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Copper-promoted iron oxides are commonly utilized in high-temperature water-gas shift (WGS) reactions. Although the promotional effect of Cu has been previously documented, the nature of the active sites for Cu/Fe 3 O 4 remains debated and the role of the crystallite size of Fe 3 O 4 has not been tackled. In this study, a wide range of Cu/Fe 3 O 4 catalysts were designed by hosting Cu species onto Fe 3 O 4 of two contrasting crystallite sizes (approximately 10 and 160 nm) and by utilizing different preparation methods (ammonia evaporation and deposition-precipitation). The evaluation of their catalytic WGS performances revealed a remarkable and previously undocumented phenomenon: the addition of Cu resulted in universal activity enhancements only for small Fe 3 O 4 crystals, while the larger analogues displayed decreased activity. This peculiar phenomenon can be explained by the creation of Cu–Fe 3 O 4 interfaces present in the iron oxides of small crystallite sizes. Thorough characterizations, such as advanced electron microscopic, in situ powder X-ray diffractions, in situ diffuse reflectance infrared Fourier transform spectroscopy, and computational studies, suggest strong electronic interactions between the different metal species, facilitated reductions of the individual oxides, and more favorable CO activation at the interfacial sites, all accounting for the promoted activity. [Display omitted] • Influence of Fe 3 O 4 crystallite size in water-gas shift reaction was examined. • Performance of Cu/Fe 3 O 4 in water-gas shift reaction was studied. • The formation of Cu–Fe 3 O 4 interfaces existed on small Fe 3 O 4 crystals. • Promotional effect of Cu was only found on small Fe 3 O 4 crystals. [ABSTRACT FROM AUTHOR]

This work designed a mesoscale method of multi-step reduction of Fe 2 O 3 with H 2 based on Lattice Gas Cellular Automata (LGCA). Particles in the LGCA were marked to distinguish all the reactants, intermediates, products, and inert. A self-organized evolutionary mechanism is designed. The hydrogen reduction of Fe 2 O 3 in the temperature range of 460–550 °C and 650–800 °C was simulated. Results show that the intermediate product Fe 3 O 4 was found in both conditions, and its mass fraction quickly reach a peak at ∼0.8 and gradually decrease thereafter. An "induction period" can be identified in the initial stage of the reaction at 650–800 °C, where the reduction rate is slow due to the hindered formation of FeO. The porosity inside the Fe 2 O 3 particles increases continuously through the reduction process, resulting in significant changes in the flow field around the particles. Consequently, the wake vortex gradually decreases and disappears eventually. • The multiple step reduction of Fe 2 O 3 by hydrogen is investigated in mesoscale. • A mesoscale method with self-organized evolutionary mechanism is developed. • Three obvious reaction rate transitions can be identified at 650–800 °C by the method. • The flow field is altered from internal structural of Fe 2 O 3 changes during reduction. [ABSTRACT FROM AUTHOR]

The utilization of nanoparticles to enhance bacterial activity and boost hydrogen production in fermentation processes has gained significant attention due to their unique properties such as high specific surface area and quantum size. This research aimed to improve the biohydrogen yield from food waste by adding iron oxide nanoparticles (Fe 3 O 4) at various concentrations (50, 75, 100, 150, and 200 mg/l) and titanium dioxide (TiO 2) at different amounts (25–150 mg/l) to a single-stage hybrid (dark/photo) fermentation reactor. After obtaining the optimal amount of these two nanoparticles, the effect of synergic addition of nanoparticles on hydrogen production yield, was investigated at ratios of Fe 3 O 4 /TiO 2 = 50/50 and 100/50 mg/mg. At the ratio of Fe 3 O 4 /TiO 2 = 100/50, the cumulative hydrogen production and yield of hydrogen have increased from 1613 to 3392 ml and 101.60 to 213.66 mlH 2 /gVS, respectively, compared to the control experiment. We also found that the COD removal rate has enhanced from 28% to 40.1%. In the optimal value, the bacterial growth lag phase has also remarkably decreased from 8.19 to 4.81 h. • Synergic application of TiO 2 and Fe 3 O 4 significantly increased biohydrogen purity and production yield. • TiO 2 played an important role in the activity of bacteria in the photo fermentation process. • Fe 3 O 4 played an important role in the dark fermentation system. • Nanoparticles may act as a scaffold for enzyme and substrate binding. • Optimal nanoparticle concentration may differ for different bioreactors. [ABSTRACT FROM AUTHOR]

Chemical Looping Hydrogen (CLH) allows the direct production of pure hydrogen exploiting the redox properties of Fe, with high flexibility on the type of reductant used. In this work, a highly pure hydrogen stream suitable for the direct use into Proton Exchange membrane Fuel Cells was produced, using bioethanol as renewable fuel. The influence of both redox temperature (675°C–750 °C) and chemical composition of the Fe-based particles (2 wt% and 40 wt% of alumina added) on the carbon formation rate during reduction step was also deeply analyzed. Al 2 O 3 changed both Fe x O y redox kinetics and equilibrium phases, leading to a complete iron deactivation at high Al 2 O 3 concentration. The addition of an air oxidation step (3 steps CLH) is fundamental to restore the redox activity, with a constant efficiency of about 30% at 750 °C for 10 cycles. Furthermore, Al 2 O 3 promotes the ethanol conversion into carbon, undermining the hydrogen purity. [Display omitted] • Pure H 2 suitable for PEMFCs is obtained using bioethanol as renewable fuel. • The influence of Fe/Al interaction on H 2 yields and H 2 purity was studied. • 3 steps CLH allows the use of Fe 2 O 3 -40 wt% Al 2 O 3 with no reduction in performance. • Fe 2 O 3 -2 wt% Al 2 O 3 withstands 10 redox cycles in the temperature range 675–750 °C. • A process efficiency of 30% was achieved at 750 °C for 10 consecutive redox cycles. [ABSTRACT FROM AUTHOR]

Fe 2-x Sn x O 3 structures grown by RF-DC magnetron co-sputtering. The band gap of Fe 2 O 3 , SnO 2 , Fe 2-x Sn x O 3 structure was calculated as 2.86, 4.06, 2.77 eV, respectively. The Fe 2 O 3 thin film has shown a tetragonal as well as the SnO 2 structure, however, the Fe 2-x Sn x O 3 (0 < x < 1) has shown rhombohedral structure. XPS measurements have shown change in binding energy which is due to the electron exchange of tin-iron with oxygen, and iron - tin oxide structure. This binding energy increases slightly with the chemical environment effect. The films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM). In AFM images was seen that the iron oxide structure was pyramidal and the tin oxide structure was spherical, similar to the SEM image. The response of the film to hydrogen gas was measured at flow values of 100, 500 and 1000 ppm at 300 °C. Fe 2 O 3 thin films show 46%, SnO 2 61% and, Fe 2-x Sn x O 3 6.5% response to 1000 ppm H 2 gas. It is seen that the gas sensor response was affected by the morphological and structural features of the grown film. Current vs. time graph for thin films gas sensor. [Display omitted] • Thin films were successfully grown by RF-DC co-sputtering system. • Metal oxide hydrogen gas sensor devices were measured depending on different grown structures. • Fe 2 O 3 , SnO 2 , Fe 2-x Sn x O 3 thin films show 46%, 61%, 6.5% response to 1000 ppm H 2 gas. • Iron oxide and tin oxide have n-type carrier, while iron tin oxide has p-type carrier. [ABSTRACT FROM AUTHOR]

Materials composed of various constituents with distinct physical or chemical features are named composites. Merging components in the composite structure leads to new properties creation or the intrinsic properties magnification of the components, or synergetic effects. Here, the ternary nanocomposite of copper, nickel, and iron oxides was electrodeposited on the glassy carbon electrode (GCE) surface to facilitate the ethanol electro-oxidation reaction (EOR) and overcome the electrode fouling problem while prolonging its efficiency. The GCEs were modified by three different procedures and activated by CV cycling in an alkaline solution, and their electro-catalytic activity was tested toward EOR. The ternary electrocatalysts prepared by two-steps electrodeposition of their components (Ni,Fe 2 O 3 /Cu and Cu/Ni,Fe 2 O 3) demonstrated higher peak current and more negative peak potential (E pa = 476 mV, I pa = 492 μA, and E pa = 510 mV, I pa = 644 μA, respectively) than the binary electrocatalyst of Ni,Fe 2 O 3 toward EOR. The best electro-catalytic efficiency was acquired for the simultaneous electrodeposition of nano Cu, Ni, and Fe 2 O 3 on the GCE surface (Cu,Ni,Fe 2 O 3 , E pa = 530 mV, I pa = 3179 μA). The physicochemical and electro-catalytic characterizations of the fabricated electrocatalysts were evaluated by various techniques. The fast and facile engineered design of the GCE modification with the ternary Cu,Ni,Fe 2 O 3 components led to a high current density of about 101 mA/cm2 with increased tolerance against poisoning intermediates resulting in longtime stability for EOR in alkaline media. The synergistic effect between nano Ni, Cu, and Fe oxides provided promising properties for the EOR pursuing the construction of a powerful device with commercialization potential. • On-step electrodeposition of Cu,Ni,Fe 2 O 3 ternary nano-composite • Improvement of the electron transfer kinetic of EOR • High tolerance against poisoning intermediates and longtime stability for EOR • Promising electro-catalytic performance of Cu,Ni,Fe 2 O 3 /GCE for EOR • Achievement of a high current density of ∼101 mA/cm2 for EOR [ABSTRACT FROM AUTHOR]

Solar redox reforming is a process that uses solar radiation to drive the production of syngas from natural gas. This approach caught attention in recent years, because of substantially lower reduction temperatures compared to other redox cycles. However, a detailed and profound comparison to conventional solar reforming has yet to be performed. We investigate a two-step redox cycle with iron oxide and ceria as candidates for redox materials. Process simulations were performed to study both steam and dry methane reforming. Conventional solar reforming of methane without a redox cycle, i.e. on an established catalyst was used as reference. We found the highest efficiency of a redox cycle to be that of steam methane reforming with iron oxide. Here the solar-to-fuel efficiency is 43.5% at an oxidation temperature of 873 K, a reduction temperature of 1190 K, a pressure of 3 MPa and a solar heat flux of 1000 kW/m2. In terms of efficiency, this process appears to be competitive with the reference process. In addition, production of high purity H 2 or CO is a benefit, which redox reforming has over the conventional approach. • Solar redox reforming and solar conventional reforming are simulated. • Iron oxide and ceria-based redox cycles are compared. • Efficiency and product quality are evaluated. • Impact of solar flux and solid-solid heat recovery is analyzed. [ABSTRACT FROM AUTHOR]

ReaxFF molecular dynamics simulation has been employed to investigate the iron oxide-catalyzed supercritical water gasification (SCWG) of naphthalene (NAP), a common component of refractory polycyclic aromatic hydrocarbons. Simulation results showed that synergistic effects between SCW and iron oxide catalyst enormously promoted the degradation of NAP and the production of H 2 and CO. During the gasification process, SCW served not only as H source for H 2 generation but also as O source for CO generation and lattice oxygen recompense, while the major roles of iron oxide catalyst were to provide lattice oxygen with high hydrogen-abstraction ability, catalyze SCW to produce more active species, and weaken the C–C bonds. The effects of different parameters were subsequently revealed: increasing the use of H 2 O molecules raised H 2 and CO yields along with the lattice oxygen supplement but slowed the rate of CO generation, high hydrogen recovery was achieved at high NAP concentration accompanied by a low carbon gasification efficiency. Our simulated results further demonstrated that the deactivation of iron oxide catalyst was caused by carbon deposition, lattice oxygen exhaustion and iron loss. SCW media effectively inhibited the iron loss, while calcination in O 2 environment could successfully regenerate the iron oxide catalyst by cleaning up the carbon deposition and replenishing the lattice oxygen. Image 1 • SCW served not only as H source but also as O source. • Iron oxide provided lattice oxygen, catalyze SCW and C–C breaking. • Carbon deposition, lattice oxygen and iron loss caused catalyst deactivation. • Catalyst regeneration mechanism in O 2 environment was also revealed. [ABSTRACT FROM AUTHOR]

Iron oxide has been widely studied in chemical looping hydrogen generation (CLHG) process as an oxygen carrier, but fast decline of its activity in redox cycles due to sintering and agglomeration is one of the main drawbacks. In this work, the colloidal crystal templated (CCT) method was applied to synthesize Fe 2 O 3 /CeO 2 oxygen carrier and the mole ratio of Fe/Ce was 8:2, aiming to inhibit adjacent grains from agglomerating and improve the contact between the fuel gas and the oxygen carrier. The redox performances were evaluated with CO as fuel in a batch fixed bed reactor for 20 redox cycles, with oxygen carriers prepared by co-precipitation (CP) and sol-gel (SG) methods as references. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), and H 2 -temperature programmed reduction (H 2 -TPR) were used for characterization. The results showed that the calcination temperature lower than 750 °C was suitable for the CCT. The redox experiments showed that the H 2 yield and the redox stability for the oxygen carrier prepared by CCT were higher than those by co-precipitation and sol-gel methods. The H 2 yield of CCT oxygen carrier kept stable from the 3rd cycle and was 8.5 mmol/gOC in the 20th cycle. The pore structures resulting from CCT were different from another two oxygen carriers before and after the cycles, but maintained well through SEM images, leading to high activity and stability during redox cycles. The crystallite sizes of Fe 2 O 3 and CeO 2 before and after redox cycles were the smallest for the CCT oxygen carrier from XRD patterns. In addition, H 2 -TPR demonstrated that CCT oxygen carrier exhibited the highest reactivity. • Colloidal crystal templated (CCT) is desirable for Fe 2 O 3 /CeO 2 preparation in CLHG. • The calcination temperature lower than 750 °C was suitable for the CCT. • The superior performance of CCT oxygen carrier can be ascribed to its pore structure. • The H 2 yield of the CCT oxygen carrier was 8.5 mmol/gOC after 20 cycles. [ABSTRACT FROM AUTHOR]

Abstract: Two typical electrolytes, i.e., 8YSZ (8mol% yttria-stabilized zirconia) and CGO10 (10mol% Gd-doped ceria), with Si contents of ∼30ppm and ≥500ppm were prepared, whose grain-boundary (GB) conductivities should be controlled by intrinsic (space-charge layer) and extrinsic (resistive siliceous films) effects, respectively. 1at% FeO1.5 was loaded into these materials via a conventional mixed-oxide method. A comparative study was carried out to demonstrate how 1at% Fe addition affected these materials with different levels of SiO2 impurities with respect to sintering, GB and GI (grain interior) conductivities. FeO1.5 was found to be a sintering promoter for both 8YSZ and CGO10 ceramics, but it is more effective to enhance the densification of ceria-based electrolytes. A reduction in sintering temperature of ∼200°C for 1at% Fe-doped CGO10 was achieved compared with ∼110°C reduction for the 8YSZ with the same amount of Fe loading. The effect of FeO1.5 loading on the electrical conduction was found to be different, depending significantly on the impurity level and the types of electrolytes. In general, the loading of FeO1.5 is positive for ceria-based ceramics since FeO1.5 has a scavenging effect on SiO2 impurity with little effect on the GI conduction. Although the scavenging behavior of FeO1.5 was also found in the impure 8YSZ, it led to a significant reduction in the GI conductivity. [Copyright &y& Elsevier]

Abstract: Two-step thermochemical water-splitting using monoclinic ZrO2-supported Fe3O4 (Fe3O4/m-ZrO2) for hydrogen production was examined at high thermal reduction temperatures of 1400–1600°C. After thermal reduction of Fe3O4/m-ZrO2, the reduced sample was quenched in liquid nitrogen, and was subsequently subjected to the water-decomposition step at 1000°C. Quenching of the solid sample was conducted for analysis of the chemical reactions, such as phase transitions, occurring at high-temperature. The hydrogen productivity of Fe3O4 on a m-ZrO2 support and the conversion of Fe3O4 to FeO were significantly enhanced with higher thermal reduction temperatures. The Fe3O4-to-FeO conversion reached 60% when the Fe3O4/m-ZrO2 was thermally reduced at 1600°C. The phase transition of m-ZrO2 support to tetragonal ZrO2 (t-ZrO2) did not occur during the thermal reduction at 1400–1500°C, but it did proceed slightly at 1600°C. Fe ions from Fe3O4 did not enter the ZrO2 lattice during high-temperature thermal reduction. Thus, the Fe3O4 loaded on a m-ZrO2 support can continuously contribute as a Fe3O4–FeO redox reactant for thermochemical water-splitting at high-temperatures of 1400–1600°C. [Copyright &y& Elsevier]

Abstract: Stable Cu-doped iron (III) oxide thin film electrodes that exhibit p-type behavior were synthesized by a spray pyrolytic deposition (SPD) method on conducting tin oxide-coated glass substrates for photoelectrochemical water splitting. The highest photocurrent density of was observed under an illumination intensity of for Cu-doped samples prepared using an optimal 0.01155M at an optimal substrate temperature of 395°C with a total spray time of 100s at 0.0V vs. SCE. These Cu-doped p- thin films were found to generate an optimum photoconversion efficiency of 1.3%. X-ray diffraction (XRD) data revealed that these films have mixed structures (- and ). The Cu dopant level in p- was found to be 0.20% from X-ray photoelectron spectroscopic (XPS) data. [Copyright &y& Elsevier]