Studies on reduction of chromium doped iron oxide catalyst using hydrogen and various concentration of carbon monoxide

Chemical reduction behaviour of 3% chromium doped (Cr–Fe₂O₃) and undoped iron oxides (Fe₂O₃) were investigated by using temperature programmed reduction (TPR). The reduced phases were characterized by X-ray diffraction spectroscopy (XRD). The reduction processes were achieved with 10% H₂ in nitrogen (%, v/v), 10% and 20% of carbon monoxide (CO) in nitrogen (%, v/v). In hydrogen atmosphere, the TPR results indicate that the reduction of Cr–Fe₂O₃ and Fe₂O₃ proceed in three steps (Fe₂O₃ → Fe₃O₄ → FeO → Fe) with Fe₃O₄ and FeO as intermediate states. A complete reduction to metallic iron for both samples occurred at 900 °C. As for CO reductant, the profiles show the reduction of Fe₂O₃ also proceeded in three steps with a complete reduction occurs at 900 °C in 10% CO with no sign of carbide formation. Nevertheless, a 20% CO was able to reduce the completely at lower temperature at 700 °C and there is a formation of iron carbide at 500 °C but the carbide disappeared as the reduction temperature increase. Meanwhile in 10% CO atmosphere, Cr–Fe₂O₃ shows a better reducibility compared to Fe₂O₃ with a complete reduction at 700 °C, which is 200 °C lower than Fe₂O₃. A Cr dopant in the Fe₂O₃ can lead to formation of various forms of iron carbides such as F₂C, Fe₅C₂, Fe₂₃C₆ and Fe₃C as the CO concentration was increased to 20%. The transformation profile of iron phases during carburization follows the following forms, Fe₂O₃ → Fe₃O₄ → iron carbides (Fe_xC). The XRD pattern shows the diffraction peaks of Cr–Fe₂O₃ are more intense with improved crystallinity for the characteristic peaks of Fe₂O₃ compare to undoped Fe₂O₃. No visible sign of chromium particles peaks in the XRD spectrum that indicates the Cr particles loaded onto the iron oxide are well dispersed. The uniform dispersion with no sign of sintering effects of the Cr dopant on the Fe₂O₃ was confirmed by FESEM. The study shows that Cr dopant gives a better reducibility of iron oxide but promotes the formation of carbides in an excess CO concentration.     

Metal oxide hydrogen,oxygen, and carbon monoxide sensors for hydrogen setups and cells

Use of hydrogen, oxygen, and carbon oxide semiconductor sensors made of metal oxides allows controlling electronically the content of these gases in operation of many hydrogen setups, cells and devices. Present review-paper gives a general idea of achievements in this field.     

Studies on influence of hydrogen and carbon monoxide concentration on reduction progression behavior of molybdenum oxide catalyst

Temperature programmed reduction (TPR) analysis was applied to investigate the chemical reduction progression behavior of molybdenum oxide (MoO₃) catalyst. The composition and morphology of the reduced phases were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). The reduction progression of MoO₃ catalyst was attained with different reductant types and concentration (10% H₂/N₂, 10% and 20% CO/N₂ (%, v/v)). Two different modes of reduction process were applied. The first approach of reduction involved non-isothermal mode reduction up to 700 °C, while the second approach of reduction involved the isothermal mode reduction for 60 min at 700 °C. Hydrogen temperature programmed reduction (H₂-TPR) results showed the reduction progression of three-stage reduction of MoO₃ (Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰) with Mo⁵⁺ and Mo⁴⁺. XRD analysis confirmed the formation of Mo₄O₁₁ phase as an intermediate phase followed by MoO₂ phase. After 60 min of isothermal reduction, peaks of metallic molybdenum (Mo) appeared. Whereas, FESEM analysis showed porous crater-like structure on the surface cracks of MoO₂ layer which led to the growth of Mo phase. Meanwhile, the reduction of MoO₃ catalyst in 10% carbon monoxide (CO) showed the formation of unstable intermediate phase of Mo₉O₂₆ at the early stage of reduction. Furthermore, by increasing 20% CO led to the carburization of MoO₂ phase, resulted in the formation of Mo₂C rather than the formation of metallic Mo, as confirmed by XPS analysis. Therefore, the presented study shows that hydrogen gave better reducibility due to smaller molecular size, which contributed to high diffusion rate and achieved deeper penetration into the MoO₃ catalyst compared to carbon monoxide reductant. Hence, the reduction of MoO₃ in carbon monoxide atmosphere promoted the formation of Mo₂C which was in agreement with the thermodynamic assessment.     

Electrochromism in nickel oxide and tungsten oxide thin films: Ion intercalation from different electrolytes

Electrochromic (EC) NiO_z and WO_y thin films were prepared by sputtering and were used in a feasibility study aimed at investigating mixtures of these two oxides. The object was to identify a suitable electrolyte, compatible with both NiO_z and WO_y. To that end we carried out cyclic voltammetry (CV) in potassium hydroxide (KOH), propionic acid, and lithium perchlorate in propylene carbonate (Li-PC). WO_y could be coloured in propionic acid and Li-PC, while NiO_z could be coloured only in KOH. Both films showed best stability in Li-PC, which hence is well suited for further studies of mixed NiO_z and WO_y.     

Highly efficient and durable phosphine reduced iron-doped tungsten oxide/reduced graphene oxide nanocomposites for the hydrogen evolution reaction

The design and development of inexpensive and highly efficient electrocatalysts for hydrogen production from water splitting are highly crucial for green energy and the hydrogen economy. Herein, we report phosphine reduced an iron-doped tungsten oxide nanoplate/reduced graphene oxide nanocomposite (Fe-WOxP/rGO) as an excellent electrocatalyst for the hydrogen evolution reaction. This electrocatalyst was synthesized using a hydrothermal method, followed by reduction with phosphine (PH₃), which was generated from sodium hypophosphite. The catalyst onset potential, Tafel slope, and stability were investigated. Accordingly, Fe-WOxP/rGO exhibited impressively high electrocatalytic activity with a low overpotential of 54.60 mV, which is required to achieve a current density of 10 mAcm^?2. The Tafel slope of 41.99 mV dec^?1and the linear sweep voltammetry curve is almost the same as 2000 cycles and electrolysis under static overpotential (54.60 mV) is remain for more than 24 h in 0.5 M H₂SO₄. The catalytic activity and conductivity of Fe-WOxP/rGO were higher than WO_XP, Fe-WOxP and WOxP/rGO. Such an outstanding performance of the Fe-WOxP/rGO nanocomposite is attributed to the coupled synergic effect between high oxygen vacancies formation on tungsten oxide in the nanoplate-like structure of Fe-WOxP and rGO nanosheet, making it as an excellent electrocatalyst for hydrogen evolution reaction.     

Enhanced electrocatalytic performance for hydrogen oxidation reaction on gold nanoparticles supported on tungsten oxide (VI) modified carbon

We report on a hydrogen oxidation reaction (HOR) catalyst system composed of gold nanoparticles (Au NPs) and tungsten oxide (WO₃). Previously, we reported that Au NPs could be activated for HOR by sonochemical heating and quenching. However, we also found that the activated Au NPs were poisoned by protons, the HOR product. In order to further improve the catalytic behavior of Au NPs, we employed tungsten oxide as a part of the support and a co-catalyst, by which proton spillover could be achieved. Au NPs supported on WO₃/C were synthesized. The intermediates and final product were characterized by powder X-ray diffraction, energy dispersive X-ray spectroscopy, and transmission electron microscopy. Electrocatalytic activity of the samples for HOR was investigated by the linear sweep voltammetry with rotating disk electrode technique, which showed the disappearance of the proton poisoning of Au NPs in contact with WO₃. Therefore, with sonication treatment, the Au NPs and WO₃ composite showed a very high and stable activity for HOR.     

Interaction of hydrogen in carbon matrix with impurities of nickel. Effects of spin fluctuation

This work aims to define general criteria to allow theoretical and experimental design of new materials with high hydrogen content, with a view to their potential application as moderators in reactors at high temperatures and hydrogen storage materials.     

Kinetic interplay between hydrogen and carbon monoxide in syngas-fueled catalytic micro-combustors

The combined oxidation of hydrogen and carbon monoxide over platinum in micro-combustors at catalytic surface temperatures below 600 K was studied numerically, using a two-dimensional computational fluid dynamics (CFD) model with detailed heterogeneous and homogeneous reaction mechanisms and multicomponent transport. Simulations were performed at different surface temperatures and feed compositions to study the kinetic interplay between hydrogen and carbon monoxide. A sensitivity analysis of the heterogeneous reaction mechanism was performed to identify the rate-controlling steps. Finally, possible mechanisms for the observed behavior were discussed. It was shown that there is significant kinetic interplay between hydrogen and carbon monoxide. Carbon monoxide significantly inhibits the catalytic oxidation of hydrogen. In contrast, the presence of hydrogen was found to promote the catalytic oxidation of carbon monoxide, with the largest effect shown for the small addition of hydrogen, then this effect progressively decreases with the further increase of hydrogen concentration. Accordingly, the apparent reaction order with respect to hydrogen changes from positive to negative, then to zero. The promoting effect of hydrogen can be attributed to the carboxyl pathway, which is crucial to describe the process.     

Influence of hydrogen and carbon monoxide on reduction behavior of iron oxide at high temperature: Effect on reduction gas concentrations

The purposes of this study are to reduce Fe₂O₃ using hydrogen (H₂) and carbon monoxide (CO) gases at a high temperature zone (500 °C–900 °C) by focusing on the influence of reduction gas concentrations. Reduction behavior of hematite (Fe₂O₃) at high temperature was examined using temperature programmed reduction (TPR) under non-isothermal conditions with the presence of 10% H₂/N₂, 20% H₂/N₂, 10% CO/N₂, 20% CO/N₂ and 40% CO/N₂. The TPR_CO results indicated that the first and second reduction peaks of Fe₂O₃ at a temperature below 660 °C appeared rapidly when compared to TPR_H2. However, TPR_H2 exhibited a better reduction in which Fe₂O₃ entirely reduced to Fe at temperature 800 °C (20% H₂) without any remaining of wustite (FeO) whereas a temperature above 900 °C is needed for a complete reduction in 10% H₂/N₂, 10% and 20% CO/N₂. Furthermore, the reduction of hematite could be improved when increasing CO and H₂ concentrations since reduction profiles were shifted to a lower temperature. Thermodynamic calculation has shown that enthalpy change of reaction (ΔHr) for all phases transformation in CO atmosphere is significantly lower than in H₂. This disclosed that CO is the best reductant as it is a more exothermic, more spontaneous reaction and able to initiate the reduction at a much lower temperature than H₂ atmosphere. Nevertheless, the reduction of hematite using CO completed at a temperature slightly higher compared to H₂. It is due to the presence of an additional carburization reaction which is a phase transformation of wustite to iron carbide (FeO → Fe₃C). Carburization started at the end of the second stage reduction at 600 °C and 630 °C under 20% and 40% CO, respectively. Therefore, reduction by CO encouraged the formation of carbide, slower the reduction and completed at high temperature. XRD analysis disclosed the formation of austenite during the final stage of a reduction under further exposure with high CO concentration. Overall, less energy consumption needed during the first and second stages of reduction by CO, the formation of iron carbide and austenite were enhanced with the presence of higher CO concentration. Meanwhile, H₂ has stimulated the formation of pure metallic iron (Fe), completed the reduction faster, considered as the strongest reducing agent than CO and these are effective at a higher temperature. Proposed iron phase transformation under different reducing agent concentrations are as followed: (a) 10% H₂, 20% H₂ and 10% C; Fe₂O₃ → Fe₃O₄ → FeO → Fe, (b) 20% CO; Fe₂O₃ → Fe₃O₄ → FeO → Fe₃C → Fe and (c) 40% CO; Fe₂O₃ → Fe₃O₄ → FeO → Fe₃C → Fe → F,C (austenite).     

Micro-contacted self-assembled tungsten oxide nanorods for hydrogen gas sensing

Electron beam lithography was used to fabricate platinum μ-contacts over tungsten oxide nanorods formed on a mica substrate. This made possible the measurement of sensorial response of these self-assembled tungsten oxide nanorods to hydrogen gas for the first time. The nanorods were prepared by thermal evaporation from an oxide source. Consequently, two types of conductometric sensors were assembled: a) percolating network of nanorods and b) set of individually contacted WO₃ nanorods. The preparation procedures are described in detail and the comparison of response of both types of assemblies is given. The first sensorial measurements revealed a good response of the b) type of sensor and the minimum repeatedly detected concentration of H₂ was 50 ppm.     

Effect of hydrogen spillover on the surface of tungsten oxide on hydrogenation of cyclohexene and N-propylcarbazole

The tungsten oxide nanorods loaded with ruthenium nanoparticles (Ru-WO₃) nanocomposite were synthesized by hydrothermal method and impregnation method. The properties of Ru-WO₃ catalysts were characterized by various methods, such as BET, XRD, SEM, TEM, EDS and XPS. The results show that hydrogen spillover occurs on the surface of WO₃ and the catalytic activity of Ru-WO₃ in hydrogenation of cyclohexene increases with the increase of reaction time. Subsequently, the Ru-WO₃ catalysts was used to hydrogenate N-propylcarbazole (NPCZ). Compare with commercial 0.5 wt% Ru–Al₂O₃ catalyst, Ru-WO₃ can realize the rapid hydrogen uptake of NPCZ at a lower metal loading (0.34 wt%) and lower temperature (150 °C), which is attributed to the increase of reactive sites caused by hydrogen spillover.     

Improving hydrogen storage in Ni-doped carbon nanospheres

The effect of nickel distribution and content in Ni-doped carbon nanospheres on hydrogen storage capacity under conditions of moderate temperature and pressure was studied. It was found that the nickel distribution, obtained by using different doping techniques and conditions, has a noticeable influence on hydrogen storage capacity. The samples with the most homogeneous nickel distribution, obtained by pre-oxidising the carbon nanospheres, displayed the highest storage capacity. In addition, storage capacity is influenced by the amount of nickel. It was found a higher storage capacity in samples containing 5 wt.% of Ni. This is due to the greater interactions between the nickel and the support that produce a higher activation of the solid through a spillover effect.     

A platinum modulated tungsten oxide on Ag nanowires network as an indicator for in-situ visualized evaluation of the hydrogen evolution performance

The development of the real-time evaluation for the catalytic hydrogen evolution performance under a simple and convinient condiction is urgently needed, but still a great challenge. Herein, a platinum modulated WO_x on Ag nanowires (Pt-WO_x@Ag NWs) is developed as an optical-electrochemical catalyst to realize an in-situ intuitive evaluation for the hydrogen evolution performance, in which the color of as-prepared Pt-WO_x@Ag NWs catalyst changes from the transparent to the deep blue with the increase of the applied potential. The real-time H₂ evolution with an H₂ turnover frequency (from 0 to 2.26 s^?1 per site), optical transmittance (from 80.3% to 48.7% at the wavelength of 630 nm) and energy consumption (from 0 to 0.74 W h in 1 h) is established. The charge transfer and mass transport are greatly promoted by the three demensional Ag NWs conductive network and abundant active sites, which are provided by the platinum modulated WO₃ on the Ag substrate. Density functional theory (DFT) calculations indicate that the modified WO_x shows the preferred adsorption affinity toward H₂O (ΔG_H2O, ?0.17 eV), which reach a high coloration efficiency and optical modulation range for the electrochromic reaction. The Pt sites on WO_x with a suitable H binding energy (ΔG_H1, 0.38 eV) efficiently promote the H1 conversion and H₂ release of water splitting. This work propose an intelligent hydrogen evolution indicator by real-time color change to boost the high-quality development of green hydrogen energy.     

Periodically regenerating diesel particulate filter with a hydrogen/carbon monoxide mixture addition

This investigation analyses the effect of introducing a H₂/CO mixture, upstream of a diesel particulate filter (DPF), in an attempt to support the regeneration process. The introduction of the mixture was achieved via various periodic strategies in an attempt to reduce the volume of mixture required while still maintaining proficient regeneration qualities. In addition to this, the effect of space velocity and engine load on the regeneration process was also investigated. The experimental data showed that the mixture addition supported the regeneration process by increasing the filter temperature via an exothermic reaction. The most beneficial spraying strategy introduced the mixture to the DPF every 20 s, with each injection event lasting for a period of 10 s. This strategy required 50% less mixture volume than the constant spray strategy but still induced similar regeneration capabilities. In addition to this, it was noted that a decrease in space velocity reduced the rate of temperature increase but improved the peak filter temperature resulting in increased regeneration proficiency. It was also noted that a reduction in engine load reduced the mean filter temperature but overall had minimal effect on the regeneration process.     

A new approach to the manufacturing of elemental boron from boron oxide by carbon monoxide

Elemental boron is one of the most valuable high-tech boron products and it has highest energy density 14 kcal/g in the world for this type of product. With the rapid advancements in technology in recent years, a demand has grown for a light materials with functionality and excellent properties such as high hardness, high melting point, high strength, high chemical resistance and nuclear characteristics that can be used in the fields of aerospace, aviation, automotive and solar cells. In this study boron oxide was reduced using carbon monoxide via a batch system to produce elemental boron. To determine the most suitable conditions for the reduction reaction different temperatures and different CO/B₂O₃ mol ratio parameters were studied. As a result of thermodynamic calculations for the most efficient parameters for reaction temperature was 140–210 °C and the CO/B₂O₃ mol ratio being studied was 3/1 and 2/1 for the batch system. Boron oxide reduction was performed by carbon monoxide gas with the pressure set at 10 bar. Characterization of the product was carried out by using X-Ray Diffractometer (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM) at optimum temperature and mol ratio (140 °C and 3/1). Boron phase was seen in both XRD and FT-IR analysis. Also, SEM analysis was performed in order to observe morphological structure of elemental boron.     

Long-term behaviour of tungsten oxide hydrate gels in an alkali containing aqueous environment

The room temperature ageing process of tungsten oxide dihydrate grains (H₂WO₄·H₂O) prepared by the methods of Zocher and Jacobson (Kolloidchem. Beih. 28 (1929) 167) and Freedman (J. Am. Chem. Soc. 81 (1959) 3834) has been studied. A comparison between these two preparation methods and the ageing characteristics is reported. Zocher and Jacobson-type grains, spindle like in shape, have a strong tendency to morphological conversion depending on the pH value of the surrounding aqueous solution. Under the same conditions the Freedman-type irregularly shaped particles preserve their morphology. Scanning electron microscopy and Fourier transform infrared spectroscopy studies have shown that this structural and morphological stability of Freedman-type grains can be altered by the presence of alkaline (Li⁺, Na⁺, K⁺) and NH₄⁺ ions. A limited incorporation of cations into the tungstate structure was observed.     

Effects of supports on hydrogen production and carbon deposition of Fe-based oxygen carriers in chemical looping hydrogen generation

Chemical looping hydrogen generation (CLHG) can produce high purity hydrogen from fuel gases with inherent separation of CO₂. However, the performance of oxygen carrier in CLHG varies with the support materials. In this paper, the reactivity, carbon deposition, redox stability, hydrogen yield and purity, and sintering behavior of the Fe-based oxygen carriers were analyzed to investigate the effects of supports, i.e. Al₂O₃, SiO₂, MgAl₂O₄, ZrO₂ and YSZ (yttrium-stabilized zirconia). The results showed that the properties of the oxygen carriers, e.g. carbon deposition, reactivity and stability, mainly depended on the support and its interaction with iron oxides. The reactivity and hydrogen yield for the oxygen carriers investigated followed the order: Fe₂O₃/MgAl₂O₄ > Fe₂O₃/ZrO₂ > Fe₂O₃/YSZ > Fe₂O₃/Al₂O₃ > Fe₂O₃/SiO₂, and the order of hydrogen purity was identical with that of hydrogen yield as a result of carbon deposition. Furthermore, the hydrogen purity of the Fe-based oxygen carriers supported by MgAl₂O₄, ZrO₂, or YSZ could reach above 99.5% and Fe₂O₃/YSZ showed the lowest carbon deposition. The oxygen carriers, Fe₂O₃/MgAl₂O₄ and Fe₂O₃/SiO₂, were selected to be characterized by SEM images and XRD patterns before and after the redox cycles.     

Analysis of the effects of reformate (hydrogen/carbon monoxide) as an assistive fuel on the performance and emissions of used canola-oil biodiesel

Evolving technology and a reoccurring energy crisis creates a continued investigation into the search for sustainable and clean-burning renewable fuels. One possibility is hydrogen that has many desirable qualities such as a low flammability limit promoting ultra-lean combustion, high laminar flame speed for increased thermal efficiency and low emissions. However, past research discovered certain limiting factors in its use such as pre-ignition in spark ignition engines and inability to work as a singular fuel in compression ignition engines. To offset these issues, this work documents manifold injection of a hydrogen/carbon monoxide mixture in a dual-fuel methodology with biodiesel. While carbon monoxide does degrade some of the desirable properties of hydrogen, it acts partially like a diluent to restrict pre-ignition. The result of this mixture addition allows the engine to maintain power while reducing biodiesel fuel consumption with a minimal NO_x emissions increase.     

Multi-walled carbon nanotubes supported porous nickel oxide as noble metal-free electrocatalysts for efficient water oxidation

Herein we report for the first time to use multi-walled carbon nanotubes (MWCNTs) supported porous nickel oxide (NiO_x) as non-precious electrocatalysts for oxidation of water at low overpotentials. The nickel oxide catalyst was facilely electrodeposited on MWCNTs in a 0.1 M KBi buffered solution at pH 9.2 containing 0.1 mM Ni²⁺ with an applied anodic potential. The current density of bulk electrolysis is 2.2 mA/cm² at +1.1 V (vs Ag/AgCl) using NiO_x-MWCNTs as the working electrode at pH 9.2, which is much higher than that in a system containing no MWCNTs. Tafel plot indicates that the present NiO_x-MWCNTs catalyst requires the overpotential of only 200 mV to catalyze the water oxidation reaction at pH 9.2. The Faradaic efficiency of >95% has been achieved at +1.1 V. The highly porous character of the NiO_x catalyst materials were further studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray analysis (EDX).     

Activation of dispersed PtSn/C nanoparticles by tungsten oxide matrix towards more efficient oxidation of ethanol

A novel electrocatalytic system for oxidation of ethanol, in which carbon-supported PtSn nanoparticles were modified with ultra-thin films/deposits of tungsten oxide, was proposed, fabricated and characterized here using electrochemical as well as spectroscopic (X-ray diffraction) and microscopic (transmission electron) techniques. The enhancement effect was evident from comparative diagnostic electrochemical experiments utilizing WO₃-modified and bare (unmodified) PtSn nanoparticles in acid medium (0.5 mol dm⁻³ H₂SO₄) at room temperature in the presence of ethanol. It is noteworthy that, the chronoamperometric electrocatalytic currents measured at potentials as low as 0.3 V (vs. RHE) were significantly larger for WO₃-modified PtSn/C relative to bare PtSn/C. In another diagnostic “stripping” experiment, it was found that oxidation of CO-adsorbate occurred in the presence of WO₃ at potentials almost 100 mV lower in comparison to the unmodified system. The overall activation effect may have origin in interactions of tungsten oxide with tin (from PtSn alloy nanoparticles) leading to stabilization of the catalytic tin oxo species. WO₃ may also provide large population of reactive oxo groups at the Pt/Sn-based electrocatalytic interface.