Thermochemical splitting of CO_(2) on perovskites for CO production: A review

Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.

A simple and novel effective strategy using mechanical treatment to improve the oxygen uptake/release rate of YBaCo_(4)O_(7+δ) for thermochemical cycles

In recent years,oxygen storage materials(OSMs)have been widely used in many fields.It would be particularly important for researchers to design high-oxygen-uptake/release-rate materials.In this study,various synthesis processes were used to successfully synthesize YBaCo_(4)O_(7+δ)and comprehensively investigate their potential applications.Compa red with traditional solid-state reaction method and co-precipitation method,the results demonstrated that the utilization of mechanical ball milling treatment on co-precipitated precursors could lead to samples with reversible oxygen uptake/release under an oxidative atmosphere at low temperatures.The resultant materials exhibited fast oxygen absorption/desorption rate that could uptake/release oxygen directly to the equilibrium state within 9 min and20 min,respectively.The mechanochemically ball-milled sample possessed outstanding oxygen sto rage performance,which could be attributed to their small particle size,the active outer surface of particles,large specific surface area,and relatively low activation energy.Moreover,the ball-milled sample also exhibited excellent cycling stability during relatively short time spacing.TG results also demonstrated that the ball-milled samples could reversibly uptake/release 2.90 wt.%of excess oxygen(while only 0.70 wt.%for solid-state samples)by adjusting the ambient temperature under pure O_(2) atmosphere,which would make them promising candidates in various applications.This research demonstrated that mechanical treatment could be an effective strategy to tune the properties and oxygen storage capacity(OSC)performances of YBaCo_(4)O_(7+δ).

Occurrence of the Bunsen side reaction in the sulfur-iodine thermochemical cycle for hydrogen production

This study aimed to establish a closed-cycle operation technology with high thermal efficiency in the thermochemical sulfur-iodine cycle for large-scale hydrogen production.A series of experimental studies were performed to investigate the occurrence of side reactions in both the H2SO4 and HI x phases from the H2SO4/HI/I2/H2O quaternary system within a constant temperature range of 323-363 K.The effects of iodine content,water content and reaction temperature on the side reactions were evaluated.The results showed that an increase in the reaction temperature promoted the side reactions.However,they were prevented as the iodine or water content increased.The occurrence of side reactions was faster in kinetics and more intense in the H2SO4 phase than in the HI x phase.The sulfur or hydrogen sulfide formation reaction or the reverse Bunsen reaction was validated under certain conditions.

Thermogravimetric Analysis of Zirconia-Doped Ceria for Thermochemical Production of Solar Fuel

Developing an efficient redox material is crucial for thermochemical cycles that produce solar fuels (e.g. H2 and CO), enabling a sustainable energy supply. In this study, zirconia-doped cerium oxide (Ce1-xZrxO2) was tested in CO2-splitting cycles for the production of CO. The impact of the Zr-content on the splitting performance was investigated within the range 0 ≤ x < 0.4. The materials were synthesized via a citrate nitrate auto combustion route and subjected to thermogravimetric experiments. The results indicate that there is an optimal zirconium content, x = 0.15, improving the specific CO2-splitting performance by 50% compared to pure ceria. Significantly enhanced performance is observed for 0.15 ≤ x ≤ 0.225. Outside this range, the performance decreases to values of pure ceria. These results agree with theoretical studies attributing the improvements to lattice modification. Introducing Zr4+ into the fluorite structure of ceria compensates for the expansion of the crystal lattice caused by the reduction of Ce4+ to Ce3+. Regarding the reaction conditions, the most efficient composition Ce0.85Zr0.15O2 enhances the required conditions by a temperature of 60 K or one order of magnitude of the partial pressure of oxygen p(O2) compared to pure ceria. The optimal composition was tested in long-term experiments of one hundred cycles, which revealed declining splitting kinetics.

In-Depth Energy and Irreversibility Analysis in the Solar Driven Two-Step Thermochemical Water Splitting Cycle for Hydrogen Production

Hydrogen production via a two-step thermochemical cycle based on solar energy has attracted increasing attention.However,the severe irreversible loss causes the low efficiency.To make sense of the irreversibility,an in-depth thermodynamic model for the solar driven two-step thermochemical cycles is proposed.Different from previous literatures solely focusing on the energy loss and irreversibility of devices,this work decouples a complex energy conversion process in three sub-processes,i.e.,reaction,heat transfer and re-radiation,acquiring the cause of irreversible loss.The results from the case study indicate that the main irreversibility caused by inert sweeping gas for decreasing the reduction reaction temperature dominates the cycle efficiency.Decreasing reduction reaction temperature without severe energy penalty of inert sweeping gas is important to reducing this irreversible loss.A favorable performance is achieved by decreasing re-oxidation rate,increasing hydrolysis conversion rate and achieving a thermochemical cycle with a lower equilibrium temperature of reduction reaction at atmosphere pressure.The research clarifies the essence of process irrrversibility in solar thermichemical cycles,and the findings point out the potential to develop efficient solar driven two-step thermochemical cycles for hydrogen production.

Electricity Generation from Low Temperature Waste Heat with Application to Hydrogen Production from Water

This paper presents an extensive study of the heat pump cycle and associated working fluids to generate electricity from low temperature industrial waste heat. An Aspen Plus simulation has been developed to evaluate the effect of various working fluids on the net heat pump efficiency over a wide range of turbine inlet temperatures between 50℃ and 250℃. One hundred eight （108） refi＇igerants were investigated from the environmental classifications of Hydrochlorofluorocarbons （HCFC）, Hydrofluorocarbons （HFC）, Chlorofluorocarbons （CFC） and Hydrocarbons （HC） with boiling points between -88.65 ℃ and 110.65℃. Net efficiency, which ranged from 0.1% to 25.8% in this work tends to increases with the temperature of the waste heat. Results of the present study demonstrate that working fluid R41 （with source temperature of 44 ℃） provides the maximum efficiency among those evaluated. Refrigerants R13B1 and R32 provide the best efficiency for waste heat source temperatures ranges 60 - 67 ℃ and 68 - 78℃ respectively. Ammonia shows the highest efficiency from 79℃ to 132 ℃. Refrigerants R31, R21, 17,30 and benzene perform well in the temperature ranges 133-151 ℃, 152-178 ℃, 179-236℃ and 237-250 ℃respectively. The optimal heat pump systems are applied to the hybrid copper sulfate-copper oxide thermochemical cycle for hydrogen production from water. 100.8 MW of electrical energy is produced, which increased the efficiency from 24.1% to 25.9%.

Using a simulation software to perform energy and exergy analyses of the sulfur-iodine thermochemical process

The objective of this work is to demonstrate the utilization of the power of simulation tools to perform an exergy analysis of a process.Exergy analysis,being a new and useful thermodynamics tool,will be applied to one of the newest research fields in hydrogen production.One of the many advantages of computer simulation is elimination of the need to construct a pilot plant.Presently,extensive research is underway to come up with the production and use of clean fuels.The research entails performing pilot studies and proof of concept experiments using validated models.The research is further extended to various analyses such as safety,economic sustainability and energy efficiency of the processes involved.The production of hydrogen through thermochemical water splitting processes is one of the newest technologies and is expected to compete with the existing technologies.Among a wide range of thermochemical cycles,the sulfur-iodine(SI)thermochemical cycle process has been proposed as a promising technology for the production of hydrogen.In this research,we demonstrate how a commercial simulator can be used to perform an energy and exergy analysis of the SI water splitting process.Using a commercial simulator,a process flowsheet is developed based on research findings presented by other authors and an energy-exergy analysis is carried out on the process.The method of energy–exergy analysis used in this presentation indicates that an energy and exergy efficiency of 17%and 24%can be attained,respectively,in the conceptual design of the SI cycle.

Thermochemical splitting of carbon dioxide by lanthanum manganites-understanding the mechanistic effects of doping

This review investigates the effect of different dopants on the oxygen evolution and carbon dioxide splitting abilities of the lanthanum manganites.Particular focus was placed on the lanthanide,alkaline earth metals,redox-active transition metal,and non-redox active Group 3 metals.The review suggests that a small ionic radius lanthanide on the A-site can increase the size discrepancy,leading to Mn-O_(6) octahedra tilting and more facile Mn-O bond breaking.Doping the A-site with a divalent alkaline earth element can increase the valance of the transition metal,leading to greater reduction capabilities.A transition metal with one electron in the e_(g) orbital is the most effective for reduction while for oxidation,zero electrons in the high-energy e_(g) orbitals is optimal.Finally,doping of the B-site with metals such as gallium or aluminium aids in sintering resistance and allows reactivity to remain constant over multiple cycles.Higher reduction temperatures and moderate re-oxidation temperatures also promote higher fuel yields as does the active reduction of the perovskite under hydrogen,although the total energy consumption implications of this are unknown.Far more is known about the mechanism of the reduction reaction than the oxidation reaction,therefore more research in this area is required.