Improved iron oxide oxygen carriers for chemical looping hydrogen generation using colloidal crystal templated method

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 Fe₂O₃/CeO₂ 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 H₂-temperature programmed reduction (H₂-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 H₂ yield and the redox stability for the oxygen carrier prepared by CCT were higher than those by co-precipitation and sol-gel methods. The H₂ 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 Fe₂O₃ and CeO₂ before and after redox cycles were the smallest for the CCT oxygen carrier from XRD patterns. In addition, H₂-TPR demonstrated that CCT oxygen carrier exhibited the highest reactivity.     

Enhanced sintering resistance of Fe2O3/CeO2 oxygen carrier for chemical looping hydrogen generation using core-shell structure

CeO₂-supported Fe₂O₃ is a satisfactory oxygen carrier for chemical looping hydrogen generation (CLHG). However, the sintering problem restrains its further improvement on redox reactivity and stability. In the present work, a core-shell-structured Fe₂O₃/CeO₂ (labeled Fe₂O₃@CeO₂) oxygen carrier prepared by the sol-gel method was studied in a fixed bed. The effect of the core-shell structure on the sintering resistance and redox performance was investigated with a homogenous composite sample of Fe₂O₃/CeO₂ as a reference. The results showed that the Fe₂O₃@CeO₂ exhibited much higher redox reactivity and stability than the Fe₂O₃/CeO₂ with no CO or CO₂ observed in the generated hydrogen, while the hydrogen yield for Fe₂O₃/CeO₂ decreased with redox cycles due to serious sintering. The satisfactory performance of Fe₂O₃@CeO₂ can be ascribed to its high sintering resistance, since the core-shell structure suppressed the outward migration of Fe cations from the bulk to the surface of the particles. On the other hand, the migration of Fe cations and their subsequent enrichment on the particle surface led to the serious sintering of Fe₂O₃/CeO₂. The crystallite size evolution of Fe₂O₃ and CeO₂ in redox cycles further demonstrated the higher sintering resistance of Fe₂O₃@CeO₂. Further, the particle size distribution (PSD) results indicated the agglomeration of Fe₂O₃/CeO₂ after cycles. In addition, the CeO₂ shell could facilitate the transport of oxygen ions between the iron oxide nanoparticle core and the shell surface. Therefore, the coating of nanoscale Fe₂O₃ with a CeO₂ shell did not reduce the redox reactivity and stability of Fe₂O₃@CeO₂, but rather promoted it, though less oxygen-ionic-conductive CeFeO₃ was generated.     

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.     

Enhanced performance of hematite oxygen carrier by CeO2 for chemical looping hydrogen generation

Natural hematite is a promising oxygen carrier for chemical looping hydrogen generation (CLHG) owing to its abundance and low price. However, the reactivity of hematite is poor compared with the artificial oxygen carriers. To solve this problem, modified hematite with different CeO₂ loading amounts were prepared, and the redox reactivity, cyclic stability, sintering and carbon deposition resistance were investigated with the original hematite (0%CeO₂) as the control group. It was found that the CeO₂-modified hematite presented far higher H₂ yield and purity than 0%CeO₂, and the hematite with CeO₂ loading amount of 20 wt % (20%CeO₂) displayed the highest reactivity, carbon deposition resistance, and satisfactory cyclic stability. The H₂ yield of 20%CeO₂ was 110% higher than that of 0%CeO₂, and the H₂ purity of the former was 99.71% vs 98.36% for the latter. The desirable performance of 20%CeO₂ could be ascribed to the promotion effects of CeO₂ on the lattice oxygen mobility. Specifically, the cubic fluorite CeO₂ and the generated perovskite CeFeO₃ provided channels for the lattice oxygen transport, enhancing the redox reactivity. The CeO₂ modification could also inhibit the Fe outward migration to particle surface and thus increase the sintering resistance. The generation of cerium silicate could be inimical to the oxygen mobility, however, it could restrain the growth of CeO₂ crystallite. Moreover, the interaction between CeO₂ and Fe₂O₃ could decrease their crystallite sizes and further promote the sintering resistance.     

Chemical looping glycerol reforming for hydrogen production by Ni@ZrO2 nanocomposite oxygen carriers

The research describes the synthesis of nanocomposite Ni@ZrO₂ oxygen carriers (OCs) and lanthanide doping effect on maintaining the platelet-structure of the nanocomposite OCs. The prepared OCs were tested in chemical looping reforming of glycerol (CLR) process and sorption enhanced chemical looping reforming of glycerol (SE-CLR) process. A series of characterization techniques including N₂ adsorption-desorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution transmission electron microscopy (HRTEM), H₂ temperature-programmed reduction (H₂-TPR), H₂ pulse chemisorption and O₂ temperature-programmed desorption (O₂-TPD) were used to investigate the physical properties of the fresh and used OCs. The results show that the platelet-stack structure of nanocomposite OCs could significantly improve the metal support interaction (MSI), thus enhancing the sintering resistance. The effect of lanthanide promotion on maintaining this platelet-stack structure increased with the lanthanide radius, namely, La³⁺ > Ce³⁺ > Pr³⁺ > Yb³⁺. Additionally, the oxygen mobility was also enhanced because of the coordination of oxygen transfer channel size by doping small radius lanthanide ions. The CeNi@ZrO₂ showed a moderate ‘dead time’ of 220 s, a high H₂ selectivity of 94% and a nearly complete glycerol conversion throughout a 50-cycle CLR test. In a 50-cycle SE-CLR stability test, the CeNi@ZrO₂CaO showed high H₂ purity of 96.3%, and an average CaCO₃ decomposition percentage of 53% without external heating was achieved.     

Sulfur behavior in chemical looping combustion with NiO/Al2O3 oxygen carrier

Chemical looping combustion (CLC) is a novel technology where CO₂ is inherently separated during combustion. Due to the existence of sulfur contaminants in the fossil fuels, the gaseous products of sulfur species and the interaction of sulfur contaminants with oxygen carrier are a big concern in the CLC practice. The reactivity of NiO/Al₂O₃ oxygen carrier reduction with a gas mixture of CO/H₂ and H₂S is investigated by means of a thermogravimetric analyzer (TGA) and Fourier Transform Infrared spectrum analyzer in this study. An X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM) are used to evaluate the phase characterization of reacted oxygen carrier, and the formation mechanisms of the gaseous products of sulfur species are elucidated in the process of chemical looping combustion with a gaseous fuel containing hydrogen sulfide. The results show that the rate of NiO reduction with H₂S is higher than the one with CO. There are only Ni and Ni₃S₂ phases of nickel species in the fully reduced oxygen carrier, and no evidence for the existence of NiS or NiS₂. The formation of Ni₃S₂ is completely reversible during the process of oxygen carrier redox. A liquid phase sintering on the external surface of reduced oxygen carriers is mainly attributed to the production of the low melting of Ni₃S₂ in the nickel-based oxygen carrier reduction with a gaseous fuel containing H₂S. Due to the sintering of metallic nickel grains on the external surface of the reduced oxygen carrier, further reaction of the oxygen carrier with H₂S is constrained, and there is no increase of the sulfidation index of the reduced oxygen carrier with the cyclical reduction number. Also, a continuous operation with a syngas of carbon monoxide and hydrogen containing H₂S is carried out in a 1 kW_th CLC prototype based on the nickel-based oxygen carrier, and the effect of the fuel reactor temperature on the release of gaseous products of sulfur species is investigated.     

Modified CeO2 as active support for iron oxides to enhance chemical looping hydrogen generation performance

Chemical looping hydrogen generation (CLG) is a promising pathway that can offer both the high purity hydrogen as well as the efficient CO₂ capture capability. However, this process was significantly hindered by the lack of active oxygen carriers at relatively low temperatures. Mixed ionic-electronic (MIEC) supported iron oxides exhibit desirable redox performance for the improved oxygen-ion conductivity. In this work, we prepared several A_xCe_1-xO_2-δ (A = Gd, La; x = 0, 0.1, 0.3) supported Fe₂O₃ for hydrogen production at 750 °C. It was shown that Fe₂O₃/Gd_0.3Ce_0.7O_2-δ shows the highest hydrogen generation performance and stability over 50 redox cycles. The reactivity follows the sequence of: Fe₂O₃/Gd_0.3Ce_0.7O_2-δ > Fe₂O₃/La_0.1Ce_0.9O_2-δ > Fe₂O₃/Gd_0.1Ce_0.9O_2-δ > Fe₂O₃/La_0.3Ce_0.7O_2-δ. The fundamental investigation shows that the doping of rare earth (Gd, La) into CeO₂ contributes to the formation of oxygen vacancies, thus improving the lattice oxygen diffusion. The enhanced hydrogen generation performance attributes to the high lattice oxygen diffusion to improve the reactivity and inhibiting outward diffusion of Fe. The roughly linear relation between the oxygen vacancy concentration and chemical looping performance can be extended to predict the performance of oxygen carriers for other chemical looping applications, methane reforming, combustion, and ethane dehydrogenation, etc.     

Research of coal-direct chemical looping hydrogen generation with iron-based oxygen carrier modified by potassium

Coal-direct chemical looping hydrogen generation (CLHG) is a promising process for hydrogen production with high coal conversion efficiency and low carbon footprint. In this work, experiments on coal-direct CLHG process were carried out using K₂CO₃ modified Fe₂O₃/ZrO₂ as oxygen carrier (OC) and Shenmu (SM) char as fuel in a fixed-bed reactor. The effect of char/OC mass ratio on CO₂/CO volume ratio, H₂ production and phase transformation was investigated. Multicycle tests with SM char and deashed SM char were conducted to investigate the activity stability of OC and the reason for the deactivation of OC. The results confirm the feasibility of coal-direct CLHG process. Higher char/OC mass ratio could enhance the H₂ production and decrease the CO₂/CO volume ratio and oxidation state of iron oxides in OC. In the multicycle tests with SM char, carbon conversion and H₂ production remained almost constant during the first 2 redox cycles and then decreased abruptly in the 3rd cycle. During the 3 cycles, the phases of OC residues remained unchanged and no detectable surface sintering was observed. Furthermore, the K contents of residues decreased slightly. In the multicycle tests with deashed SM char, the carbon conversion and accumulation H₂ production were stable during the first 10 cycles and then decreased slowly. Some morphology features changes appeared during the 11 cycles, but no obvious surface sintering was observed. The K contents of residues declined by 2/3 after the 10th cycle.     

N-desorption or NH3 generation of TiO2-loaded Al-based nitrogen carrier during chemical looping ammonia generation technology

As a terrific hydrogen carrier, NH₃ can be wildly used as non-carbon gas fuel in energy area, because NH₃ can store a high density of H₂ and can be liquefied easily in ambient temperature and pressure. Chemical Looping Ammonia Generation (CLAG) is known to be a novel, efficient and environmentally friendly synthesis method for ammonia, in which the N-sorption/desorption of nitrogen carrier are included. The N-sorption step, which is known as the carbothermal reduction, is well studied while there are few reports on N-desorption step. Therefore, in this paper, stationary bed reactor and thermo-gravimetric analyzer (TGA) were used to study the N-desorption performance of the TiO₂-loaded Al-based N-carrier and the corresponding NH₃ generation during the N-desorption reaction. The results showed that, TiO₂ performed a good catalytic effect on the N-desorption reaction, which is due to the good dissociative adsorption performance of H₂O on TiO₂ surface, and the released hydroxyl (OH) plays an important role in the N-desorption reaction. The conversion amount of aluminum nitride and the yield of NH₃ increased with the TiO₂ loading in the reactants, the reaction temperatures and the steam concentrations in the atmosphere, while the conversion efficiency of NH₃, which is significantly affected by temperature, didn't affected by the TiO₂ loadings.     

Synergistic effects of binary oxygen carriers during chemical looping hydrogen production

The use of binary oxygen carrier allows for the materials of enhanced activity or stability during chemical looping process. However, the lack of mechanical understanding of the origin of the improvements hindered the rational design and control of the doping process in the oxygen carrier production. Here, we synthesized a series of M_0.6Fe_2.4O_y (M = Ni, Cu, Co, Mn) binary spinel materials and carried out various characterization techniques to study how the dopants influenced the material phase change, the oxygen transfer as well as the chemical looping performance. The results showed the chemical looping reactivity can be related to the oxygen transformation between lattice oxygen and oxygen vacancy, which was determined by the redox properties of both dopants and iron. The metal in tetrahedral site for Cu, Mn, Ni-doped sample were relatively stable, limiting oxygen transformation ability. In comparison, Co dopant promoted the reducibility of iron in tetrahedral site as well as metals in other sites, making almost all lattice oxygen rapidly transformed to oxygen vacancy during reduction. This was the main cause for the subsequent high hydrogen production rate (average ∼0.02 mmol. g⁻¹.s⁻¹) and yield (∼15.9 mmol.g⁻¹). Upon cycling, the phase separation of single oxides from Co_0.6Fe_2.4O_y and Mn_0.6Fe_2.4O_y spinels led to the decreased ability of oxygen transformation. However, the performance was extremely stable for Cu_0.6Fe_2.4O_y with reversible phase change between spinel and (Fe, Cu) wusitite by the Cu-Fe interaction. Based on the current results, this work points to a promising Cu-Co co-doping material with both good reactivity and stability.     

Nickel-iron modified natural ore oxygen carriers for chemical looping steam methane reforming to produce hydrogen

Chemical looping steam methane reforming (CL-SMR) is a promising and efficient method to produce hydrogen and syngas. However, oxygen carrier (OC) prepared by synthesis are complex, expensive and poor mechanical performance, while natural ore OCs are low activity and poor selectivity. In order to avoid these problems, Ni/Fe modification of natural ores were proposed to improve the reactivity and stability of OC to CL-SMR. The results indicated that the modified calcite recombined and improved the structural phase during the reaction, enhancing performance and inhibiting agglomeration. Moreover, high ratio of iron to nickel was easy to sinter and decline the OC performance. In addition, with the increase of steam flow, both CH₄ conversion and carbon deposition decreased. Thereinto, the highest H₂ concentration, CH₄ conversion efficiency and H₂ yield were obtained when the ratio of steam to OC was 0.05. Furthermore, CH₄ flow rate had a great impact on CL-SMR performance. When the ratio of CH₄ to OC was 0.04, it achieved the highest CH₄ conversion efficiency of 98.96%, the highest H₂ concentration of 98.83% and the lowest carbon deposition of 3.23%. However, the carbon deposition increased with the increase of CH₄ flow rate. After a long-time chemical looping process, the Ni/Fe modified calcite showed a consistently stable performance with average H₂ concentration of 93.08%, CH₄ conversion efficiency of 88.03%, and carbon deposition of 2.15%.     

Double perovskite (La2-xCa-Bax)NiO4 oxygen carriers for chemical looping reforming applications

Double perovskites La_2-xNiO_4-δ doped with Ca and Ba were synthesized via microwave-assisted combustion method and studied as an alternative oxygen carrier (OC) for chemical looping reforming processes (CLR). The OCs, La₂NiO₄, La_1.8Ca_0.2NiO₄, La_1.8Ba_0.2NiO₄ and La_1.8Ca_0.1Ba_0.1NiO₄ were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature-programmed reduction and oxidation (TPR/TPO) and cyclic thermogravimetric analysis (TGA). Rietveld's refinement, performed after each redox cycle, confirmed that doping allows smaller amounts of nickel to migrate from the perovskite structure. The double perovskites synthesized for the chemical looping reforming process behave as simple nickel oxide and are considered as alternative oxygen carriers to solve the problems of deactivation due to the interaction of NiO with the support. The Ca-doped OC (La_1.8Ca_0.2NiO₄) showed lower NiO concentration outside the structure and smaller crystallite size after the redox cycles, which was associated with a change in the crystal structure, presenting superior performance and stability. The results show that all perovskites have high reactivity in both reduction and oxidation reactions, however the perovskites were not able to uncouple oxygen, which is an unsual behavior for perovskites.     

Gd,La co-doped CeO2 as an active support for Fe2O3 to enhance hydrogen generation via chemical looping water gas shift

Support materials are indispensable to promote the durability of iron oxides for chemical looping applications. However, the dilution effect of supports on the active phase would lead to decreased bulk oxygen conduction, thus leading to compromised activity. Here, we propose several Gd³⁺, La³⁺ and Nd³⁺ doped CeO₂ as active supports for iron oxides and investigate the support effect to improve hydrogen generation via chemical looping water gas shift. The characterizations show that the dopants improve the oxygen vacancy concentration in the CeO₂ lattice and Fe₂O₃/Ce_0.8Gd_0.1La_0.1O_2-δ exhibits the most oxygen vacancy concentration among all the oxygen carriers. Pulse reactions of oxygen carriers show that an abundance of oxygen vacancy concentration can promote the lattice oxygen transfer in bulk, thus contributing to improved redox reactions. The high oxygen conductivity mitigates the dilution effect on the active phase. Therefore, Fe₂O₃/Ce_0.8Gd_0.1La_0.1O_2-δ shows the highest hydrogen yield (～9.49 mmol^?1.g^?1) and hydrogen generation rate (～0.632 mmol.g^?1.min^?1) with only a slight decrease at 650 °C over 100 cycles. Overall, this work highlights the influence of support properties on the redox reactivity of iron oxides for chemical looping applications.     

Thermodynamic screening of suitable oxygen carriers for a three reactor chemical looping reforming system

Hydrogen (H₂) production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative process which utilizes fossil fuels as feed stocks. This process occurs in three steps by employing an oxygen carrier (OC), which is generally a transition metal. As the OC plays an important role, its selection should be done after carefully considering the chemical and physical properties of the material. In this study, various candidate materials for use in a TRCLR process, with methane (CH₄) as a fuel stock, were investigated. The results show that the iron (Fe)- and molybdenum (Mo)-based OCs oxidize CH₄ completely in the FR at low temperatures. In terms of H₂ yield, tungsten (W)-based OCs produce the highest yield, ～3.9 mol-H₂/mol-CH₄. The equilibrium oxygen partial pressures and the solid circulation rates are the highest for Fe-based OCs. The oxygen carrying capacity of Fe-based OCs is relatively high while its price is low. Therefore, among the OCs investigated, Fe-based OCs were identified as the preferred OC option for a TRCLR process.     

Performance of hydrogen and power co-generation system based on chemical looping hydrogen generation of coal

An integrated hydrogen and power co-generation system based on slurry-feed coal gasification and chemical looping hydrogen generation (CLH) was proposed with Shenhua coal as fuel and Fe₂O₃/MgAl₂O₄ as an oxygen carrier. The sensitivity analyses of the main units of the system were carried out respectively to optimize the parameters. The syngas can be converted completely in the fuel reactor, and both of the fuel reactor and steam reactor can maintain heat balance. The purity of hydrogen produced after water condensation is 100%. The energy and exergy analyses of the proposed system were studied. Pinch technology was adopted to get a reasonable design of the heat transfer network, and it is found pinch point appears at the hot side temperature of 224.7 °C. At the given status of the proposed system, the hydrogen yield is 1040.11 kg·h⁻¹ and the CO₂ capture rate is 94.56%. At the same time, its energy and exergy efficiencies are 46.21% and 47.22%, respectively. According to exergy analysis, the degree of exergy destruction is ranked. The gasifier unit has the most serious exergy destruction, followed by chemical looping hydrogen generation unit and the heat recovery steam generator unit.     

Interaction of yttria stabilized zirconia electrolyte with Fe2O3 and Cr2O3

Yttria stabilized zirconia electrolytes were sintered with addition of iron oxide or chromium oxide. The phase composition of the composites, sintering properties and DC and AC electrical properties are evaluated and compared with available data. Results show, that after sintering there is only single-phase material found in the XRD patterns. Iron can be considered as a sintering promoter while chromium decreases the apparently sintering process. Addition of either oxide decreases total electrical conductivity in comparison to pure samples. Based on impedance spectra it can be concluded that chromium mainly influences electrical conductivity of grain boundary, while iron influences electrical conductivity of both grain and grain boundary, with a solubility limit at grain boundaries estimated at about 2 mol% Fe.     

Clean hydrogen production and electricity from coal via chemical looping: Identifying a suitable operating regime

In this paper, a chemical looping combustion (CLC) system, using haematite (Fe₂O₃) as an oxygen carrier, has been simulated in conjunction with a steam–coal gasification process. The analysis has assumed thermodynamic equilibrium throughout. Full heat integration was considered for a range of operating conditions (e.g. by varying oxygen carrier recycle rate). It was found that for low to moderate flows of oxidising steam, it was possible to operate within a regime which could be fully heat-integrated. Furthermore, the size of this operating regime increases with the recycle rate of oxygen carrier. The peak exergetic efficiencies achieved for fully heat-integrated systems were 48.4% and 58.3% at operating pressures of 1 atmosphere and 10 atmospheres respectively, and these were increased respectively to 53.7% and 59.7% when a bottoming steam turbine cycle was included to utilise waste heat. These values compare favourably with those achieved by hydrogen production via steam reformation of methane. The range of suitable operating conditions available at both pressures was encouraging, and showed considerable promise for the successful coupling of a chemical looping system with a gasifier.     

Effect of copper dopant on the mixed cobalt-iron oxides for hydrogen generation via chemical looping redox cycles

The long-term stability of oxygen carriers can be significantly improved by operating chemical looping at mild conditions, enabling the potential for large-scale applications. However, the diminished temperature has a detrimental effect on the kinetics, resulting in the decreased chemical looping performance. Although doping of noble metals can promote the performance of oxygen carriers at mid-temperatures, the high cost significantly impeded the scalable use of these oxygen carriers. Here we report the use of copper to dope mixed cobalt-iron oxides as oxygen carriers for hydrogen generation via chemical looping redox cycles. Cu_0.25Co_0.75Fe₂O₄ shows satisfactory hydrogen yield (~9.39 mmol g⁻¹) and average hydrogen generation rate (~0.47 mmol g⁻¹ min⁻¹) with high stability over 20 redox cycles at 550 °C. The characterizations substantiate that the improved performance is a consequence of Cu to enhance the oxygen-ion conductivity through the bulk and promote the reactivity of the oxygen carriers with reactant gases on the surface. The performance of the samples in this work is comparable to those contains noble metals.     

Chemical looping reforming of ethanol-containing organic wastewater for high ratio H2/CO syngas with iron-based oxygen carrier

This work focused on chemical looping reforming (CLR) of ethanol-containing wastewater using iron-based oxygen carrier for high ratio H₂/CO syngas. Effects of various operating parameters on CLR experiments have been investigated. High temperature promotes the reactivity of oxygen carrier and release more lattice oxygen for CLR of ethanol-containing wastewater to realize maximum carbon conversion. 5% ethanol-containing wastewater, closed to the actual concentration of alcohol distillery wastewater, favors syngas yield. Ethanol-containing wastewater CLR processes could be divided into three stages, including the catalytic cracking, combination of catalytic cracking and reforming, and mainly catalytic reforming of ethanol, corresponding to three reduction periods Fe₂O₃ → Fe₃O₄, Fe₃O₄ → Fe₂O_2.45, and Fe₂O_2.45 → FeO, respectively. The whole process of ethanol-containing organic wastewater CLR is exothermic. Reaction heat released from the oxidation process of the reduced oxygen carrier can meet heat demand for CLR process. Ethanol-containing organic wastewater CLR opens up a new direction for hydrogen generation and waste treatment.     

Nanostructured Zn-Fe2O3 thin film modified by Fe-TiO2 for photoelectrochemical generation of hydrogen

Nanostructured semiconductor thin films of Zn-Fe₂O₃ modified with underlying layer of Fe-TiO₂ have been synthesized and studied as photoelectrode in photoelectrochemical (PEC) cell for generation of hydrogen through water splitting. The Zn-Fe₂O₃ thin film photoelectrodes were designed for best performance by tailoring thickness of the Fe-TiO₂ film. A maximum photocurrent density of 748 μA/cm² at 0.95 V/SCE and solar to hydrogen conversion efficiency of 0.47% was observed for 0.89 μm thick modified photoelectrode in 1 M NaOH as electrolyte and under 1.5 AM solar simulator. To analyse the PEC results the films were characterized for various physical and semiconducting properties using XRD, SEM, EDX and UV–Visible spectrophotometer. Zn-Fe₂O₃ thin films modified with Fe-TiO₂ exhibited improved visible light absorption. A noticeable change in surface morphology of the modified Zn-Fe₂O₃ film was observed as compared to the pristine Zn-Fe₂O₃ film. Flatband potential values calculated from Mott–Schottky curves also supported the PEC response.