CN113426393A - Cheap and simple method for enhancing plasmon-driven photoreduction reaction at interface - Google Patents
Cheap and simple method for enhancing plasmon-driven photoreduction reaction at interface Download PDFInfo
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- CN113426393A CN113426393A CN202110677349.9A CN202110677349A CN113426393A CN 113426393 A CN113426393 A CN 113426393A CN 202110677349 A CN202110677349 A CN 202110677349A CN 113426393 A CN113426393 A CN 113426393A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
Abstract
The invention provides a method for enhancing a photoreduction reaction driven by plasma metal at an interface of the plasma metal and graphene oxide by adsorbing a positively charged molecular promoter on a composite structure of the plasma metal and the graphene oxide. In the method, the dye molecule cocatalyst can physically adsorb the surface of the graphene oxide through pi-pi conjugation, the raw materials are economical and cheap, and the operation process is simple, convenient and quick. The method has proved that the method can adsorb positively charged molecules to enhance the reduction reaction of p-nitrobenzophenol (PNTP) driven by plasmon at the interface. In addition, the method further proves that the hot carrier driven photocatalytic reaction generated by plasma at the interface can be regulated and controlled by adsorbing other charged molecules.
Description
Technical Field
The invention relates to a cheap and simple method for enhancing plasmon driving at an interface of plasma metal and graphene oxide, in particular to a photochemical reaction driven by hot carriers generated by plasmon at the interface, and belongs to the technical field of catalytic energy.
Background
Solar energy is a clean and renewable energy source, and the effective collection of solar energy is one of the important methods for solving the global energy crisis and environmental pollution problems, and photochemical conversion is an effective way. Originally, semiconductors were often used as photocatalysts for photochemical conversion, but their solar energy utilization efficiency was low due to problems such as an excessively large band gap and low stability of the semiconductor. In order to improve the utilization rate of sunlight, a plasma metal catalyst is an effective method for solving the problem. Under light excitation, the plasma metal can generate hot carriers, i.e., electron-hole pairs, and the generated hot carriers can drive many photochemical reactions, such as water decomposition, inorganic nanocrystal conversion, and organic matter conversion. However, plasma metals are generally not efficient in participating in chemical reactions because the hot carrier current is highly recombination causing short lifetimes. Therefore, by effectively promoting hot carrier separation, the photochemical reaction efficiency can be expected to be significantly improved.
To applicants' knowledge, currently common methods for facilitating hot carrier separation often build heterostructures from plasma metals and semiconductors. However, this method usually requires energy band matching between the plasma metal and the semiconductor, but it is not easy to precisely adjust the energy band structure of the semiconductor, and the semiconductor has low stability, which further limits the effective construction of the heterostructure of the plasma metal and the semiconductor. In addition, it has also been proposed to modify thiol or thiophenol molecules on the surface of plasmonic metals to modulate plasmon-driven photochemical reactions. However, this reaction requires the formation of chemical bonds between the plasma metal and the molecule, which greatly limits the scope of regulating the plasma metal driven chemical reaction.
Disclosure of Invention
The technical problem solved by the invention is as follows: effectively solves the problem of short service life of plasma metal excited hot carriers and effectively promotes charge separation. The selection range of the molecular cocatalyst is expanded. Reduce the cost of raw materials for constructing a suitable structure for charge separation, and simplify the operation steps.
The technical scheme provided by the invention is as follows: a cheap and simple method for enhancing plasmon-driven photoreduction reaction at an interface, a novel method for plasma metal mediated photoreduction, soaking a graphene oxide sheet after ultrasonic treatment after 3-Aminopropyltriethoxysilane (APS) modification on the surface of a cover glass, sputtering according to proper parameters, soaking the structure in a p-nitrophenol ethanol solution, adsorbing reactant molecules by forming plasma metal-sulfur chemical bonds on plasma metal, and soaking the structure in a positively charged benzene ring-containing organic molecule solution to obtain a graphene oxide and plasma metal composite catalytic structure adsorbing a positively charged molecular promoter; the reaction from p-nitrobenzophenol to p-mercaptoazobenzene is monitored through in-situ Raman spectroscopy, and it is known that the plasmon-driven photoreduction reaction can be effectively and simply enhanced by adsorbing positively charged benzene ring-containing organic molecules on the surface of graphene oxide.
Preferably, the novel method for plasma metal dielectric light reduction comprises the steps of modifying 3-Aminopropyltriethoxysilane (APS) on the surface of a cover glass, soaking a graphene oxide sheet which is subjected to ultrasonic treatment for 30 minutes for 30s, performing uninterrupted sputtering for 10 times with the parameter of 20s of 8mA each time, soaking the structure in a p-nitrophenol ethanol solution for 2 hours to obtain a composite catalytic structure of graphene oxide and plasma metal for adsorbing a positively charged molecular cocatalyst by forming a plasma metal-sulfur chemical bond on the plasma metal, and soaking the structure in a positively charged benzene ring-containing organic molecular solution for 30 minutes; the reaction from p-nitrobenzophenol to p-mercaptoazobenzene is monitored through in-situ Raman spectroscopy, and it is known that the plasmon-driven photoreduction reaction can be effectively and simply enhanced by adsorbing positively charged benzene ring-containing organic molecules on the surface of graphene oxide.
Preferably, the plasma metal refers to gold, silver, copper, aluminum and alloy, and the alloy may be a complex of gold, silver, copper and aluminum, or an alloy of gold, silver, copper and aluminum with platinum and palladium.
Preferably, the composite catalytic structure is a composite structure of graphene oxide and plasma metal using an adsorbed molecular promoter.
Preferably, the graphene oxide can effectively adsorb low-cost positively charged benzene ring-containing organic molecules, and the reduction reaction of p-nitrobenzophenol driven by plasmons at the metal interface of the graphene oxide and the plasma can be remarkably enhanced.
Preferably, the positively charged organic molecule containing benzene ring is dye molecule methyl violet or rhodamine 110.
Preferably, the graphene oxide can effectively adsorb other organic molecules with different charges, and can effectively enhance or inhibit the photoreduction reaction driven by plasma at the metal interface of the graphene oxide and the plasma.
Preferably, the graphene oxide is a high-yield and low-defect sheet material; the preparation process comprises the following steps:
graphite (0.75g,<325 mesh) and KMnO4(4.5g) were mixed well and placed in a 250mL single-neck flask (magnetons were placed in the flask in advance). Placing the flask in an oil bath pan, adjusting the magneton at medium speed, setting the temperature at 50 ℃, and adding 10mL of concentrated H3PO4And 90mL of concentrated H2SO4The mixed acid solution flows along the wall of the bottle and is slowly dripped; when the temperature rises to 50 ℃, the reaction is carried out for 12 h. After 12h, the mixture was cooled to room temperature using an ice bath, at which point the reaction turned purple-green and 100mL of ice-water mixture was slowly added dropwise. Then 30% H was gradually added2O2Removing the excess oxidant, adding dropwise and stirring, the solution becoming bright yellow when the last drop is added; finally, the slurry was transferred to a centrifuge tube and centrifuged at 8000rpm for 10 minutes to remove the colorless supernatant, and a precipitate, i.e., graphene oxide sheets, was obtained, which could be dispersed in an aqueous or ethanol solution.
Preferably, the composite material is a highly uniform raman-enhanced substrate prepared by: performing APS (3-aminopropyltriethoxysilane) modification on the surface of a cover glass, soaking a graphene oxide sheet which is subjected to ultrasonic treatment for 30min for 30s, performing uninterrupted sputtering for 10 times with a parameter of 20s of 8mA each time, soaking the structure in a p-nitrophenol ethanol solution for 2 hours, forming a chemical bond with sulfur through plasma metal to adsorb a reactant p-nitrophenol, and finally soaking the structure in a positively charged benzene ring-containing organic molecular solution for 30min to obtain the graphene oxide and plasma metal composite catalytic structure adsorbing the positively charged molecular promoter.
The method has the advantages that the photo-reduction reaction driven by plasma metal at the interface of the plasma metal and the graphene oxide can be simply and effectively enhanced by adsorbing positively charged organic molecules on the surface of the graphene oxide, the method is simple and convenient to operate, the raw material price is low, and the method can be widely applied. In application, the method is proved to be used for enhancing the reduction reaction of the p-nitrobenzophenol driven by the plasmon at the interface. In addition, organic molecules with different chargeability are selected to effectively regulate and control the photoreduction of the p-nitrobenzothiophenol driven by plasma at the interface.
The invention has the beneficial effects that:
the invention provides a method for enhancing a plasmon-driven photoreduction reaction at an interface. That is, the positive organic molecules containing benzene rings are adsorbed on the surface of the graphene oxide, so that the photoreduction reaction driven by plasma metal can be effectively enhanced at the interface; meanwhile, we prove that the reduction reaction of p-nitrobenzophenol can be effectively enhanced or inhibited at the metal interface of graphene oxide and plasma by changing the molecular charge.
The graphene oxide sheet prepared by the method has high yield and low defect degree. Firstly, the method does not contain sodium nitrate and other substances which are easy to explode, and is safe to operate. The graphene oxide can better adsorb organic molecules containing benzene rings due to low defect degree, and the graphene oxide and plasma metal form a composite structure to better promote charge separation. Compared with the ultra-low defect graphene oxide prepared only at 5 ℃, the yield of the graphene oxide flake is close to 100%, and the yield prepared at 5 ℃ is only about 10%.
The methyl violet Molecule (MV) with positive charges is adsorbed by the invention, and is easy to ionize into three groups with positive charges because of the three amino groups, so that the reduction reaction of p-nitrobenzothiophenol can be obviously enhanced by 4-5 times in the catalytic structure. In addition, the rhodamine 110 molecule containing amino oil and carboxyl generally has a positive charge, so the rhodamine 110 molecule is enhanced by 2-3 times. In addition, the adsorption of the negatively charged methyl blue inhibits the reduction of p-nitrobenzophenol by about 0.3 times, since it is essentially negatively charged. This reveals that the more positively charged the molecule contained, the better the reaction is enhanced for p-nitrobenzophenol.
Compared with other technologies, the dye molecule has the advantages of low cost and low price in terms of raw materials because the dye molecule is developed well. The yield of graphene oxide approaches 100%. The silver target material required by sputtering has greatly reduced cost compared with the synthesis required by other technologies. In the aspect of the preparation method: the preparation method of the graphene oxide is simple, safe and mature. Compared with other technologies, the method is safer and has high yield. The graphene oxide and plasma metal composite structure can be prepared by simple sputtering, and is simple compared with other technologies. The molecular adsorption only needs to put the composite structure into the solution for soaking, and the operation is simple and convenient.
Compared with the prior art, the method has the advantages that the separation of the current carriers excited by the plasma metal can be easily and effectively adjusted by adsorbing the organic molecules containing the benzene rings with different electrical properties on the graphene oxide, so that the photochemical reaction driven by the plasma can be effectively promoted. Meanwhile, the adsorption is simple physical adsorption (pi-pi conjugation), and the structure can be expected to be applied to other redox chemical reactions.
Drawings
The invention will be further explained with reference to the drawings.
In FIG. 1, a is a structure diagram of plasmon at a positively charged molecule enhanced interface, and b is a schematic diagram of hot carrier separation behavior in a process of driving reduction of p-nitrobenzothiophenol;
FIG. 2 is a schematic diagram of the steps for synthesizing graphene oxide;
FIG. 3 is an SEM image of graphene oxide before ultrasonic treatment in a, and a result image of graphene oxide after ultrasonic treatment for 30min in b;
FIG. 4 is a PNTP reduction Raman spectrum under different sputtering parameters, and b is a PNTP Raman intensity graph under different sputtering parameters;
fig. 5 is a composite structural view of graphene oxide and silver nanoparticles;
FIG. 6a is a plasmon mediated PNTP reduction reaction at positively charged methyl violet enhanced interface
As a result of the course of the reaction (wherein
Showing the characteristic peak intensity of the product to mercaptoazobenzene,
representing the characteristic peak intensity of the product p-nitrothiophenol), b enhancing the reaction rate of the plasmon-mediated p-nitrothiophenol reduction by methyl violet under different powers and c under different wavelengths, and d is the ultraviolet absorption spectrum of the composite structure of graphene oxide and plasma metal silver after the methyl violet is adsorbed;
FIG. 7a is a graph showing the results of the organic molecules with different positive charges and negative charges regulating the reaction process of the plasmon mediated reduction reaction of p-nitrophenol, and b is a graph showing the rates of the organic molecules with different positive charges and negative charges regulating the reaction process of the plasmon mediated reduction reaction of p-nitrophenol;
FIG. 8a is a conductivity point diagram for changing the chargeability of rhodamine 110 molecules under different pH values, and b is a result of regulating the reduction rate of plasmon-driven p-nitrobenzophenol by the rhodamine 110 molecules under different pH values.
Detailed Description
Example 1
Adsorbing positively charged benzene ring-containing organic molecules on graphene oxide to enhance the principle of a method for reducing by plasma driving light at an interface.
It is well known that there are electrostatic forces between positive and negative charges that attract each other. Likewise, the effect is also present in the microscopic material. In a heterostructure constructed by graphene oxide and a plasma metal, charged organic molecules are adsorbed on the graphene oxide through physical adsorption, and from the quantum theory, when the organic molecules are theoretically positively charged, the transfer of electrons can be induced, and when the organic molecules are negatively charged, the transfer of electrons can be inhibited (the transfer of holes is promoted, and the hole mean free path is short, so that the phenomenon that the negative charges repel each other is mainly shown). Also, unlike the band structure of a common semiconductor, the chargeability of a molecule can be adjusted by adding (or removing) a substituent or changing the chargeability of a substituent. For example, when an organic molecule is changed to change the chargeability of a substituent, the chargeability of the molecule is changed. Therefore, the hot carrier separation behavior can be accurately regulated and controlled theoretically by adsorbing the charged organic molecules on the graphene oxide through physical adsorption, and the efficiency of the chemical reaction is further influenced. Taking the adsorption of positively charged molecules as an example, the adsorption of positively charged organic molecules on graphene oxide can significantly enhance the plasma-driven photoreduction at the interface, as shown in fig. 1. In addition, the organic molecules which are physically adsorbed on the graphene oxide to adsorb charges are simple, convenient and quick in operation process. In addition, cost can be reduced by selecting some cheap dye molecules. In conclusion, the method has unique advantages in the aspects of regulating and controlling hot carrier separation and improving catalytic efficiency.
Example 2
And (3) preparing a graphene oxide and plasma metal composite structure. Firstly, a GO nano material is synthesized by using an improved Hummer method, as shown in a figure 2, and a single-layer GO nano sheet is obtained by ultrasonic treatment for 30min, as shown in a figure 3.
The preparation method comprises the following steps: graphite (0.75g,<325 mesh) and KMnO4(4.5g) were mixed well and placed in a 250mL single-neck flask (magnetons were placed in the flask in advance). Placing the flask in an oil bath pan, adjusting the magneton at medium speed, setting the temperature at 50 ℃, and adding 10mL of concentrated H3PO4And 90mL of concentrated H2SO4The mixed acid solution flows along the wall of the bottle and is slowly dripped; when the temperature rises to 50 ℃, the reaction is carried out for 12 h. After 12h, the mixture was cooled to room temperature using an ice bath, at which point the reaction turned purple-green and 100mL of ice-water mixture was slowly added dropwise. Then 30% H was gradually added2O2Removing the excess oxidant, adding dropwise and stirring, the solution becoming bright yellow when the last drop is added; finally, the slurry was transferred to a centrifuge tube and centrifuged at 8000rpm for 10 minutes to remove the colorless supernatant, and a precipitate, i.e., graphene oxide sheets, was obtained, which could be dispersed in an aqueous or ethanol solution.
The composite material is a highly uniform Raman enhanced substrate and is prepared by the following steps: performing APS (3-aminopropyltriethoxysilane) modification on the surface of a cover glass, soaking a graphene oxide sheet which is subjected to ultrasonic treatment for 30min for 30s, performing uninterrupted sputtering for 10 times with a parameter of 20s of 8mA each time, soaking the structure in a p-nitrophenol ethanol solution for 2 hours, forming a chemical bond with sulfur through plasma metal to adsorb a reactant p-nitrophenol, and finally soaking the structure in a positively charged benzene ring-containing organic molecular solution for 30min to obtain the graphene oxide and plasma metal composite catalytic structure adsorbing the positively charged molecular promoter.
The surface of the glass slide is modified (3-aminopropyltriethoxysilane), so that the surface activity is improved, and the GO nano-sheet can be favorably adsorbed. Next, sputtering of silver nanoparticles was performed at a parameter of 10 times per 8mA for 20 seconds, as shown in fig. 4, to produce a desired structure, as shown in fig. 5.
Example 3
Adsorbing positively charged methyl violet molecules to enhance the plasmon mediated reduction reaction of p-nitrobenzophenol.
The graphene oxide and silver nanoparticle composite structure is used as a surface plasmon polariton photocatalyst to catalyze p-nitrobenzophenol (PNTP) to be reduced into p-mercaptoazobenzene (DMAB). Wherein the reaction rate and degree of reaction are determined by the characteristic peak (. gamma.) of DMABN＝N) Area and characteristic peak of PNTP (. gamma.)cs) Raman scattering intensity ratio of
The time profile is shown in fig. 6 a. When positively charged methyl violet is adsorbed on the surface of the silver nanoparticles, the reaction rate of PNTP reduction is obviously accelerated, and the degree of reduction reaction is also obviously enhanced. In addition, through calculation of PNTP reduction
The reaction rate is calculated in the first few seconds, as shown in fig. 6b, after the positively charged methyl violet is adsorbed on the surface of the graphene oxide, the reaction rate of PNTP reduction is obviously increased, and the enhancement effect is gradually enhanced along with the reduction of the laser power, which indicates that the reduction reaction of PNTP at the interface between the silver nanoparticle and the graphene oxide can be significantly promoted by adsorbing the positively charged methyl violet on the surface of the graphene oxide. In addition, excitation of different laser wavelengths is carried out according to ultraviolet absorption, and the absorption of methyl violet by 532nm excitation is enhanced more obviously than that by 632.8nm excitation. As shown in fig. 6 c-d.
Example 4
Adsorbing the negatively charged methyl blue molecules and the negatively charged rhodamine 110 molecules to regulate plasmon mediated PNTP reduction reaction. As shown in fig. 7, the reduction of PNTP is inhibited by negatively charged methyl blue molecules and is promoted by positively charged rhodamine 110 molecules.
Example 5
The charge of the rhodamine organic molecule is changed to regulate and control the plasmon mediated PNTP reduction reaction.
Because the rhodamine 110 molecule has both amino and carboxyl, the charge property can be different by changing the pH value. The isoelectric point of rhodamine 110, which can be obtained by a two-electrode test current, is about 11.5, as shown in fig. 7 a. The rhodamine 110 is shown to be positive when the pH value is less than 11.5, and the rhodamine 110 is shown to be negative when the pH value is more than 11.5. The influence of the rhodamine on PNTP reduction is further tested, and the rhodamine 110 inhibits the reduction reaction of the p-nitrobenzothiophenol after the pH value is more than 11. As shown in fig. 7 b.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.
Claims (9)
1. A cheap and simple method for enhancing plasmon-driven photoreduction reaction at an interface, which is characterized in that: a novel method for dielectric light reduction of plasma metal comprises the steps of modifying 3-Aminopropyltriethoxysilane (APS) on the surface of a cover glass, soaking an oxidized graphene sheet subjected to ultrasonic treatment, sputtering according to proper parameters, soaking the structure in a p-nitrophenol ethanol solution, adsorbing reactant molecules by forming plasma metal-sulfur chemical bonds on the plasma metal, and soaking the structure in a positively charged benzene ring-containing organic molecular solution to obtain a composite catalytic structure of oxidized graphene adsorbing a positively charged molecular promoter and the plasma metal; the reaction from p-nitrobenzophenol to p-mercaptoazobenzene is monitored through in-situ Raman spectroscopy, and it is known that the plasmon-driven photoreduction reaction can be effectively and simply enhanced by adsorbing positively charged benzene ring-containing organic molecules on the surface of graphene oxide.
2. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: a novel method for plasma metal dielectric light reduction is characterized in that after 3-Aminopropyltriethoxysilane (APS) on the surface of a cover glass is modified, a graphene oxide sheet which is subjected to ultrasonic treatment for 30min is soaked for 30s, uninterrupted sputtering is carried out for 10 times with the parameter of 20s of 8mA each time, the structure is firstly placed in a p-nitrophenol and thiophenol ethanol solution to be soaked for 2 hours, a plasma metal-sulfur chemical bond formed on the plasma metal is obtained, and finally the structure is placed in a positively charged benzene ring-containing organic molecular solution to be soaked for 30min, so that a composite catalytic structure of graphene oxide and plasma metal, which adsorbs a positively charged molecular promoter, can be obtained; the reaction from p-nitrobenzophenol to p-mercaptoazobenzene is monitored through in-situ Raman spectroscopy, and it is known that the plasmon-driven photoreduction reaction can be effectively and simply enhanced by adsorbing positively charged benzene ring-containing organic molecules on the surface of graphene oxide.
3. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: the plasma metal refers to gold, silver, copper, aluminum and alloy, and the alloy can be the mutual combination of gold, silver, copper and aluminum, and also can be the alloy of gold, silver, copper, aluminum, platinum and palladium.
4. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: the composite catalytic structure is a composite structure of graphene oxide and plasma metal by using an adsorption molecule cocatalyst.
5. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: the graphene oxide can effectively adsorb low-cost positively charged benzene ring-containing organic molecules, and can remarkably enhance the reduction reaction of p-nitrobenzophenol driven by plasmons at the metal interface of the graphene oxide and the plasma.
6. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: the positively charged organic molecule containing benzene ring is dye molecule methyl violet or rhodamine 110.
7. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: the graphene oxide can effectively adsorb other organic molecules with different charges, and can effectively enhance or inhibit the photoreduction reaction driven by plasma at the metal interface of the graphene oxide and the plasma.
8. The inexpensive, simple method of enhancing a plasmon-driven photoreduction reaction at an interface according to claim 1, wherein: the graphene oxide is a lamellar material with high yield and fewer defects; the preparation process comprises the following steps:
graphite (0.75g,<325 mesh) and KMnO4(4.5g) were mixed well and placed in a 250mL single-neck flask (magnetons were placed in the flask in advance). Placing the flask in an oil bath pan, adjusting the magneton at medium speed, setting the temperature at 50 ℃, and adding 10mL of concentrated H3PO4And 90mL of concentrated H2SO4The mixed acid solution flows along the wall of the bottle and is slowly dripped; when the temperature rises to 50 ℃, the reaction is carried out for 12 h. After 12h, the mixture was cooled to room temperature using an ice bath, at which point the reaction turned purple-green and 100mL of ice-water mixture was slowly added dropwise. Then 30% H was gradually added2O2Removing the excess oxidant, adding dropwise and stirring, the solution becoming bright yellow when the last drop is added; finally, the slurry was transferred to a centrifuge tube and centrifuged at 8000rpm for 10 minutes to remove the colorless supernatant, and a precipitate, i.e., graphene oxide sheets, was obtained, which could be dispersed in an aqueous or ethanol solution.
9. The inexpensive, simple method of enhancing plasmon-driven photoreduction reactions at interfaces according to claim 1, characterized in that: the composite material is a highly uniform Raman enhanced substrate and is prepared by the following steps: performing APS (3-aminopropyltriethoxysilane) modification on the surface of a cover glass, soaking a graphene oxide sheet which is subjected to ultrasonic treatment for 30min for 30s, performing uninterrupted sputtering for 10 times with a parameter of 20s of 8mA each time, soaking the structure in a p-nitrophenol ethanol solution for 2 hours, forming a chemical bond with sulfur through plasma metal to adsorb a reactant p-nitrophenol, and finally soaking the structure in a positively charged benzene ring-containing organic molecular solution for 30min to obtain the graphene oxide and plasma metal composite catalytic structure adsorbing the positively charged molecular promoter.
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