml _H2/g${\mathrm{H}}_2/\mathrm{g}$ dry cell weight/h. Based on the light absorbed in the _H2${\mathrm{H}}_2$ production phase, the energy conversion efficiency from light to _H2${\mathrm{H}}_2$ was 1.5% on average and 3.9% at the maximum. Based on the light energy absorbed in the cell growth and _H2${\mathrm{H}}_2$ production phases, the energy conversion efficiency was 1.1% on average.     

Kinetic study on nonisothermal dehydrogenation of TiH2 powders

The nonisothermal dehydrogenation of TiH₂ powders was studied using thermogravimetry and differential scanning calorimetry. The reaction model was established by estimating the activation energy. The results show the nonisothermal dehydrogenation occurred in a four-step process. The hydrogen released from the TiH_1.5∼2$\text{Ti}{\mathrm{H}}_{1.5\sim 2}$ phase in the first step, which led to the decrease of activation energy. The second step was derived from the formation of βH${\beta }_H$ in δ$\delta$ phase and the reaction model was Phase boundary reaction. In the third step, the hydrogen started to release from the βH${\beta }_H$ phase, and then the βH→αH${\beta }_{\mathrm{H}}\to {\alpha }_{\mathrm{H}}$ phase transformation happened. So the activation energy Eα$E_{\alpha }$ underwent a decrease followed by a quick increase. The fourth step corresponded to the formation of αH${\alpha }_H$ in βH${\beta }_H$ phase, and the slight oxidation resulted in the small fluctuation of activation energy.     

Kinetic characteristics of sodium borohydride formation when sodium meta-borate reacts with magnesium and hydrogen

Sodium borohydride is attracting considerable interests as a hydrogen storage medium. In this paper, we investigated the effects of hydrogen pressure, reaction temperature and transition metal addition on sodium borohydride synthesis by the reaction of sodium meta-borate with Mg and _H2${\mathrm{H}}_2$. It was found that higher _H2${\mathrm{H}}_2$ pressure was beneficial to _NaBH4${\mathrm{NaBH}}_4$ formation. The increase in reaction temperature first improved _NaBH4${\mathrm{NaBH}}_4$ formation kinetics but then impeded it when the temperature was raised to near the melting point of Mg. It was also found that some additions of transition metals such as Ni, Fe and Co in the _NaBO2+Mg+_H2${\mathrm{NaBO}}_2+\mathrm{Mg}+{\mathrm{H}}_2$ system promoted the _NaBH4${\mathrm{NaBH}}_4$ formation, but Cu addition showed little effect. The activation energy of the _NaBH4${\mathrm{NaBH}}_4$ formation from Mg, _NaBO2${\mathrm{NaBO}}_2$ and _H2${\mathrm{H}}_2$ was estimated to be 156.3 kJ/mol _NaBH4${\mathrm{NaBH}}_4$ according to Ozawa analysis method.     

Fuel-rich methane oxidation in a high-pressure flow reactor studied by optical-fiber laser-induced fluorescence,multi-species sampling profile measurements and detailed kinetic simulations

A versatile flow-reactor design is presented that permits multi-species profile measurements under industrially relevant temperatures and pressures. The reactor combines a capillary sampling technique with a novel fiber-optic Laser-Induced Fluorescence (LIF) method. The gas sampling provides quantitative analysis of stable species by means of gas chromatography (i.e. _CH4${\mathrm{CH}}_4$, _O2,CO,_CO2${\mathrm{O}}_2\text{,}\mathrm{CO}\text{,}{\mathrm{CO}}_2$, _H2O,_H2${\mathrm{H}}_2\mathrm{O}\text{,}{\mathrm{H}}_2$, _C2${\mathrm{C}}_2$_H6${\mathrm{H}}_6$, _C2${\mathrm{C}}_2$_H4${\mathrm{H}}_4$), and the fiber-optic probe enables in situ detection of transient LIF-active species, demonstrated here for C_H2${\mathrm{H}}_2$O. A thorough analysis of the LIF correction terms for the temperature-dependent Boltzmann fraction and collisional quenching are presented. The laminar flow reactor is modeled by solving the two-dimensional Navier–Stokes equations in conjunction with a detailed kinetic mechanism. Experimental and simulated profiles are compared. The experimental profiles provide much needed data for the continued validation of the kinetic mechanism with respect to _C1${\mathrm{C}}_1$ and _C2${\mathrm{C}}_2$ chemistry; additionally, the results provide mechanistic insight into the reaction network of fuel-rich gas-phase methane oxidation, thus allowing optimization of the industrial process.     

A comparison of hydrogen storage technologies for solar-powered stand-alone power supplies: A photovoltaic system sizing approach

This paper compares the performance of three different solar based technologies for a stand-alone power supply (SAPS) using different methods to address the seasonal variability of solar insolation—(i) photovoltaic (PV) panels with battery storage; (ii) PV panels with electrolyser and hydrogen (_H2)$({\mathrm{H}}_2)$ storage; and (iii) photoelectrolytic (PE) dissociation of water for _H2${\mathrm{H}}_2$ generation and storage. The system size is determined at three different Australian locations with greatly varying latitudes—Darwin (12^°S${12}^{°}\mathrm{S}$), Melbourne (38^°S${38}^{°}\mathrm{S}$) and Macquarie Island (55^°S${55}^{°}\mathrm{S}$). While the PV/electrolyser system requires fewer PV panels compared to the PV/battery scenario due to the seasonal storage ability of _H2${\mathrm{H}}_2$, the final number of PV modules is only marginally less at the highest latitude due to the lower energy recovery efficiency of _H2${\mathrm{H}}_2$ compared to batteries. For the PE technology, an upper limit on the cost of such a system is obtained if it is to be competitive with the existing PV/battery technology.     

Hydrogen production from Chlamydomonas reinhardtii biomass using a two-step conversion process: Anaerobic conversion and photosynthetic fermentation

Chlamydomonas reinhardtii UTEX 90 accumulated 1.45 g dry cell weight and 0.77 g starch/L during photosynthetic growth using TAP media at 25 ^°C${}^{°}\mathrm{C}$ in presence of 2% _CO2${\mathrm{CO}}_2$ for 3 days. C. reinhardtii biomass was concentrated and then converted into hydrogen and organic acids by anaerobic fermentation with Clostridium butyricum. Organic acids in the fermentate of algal biomass were consecutively photo-dissimilated to hydrogen by Rhodobacter sphaeroides KD131. In the concentrated algal biomass 52% of the starch was hydrolyzed to 37.1 mmol _H2${\mathrm{H}}_2$/L-concentrated algal biomass and 13.6, 25.5, 7.4 and 493 mM of formate, acetate, propionate, and butyrate, respectively by C. butyricum. R. sphaeroides KD131 evolved 5.72 mmol _H2${\mathrm{H}}_2$ per ml-fermentate of algal biomass under illumination of 8 klux at 30 ^°C${}^{°}\mathrm{C}$. Only 80% of the organic acids, mainly butyrate, were hydrolyzed during photo-incubation. During anaerobic conversion, 2.58 mol _H2/mol${\mathrm{H}}_2/\mathrm{mol}$ starch–glucose was evolved using C. butyricum and then 5.72 mol _H2/L${\mathrm{H}}_2/\mathrm{L}$-anaerobic fermentate was produced by R. sphaeroides KD131. Thus, the two-step conversion process produced 8.30 mol _H2${\mathrm{H}}_2$ from 1 mol starch–glucose equivalent algal biomass via organic acids.     

Hydrogen production by autothermal reforming of LPG for PEM fuel cell applications

Indirect partial oxidation, or oxidative steam reforming, tests of a bimetallic Pt–Ni catalyst supported on δ$\delta$-alumina were conducted in propane–n  -butane mixtures (LPG) used as feed. _H2${\mathrm{H}}_2$ production activity and _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ selectivity were investigated in response to different S/C, C/_O2$\mathrm{C}/{\mathrm{O}}_2$ and W/F ratios. It was confirmed that higher steam content in the reactant stream increases both the activity and the _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ selectivity of the process. Low residence times created a positive impact on catalyst activity not only for hydrogen but also for carbon monoxide production due to the increased amount of fresh hydrocarbon in the feed stream. Hence, the highest selectivity level was obtained at intermediate residence times. The response of the system to C/_O2$\mathrm{C}/{\mathrm{O}}_2$ ratio was found to depend on the available steam content due to the complex nature of IPOX. The Pt–Ni catalyst was very prone to catalyst deactivation at low S/C ratios accompanied by high C/_O2$\mathrm{C}/{\mathrm{O}}_2$ ratios, but this problem was not encountered at high S/C ratios. A comparison of catalyst performance for different propane-to-n-butane ratios in the LPG feed indicated that the Pt–Ni catalyst has slightly better activity and selectivity at higher n-butane contents at the expense of becoming more sensitive to coke deposition.     

CO2 reforming of CH4 by combination of thermal plasma and catalyst

Experiments on synthesis gas preparation from dry reforming of methane by carbon dioxide with thermal plasma only and cooperation of thermal plasma with commercial catalysts have been performed. In all experiments, nitrogen gas was used as the plasma gas to form a high-temperature jet injected into a tube reactor. A mixture of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ was fed vertically into the jet. Both kinds of experiments were conducted in the same conditions, such as total flux of feed gases, the molar ratio of _CH4/_CO2${\mathrm{CH}}_4/{\mathrm{CO}}_2$, and the plasma power except with or without catalysts in the tube reactor. Higher conversion of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$, higher selectivity of _H2${\mathrm{H}}_2$ and CO, and higher specific energy of the process were achieved by thermal plasma with catalysts. For example, the conversions of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ were high to 96.33% and 84.63%, and the selectivies of CO and _H2${\mathrm{H}}_2$ were also high to 91.99% and 74.23%, respectively. Both were 10–20%$10–20\%$ higher than those by thermal plasma only.     

Hydrogen storage and induced properties in non-metallic catalytic materials

Particular active sites, ^xM${}^x\mathrm{M}$–^yM^′${}^y{\mathrm{M}}^{\prime }$ (where x$x$ and y$y$ are the number of unsaturations, i.e. anionic vacancies, on each cation M and M^′${\mathrm{M}}^{\prime }$) involving reactive hydrogen are created during the activation of non-metallic catalytic materials. The anionic vacancies created in bulk and at the surface of the solid, by the loss of _H2O${\mathrm{H}}_2\mathrm{O}$ or _H2S${\mathrm{H}}_2\mathrm{S}$, are able to receive hydrogen in a hydridic form according to a heterolytic dissociation (X^2-Mⁿ⁺□+_H2→XH^-Mⁿ⁺H^-${\mathrm{X}}^{2-}{\mathrm{M}}^{n+}\square +{\mathrm{H}}_2\to {\mathrm{XH}}^{-}{\mathrm{M}}^{n+}{\mathrm{H}}^{-}$ with X=O$\mathrm{X}=\mathrm{O}$ or S). The non-metallic catalytic materials become catalytic hydrogen reservoirs. Besides a high reactivity, the hydrogen species, stored in the solid, present marked diffusion properties leading to a dynamic behavior of the solid and active sites.     

A new gaseous and combustible form of water

In this paper we present, apparently for the first time, various measurements on a mixture of hydrogen and oxygen called HHO gas produced via a new electrolyzer (international patents pending by Hydrogen Technologies Applications, Inc. of Clearwater, Florida), which mixture is distinctly different than the Brown and other known gases. The measurements herein reported suggest the existence in the HHO gas of stable clusters composed of H and O atoms, their dimers H–O, and their molecules _H2${\mathrm{H}}_2$, _O2${\mathrm{O}}_2$ and _H2O${\mathrm{H}}_2\mathrm{O}$ whose bond cannot entirely be of valence type. Numerous anomalous experimental measurements on the HHO gas are reported in this paper for the first time. To reach their preliminary, yet plausible interpretation, we introduce the working hypothesis that the clusters constituting the HHO gas constitute another realization of a recently discovered new chemical species called for certain technical reasons magnecules   as well as to distinguish them from the conventional “molecules” [Santilli RM. Foundations of hadronic chemistry with applications to new clean energies and fuels. Boston, Dordrecht, London: Kluwer Academic Publisher; 2001]. It is indicated that the creation of the gaseous and combustible HHO from distilled water at atmospheric temperature and pressure occurs via a process structurally different than evaporation or separation, thus suggesting the existence of a new form of water, apparently introduced in this paper for the first time, with the structure (H×H)$(\mathrm{H}\times \mathrm{H})$–O where “×$\times$” represents the new magnecular bond and “-$-$” the conventional molecular bond. The transition from the conventional H–O–H species to the new (H×H)$(\mathrm{H}\times \mathrm{H})$–O species is predicted by a change of the electric polarization of water caused by the electrolyzer. When H–O–H is liquid, the new species (H×H)$(\mathrm{H}\times \mathrm{H})$–O can only be gaseous, thus explaining the transition of state without evaporation or separation energy. Finally, the new species (H×H)$(\mathrm{H}\times \mathrm{H})$–O is predicted to be unstable and decay into H×H$\mathrm{H}\times \mathrm{H}$ and O, by permitting a plausible interpretation of the anomalous constituents of the HHO gas as well as its anomalous behavior. Samples of the new HHO gas are available at no cost for independent verifications, including guidelines for the detection of the new species.