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Perovskite oxide and preparation thereof, and application during photothermal chemical conversion of solar energy

A technology of perovskite oxides and oxides, applied in inorganic chemistry, cobalt compounds, carbon monoxide, etc., can solve the problems of less oxygen vacancies, high reduction temperature of metal oxides, and cycle stability to be improved, and achieve a synthesis method. Simple, easy to synthesize effects at scale

Active Publication Date: 2018-10-02
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Application Information

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Problems solved by technology

However, for ZnO, V 2 o 5 , SnO 2 and GeO 2 How to solve the volatility problem of volatile oxide circulation system has always been a difficult problem
[0011] In summary, the present two-step thermochemical cycle for the decomposition of H 2 O / CO 2 The research is still in the basic research stage, and there is still a certain distance from industrial application. The main problems of most circulation systems are: (1) high reduction temperature of metal oxides; (2) less oxygen vacancies that can be recycled; ( 3) Cycle stability needs to be improved
Demont, Antoine and others have tried to develop Fe-based perovskite systems, and they found that although Fe perovskite has a high oxygen storage capacity, its reoxidation degree is generally lower than 10% (The Journal of Physical Chemistry C, 2014 ,118(24):12682-12692)
These perovskite oxide circulation systems currently developed still have more or less certain problems, and the solution of these problems requires more research and development work

Method used

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  • Perovskite oxide and preparation thereof, and application during photothermal chemical conversion of solar energy
  • Perovskite oxide and preparation thereof, and application during photothermal chemical conversion of solar energy
  • Perovskite oxide and preparation thereof, and application during photothermal chemical conversion of solar energy

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Weigh 4.3301g (10mmol) lanthanum nitrate, 0.4177 (10-n) g ((10-n) mmol) gallium nitrate, 0.2910 n g (nmmol, n=0-10) cobalt nitrate and dissolve in 20-100ml deionized water, Stir at room temperature for 30 minutes; at 60-100°C, evaporate the excess water to a sol-like substance; transfer to a muffle furnace at 500°C for ignition, and heat-preserve and roast for 0.5-2h; then, at a heating rate of 2-5°C Raise the temperature to 800°C, and heat-preserve and roast for 3-6h. Select different types of rare earth metal or alkaline earth metal nitrates (such as one or more of metal nitrates such as La, Nd, Sm, Gd, Dy, Y, Sr, Ca, Ba, Bi, Ce, etc.) and transition metals Or alkaline earth metal nitrates (such as Fe, Mn, Cu, Co, Ni, Al, Cr, Sc, Mg and other metal nitrates or two or more); adjust the doping of different elements in the A-position and B-position Impurity ratio (0-100atom%); a series of A-site and B-site doped perovskite oxide AGa 1-x B x o 3-δ , with figure 2 XR...

Embodiment 2

[0040]Weigh 4.3301g (10mmol) lanthanum nitrate, 0.4177 (10-n) g ((10-n) mmol) gallium nitrate, 0.2910 n g (nmmol, n=0-10) cobalt nitrate and dissolve in 20-100ml deionized water, Stir at room temperature for 30 minutes; then add NaOH solution or KOH solution or ammonia water with a concentration of 1-3mol / L, adjust the pH of the solution to 7.0-12.0, stir evenly; transfer to a hydrothermal kettle, and react at 80°C-200°C for 3- 12h; after cooling to room temperature, filter, wash and dry. Select different types of rare earth metal or alkaline earth metal nitrates (such as one or more of metal nitrates such as La, Nd, Sm, Gd, Dy, Y, Sr, Ca, Ba, Bi, Ce, etc.) and transition metals Or alkaline earth metal nitrates (such as Fe, Mn, Cu, Co, Ni, Al, Cr, Sc, Mg and other metal nitrates or two or more); adjust the doping of different elements in the A-position and B-position Impurity ratio (0-100atom%); a series of A-site and B-site doped perovskite oxide AGa 1-x B x o 3-δ .

Embodiment 3

[0042] Weigh 3.2581g (10mmol) lanthanum oxide, 0.1874 (10-n) g ((10-n) mmol) gallium oxide, 0.1189ng (nmmol, n=0-10) cobalt carbonate; grind evenly with a mortar, Under the protection of a certain atmosphere, heat to 1100°C at a rate of 10-20°C / min, keep it warm for 6-12h, and then cool down to room temperature; the composition of the atmosphere is: the volume ratio is air (0-100%) and CO 2 (100-0%) mixed gas, the total flow rate is 100mL / min. Select different types of rare earth metal or alkaline earth metal carbonates or oxides (such as La, Nd, Sm, Gd, Dy, Y, Sr, Ca, Ba, Bi, Ce and other metal carbonates or oxides) or two or more) and transition metal or alkaline earth metal carbonates or oxides (such as Fe, Mn, Cu, Co, Ni, Al, Cr, Sc, Mg and other metal carbonates or oxides or one or both more than one species); adjust the doping ratio (0-100atom%) of different elements of A-site and B-site; obtain a series of A-site and B-site doped perovskite oxide AGa 1-x B x o 3-δ ....

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Abstract

The invention relates to a method that takes a novel Ga based perovskite oxide as a redox cycle active material to decompose H2O and / or CO2 through a two-step thermochemical cycle so as to generate H2and / or CO. Oxygen vacancy formation energy of the Ga based perovskite oxide can be regulated through A-site and B-site wide doping. The thermochemical cycle reaction mainly includes the following steps: (1) reducing the active material to release oxygen at a high temperature; and (2) reacting the active material containing large amounts of oxygen vacancies with H2O and / or CO2 at a lower temperature to release H2 and / or CO. That the novel Ga based perovskite oxide can be used as the active material to realize the decomposition of H2O and / or CO2 through the thermochemical cycle is discovered for the first time. The active material can utilize the high temperature heat generated by solar energy focusing as energy sources, and takes H2O and / or CO2 as reaction raw materials to generate H2 and / or CO; and the perovskite oxide is clean and pollution-free, and is hopeful to become an effective material for preparing chemical fuel by reducing H2O and / or CO2 through the solar energy.

Description

technical field [0001] The present invention relates to a two-step thermochemical cycle for splitting water and / or carbon dioxide. Specifically, perovskite oxides are used as redox active materials to split water and / or carbon dioxide to produce hydrogen and / or carbon monoxide through a two-step thermochemical cycle. The system uses solar energy as a heat source to convert water and / or carbon dioxide into chemical fuels, and has very broad application prospects in energy saving, emission reduction and environmental protection. Background technique [0002] Under the background of energy crisis and environmental crisis, the unsustainability of fossil energy is becoming more and more obvious, and the greenhouse effect and environmental pollution caused by excessive use of fossil energy are becoming more and more prominent. A renewable energy system is imminent. my country is currently CO 2 The second largest country in terms of emissions, CO 2 Emissions show a trend of rap...

Claims

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Application Information

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IPC IPC(8): C01F17/00C01G51/00C01B3/04C01B3/16C01B32/40
CPCC01B3/042C01B3/16C01G51/006C01P2002/72C01P2002/80C01F17/32Y02E60/36Y02P20/133
Inventor 李灿陈真盘蒋宗轩蒋青青杨民
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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