Oxygen Transport Membranes Research Articles

Recycling of hydrogen tolerant La0.6Ca0.4Co0.2Fe0.8O3–d oxygen transport membranes with integrated life cycle assessment for plasma-assisted CO2-conversion

In this study, a recycling approach was adapted for the hydrogen tolerant La0.6Ca0.4Co0.2Fe0.8O3–d (LCCF_6428) oxygen transport membranes that have great potential in plasma-assisted CO2 conversion techniques for producing industrial fuels such as methanol. The major focus was the incorporation of sustainability measures such as integrating life cycle assessment (LCA) into the materials development at an early stage to study and compare the environmental feasibility of the recycled membrane with the primary membrane. The aim was also to ensure reduced resource depletion of critical raw materials such as cobalt and lanthanum by means of recycling. It consisted of microwave-assisted dissolution of the membrane followed by ultrasonic spray synthesis. The recycled membrane exhibited at least 83 % of the oxygen permeability of the primary membrane and maintained hydrogen tolerance up to 600 °C for 25 h which is a remarkable result for LCCF_6428 in terms of potentially enhancing its life span. As per the LCA, recycling did result in lower resource depletion. However, the recycled LCCF had a higher overall environmental impact compared to the primary LCCF, mainly due to increased electricity consumption during recycling. These results accentuate the need for a transition towards more efficient processes accompanied by cleaner and renewable sources of energy and critically indicate integration of LCA into materials development to establish the sustainability profile of materials.

Computational Fluid Dynamics Modelling of Hydrogen Production via Water Splitting in Oxygen Membrane Reactors.

The utilization of oxygen transport membranes enables the production of high-purity hydrogen by the thermal decomposition of water below 1000 °C. This process is based on a chemical potential gradient across the membrane, which is usually achieved by introducing a reducing gas. Computational fluid dynamics (CFD) can be used to model reactors based on this concept. In this study, a modelling approach for water splitting is presented in which oxygen transport through the membrane acts as the rate-determining process for the overall reaction. This transport step is implemented in the CFD simulation. Both gas compartments are modelled in the simulations. Hydrogen and methane are used as reducing gases. The model is validated using experimental data from the literature and compared with a simplified perfect mixing modelling approach. Although the main focus of this work is to propose an approach to implement the water splitting in CFD simulations, a simulation study was conducted to exemplify how CFD modelling can be utilized in design optimization. Simplified 2-dimensional and rotational symmetric reactor geometries were compared. This study shows that a parallel overflow of the membrane in an elongated reactor is advantageous, as this reduces the back diffusion of the reaction products, which increases the mean driving force for oxygen transport through the membrane.

Effects of lanthanides on the structure and oxygen permeability of Ti-doped dual-phase membranes

The trade-off effect of the oxygen permeability and stability of oxygen transport membranes (OTMs) still exists in working atmospheres containing CO2. Herein, we reported a new series of 60 wt%Ce0.9Ln0.1O2-δ-40 wt%Ln0.6Sr0.4Fe0.9Ti0.1O3-δ (CLnO-LnSFTO, Ln = La, Pr, Nd, Sm, Gd, Tb) dual-phase OTMs by selecting different Ln elements based on the reported highly stable Ti-doped CPrO-PrSFTO. The effects of different Ln elements on the structure and oxygen permeability of Ti-doped dual-phase OTMs were systematically studied. Basically, as the atomic number of Ln elements increases, the unit cell parameters of both the fluorite phase and the perovskite phase become smaller. The unit cell volume and spatial symmetry of the perovskite phase are reduced, resulting in a reduction in oxygen permeability. The optimal CLaO-LaSFTO showed JO2 of 0.60 and 0.54 mL min−1 cm−2 with He and CO2 sweeping at 1000 °C, respectively. In addition, all CLnO-LnSFTO OTMs could work for more than 100 h with no significant performance degradation in a CO2 atmosphere, maintaining excellent stability. This work explores candidate OTM materials for CO2 capture and oxygen separation, as well as provides some ideas for addressing the trade-off effect.

Optimizing oxygen transport properties in Al-substituted La0.5Sr0.5Co0.8Fe0.2-xAlxO3-δ (x = 0–0.20) perovskites

In recent years, there has been a surge in the investigation of perovskite-type complex oxides, with a particular focus on La1-xSrxCo1-yFeyO3, renowned for their exceptional mixed ionic-electronic conducting (MIEC) properties. La0.6Sr0.4Co1-yFeyO3 compositions have prominently emerged in this research domain. The hypothesis of enhancing redox stability and mitigating oxygen variations by incorporating trivalent aluminum (Al3+) into the B-site of perovskite structures has gained attention. In this study, single-phase La0.5Sr0.5Co0.8Fe0.2-xAlxO3-δ (x = 0–0.20) perovskite oxides were synthesized using the solution combustion technique. The physicochemical properties of the synthesized materials were thoroughly characterized, including their morphology, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) analysis, oxygen nonstoichiometry, and electrical transport properties. Results revealed lattice parameter variations associated with oxygen nonstoichiometry and B-site cation size, exhibiting a decline up to x = 0.10 followed by an increase. Al-substitution significantly influenced surface morphology, oxygen nonstoichiometry, and electrical conductivity. Notably, La0.5Sr0.5Co0.8Fe0.1Al0.1O3-δ displayed lower electrical conductivity (676 S cm−1 at 300 °C) among the studied oxides. Oxygen nonstoichiometry had a significant impact on oxygen transport parameters, with these perovskites demonstrating improved chemical diffusion coefficient, Dchem (5.5 × 10-5 cm2 s−1), and the oxygen surface exchange coefficient, Kchem (2.32 × 10-5 cm s−1) at 900 °C, suggesting its potential as an oxygen transport membrane. These findings underscore the promising role of Al-substituted perovskite oxides in various advanced applications.

Exceptional High‐Performance Oxygen Transport Membrane and Comprehensive Study on Mass/Charge Transport Properties

This study focuses on mixed‐conducting perovskite membranes for efficient oxygen supply, aiming to replace energy‐intensive cryogenic distillation with a more practical alternative. A La and Nb co‐doped BaCoO3−δ perovskite is introduced, Ba0.95La0.05Co0.8Fe0.12Nb0.08O3−δ (BLCFN) with a record‐breaking oxygen permeation flux, surpassing all known single‐phase perovskite membranes. To elucidate its superior membrane performance, the mass/charge transport properties and equilibrium bulk properties are investigated and quantitative indicators (DO = 5.8 × 10−6 cm2 s−1, kO = 1.0 × 10−4 cm s−1, σion = 0.93 S cm−1 at 900 °C) reveal fast diffusion and excellent surface gas‐exchange kinetics. The oxygen permeability of 12.4 mL cm−2 min−1 and over 200 h of long‐term stability is achieved in an air/He atmosphere at 900 °C. By presenting a material that demonstrates higher performance than Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF), currently known for its highest permeability, it is believed that this marks a significant step toward innovative performance enhancement of perovskite oxide‐based membranes.

High-efficient N2O decomposition over dual-phase hydrogen/oxygen-transporting membrane reactors

Nitrous oxide (N2O) emissions sourced from agricultural and industrial activities have gained much attention because of their contribution to the global greenhouse effect and ozone layer depletion. Significant efforts have been devoted to developing the cost-effective and highly efficient technologies for N2O removal. The direct N2O decomposition is limited by the thermodynamic equilibrium at high temperatures. Recently, catalytic reduction of N2O with carbon-free hydrogen derived from in situ ammonia decomposition is considered as an ideal approach. Herein, thermal decomposition of N2O is investigated by employing a BaCe0.85Fe0.15O3-δ-BaCe0.15Fe0.85O3-δ (BCF8515-BCF1585) hydrogen-transporting membrane or a Ce0.85Sm0.15O1.925-Sm0.6Sr0.4FeO3-δ (SDC-SSF) oxygen-transporting membrane respectively. It is noted that the membrane catalysis of N2O decomposition by reacting with permeated hydrogen or via in-situ oxygen removal displayed significant advantages over the direct thermal decomposition of N2O under a fixed bed condition. Moreover, the N2O conversion as well as hydrogen/oxygen permeability of such membranes were greatly improved by the introduction of porous Ni–CeO2 or SDC-NCO layers due to the increased catalytic activities and hydrogen/oxygen surface exchange kinetics.

A co-doped strategy for simultaneously improving oxygen permeability and stability of BaCoO3-δ ceramic membrane

Perovskite-type oxygen transport membrane (OTM) has considerable potential in the application of oxygen-enriched combustion, which can prepare low-cost, low-energy, and high-purity oxygen. BaCoO3-δ-based OTM, as a promising candidate, possesses high oxygen permeability, but poor stability limits its application. In this study, the strategy of Y3+ and W6+ co-doping BaCo0·8Y0.2-xWxO3-δ (BCYW-x) was proposed firstly to control the trade-off effect between oxygen permeability and stability by considering the radius and valence of ions. Y3+ and W6+ co-doping stabilize the perovskite cubic structure to room temperature of the BCYW-x, and the average bond energy of metal-oxygen increases with W6+ doping, enhancing the structure stability. Although oxygen vacancy concentration and critical radius decrease, the migration of oxygen ions is accelerated with the increase of W6+ content at high temperatures. The BCYW-0.1 shows the exceptional oxygen permeation flux of 1.90 mL･cm−2･min−1 at 900 °C and stably operates at 900 °C and 800 °C. Furthermore, the kinetic model calculation indicates that the permeation resistance decreases because of the acceleration of the oxygen surface exchange reaction as W6+ doping, contributing to the oxygen permeation process. This study provides a feasible and effective co-doping strategy to improve the oxygen permeability and stability of perovskite OTMs simultaneously.

WITHDRAWN: Optimization of Thermochemical Stability of La-based/Zr-based Dual-Phase Composites for Oxygen Transport Membranes via Computational Thermodynamics

The current investigation deploys a computational thermodynamics approach to develop new materials for dual-phase composites. The chemical stability of (La0.9Sr0.1)0.95CrxFe1-xO3-δ and (La0.8Sr0.2)0.95CrxFe1-xO3-δ (x=0.5, 0.7, 0.8, and 0.9) with three fluorite phases of 8YSZ, 10Sc1YSZ, and 10Sc1CeSZ has been examined. The changes in the Sr-content and the Cr: Fe ratio in the perovskite phase have also been investigated under oxidizing and reducing atmospheres at elevated temperatures. The results show that SrZrO3 as the dominant secondary phase together with limited formations of (La0.5Zr0.5)O1.75 and La2O3. The experimental results have been incorporated into simulations performed by computational thermodynamics. Involved mechanisms to improve the chemical stability have been discussed based on correlations between the content of dopants and applied conditions. The results promote knowledge for the development of ceramic-based dual-phase composite membranes.

Grain boundary segregation in iron doped strontium titanate: From dilute to concentrated solid solutions

Strontium titanate, a perovskite oxide, is a frequently studied material for a large variety of applications. When acceptor-doped (with Fe, for example), the material is useful for its mixed oxygen and electronic conductivity, with potential use in oxygen transport membranes or as a cathode for solid oxide fuel cells. A barrier to conductivity in perovskites is the presence of space charge regions at the grain boundaries, which form due to the segregation of charged point defects. Typically, space charge theory assumes bulk dopant concentrations beneath the dilute limit, however concentrated solid-solutions are often utilized in applications. The current work aims to address this disparity: grain boundary segregation in strontium ferrite-strontium titanate solid-solutions is analyzed at three compositions, with Fe contents ranging from near the dilute limit to well above the dilute limit (Fe contents of 2 %, 5 %, and 25 % on the B-site of the perovskite). Electrochemical impedance spectroscopy shows an increase in material conductivity as Fe is added. High-resolution STEM imaging and spectral mapping is utilized, showing that Fe segregates to the grain boundary core, contrary to what is expected from space charge theory. As the Fe content is increased, the amount of Fe segregated to the boundary increases significantly, but the segregation width of Fe at the boundary remains consistent.

Advancing oxygen separation: insights from experimental and computational analysis of La0.7Ca0.3Co0.3Fe0.6M0.1O3−δ (M = Cu, Zn) oxygen transport membranes

Advancing oxygen separation: insights from experimental and computational analysis of La0.7Ca0.3Co0.3Fe0.6M0.1O3−δ (M = Cu, Zn) oxygen transport membranes

Thermochemical and mechanical properties of Ce0.9Pr0.1O2-δ-Pr0.6Sr0.4Fe0.9Al0.1O3-δ dual-phase membrane

The fluorite-perovskite dual-phase Ce0.9Pr0.1O2-δ-Pr0.6Sr0.4Fe0.9Al0.1O3-δ (CP-PSFA) oxygen transport membrane (OTM) was developed to explore the properties and interaction of the two phases on the crystal structure, sintering behavior, thermochemical expansion, and oxygen release property, mechanical strength, and stability of the dual-phase membrane. The migration of oxygen vacancies between two phases causes the shrinking and expansion of the lattice of CP and PSFA phases, and the lattice of PSFA with higher TEC is compressed while the CP is stretched in the dual-phase membrane at the high-temperature range. The CP phase can significantly improve the mechanical properties of the dual-phase membrane, among which the flexural strength of the CP-PSFA reaches 303±42 MPa, almost twice that of PSFA membrane. Moreover, the high reducing gas resistance of the CP phase gives the CP-PSFA membrane more excellent high-temperature chemical stability. These results offer new insights into developing mixed ionic-electronic conducting dual-phase OTMs.

Integration of biomass gasification and O2/H2 separation membranes for H2 production/separation with inherent CO2 capture: Techno-economic evaluation and artificial neural network based multi-objective optimization

This study delves into the thermodynamic and techno-economic intricacies of a cutting-edge hydrogen production system driven by biomass gasification. The quest for zero emissions propels our innovative integration of an oxygen transport membrane and a hydrogen separation membrane, strategically optimized through artificial intelligence. By situating the oxygen transport membrane near the gasifier, efficient heat transfer and oxygen production synergistically enhance the molar fraction of hydrogen in the syngas. Subsequent utilization of the hydrogen separation membrane, coupled with water gas shift reactors, not only facilitates hydrogen separation and purification but also achieves inherent carbon dioxide capture and storage. This novel membrane-based approach obviates the need for a conventional carbon capture system. Before optimization, our system exhibited a generation rate of approximately 10.29 tons of H2 per day. The levelized cost of production stands at $2.78 per kilogram of hydrogen, with power consumption estimated at 2.99 kWh/kg-H2. The calculated payback period is 9.96 years, considering a sales cost of $3.50 per kg-H2. Multi objective optimization reveals promising prospects, with a potential 26% reduction in power consumption in one scenario. An alternative scenario indicates a remarkable 20% decrease in the system's payback period, accompanied by an 8% dip in the levelized cost of H2. These findings underscore the economic and energy benefits of our membrane-integrated hydrogen production system.

Electrifying Ba0.5Sr0.5Co0.8Fe0.2O3−δ for focalized heating in oxygen transport membranes

Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources, especially biomass and solar/wind electricity. In the case of pure oxygen production, oxygen transport membranes (OTMs) appear as an alternative technology for the cryogenic distillation of air, the industrially-established process of producing oxygen. Moreover, OTMs could provide oxygen from different sources (air, water, CO2, etc.), and they are more flexible in adapting to current processes, producing oxygen at 700–1000 °C. Furthermore, OTMs can be integrated into catalytic membrane reactors, providing new pathways for different processes. The first part of this study was focused on electrification on a traditional OTM material (Ba0.5Sr0.5Co0.8Fe0.2O3−δ), imposing different electric currents/voltages along a capillary membrane. Thanks to the emerging Joule effect, the membrane-surface temperature and the associated O2 permeation flux could be adjusted. Here, the OTM is electrically and locally heated and reaches 900 °C on the surface, whereas the surrounding of the membrane was maintained at 650 °C. The O2 permeation flux reached for the electrified membranes was ∼3.7 NmL min−1 cm−2, corresponding to the flux obtained with an OTM non-electrified at 900 °C. The influence of depositing a porous Ce0.8Tb0.2O2−δ catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures (830 °C) were detected at the same imposed electric power. Finally, the electrification concept was demonstrated in a catalytic membrane reactor (CMR) where the oxidative dehydrogenation of ethane (ODHE) was carried out. ODHE reaction is very sensitive to temperature, and here, we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O2 injection into the reaction can be easily fine-tuned.

All that seems green might be a smokescreen – a case study on microwave-integrated process development of oxygen transport membrane material

To pursue genuine sustainability in materials development, it is essential to incorporate environmental impact assessment right from the outset of the development process. Our case study involving an oxygen transport membrane material illustrates the significance of this coupling. It reveals that, despite bearing products of equivalent functionality, incorporating a commonly perceived green technology may not necessarily result in the expected environmental benefits.

(Digital Presentation) New Magnetron Sputtering Fabrication Process for Ba0.5Sr0.5Co0.8Fe0.2O3- δ Miec Thin Film Membranes on Porous Support for Oxygen Permeation Applications

Mixed ionic electronic conductor (MIEC) membranes provide a great route for introducing oxygen to combustion and reforming processes of new fuels such as green ammonia. Ba0.5Sr0.5Co0.8Fe0.2O3- δ (BSCF) is known to be one of the most widely utilized perovskite material applied as oxygen transport membrane, as it possesses elevated oxygen permeability up to 7 ml(STP)·min-1·cm-2 at a temperature range of 850-900°C. Application of thin MIEC films of thicknesses of around 500 nm – 5 µm allow for reduction of Ohmic resistance for transport processes and sufficient oxygen permeation at lower temperatures as compared to bulk membranes, which is of great advantage with regard to materials stability and quality of sealing. However, fabrication techniques of thin MIEC membranes staunchly influence their phase purity. Crystallinity, microstructure and correlated oxygen diffusion properties as well as stability of membrane-substrate interfaces. Physical vapour deposition (PVD) such as magnetron sputtering (MS) is successfully applied to produce a dense and pinhole-free membrane with thicknesses ranging from 100 nm nanometer to a few micrometers. Challenges due to large size porosity of the ceramic substrate were addressed by tuning of the substrate porosity, ensuring formation of a continues layer and stability of the thin membranes. In this work, we report on the influence of the MS process parameters, as well as subsequent annealing techniques of both thermal annealing (TA) and line beam Laser annealing (LA) on the microstructure of a fabricated asymmetric membrane (AsM) consisting of BSCF thin membrane on a BSCF support wit tunable pore sizes. Oxygen permeability of the AsM was investigated at high temperatures (850-900 °C). For a substrate pore size of around 3 µm, BSCF membrane thicknesses of 1 to 5 µm could be applied for fabrication of AsM, resulting in a 2-fold increase of oxygen permeability ~5 ml.min-1.cm-2 at a temperature of 900 °C as compared to a bulk BSCF support of ~2 mm thickness, whereas comparable oxygen permeation is already reached at a temperature of 700°C by the thin membrane. Contrariwise, the one with high porosity (~10 µm) required the deposition of thicker layers, which obstruct the oxygen diffusion and inhibited the permeation. The results have optimised sputtering process parameters, supports porosity and TA&/SLA parameters, are key factors for producing thin film membrane exhibiting high oxygen flux and good stability.

Preparation of Textured Polycrystalline La2NiO4+ δ Membranes and Their Oxygen-Transporting Properties

Due to its high chemical and thermal stability in CO2 atmosphere and its anisotropic crystal structure, the Ruddlesden-Popper phase La2NiO4+δ has attracted considerable attention in the research field of oxygen-transporting membranes. The anisotropic properties of La2NiO4+δ can be exploited in textured polycrystalline membranes to control the oxygen diffusion through this material. To fabricate textured La2NiO4+δ membranes, powder mixtures consisting of fine-grained equiaxial La2NiO4+δ matrix particles and large plate-like La2NiO4+δ template particles in different mass ratios were uniaxially pressed and then sintered in air. For this purpose, the anisotropic template particles were synthesized by molten-flux method using NaOH as flux [1]. In the powder mixture, the La2NiO4+δ template particles can be aligned perpendicular or parallel to the pressing direction, depending on the geometry of the pressing tool and the sample preparation. After the sintering process, textured La2NiO4+δ membranes were obtained, which was verified by measuring X-ray diffraction patterns and pole figures. Further X-ray diffraction measurements together with the calculation of the Lotgering orientation factor revealed that an increasing content of the template particles in the ceramic materials leads to a stronger texturing. Scanning electron microscopy micrographs show some individual plate-like La2NiO4+δ grains well embedded in the matrix. Homogeneous distribution of lanthanum, nickel and oxygen in the ceramics was confirmed by energy-dispersive X-ray spectroscopy. Finally, the influence of the template particle content in the La2NiO4+δ membranes on the oxygen permeation performance is discussed. [1] Escobar Cano, G.; Brinkmann, Y.; Zhao, Z.; Kißling, P.A.; Feldhoff, A. Sol–Gel-Process-Based Molten-Flux Synthesis of Plate-like La2NiO4+ δ Particles. Crystals 2022, 12, 1346. https://doi.org/10.3390/cryst12101346

Co2MnO4/Ce0.8Tb0.2O2−δ Dual-Phase Membrane Material with High CO2 Stability and Enhanced Oxygen Transport for Oxycombustion Processes

Co₂MnO₄/Ce_0.8Tb_0.2O_2−δ Dual-Phase Membrane Material with High CO₂ Stability and Enhanced Oxygen Transport for Oxycombustion Processes

Highly stable dual-phase Ce0.9Pr0.1O2-δ-Pr0.6Sr0.4Fe1-xTixO3-δ oxygen transport membranes

Mixed ionic-electronic conducting (MIEC) oxygen transport membranes (OTMs) could be used for high-temperature oxygen separation, solid oxide fuel cells (SOFC), and membrane reactors. However, many high-performance OTM materials are chemically unstable in high-temperature CO2 and reducing atmospheres. Here, we proposed a series of 60 wt%Ce0.9Pr0.1O2-δ-40 wt%Pr0.6Sr0.4Fe1-xTixO3-δ (CPO-PSFTxO, x = 0.05, 0.1, 0.2, 0.3, 0.4, 0.6, 0.8, 1) OTMs through Ti doping in Fe-based dual-phase membranes. A small amount of Ti doping increased the oxygen vacancy concentration and simultaneously enhanced the structural stability at high temperatures. The optimal CPO-PSFT0.1O membrane could maintain oxygen permeation fluxes of 0.512 mL min−1 cm−2 and 0.306 mL min−1 cm−2 over 150 h under He and CO2 sweeping at 1000 °C. Furthermore, co-doping with Cu improved oxygen permeability by more than 50 % while maintaining performance stability. Simultaneously, CPO-PSFT0.1O had excellent CO2 resistance and could maintain structural stability in 5 % H2/Ar at 800 °C. This material has potential applications in constructing membrane reactors containing reducing atmospheres and high-temperature SOFC.

WITHDRAWN: Integration of an O2 transport membrane and a biomass-fueled SCO2 cycle for liquid CO2/freshwater/power production: ANN-based optimization and techno-economic evaluation

This research presents a sustainable approach leveraging biomass as a renewable energy source and separation technology to produce liquid carbon dioxide for the food industry, alongside power and freshwater. The proposed system comprises five key sections. The biomass gasification section produces pure oxygen as a gasification agent using an oxygen transport membrane. The power generation section employs supercritical carbon dioxide oxy-fuel, enabling simultaneous power generation and carbon dioxide separation and purification. The freshwater production department uses a Multi-Stage Flash unit for desalination, drawing heat from the power generation cycle. The oxygen production section, based on oxygen transport membrane technology, supplies oxygen for the power generation cycle. The liquefaction section, utilizing the Claude cycle, facilitates carbon dioxide storage and transportation. The proposed system underwent rigorous techno-economic analysis and was further explored through multi-objective optimization based on artificial intelligence, aiming to minimize liquid carbon dioxide production costs and maximize net power output. Under pre-optimized conditions, the system exhibited a net power of 850 kW and a carbon dioxide price of $0.6/kg. Optimization results revealed a 12-year payback period, with a minimum carbon dioxide price of $0.51/kg and a maximum net power of 1692 kW. Comparative analysis under minimum carbon dioxide price conditions showed a 15% decrease in liquid carbon dioxide price and an 89% decrease in net power compared to pre-optimized conditions. Conversely, comparing the system's maximum net power after optimization to pre-optimized conditions demonstrated a 17% increase in liquid carbon dioxide price and a remarkable 99% increase in net power, highlighting substantial economic benefits.

Surface modification of dual-phase ceramic membrane reactor for coupling catalytic CO2 conversion with partial oxidation of methane

The oxygen transport membrane (OTM) reactor is a particularly promising process for CO2 conversion and utilization through coupling the thermochemical decomposition of CO2 with the partial oxidation of methane (POM). However, its low CO2 decomposition efficiency and poor operational stability in corrosive atmospheres are the main challenges for practical application. In this work, the porous layers of LaMO3-δ (M = Fe, Co, Ni) and Ce0.8Zr0.2O2-δ (CZ), with different functions separately, were coated on both sides of the Ce0.9Pr0.1O2-δ-Pr0.6Sr0.4Fe0.9Al0.1O3-δ (CP-PSFA) dual-phase membrane. The presence of oxygen vacancy and transition ions M with the valence of +2/+3 in the LaMO3-δ is conducive to catalyzing CO2 conversion. The LaCoO3-δ porous layer exhibits the best oxygen permeability and CO2 conversion, and the performance of POM is greatly enhanced by the in situ Ni-doped CZ porous layer. After a long-term test at 925 °C, the oxygen permeation flux of the LaCoO3-δ/CP-PSFA/CZ-Ni maintains at 0.96 mL cm−2 min−1, the conversion rate of CH4 and CO2 maintains at 23 % and 45 % respectively, and the syngas yield reaches 6.3 mL cm−2 min−1. The sandwich-like OTM reactor with functional porous layers has broad research prospects in the CO2 conversion and utilization field.