阅读说明：本技术 阳光液态能量存储-太阳能制氢-燃料电池循环利用方法 (Sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method ) 是由 李长明 胡俊蝶 沈杨彬 于 2020-05-13 设计创作，主要内容包括：本发明公开了一种阳光液态能量存储-太阳能制氢-燃料电池循环利用方法,其特征在于：包括如下步骤：(1)聚光太阳能,在反应器内通入二氧化碳和水,在第一催化剂的作用下生成有机液体,存储得到的有机液体；2)在聚光太阳能加热的条件下,利用第二催化剂将所述有机液体催化生成氢气和二氧化碳；利用生成的氢气驱动燃料电池,产生电能；所述第一催化剂采用但不限于二氧化钛(TiO-(2))、氮化碳材料(g-C-(3)N-(4))和硫化镉(CdS)中的至少一种。本发明的阳光液态能量存储-太阳能制氢-燃料电池循环利用方法,可实现“太阳能—液态燃料能源—氢能源—电能”的循环转化,同时实现太阳能的存储、清洁新能源的制备、燃料电池的利用串联反应。(The invention discloses a sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method, which is characterized by comprising the following steps: the method comprises the following steps: (1) concentrating solar energy, introducing carbon dioxide and water into a reactor, generating organic liquid under the action of a first catalyst, and storing the obtained organic liquid; 2) under the condition of concentrating solar energy heating, catalyzing the organic liquid by using a second catalyst to generate hydrogen and carbon dioxide; driving a fuel cell by using the generated hydrogen to generate electric energy; the first catalyst is titanium dioxide (TiO), but is not limited to 2 ) Carbon nitride Material (g-C) 3 N 4 ) And cadmium sulfide (CdS). The invention relates to a method for recycling a sunlight liquid energy storage-solar hydrogen production-fuel cell, which can realize' solar energy-liquid state energy storage-solar hydrogen production-fuel cellThe cyclic conversion of fuel energy, hydrogen energy and electric energy is realized, and simultaneously, the storage of solar energy, the preparation of clean new energy and the utilization series reaction of a fuel cell are realized.)

1. A sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method is characterized in that: the method comprises the following steps:

(1) concentrating solar energy, introducing carbon dioxide and water into a reactor, generating organic liquid under the action of a first catalyst, and storing the obtained organic liquid;

(2) under the condition of concentrating solar energy heating, catalyzing the organic liquid by using a second catalyst to generate hydrogen and carbon dioxide; driving a fuel cell by using the generated hydrogen to generate electric energy;

the first catalyst is titanium dioxide (TiO), but is not limited to₂) Carbon nitride Material (g-C)₃N₄) And cadmium sulfide (CdS).

2. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 1, characterized in that: and the catalytic efficiency and selectivity of the first catalyst are improved by adopting an auxiliary catalyst modification method.

3. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 2, characterized in that: the modification reduction promoter adopted by the auxiliary catalyst modification method comprises noble metals and non-noble metals, wherein the noble metals comprise but are not limited to at least one of Pt, Ag, Pd, Ru and Au, and the non-noble metals comprise but are not limited to at least one of Cu, Ni and Co or oxides of at least one of Cu, Ni and Co.

4. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 2, characterized in that: the oxidation promoters employed in the helper catalyst modification process include, but are not limited to, RuO₂And MnO_xAt least one of (1).

5. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 1, characterized in that: the organic liquid includes, but is not limited to, methanol, formic acid, or formaldehyde.

6. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 1, characterized in that: the second catalyst adopts, but is not limited to, metal organic compound and/or supported monatomic catalyst.

7. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 6, wherein: the metal organic compound includes, but is not limited to, at least one of organoiridium, organoruthenium, and organorhodium.

8. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 6, wherein: the supported monatomic catalyst includes, but is not limited to, at least one of a zirconium nitride supported monatomic platinum catalyst, a zirconium nitride supported monatomic iridium catalyst, and a zirconium nitride supported monatomic rhodium catalyst.

9. The sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to claim 1, characterized in that: and (3) taking the carbon dioxide gas generated in the step (2) as a carbon dioxide raw material in the step (1) to realize the recycling of the carbon dioxide.

Technical Field

The invention belongs to the technical field of solar energy utilization, and particularly relates to a sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method.

Background

At present, human beings mainly rely on non-renewable fossil fuels (such as coal, petroleum, natural gas and the like) as main energy sources, which not only brings huge energy crisis, but also causes serious air pollution (such as carbon dioxide CO)₂Explosive growth causes greenhouse effect, etc.). With the rapid development of global industry, the energy consumption is increased sharply, and reaches 15 Terawatts (TW) in 2010 according to statistics, and is expected to reach 27TW in 2050; the international committee on climate change forecasts that by 2100 years CO is present in the global atmosphere₂The total would reach 590ppm and the global average temperature would rise by 1.9 c with catastrophic consequences. Therefore, there is an urgent need to develop a new green, clean and renewable energy source to replace the traditional fossil fuel, thereby reducing the global energy and environmental pressure. Solar energy is widely considered to be a clean, abundant, free renewable energy source, providing about 120 ten thousand TW of energy to the earth each year, and meeting the expected energy demand in 2050 if one-tenth of the solar energy is utilized at 0.3% conversion by the earth's surface. Therefore, how to effectively convert solar energy into chemical energy is the focus of our research and has great significance for the sustainable development of human beings.

Inspired by photosynthesis of plants in nature, it has been found that CO can be catalyzed by light₂Experiments such as reduction and the like realize the conversion of solar energy to liquid energy (such as methanol, formic acid, formaldehyde, ethanol and the like), effectively realize the storage of the solar energy and solve the problem of greenhouse effect. But at present CO₂The reduction efficiency is low, the selectivity is poor, the conversion rate of solar energy is severely inhibited, and the method is a great challenge. In addition, the energy density of liquid fuels such as methanol is low, so that efficient utilization of energy cannot be realized, and the energy requirements in the fields of new energy automobiles and the like cannot be met, so that how to realize conversion of sunlight liquid energy (fuels such as methanol) into high-energy-density hydrogen is also a difficult point of current research.

Disclosure of Invention

In view of the above, the present invention provides a method for recycling a sunlight liquid energy storage-solar hydrogen production-fuel cell, which can realize the recycling conversion of "solar energy-liquid fuel energy-hydrogen energy-electric energy", and simultaneously realize the series reaction of solar energy storage, clean new energy preparation and fuel cell utilization.

In order to achieve the purpose, the invention provides the following technical scheme:

a sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method is characterized in that: the method comprises the following steps:

(1) concentrating solar energy, introducing carbon dioxide and water into a reactor, generating organic liquid under the action of a first catalyst, and storing the obtained organic liquid;

(2) under the condition of concentrating solar energy heating, catalyzing the organic liquid by using a second catalyst to generate hydrogen and carbon dioxide; driving a fuel cell by using the generated hydrogen to generate electric energy;

the first catalyst is titanium dioxide (TiO), but is not limited to₂) Carbon nitride Material (g-C)₃N₄) And cadmium sulfide (CdS).

Further, an auxiliary catalyst modification method is adopted to improve the catalytic efficiency and selectivity of the first catalyst.

Further, the modification reduction promoter used in the auxiliary catalyst modification method comprises noble metals including but not limited to at least one of Pt, Ag, Pd, Ru and Au, and non-noble metals including but not limited to at least one of Cu, Ni and Co or oxides of at least one of them.

Further, the oxidation promoters employed in the helper catalyst modification process include, but are not limited to, RuO₂And MnO_xAt least one of (1).

Further, the organic liquid includes, but is not limited to, methanol, formic acid, or formaldehyde.

Further, the second catalyst adopts, but is not limited to, metal organic compound and/or supported monatomic catalyst.

Further, the metal organic compound includes, but is not limited to, at least one of organoiridium, organoruthenium, and organorhodium.

Further, the supported monatomic catalyst includes, but is not limited to, at least one of a zirconium nitride supported monatomic platinum catalyst, a zirconium nitride supported monatomic iridium catalyst, and a zirconium nitride supported monatomic rhodium catalyst.

Further, the carbon dioxide gas generated in the step (2) is used as the carbon dioxide raw material in the step (1), so that the recycling of the carbon dioxide is realized.

The invention has the beneficial effects that:

the invention relates to a sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method, which comprises the steps of firstly converting carbon dioxide and water into organic liquid by using solar energy, converting the solar energy into sunlight liquid energy, and facilitating storage and transportation of the organic liquid; in the energy utilization process, the organic liquid is decomposed to generate hydrogen by utilizing solar thermal catalysis, the conversion from solar energy to hydrogen energy is realized, the fuel cell can be directly driven to generate electric energy by utilizing the hydrogen, the conversion from the hydrogen energy to the electric energy is realized, the whole process only needs water and carbon dioxide as reactants, the photo-thermal conversion can be efficiently realized by utilizing the solar energy, the conversion, the storage and the utilization of the solar energy can be completed, the heat engine process that the energy conversion efficiency is lower and is limited by Carnot cycle is avoided, and the liquid solar energy high-efficiency conversion scheme is provided.

Drawings

In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:

FIG. 1 is a schematic diagram of a sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to the present invention;

FIG. 2 is a schematic diagram of catalytic reduction of carbon dioxide using a first catalyst;

fig. 3 is a schematic structural view of the second catalyst.

Detailed Description

The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.

Fig. 1 is a schematic diagram of a sunlight liquid energy storage-solar hydrogen production-fuel cell recycling method according to the present invention. The method for recycling the sunlight liquid energy storage-solar hydrogen production-fuel cell is characterized by comprising the following steps: the method comprises the following steps:

(1) concentrating solar energy, introducing carbon dioxide and water into a reactor, generating organic liquid under the action of a first catalyst, and storing the obtained organic liquid;

(2) under the condition of concentrating solar energy heating, catalyzing the organic liquid by using a second catalyst to generate hydrogen and carbon dioxide; driving a fuel cell by using the generated hydrogen to generate electric energy;

the first catalyst is titanium dioxide (TiO), but is not limited to₂) Carbon nitride Material (g-C)₃N₄) And cadmium sulfide (CdS). Specifically, the present example employs an auxiliary catalyst modification method to improve the catalytic efficiency and selectivity of the first catalyst. The modification reduction promoter used in the Co-catalyst modification method comprises a noble metal including but not limited to at least one of Pt, Ag, Pd, Ru and Au and a non-noble metal including but not limited to at least one of Cu, Ni and Co or an oxide of at least one of Cu, Ni and Co. The oxidation promoter used in the co-catalyst modification method of this example includes, but is not limited to, RuO₂And MnO_xAt least one of (1).

Organic/inorganic semiconductor materials are widely recognized as photocatalytic CO₂Effective catalysts for reduction, and the photocatalytic materials currently in use mostly include titanium dioxide (TiO)₂) Carbon nitride Material (g-C)₃N₄) Cadmium sulfide (CdS), etc., but the above semiconductor materials rapidly undergo recombination of photo-generated electrons and holes generated under irradiation of sunlight, and the carrier utilization is very low, resulting in photocatalytic CO₂Low reduction efficiency and poor selectivity. This example uses a method for the modification of an auxiliary catalyst to enhance TiO₂、g-C₃N₄The catalytic efficiency and selectivity of the semiconductor material are equal, and by simultaneously modifying the reduction catalyst promoter and the oxidation catalyst promoter,the method effectively realizes the effective separation and migration of photo-generated electrons and holes, successfully inhibits the recombination of photo-generated charges, and improves the utilization rate of carriers. Such as in TiO₂、g-C₃N₄Noble metals such as Pt, Ag, Pd, Ru and Au are modified on the surface of the semiconductor material, or Cu, Ni, Co and oxides thereof are modified to promote the rapid migration and utilization of photo-generated electrons, so that CO is realized under the irradiation of sunlight₂The reduction is carried out efficiently; while in TiO₂、g-C₃N₄Surface modification of RuO on semiconductor material₂And MnO_xEtc. as promoters for photogenerated holes to efficiently achieve H over the hole₂O→O₂The semi-reaction is smoothly carried out, thereby achieving the purpose of photocatalysis of CO₂High efficiency and high selectivity of reduction. Final reduction of CO by photocatalysis₂The conversion of solar energy to liquid fuel is realized, and the purpose of storing the liquid energy of sunlight is achieved.

Further, the organic liquid includes, but is not limited to, methanol, formic acid, or formaldehyde. The stored sunlight liquid energy (methanol, formic acid, formaldehyde and the like) can be further used for preparing hydrogen energy with high energy density to generate hydrogen and CO₂In which CO is formed₂And carrying out photocatalytic reduction again to convert the liquid chemical energy. The second catalyst is selected from metal organic compound and/or supported single atom catalyst. The metal organic compound includes, but is not limited to, at least one of organoiridium, organoruthenium, and organorhodium. The supported monatomic catalyst includes, but is not limited to, at least one of a zirconium nitride supported monatomic platinum catalyst, a zirconium nitride supported monatomic iridium catalyst, and a zirconium nitride supported monatomic rhodium catalyst.

Methanol, formic acid and formaldehyde can be used for storing hydrogen atoms and generating hydrogen and carbon dioxide under the action of a second catalyst. The reaction equation is as follows:

reaction 1: CH (CH)₃OH+H₂O→3H₂+CO₂

Reaction 2: HCHO + H₂O→2H₂+CO₂

Reaction 3: HCOOH → H₂+CO₂

In the reaction 1, the catalyst may be prepared by using organic Ir, Ru, Rh, etc., or a catalyst such as monoatomic Pt, Ir, Rh, etc. supported on zirconium nitride; in reaction 2, an organic Ru or zirconium nitride supported monatomic Ru catalyst may be used; in reaction 3, organic Ir and organic Rh can be used for catalytic completion. The organic Ir, Ru and Rh described in the text are mainly metal complexes of the Ir, Ru and Rh, and are coordinated with a nitrogen-containing heterocycle, as shown in the attached figure 3.

Preferably, the carbon dioxide gas generated in the step (2) is used as a carbon dioxide raw material in the step (1) to recycle carbon dioxide.

In the process of converting the chemical energy of the sunlight liquid energy into the hydrogen energy, the catalyst has higher activity and selectivity, so the generated hydrogen can be directly used for a hydrogen-oxygen fuel cell, the conversion of the chemical energy into the electric energy is realized, and a new path is opened for the safe and efficient use of new energy automobiles. The invention finally realizes the cyclic conversion of solar energy, liquid fuel energy, hydrogen energy and electric energy by constructing a series of series reactions.

The following describes a specific embodiment of the present embodiment in detail with reference to specific examples.

Preparing TiO by using tetrabutyl titanate as precursor and adopting hydrothermal method or high-temperature calcination method₂The material or the g-C is prepared by taking organic molecules with high nitrogen element content such as urea, melamine, dicyandiamide and the like as precursors under the polymerization action of high temperature (400-₃N₄A material. Modifying Pt, Ag, Pd, Ru, Au or Cu, Ni, Co metal nano particles or oxides thereof to TiO by adopting a deposition method and an immersion method₂Or g-C₃N₄The surface of the material is used as a reduction promoter, and then RuO is further modified₂And MnO_xAnd taking the oxide as an oxide promoter to successfully prepare the photocatalytic material of the type of 'reduction promoter/semiconductor material/oxidation promoter'. The material can convert CO into CO under the irradiation of sunlight at room temperature₂The gas is reduced into liquid fuels such as methanol, formic acid, formaldehyde and the like, so that the conversion from solar energy to chemical energy and the storage of sunlight liquid energy are realized.

Introducing the collected sunlight liquid energy (methanol, formic acid, formaldehyde) into a reactor, adding appropriate amount of water, increasing the temperature of the reactor (80-200 deg.C), adding organic metal catalyst (organic Ir, organic Ru, organic Rh or zirconium nitride loaded single atom Pt, Ir, Rh catalyst, etc.) shown in figure 3, and decomposing liquid fuel such as methanol, formic acid, formaldehyde, etc. into hydrogen and CO respectively under the action of the catalyst₂And hydrogen energy with high energy density is successfully prepared. CO produced in the process₂The gas can be recycled to reuse CO₂Converted into a liquid fuel.

The generated hydrogen is directly input into a proton exchange membrane fuel cell (such as a hydrogen-oxygen fuel cell) to realize the conversion of hydrogen energy → electric energy, and the generated hydrogen energy or electric energy can be directly used in the field of new energy automobiles.

The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.