阅读说明：本技术 用于产生长链烃分子的等离激元纳米颗粒催化剂和方法 (Plasmonic nanoparticle catalysts and methods for producing long chain hydrocarbon molecules ) 是由 王琮 任海洲 于 2016-01-11 设计创作，主要内容包括：本申请涉及用于产生长链烃分子的等离激元纳米颗粒催化剂和方法。具体地,本申请涉及一种通过光辐射产生烃分子的等离激元纳米颗粒催化剂,其包含至少一种等离激元供体和至少一种催化特性供体,其中等离激元供体和催化特性供体可相互接触或距离小于200nm,并且由光辐射产生的烃分子的分子组成是温度依赖性的。以及一种利用等离激元纳米颗粒催化剂通过光辐射产生烃分子的方法。(The present application relates to plasmonic nanoparticle catalysts and methods for producing long-chain hydrocarbon molecules. In particular, the present application relates to a plasmonic nanoparticle catalyst for the generation of hydrocarbon molecules by photo-irradiation comprising at least one plasmonic donor and at least one catalytic property donor, wherein the plasmonic donor and the catalytic property donor may be in contact with each other or at a distance of less than 200nm, and the molecular composition of the hydrocarbon molecules generated by the photo-irradiation is temperature dependent. And a method of generating hydrocarbon molecules by light irradiation using a plasmonic nanoparticle catalyst.)

1. A plasmonic nanoparticle catalyst for producing hydrocarbon molecules by optical radiation, comprising:

at least one plasmon donor; and

at least one catalytic property donor, wherein

The plasmon donor and the catalytic property donor are in contact with each other or at a distance of less than 200nm, and

the molecular composition of the hydrocarbon molecules produced by light irradiation is temperature dependent.

2. The plasmonic nanoparticle catalyst of claim 1, wherein

The at least one plasmon donor and the at least one catalytic property donor are provided in one nanoparticle, and

the nanoparticles comprise one chemical element that acts as a plasmon donor and a catalytic property donor, or an alloy comprising two or more chemical elements that each act as a plasmon donor or a catalytic property donor.

3. The plasmonic nanoparticle catalyst of claim 1 or 2, wherein

The plasmon donor is selected from the group consisting of Co, Fe, Al, Ag, Au, Pt, Cu, Ni, Zn, Ti, C and alloys of two or more of the chemical elements thereof.

4. The plasmonic nanoparticle catalyst of claim 1 or 2, wherein

The catalytic property donor is selected from the group consisting of Co, Fe, Ru, Rh, Pd, Os, Ir, La, Ce, Cu, Ni, Ti, C and oxides, chlorides, carbonates and bicarbonates thereof.

5. The plasmonic nanoparticle catalyst of any of claims 1 to 4, wherein

The plasmonic nanoparticles are sized to be from about 1nm to about 1000nm long, wide, and high.

6. The plasmonic nanoparticle catalyst of claim 5, wherein

The shape of the plasmon nanoparticle catalyst is spherical, cylindrical, polyhedral, three-dimensional pyramidal, cubic, flaky, hemispherical, irregular three-dimensional shape, porous structure or any combination thereof.

7. The plasmonic nanoparticle catalyst of any of claims 1 to 6, wherein

The plasmonic nanoparticle catalyst has a solar conversion chemical energy efficiency of greater than 10% at a temperature between about 20 ℃ and about 800 ℃.

8. A method of producing hydrocarbon molecules by photoradiation, comprising:

contacting the plasmonic nanoparticle catalyst with at least one carbon-containing source and at least one hydrogen-containing source; and

irradiating the plasmonic nanoparticle catalyst, the carbon-containing source, and the hydrogen-containing source with light to produce a hydrocarbon molecule, wherein

The plasmonic nanoparticle catalyst comprises at least one plasmonic donor and at least one catalytic property donor,

the plasmon donor and the catalytic property donor are in contact with each other or at a distance of less than 200nm, and

the molecular composition of the hydrocarbon molecules produced by light irradiation is temperature dependent.

9. The method of claim 8, wherein

The light radiation is carried out at a temperature between about 20 ℃ and about 800 ℃ and

the solar energy conversion efficiency is greater than 10%.

10. A method as claimed in claim 8 or 9, wherein

The light radiation is carried out at a temperature between about 20 ℃ and about 200 ℃ and

the hydrocarbon molecules produced by light irradiation are mainly composed of straight-chain saturated hydrocarbons.

11. A method as claimed in claim 8 or 9, wherein

The light radiation is carried out at a temperature between about 200 ℃ and about 300 ℃ and

the hydrocarbon molecules produced by light irradiation are mainly composed of aromatic hydrocarbons.

12. A method as claimed in claim 8 or 9, wherein

The light radiation is carried out at a temperature between about 300 ℃ and about 800 ℃ and

the hydrocarbon molecules produced by light irradiation are mainly composed of unsaturated branched hydrocarbons.

13. The method of any one of claims 8 to 12, wherein

The light radiation increases the temperature of the plasmonic nanoparticle catalyst, the carbon-containing source, and the hydrogen-containing source.

14. The method of any one of claims 8 to 13, wherein

The carbon-containing source comprises CO₂Or CO.

15. The method of any one of claims 8 to 13, wherein

The hydrogen-containing source comprises water.

16. The method of any one of claims 8 to 15, wherein

The at least one plasmon donor and the at least one catalytic property donor are provided in one nanoparticle, and

the nanoparticles comprise one chemical element that acts as a plasmon donor and a catalytic property donor, or an alloy comprising two or more chemical elements that each act as a plasmon donor or a catalytic property donor.

17. The method of any one of claims 8 to 16, wherein

The plasmon donor is selected from the group consisting of Co, Fe, Al, Ag, Au, Pt, Cu, Ni, Zn, Ti, C, and alloys of two or more of the chemical elements thereof.

18. The method of any one of claims 8 to 17, wherein

The catalytic property donor is selected from the group consisting of Co, Fe, Ru, Rh, Pd, Os, Ir, La, Ce, Cu, Ni, Ti, C and oxides, chlorides, carbonates and bicarbonates thereof.

19. The method of any one of claims 8 to 18, wherein

The plasmonic nanoparticles are sized to be from about 1nm to about 1000nm long, wide, and high.

20. The method as set forth in claim 19, wherein

The shape of the plasmon nanoparticle catalyst is spherical, cylindrical, polyhedral, three-dimensional pyramidal, cubic, flaky, hemispherical, irregular three-dimensional shape, porous structure or any combination thereof.

Technical Field

The present invention relates generally to carbon dioxide sequestration and renewable energy sources. More specifically, the present invention relates generally to plasmonic nanoparticle catalysts and methods for producing long-chain hydrocarbon molecules.

Background

Over the past few decades, there has been an increasing interest in converting solar energy into more useful energy. Some technologies have shown great promise in this area, however there is a long way to go from commercialization. Most efforts to date have only been successful in producing short chain (C1-C2) hydrocarbons or carbohydrates with solar conversion chemical energy efficiencies that are 1 or 2 orders of magnitude lower than natural photosynthesis, which is typically 1 to 7%.

Disclosure of Invention

Herein, the present invention illustrates a novel artificial photosynthesis technique, which provides a method of utilizing CO or CO from industrial flue gas or atmosphere₂Unique catalysts and methods for producing long chain hydrocarbon molecules.

One aspect of the invention is a plasmonic nanoparticle catalyst for producing hydrocarbon molecules by photo-irradiation comprising at least one plasmonic donor and at least one catalytic property donor, wherein the plasmonic donor and the catalytic property donor are in contact with each other or at a distance of less than 200nm, and the molecular composition of the hydrocarbon molecules produced by photo-irradiation is temperature dependent.

In certain embodiments, the at least one plasmonic donor and the at least one catalytic property donor of the plasmonic nanoparticle catalyst are provided in one nanoparticle, and the nanoparticle comprises one chemical element that is both a plasmonic donor and a catalytic property donor, or an alloy comprising two or more chemical elements that are each either a plasmonic donor or a catalytic property donor.

In a preferred embodiment, the plasmon donor of the plasmonic nanoparticle catalyst is selected from Co, Fe, Al, Ag, Au, Pt, Cu, Ni, Zn, Ti, C and alloys of two or more chemical elements thereof.

In a preferred embodiment, the catalytic property donor of the plasmonic nanoparticle catalyst is selected from Co, Fe, Ru, Rh, Pd, Os, Ir, La, Ce, Cu, Ni, Ti, C and oxides, chlorides, carbonates and bicarbonates thereof.

In certain embodiments, the size of the plasmonic nanoparticles is from about 1nm to about 1000nm long, wide, and high; the shape of the plasmonic nanoparticle catalyst is spherical, cylindrical, polyhedral, three-dimensional pyramidal, cubic, sheet-like, hemispherical, irregular three-dimensional shape, porous structure, or any combination thereof.

In a preferred embodiment, the plasmonic nanoparticle catalyst has a solar conversion chemical energy efficiency of greater than 10% at a temperature between about 20 ℃ and about 800 ℃.

Another aspect of the invention is a method of producing hydrocarbon molecules by photoradiation, comprising the steps of:

contacting a plasmonic nanoparticle catalyst with at least one carbon-containing source and at least one hydrogen-containing source; and

irradiating the plasmonic nanoparticle catalyst, the carbon-containing source, and the hydrogen-containing source with light to produce a hydrocarbon molecule.

The plasmon nanoparticle catalyst of the above aspect can be utilized for this method.

In certain embodiments, the photoradiation step is performed at a temperature between about 20 ℃ to about 800 ℃, about 30 ℃ to about 300 ℃, about 50 ℃ to about 250 ℃, about 70 ℃ to about 200 ℃, about 80 ℃ to about 180 ℃, about 100 ℃ to about 150 ℃, about 110 ℃ to about 130 ℃, and the like. The solar energy conversion efficiency is greater than 10% at the above temperatures.

In a particular embodiment, the photoradiation is conducted at a temperature between about 20 ℃ and about 200 ℃, and the hydrocarbon molecules produced by the photoradiation are primarily comprised of straight chain saturated hydrocarbons.

In a particular embodiment, the photoradiation is conducted at a temperature between about 200 ℃ and about 300 ℃, and the hydrocarbon molecules produced by the photoradiation are primarily comprised of aromatic hydrocarbons.

In a particular embodiment, the photoradiation is conducted at a temperature between about 300 ℃ and about 800 ℃, and the hydrocarbon molecules produced by the photoradiation are composed primarily of unsaturated branched hydrocarbons.

In certain embodiments, the light irradiation increases the temperature of the plasmonic nanoparticle catalyst, the carbon-containing source, and the hydrogen-containing source. In certain embodiments, the temperature of the plasmonic nanoparticle catalyst, the carbon-containing source, and the hydrogen-containing source is increased only by light irradiation.

In a preferred embodiment, the carbon-containing source comprises CO₂Or CO; the hydrogen-containing source comprises water.

Drawings

FIGS. 1A-1B show GC (gas chromatography) content analysis of the products obtained at different temperatures.

FIG. 2 shows GC-MS (gas chromatography-mass spectrometry) analysis of aromatic hydrocarbons obtained at 242 ℃.

Figure 3 shows the yield of hydrocarbon molecules at different temperatures.

Detailed Description

The invention demonstrates that the plasmonic nanoparticle catalyst of the invention can be used as a catalyst, with the sole energy input being solar light, to convert CO with quantum transition efficiency₂(or CO) and water into various long-chain hydrocarbon molecules. The peak value of the solar energy conversion chemical energy efficiency recorded by the reaction is measured to be 10-20%, and the peak value can be theoretically reached to be>20% solar energy to chemical energy efficiency.

Before further describing the present invention, certain terms used in the specification, examples, and appended claims are collected in the following section.

Definition of

The definitions set forth herein should be read and understood by those skilled in the art in view of the remainder of the present disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The term "nanoparticle" as used herein refers to a particle having a size in the nanometer range, i.e., from 1nm to 1000nm in length, width and height. Nanoparticles can exhibit size-related properties that are significantly different from those observed in bulk materials. In some cases, tubes and fibers having only two dimensions in the nanometer range are also considered nanoparticles.

The term "catalyst" as used herein refers to a substance that exhibits the effect of increasing the rate of a chemical reaction by lowering the activation energy of the reaction. The rate-increasing effect is referred to as "catalysis". The catalyst is not consumed in the catalytic reaction and so they can continue to catalyze further reaction of the reactants in small quantities.

The term "plasmon donor" as used herein refers to a conductor whose real part of the dielectric constant is negative. The plasmon donor may provide a surface plasmon when excited by electromagnetic radiation.

The term "temperature dependence" as used herein refers to a characteristic that can change when temperature is changed by a given level. The temperature difference that changes the property can be any number of degrees, such as 0.1 deg.C, 1 deg.C, 5 deg.C, 10 deg.C, 100 deg.C, or 1000 deg.C.

The term "chemical element" as used herein refers to a chemical substance consisting of atoms in the nucleus of an atom having the same number of protons. Specifically, a chemical element is an element recorded in the periodic table of chemical elements. Chemical elements include natural elements and synthetic elements. Chemical elements also include elements with more than 118 protons in the nucleus not yet discovered.

The term "alloy" as used herein refers to a mixture of metals or a mixture of metals and other elements. Alloys are defined by metal bonding (metallic bonding) properties. The alloy may be a solid solution of the metal element (single phase) or a mixture of metal phases (two or more solutions).

Plasmonic nanoparticle catalysts

One aspect of the invention is a plasmonic nanoparticle catalyst. The size range of the plasmonic nanoparticles is 1-1000nm in length, width and height, so the volume is 1nm³To 1 μm³. The shape of the plasmonic nanoparticle catalyst is spherical, cylindrical, polyhedral, three-dimensional pyramidal, cubic, sheet-like, hemispherical, irregular three-dimensional shape, porous structure, or any combination thereof.

Based on our experimental results, plasmonic nanoparticle catalysts with sizes in the range of 1nm to 1000nm have solar conversion chemical energy efficiencies (10-20%) significantly higher than micron-sized catalysts such as catalysts with a size of 100 μm diameter (1-10%).

Plasmonic nanoparticles have two components. One component is a plasmon donor and the other is a catalytic character donor. The plasmon donors provide surface plasmon resonance enhancement to the catalyst localization areas. The catalytic property donor provides catalytic properties to the reaction producing the hydrocarbon. In the plasmonic nanoparticle catalyst, the plasmonic donor and the catalytic property donor are in contact with each other or at a distance of less than 200 nm. If the distance between the plasmon donor and the catalytic property donor is outside the above range, the two donors cannot cooperate with each other to function, and thus cannot catalyze the photosynthesis reaction.

The plasmon donor is a conductor whose real part of dielectric constant is negative. It may be pure substance or mixture, and its constituent elements may be selected from one or more of Co, Fe, Al, Ag, Au, Pt, Cu, Ni, Zn, Ti, C, and alloys of two or more of the chemical elements thereof. Different plasmon donors have different plasmon enhancement strengths (plasmon enhancement lengths) and active lifetimes. For example, noble metal elements such as Ag, Au, and Pt have high plasmon enhancement strength and long active lifetime. Common metal elements such as Co and Fe have low plasmon enhancement strength and short active lifetime. For reasons of efficiency and cost, Co is preferably used in the present invention.

The catalytic property donor may be pure substance or mixture, and its constituent elements may be selected from Co, Fe, Ru, Rh, Pd, Os, Ir, La, Ce, Cu, Ni, Ti, C, and one or more of its oxides, chlorides, carbonates and bicarbonates. Different catalytic performance donors also have different catalytic strengths and active lifetimes. For example, rare earth metal elements such as Ru, Rh, and Pd have the highest catalytic strength but short active life. Elements such as Co, Fe, Cu, Ni and their oxides have high to moderate catalytic strength. The chlorides or carbonates described above generally have lower catalytic strength but longer active life. Co and its oxides are preferably used in the present invention.

The plasmonic donor and the catalytic property donor may be randomly mixed or regularly mixed. In a preferred embodiment, the at least one plasmonic donor and the at least one catalytic property donor of the plasmonic nanoparticle catalyst are provided in one nanoparticle, and the nanoparticle comprises one chemical element as plasmonic donor and catalytic property donor, or an alloy comprising two or more chemical elements each as plasmonic donor or catalytic property donor. Specifically, the plasmon nanoparticle catalyst may be a nanoparticle of the aforementioned element, or a nanoparticle of the aforementioned element alloy, as long as the element can provide both plasmon characteristics and catalytic characteristics.

From the above description, it is clear that some elements exhibit both plasmon characteristics and catalytic characteristics. The plasmonic donor and the catalytic property donor of the plasmonic nanoparticle catalyst may thus be the same element, e.g. Co, Fe, Cu, Ni, C, etc., or an element and its oxides, chlorides, carbonates and bicarbonates, e.g. Co and CoO, Fe and FeO, etc.

Mixtures of different elements can alter the properties of these plasmonic nanoparticle catalysts. For example, Co/Ag and Co/Au alloys increase the active life of the catalyst and produce predominantly relatively short chain hydrocarbons (C)₃To C₆). For example, Co/C only increases the active life of the catalyst, but does not affect other aspects of the reaction.

The plasmonic nanoparticles may be used as a catalyst for generating hydrocarbon molecules by light irradiation, which function in various states, such as dispersion, aggregation or attachment/growth on the surface of other materials.

Plasmonic nanoparticle catalysts have high solar conversion chemical energy efficiency (above 10%) between temperatures of about 20 ℃ to about 800 ℃, and the molecular composition of hydrocarbon molecules produced by light irradiation is temperature dependent. For example, at relatively low temperatures (below 200 ℃), linear saturated hydrocarbons (alkanes) are the major products. When the temperature is further increased, the aromatic hydrocarbons are referred to as main products. At higher temperature ranges, the product is a mixture of alkanes, alkenes, alkynes, and aromatics.

Method for producing long-chain hydrocarbon molecules

Another aspect of the invention is a method of producing hydrocarbon molecules by light irradiation, the method comprising the steps of:

contacting the plasmonic nanoparticle catalyst with at least one carbon-containing source and at least one hydrogen-containing source; and

irradiating the plasmonic nanoparticle catalyst, the carbon-containing source, and the hydrogen-containing source with light to produce a hydrocarbon molecule.

Light irradiation initiates the reaction of a carbon-containing source and a hydrogen-containing source under the catalytic action of a plasmonic nanoparticle catalyst. Within a particular temperature range, increasing the temperature can result in higher yields of hydrocarbon molecular products. The hydrocarbon molecular products of the catalytic reaction are temperature dependent.

The photoradiation step is carried out at a temperature between about 20 ℃ to about 800 ℃, about 30 ℃ to about 300 ℃, about 50 ℃ to about 250 ℃, about 70 ℃ to about 200 ℃, about 80 ℃ to about 180 ℃, about 100 ℃ to about 150 ℃, about 110 ℃ to about 130 ℃, and the like. To obtain fuel-like hydrocarbon molecules, the temperature is preferably between about 70 ℃ and about 200 ℃. At the above temperatures, the solar energy conversion chemical energy efficiency is greater than 10%.

The light radiation mimics the wavelength composition and intensity of sunlight so it can raise the temperature of the catalyst and reaction mixture being radiated. When the radiation intensity reaches a certain level, the temperature of the plasmonic nanoparticle catalyst, the carbon-containing source and the hydrogen-containing source is increased only by light radiation.

The reaction time varies depending on the size of the reaction, the radiation intensity, the temperature, and other factors. The reaction is continued using a well-established apparatus with continuous addition of a carbon-containing source and a hydrogen-containing source.

Examples

1-5g of cobalt nanoparticles ranging in size from 1nm to 1000nm were treated with water and CO₂Sealed in a glass vial. The glass vials were irradiated under sunlight or a solar simulator for 8-20 hours at the appropriate temperature. The incident light intensity is about 1000 to 1500W/m². A thermocouple was attached to the lower half of the vial to monitor the temperature. Control experiments were performed with the same material but without light irradiation to show no contamination from the precursor.

After 8-20 hours of irradiation, the product was extracted with 1mL of dichloromethane and analyzed by the same route of gas chromatography-mass spectrometer (GC-MS). The amount of each compound is dissolved inStandard C in alkanes₇-C₂₀And (4) calibrating the alkane sample.

GC chromatograms (fig. 1A-1B) show the products obtained from the experiments at different temperatures. Discovery C₃To C₁₇Alkanes (straight chain saturated long chain hydrocarbons) are the major products. In the control sample, there are peaks for three contaminants in solvent, stabilizer in solvent, water, gas and solvent. No other material was shown in the GC chromatogram, confirming that none came from the nanoparticle catalyst, water or CO₂And (3) contamination. Traces of hydrocarbons begin to be shown in the samples obtained at 30 ℃. The yield gradually increased as the temperature remained increased. The yield reached its maximum at 125 ℃. There are several sub-peaks near the main alkane peak, which are the alkene and isomer of the main product. After the temperature exceeds this range, the yield rapidly decreases.

Further experiments showed that the yield remained at a low level between 125 ℃ and 180 ℃. After 180 ℃ the yield increases again and the product starts to change. The proportion of linear saturated hydrocarbons produced decreases and the proportion of unsaturated hydrocarbons increases. From 200 ℃ to 300 ℃, aromatic hydrocarbons were found to be the major products, as shown in fig. 2. At higher temperatures, such as from 300 ℃ to 800 ℃, the product is a mixture of alkanes, alkenes, alkynes, and aromatics.

Fig. 3 shows the yield of hydrocarbon molecules at different temperatures, which shows that the yield is not linearly related to the temperature. Below 100 ℃, the yield stays at a very low level and increases slowly. When the temperature is higher than 100 ℃, the yield increases rapidly. All products reached a peak rate at 125 ℃. Octane is the most abundant product. The yield is increased by 25 times from 71 ℃ to 125 ℃ and 22 times from 96 ℃ to 125 ℃. For hexadecane, the yield increased 10-fold from 96 ℃ to 125 ℃.

As used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The methods described herein may be performed in any order that is logically possible, except in the particular order disclosed.

The representative examples are intended to aid in the description of the invention and are not intended to, nor should they be construed to, limit the scope of the invention. Indeed, various modifications of the invention and many other embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art, including the examples and scientific and patent literature references cited herein. The embodiments contain important additional information, exemplification and guidance which can be employed in the practice of the invention in its various embodiments and equivalents.