Combustion stability limits and NOx emissions of nonpremixed ammonia-substituted hydrogen–air flames

The combustion stability (extinction) limits and nitrogen oxide (NO_x) emissions of nonpremixed ammonia (NH₃)–hydrogen (H₂)–air flames at normal temperature and pressure are studied to evaluate the potential of partial NH₃ substitution for improving the safety of H₂ use and to provide a database for the nonpremixed NH₃-substituted H₂–air flames. Considering coflow nonpremixed NH₃–H₂–air flames for a wide range of fuel and coflow air injection velocities (V_fuel and V_coflow) and the extent of NH₃ substitution, the effects of NH₃ substitution on the stability limits and NO_x emissions of the NH₃–H₂–air flames are experimentally determined, while the nonpremixed NH₃–H₂–air flame structure is computationally predicted using a detailed reaction mechanism. Results show significant reduction in the stability limits and unremarkable increase in the NO_x emission index for enhanced NH₃ substitution, supporting the potential of NH₃ as an effective, carbon-free additive in nonpremixed H₂–air flames. With increasing V_coflow the NO_x emission index decreases, while with increasing V_fuel it decreases and then increases due to the recirculation of burned gas and the reduced radiant heat losses, respectively. Given V_coflow/V_fuel the flame length increases with enhanced NH₃ substitution since more air is needed for reaction stoichiometry. The predicted flame structure shows that NH₃ is consumed more upstream than H₂ due to the difference between their diffusivities in air.     

Hydrogen production from ethanol steam reforming over core–shell structured NixOy–, FexOy–, and CoxOy–Pd catalysts

The present work focused on the investigation of the hydrogen generation through the ethanol steam reforming over the core–shell structured Ni_xO_y–, Fe_xO_y–, and Co_xO_y–Pd loaded Zeolite Y catalysts. The transmission electron microscopy (TEM) image of Ni_xO_y–Pd represented a very clear core–shell structure, but the other two catalysts, Co_xO_y– and Fe_xO_y–Pd, were irregular and non-uniform. The catalytic performances differed according to the added core metal and the support. The core–shell structured Co_xO_y–Pd/Zeolite Y provided a significantly higher reforming reactivity compared to the other catalysts. The H₂ production was maximized to 98% over Co_xO_y–Pd(50.0 wt%)/Zeolite Y at the conditions of reaction temperature 600 °C, CH₃CH₂OH:H₂O = 1:3, and GHSV (gas hourly space velocity) 8400 h⁻¹. In the mechanism that was suggested in this work, the cobalt component played an important role in the partial oxidation and the CO activation for acetaldehyde and CO₂ respectively, and eventually, cobalt increased the hydrogen yield and suppressed the CO generation.     

Efficient and stable photocatalytic hydrogen production from water splitting over ZnxCd1–xS solid solutions under visible light irradiation

A simple co-precipitation method was employed to synthesize a series of cubic zinc-blende phase of Zn_xCd_1−xS photocatalysts using Na₂S as the S source. Structural, morphological and optical properties of the samples have been investigated by XRD, SEM, EDS, XRF, ICP, N₂ physisorption and UV–vis diffuse reflectance techniques. The Zn_xCd_1−xS solid solution is not a simple compound mixture of ZnS and CdS, its XRD patterns show new structural peaks instead of mixture of original peaks. The lattice parameter a measured from the XRD patterns of the Zn_xCd_1−xS samples exhibits a slightly nonlinear relationship with the Zn mole fraction, which is slightly inconsistent with Vegard's law, thus suggesting that a nonhomogeneous alloy structure exists in Zn_xCd_1−xS solid solution. The photocatalytic H₂ evolution from water splitting in the sacrificial reagents of 0.25 M Na₂S/0.35 M K₂SO₃ under visible light at 30 °C and 55 °C were also examined in the study. It is found that Zn_xCd_1−xS solid solution with composition x = 0.4–0.5 shows the highest photocatalytic H₂ production performance. The studied Zn_xCd_1−xS exhibits at least 50 h stable photocatalytic activity under outdoor sunlight irradiation.     

Effect of Ni content on the hydrogen storage behavior of ZrCo1−xNix alloys

ZrCo_1−xNi_x (x = 0, 0.1, 0.2 and 0.3) alloys were prepared and their hydrogen storage behavior were studied. ZrCo_1−xNi_x alloys of compositions with x = 0, 0.1, 0.2 and 0.3 prepared by arc-melting method and characterized by X-ray diffraction analysis. XRD analysis showed that the alloys of composition with x = 0, 0.1, 0.2 and 0.3 forms cubic phase similar to ZrCo with traces of ZrCo₂ phase. A trace amount of an additional phase similar to ZrNi was found for the alloy with composition x = 0.3. Hydrogen desorption pressure–composition–temperature (PCT) measurements were carried out using Sievert's type volumetric apparatus and the hydrogen desorption pressure–composition isotherms (PCIs) were generated for all the alloys in the temperature range of 523–603 K. A single sloping plateau was observed for each isotherm and the plateau pressure was found to increase with increasing Ni content in ZrCo_1−xNi_x alloys at the same experimental temperature. A van't Hoff plot was constructed using plateau pressure data of each pressure–composition isotherm and the thermodynamic parameters were calculated for desorption of hydrogen in the ZrCo_1−xNi_x–H₂ systems. The enthalpy and entropy change for desorption of hydrogen were calculated. In addition, the hydrogen absorption–desorption cyclic life studies were performed on ZrCo_1−xNi_x alloys at 583 K up to 50 cycles. It was observed that with increasing Ni content the durability against disproportionation of alloys increases.     

Synthesis of (CuIn)xCd2(1−x)S2 photocatalysts for H2 evolution under visible light by using a low-temperature hydrothermal method

A new series visible-light driven photocatalysts (CuIn)_xCd_2(1−x)S₂ was successfully synthesized by a simple and facile, low-temperature hydrothermal method. The synthesized materials were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area measurement, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectroscopy (UV–Vis DRS). The results show that the morphology of the photocatalysts changes with the increase of x from 0.01 to 0.3 and their band gap can be correspondingly tuned from 2.37 eV to 2.30 eV. The (CuIn)_xCd_2(1−x)S₂ nanocomposite show highly photocatalytic activities for H₂ evolution from aqueous solutions containing sacrificial reagents, SO₃²⁻ and S²⁻ under visible light. Substantially, (CuIn)_0.05Cd_1.9S₂ with the band gap of 2.36 eV exhibits the highest photocatalytic activity even without a Pt cocatalyst (649.9 μmol/(g h)). Theoretical calculations about electronic property of the (CuIn)_xCd_2(1−x)S₂ indicate that Cu 3d and In 5s5p states should be responsible for the photocatalytic activity. Moreover, the deposition of Pt on the doping sample results in a substantial improvement in H₂ evolution than the Pt-loaded pure CdS and the amount of H₂ produced (2456 μmol/(g h)) in the Pt-loaded doping system is much higher than that of the latter (40.2 μmol/(g h)). The (CuIn)_0.05Cd_1.9S₂ nanocomposite can keep the activity for a long time due to its stability in the photocatalytic process. Therefore, the doping of CuInS₂ not only facilitates the photocatalytic activity of CdS for H₂ evolution, but also improves its stability in photocatalytic process.     

Effects of ammonia substitution on combustion stability limits and NOx emissions of premixed hydrogen–air flames

The combustion stability limits and nitrogen oxide (NO_x) emissions of burner-stabilized premixed flames of ammonia (NH₃)-substituted hydrogen (H₂)–air mixtures at normal temperature and pressure are studied to evaluate the potential of partial NH₃ substitution to improve the safety of H₂ use. The effects of NH₃ substitution, nitrogen (N₂) coflow and mixture injection velocity on the stability limits and NO_x emissions of NH₃–H₂–air flames are experimentally determined. Results show a reduction of stability limits with NH₃ substitution and coflow, supporting the potential of NH₃ as a carbon-free, green additive in H₂–air flames and indicating a different tendency from that for no coflow condition. The NO_x emission index is almost constant even with enhanced NH₃ substitution, though the absolute value of NO_x emissions increases in general. At fuel-rich conditions, the NO_x emission index decreases with increasing mixture injection velocity and the existence of coflow. The thermal deNO_x process in the post-flame region is involved in reducing NO_x emissions for the fuel-rich flames.     

Cd1−xZnxS supported on SBA-16 as photocatalysts for water splitting under visible light: Influence of Zn concentration

Cd_1−xZn_xS solid solutions (x = 0.05–0.3) supported on mesoporous silica SBA-16 substrate with 3D cubic structure were investigated for hydrogen production from water splitting under visible light. The influence of Zn concentration (x) in the Cd_1−xZn_xS solid solution and support morphology were investigated. The bare SBA-16 substrate was synthetized by the hydrothermal method whereas the Cd_1−xZn_xS photocatalysts were prepared by coprecipitation of metal sulfides from aqueous solutions of Cd²⁺ and Zn²⁺ using Na₂S as precipitating agent. An attempt has been made to determine the photocatalyst structures using several techniques including elemental analysis, N₂ adsorption–desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS) and Raman spectroscopy. Surface characterization of the samples by XPS indicates that Cd_1−xZn_xS nanoparticles are unevenly distributed on both external surface and within the pore network. An increase of the band gap energy with increasing Zn loading up to x = 0.2 in the Cd_1−xZn_xS solid solution was observed. As a consequence, H₂ evolution increases gradually with an increase of the Zn loading in the photocatalysts from 0.05 to 0.2 wt% being the Cd_0.8Zn_0.2S/SBA-16 system the most active among the catalysts studied. The highest activity of this photocatalyst was explained in terms not only of its large band gap energy but also by the enhancement of the interaction between the particles of solid solution and the SBA-16 substrate.     

Enhancement of hydrogen production rates in reformation process of methane using permeable Ni tube and chemical heat pump

Enhancement of the overall conversion efficiency from CH₄ to H₂ using a permeable-membrane Ni tube and temperature rise by a chemical heat pump system packed with hydrogen-absorbing alloys have been investigated in order to produce H₂ more efficiently using a high-temperature heat source. The two feasibilities to enhance the conversion efficiency are tested using their respective experimental apparatuses. Two things are experimentally proved that (1) Ni permeable-membrane tubes can provide measures to convert CH₄ to H₂ continuously without any deterioration in the course of partial oxidation or steam reformation and (2) two Zr(V_1−xFe_x)₂ alloys with different Fe displacement ratios can comprise a chemical heat-pump system working at higher-temperature conditions.     

HIx system thermodynamic model for hydrogen production by the Sulfur–Iodine cycle

The HI_x ternary system (H₂O–HI–I₂) is the latent source of hydrogen for the Sulfur–Iodine thermo-chemical cycle. After analysis of the literature data and models, a homogeneous approach with the Peng–Robinson equation of state used for both the vapor and liquid phase fugacity calculations is proposed for the first time to describe the phase equilibrium of this system. The MHV2 mixing rule is used, with UNIQUAC activity coefficient model combined with of hydrogen iodide solvation by water. This approach is theoretically consistent for HI_x separation processes operating above HI critical temperature. Model estimation is done on selected literature vapor–liquid, liquid–liquid, vapor–liquid–liquid and solid–liquid equilibrium data for the ternary system and the three binaries subsystems. Validation is done on the remaining literature data. Results agree well with the published data, but more experimental effort is needed to improve modeling of the HI_x system.     

New SrMo1−xCrxO3−δ perovskites as anodes in solid-oxide fuel cells

Oxides of composition SrMo_1−xCr_xO_3−δ (x = 0.1, 0.2) have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers higher than 700 mW cm⁻² at 850 °C with pure H₂ as a fuel. All the materials are suggested to present mixed ionic–electronic conductivity (MIEC) from neutron powder diffraction (NPD) experiments, complemented with transport measurements; the presence of a Mo⁴⁺/Mo⁵⁺ mixed valence at room temperature, combined with a huge metal-like electronic conductivity, as high as 340 S cm⁻¹ at T = 50 °C for x = 0.1, could make these oxides good materials for solid-oxide fuel cells. The magnitude of the electronic conductivity decreases with increasing Cr-doping content. The reversibility of the reduction–oxidation between the oxidized Sr(Mo,Cr)O_4−δ scheelite and the reduced Sr(Mo,Cr)O₃ perovskite phases was studied by thermogravimetric analysis, which exhibit the required cyclability for fuel cells. An adequate thermal expansion coefficient, without abrupt changes, and a chemical compatibility with electrolytes make these oxides good candidates for anodes in intermediate-temperature SOFC (IT-SOFCs).     

Chemical synthesis of Ca-doped CeO2—Intermediate temperature oxide ion electrolytes

Nano-crystalline fluorite-like structure CeO₂ and Ca-doped CeO₂ compounds were prepared in the temperature range of 220–400 °C using a precursor method which involves coprecipitation of Ca²⁺ and Ce⁴⁺ ions using oxalic acid from the aqueous calcium chloride and ammonium cerium nitrate solutions. The precipitated products were characterized by employing thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), infrared spectroscopy (IR), laser particle size analysis (LPSA) methods and scanning electron microscopy (SEM). TGA studies show two step weight loss in the temperature range: (i) room temperature to 200 °C and (ii) 200–400 °C for all the investigated precursors. The former loss is attributed to loss of water while the latter is due to decomposition of oxalates. The XRD study reveal a complex pattern for the as-precipitated powders, and surprisingly we see the formation of single-phase fluorite-like structure at about 220 °C for Ce_1−xCa_xO_2−x (0 < x < 0.20). However, XRD peaks were found to be very broad that sharpen with increasing temperature. The cubic fluorite-type lattice constant increases with increasing Ca-content, which is consistent with literature, and also follows the expected trend based on the ionic radii consideration. For purpose of comparison, Ce_1−xCa_xO_2−x (0 < x < 0.25) samples were also prepared by solid-state reaction using CeO₂ and CaCO₃, and lattice parameter is consistent with precipitation method samples within the experimental error. This result suggesting that doping of Ca is successful by coprecipitation. The particle size of parent and Ca-doped CeO₂ samples prepared by precipitated method was found to be in the range 10–85 nm (from PXRD) in the temperature range 400–1000 °C, while about order of higher size was observed for the ceramic method synthesized samples. The presently employed wet chemical method could be used to prepare ceria and doped materials with nano-sized particles for a large scale production at mild temperature.     

BaZr0.2Ce0.8−xYxO3−δ solid oxide fuel cell electrolyte synthesized by sol–gel combined with composition-exchange method

This study reports the synthesis of proton-conducting BaZr_0.2Ce_0.8−xY_xO_3−δ (x = 0–0.4) oxides by using a combination of citrate-EDTA complexing sol–gel process and composition-exchange method. Compared to those oxides prepared from conventional sol–gel powders, the sintered BaZr_0.2Ce_0.8−xY_xO_3−δ pellets synthesized by sol–gel combined with composition-exchange method are found to exhibit improved sinterability, a higher relative density, higher conduction, and excellent thermodynamic stability against CO₂. Moreover, the Pt/electrolyte/Pt single cell using such a BaZr_0.2Ce_0.6Y_0.2O_3−δ electrolyte shows an obviously higher maximum powder density in the hydrogen-air fuel cell experiments. Based on the experimental results, we discuss the improvement mechanism in terms of calcined particle characteristics. This work demonstrates that the BaZr_0.2Ce_0.8−xY_xO_3−δ oxides synthesized by sol–gel combined with composition-exchange method would be a promising electrolyte for the use in H⁺-SOFC applications. More importantly, this new fabrication approach could be applied to other similar ABO₃-perovskite material systems.     

Dewatering of HIx solutions by pervaporation through Nafion membranes

The Sulphur Iodine (SI) thermochemical cycle is a promising route for hydrogen production from water. It requires the processing of a complex solution, termed HI_x, which contains HI, H₂O, very high concentrations of I₂, plus a range of iodide species. Process efficiency can be improved by dewatering the HI_x stream beyond its azeotropic point. This paper reports work aimed at achieving this by pervaporation through a membrane operating at the harsh process conditions involved. Nafion^®117 and Nafion^®212 are investigated using both a batch and a continuous flow arrangement operating with a range of HI–H₂O and HI–H₂O–I₂ solution concentrations, up to the expected SI cycle composition. Permeates of almost pure water and reasonable fluxes are seen, and good correspondence is observed between the results from the two rigs. Consideration of the solution-diffusion model suggests that sorption and desorption, as well as diffusion, play a limiting role in the permeate flux.     

Novel photocatalysts based on Cd1−xZnxS/Zn(OH)2 for the hydrogen evolution from water solutions of ethanol

Multiphase photocatalysts Pt/Cd_1−xZn_xS/ZnO/Zn(OH)₂, Pt/Cd_1−xZn_xS/ZnO, and Pt/Cd_1−xZn_xS/Zn(OH)₂ were synthesized by a new two-step technique. The photocatalysts were characterized by a wide range of experimental techniques: X-ray diffraction, high-resolution transmission electron microscopy combined with energy-dispersive X-ray spectroscopy, low-temperature N₂ adsorption/desorption, and UV/VIS spectroscopy. The photocatalytic activity was tested in a batch reactor in the reaction of H₂ evolution from aqueous solutions of ethanol under visible light irradiation (λ > 420 nm). The highest achieved photocatalytic activity was 2256 μmol H₂ per gram of photocatalyst per hour; the highest quantum efficiency was 10.4%. The activity of Pt/Cd_1−xZn_xS/Zn(OH)₂ was higher than that of Pt/Cd_1−xZn_xS/ZnO/Zn(OH)₂ and Pt/Cd_1−xZn_xS/ZnO. The explanation of enhanced activity of zinc–cadmium sulfide/ε-zinc hydroxide based on quantum calculations was suggested.     

Synthesis and electrochemical properties of Li1−xFe0.8Ni0.2O2–LixMnO2 (Mn/(Fe + Ni + Mn) = 0.8) material

A new type of Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ (Mn/(Fe + Ni + Mn) = 0.8) material was synthesized at 350 °C in air atmosphere using a solid-state reaction. The material had an XRD pattern that closely resembled that of the original Li_1−xFeO₂–Li_xMnO₂ (Mn/(Fe + Mn) = 0.8) with much reduced impurity peaks. The Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell showed a high initial discharge capacity above 192 mAh g⁻¹, which was higher than that of the parent Li/Li_1−xFeO₂–Li_xMnO₂ (186 mAh g⁻¹). We expected that the increase of initial discharge capacity and the change of shape of discharge curve for the Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell is the result from the redox reaction from Ni²⁺ to Ni³⁺ during charge/discharge process. This cell exhibited not only a typical voltage plateau in the 2.8 V region, but also an excellent cycle retention rate (96%) up to 45 cycles.     

Effect of zirconium addition on the structure and properties of CuO/CeO2 catalysts for high-temperature water–gas shift in an IGCC system

A series of Ce_xZr_1−xO₂-based Cu catalysts was synthesized by the co-precipitation method. The influences of copper content, zirconium addition, and ratio of ceria to zirconia on the catalytic activity were investigated. BET, N₂O decomposition, XRD, TEM, SEM, EDS, Raman spectroscopy, H₂-TPR, TG/DTA, and XPS were used to characterize the catalysts. The catalytic activity was tested in terms of CO conversion and H₂ selectivity in H₂-rich coal-derived synthesis gas, simulating the actual gas composition of an integrated gasification combined cycle (IGCC) system. The long-term catalyst stability was also examined at 450 °C for 196 h. The addition of zirconium was found to be very important in enhancing catalytic performance. The surface area, copper dispersion, oxygen storage and mobility capacity, reducibility, as well as resistance to sintering all improved after zirconium addition.     

New fan blade-like core-shell Sb2TixSy photocatalytic nanorod for hydrogen production from methanol/water photolysis

New photocatalysts of Sb₂Ti_xS_y (x = 0, 0.5, 1.0, 1.5 mol and y = 3, 4, 5, 6 mol) fan blade-like core-shell nanorods have been designed ultimately to enhance hydrogen production. The nanorods of 500 nm long and 60–100 nm wide are Sb₂S₃ nanorod surrounded by an amorphous TiS₂ membrane, showing absorption band edges of above 600 nm. The evolution of H₂ from methanol/water (1:1) photo-splitting over Sb₂Ti_xS_y nanorods in the liquid system is doubled, compared to that over pure Sb₂S₃. Particularly, 52 μmol of H₂ gas is produced after 10 h when 0.5 g of Sb₂Ti_1.0S₅ nanorods is used at pH = 7, and the performance is increased by more than 50% at higher pH. Based on cyclic voltammetry (CV) and UV-Visible absorption spectra, the high photocatalytic activity can be attributed to the existence of an appropriate band-gap state, which includes the scope of the redox potential of water in Sb₂Ti_1.0S₅ nanorods, resulting in the promotion of the redox reaction of water.     

Electrochemical properties of doped lithium titanate compounds and their performance in lithium rechargeable batteries

Several substituted titanates of formula Li_4−xMg_xTi_5−xV_xO₁₂ (0 ≤ x ≤ 1) were synthesized (and investigated) as anode materials in rechargeable lithium batteries. Five samples labeled as S1–S5 were calcined (fired) at 900 °C for 10 h in air, and slowly cooled to room temperature in a tube furnace. The structural properties of the synthesized products have been investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transmission infrared (FTIR). XRD explained that the crystal structures of all samples were monoclinic while S1 and S3 were hexagonal. The morphology of the crystal of S1 was spherical while the other samples were prismatic in shape. SEM investigations explained that S4 had larger grain size diameter of 15–16 μm in comparison with the other samples. S4 sample had the highest conductivity 2.452 × 10⁻⁴ S cm⁻¹. At a voltage plateau located at about 1.55 V (vs. Li ⁺), S4 cell exhibited an initial specific discharge capacity of 198 mAh g⁻¹. The results of cyclic voltammetry for Li_4−xMg_xTi_5−xV_xO₁₂ showed that the electrochemical reaction was based on Ti⁴⁺/Ti³⁺ redox couple at potential range from 1.5 to 1.7 V. There is a pair of reversible redox peaks corresponding to the process of Li⁺ intercalation and de-intercalation in the Li–Ti–O oxides.     

Synthesis and photoelectrochemical study of BiWxV1−xO4+x/2 films by a polymer-assisted method

A series of BiW_xV_1−xO_4+x/2 films were coated on fluorine-doped tin oxide (FTO) glass by a polymer-assisted method and examined as photoelectrodes for photoelectrochemical measurements under Xe lamp light irradiation in a 0.5 M Na₂SO₄ solution. The compositions, structural, optical and morphologic properties of the films were characterized by XPS, XRD, UV–vis and SEM. The results showed the successfully synthesized films and their photoelectrochemical activities, revealing that the amount of tungsten had an important effect on the photoelectrochemical activities of BiW_xV_1−xO_4+x/2 films and the highest incident photon to current conversion efficiency (IPCE) was obtained when x equaled 0.1.     

Cd1−xZnxS solid solutions supported on ordered mesoporous silica (SBA-15): Structural features and photocatalytic activity under visible light

A series of Cd_1−xZn_xS (x = 0.05–0.3) photocatalysts supported on ordered mesoporous silica (SBA-15) were prepared and investigated for hydrogen production from water splitting under visible light. Textural, structural and surface photocatalyst properties are determined by N₂ adsorption isotherms, UV–vis, Raman and XPS and related to the activity results in hydrogen production. Raman and XRD results indicated a mutual interaction between Cd and Zn, forming nanoparticles of Cd_1−xZn_xS solid solutions. All Cd_1−xZn_xS/SBA-15 samples showed relatively high activities for hydrogen evolution. The hydrogen production rate is found to increase gradually when the zinc concentration on photocatalysts increases from 0.05 to 0.2, achieving a maximum for the photocatalyst with zinc concentration equal to 0.2. Variation in photoactivity is discussed in terms of modification in the conduction band and light absorption ability of Cd_1−xZn_xS particles derived from the changes in the Zn concentration in the Cd_1−xZn_xS solid solution.