CN110643637A - Cu2Preparation method and application of O/RGO @ SW inorganic/biological hybrid photocatalyst - Google Patents
Cu2Preparation method and application of O/RGO @ SW inorganic/biological hybrid photocatalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of inorganic/biological heterozygotes, relates to inorganic/biological heterozygotes, and particularly relates to Cu2Preparation method and application of O/RGO @ SW inorganic/biological hybrid photocatalyst. The method firstly uses an in-situ growth method to thermally dissolve Cu2O nano-particles are loaded on the surface of the reduced graphene oxide, and Shewanella oneidensis MR-1 is further introduced on the surface of the reduced graphene oxide under the vacuum oxygen-free condition through electrostatic adsorption to form an inorganic/biological hybrid photocatalyst, wherein the Shewanella oneidensis MR-1 is OD600The range is 0.5 to 4.0. The invention discloses a method for reducing graphene oxide two-dimensional carbon material as bridge impurityMethod for preparing inorganic semiconductor and biological bacteria capable of reacting Cu2O and Shewanella bacteria are respectively loaded on the surface of the reduced graphene oxide. The composite material prepared by the method has good photocatalytic hydrogen production activity, and the highest Cu content is single Cu under the same conditions246 times of O, and Cu used2O has the characteristics of environmental protection, low price, easy synthesis and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic/biological heterozygotes, relates to inorganic/biological heterozygotes, and particularly relates to Cu2Preparation method and application of O/RGO @ SW inorganic/biological hybrid photocatalyst.
Background
The photocatalytic technology for converting solar energy into hydrogen energy is widely considered as a feasible means for solving energy crisis and environmental problems. The photocatalytic hydrolysis system constructed by all inorganic materials has been studied intensively so far, but the practical application of the photocatalytic technology is restricted by the relatively low light conversion efficiency and utilization rate. In recent years, hybrid systems constructed of inorganic and biological materials have attracted more and more attention because of their ability to combine the high light absorption of inorganic materials with the high activity and high reaction frequency of biocatalysts.
Hydrogenase (such as single Fe, Fe-Fe, Ni-Fe and the like) is used as a high-efficiency proton-reducing hydrogen production catalyst, and the catalytic conversion frequency can reach 6000 to 9000 s at most-1The method is applied to inorganic/biological hybrid systems, and the photocatalytic hydrogen production efficiency and stability of various hybrid systems are obviously improved. However, there are some inevitable difficulties in the isolation and purification of naked enzymes in nature. Therefore, on the basis of naked enzyme, researchers further develop a whole-cell catalyst containing hydrogenase, which is more easily obtained and stable than naked enzyme and is more suitable for an inorganic/biological hybrid system.
The introduction of whole cells not only avoids the isolation and purification of naked enzyme, but also protects the naked enzyme from some extra-membrane damage. The introduction of whole cells, while protecting the enzyme from external damage, also isolates electron transport outside the cell. Electron transport mediators, such as methyl viologen, riboflavin, eosin, etc., play an important role in the process of intracellular and extracellular electron transport. However, these electron transport mediators have some toxic effects on intracellular enzymes, which can inhibit the catalytic activity of these enzymes. More importantly, the electron transfer from the inorganic material to the cell is random and unstable, which is carried by the electron transfer mediator. The main expression is in the following two aspects:
(i) toxicity of semiconductors and electronic media to cells;
(ii) waste caused by photo-generated electrons that are far from the transfer medium and not transferred in time.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to disclose a Cu alloy2O/RGO@SA preparation method of W inorganic/biological hybrid photocatalyst.
First, Cu is thermally dissolved by an in-situ growth method through a solvent2O nano particles are loaded on the surface of the reduced graphene oxide, and Shewanella bacteria are further introduced on the surface of the reduced graphene oxide under the vacuum and oxygen-free conditions through hydrophobic effect to form the inorganic/biological hybrid photocatalyst.
The technical scheme is as follows:
the invention firstly adopts a solvothermal method to prepare Cu2Preparing Cu on the surface of graphene by O in-situ growth2O/RGO inorganic composite material, and then the Shewanella bacteria are absorbed and loaded on the surface of the graphene through hydrophobic effect, and finally Cu is prepared2O/RGO @ SW inorganic/biological composite material, the Cu2Cu in O/RGO composite material2The mass ratio of O to RGO is 1.2:1, 1.8:1, 2.4:1, 3.0:1, 3.6:1, 4.2: 1; OD of Shewanella solution600Is 0.5, 1.0, 2.0, 3.0.
Cu2The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst comprises the following steps:
A. ultrasonically dissolving 50mg of graphene oxide in 25mL of ethanol solution, and adding Cu (NO)3)2·3H2Continuously stirring the mixture evenly, then dropwise adding ascorbic acid solution, and stirring the mixture evenly to obtain mixed solution, wherein Cu (NO) is added3)2·3H2The mass of O is 0.2-0.7 g, preferably 0.5 g; the concentration of the ascorbic acid solution is 10 g/L, and the volume of the ascorbic acid solution is 0.4-1.4 mL, preferably 1.0 mL;
B. adjusting the pH value of the mixed solution to 5-9, preferably 10, transferring the mixed solution to a high-temperature resistant reaction kettle, and carrying out solvothermal reaction at 120-180 ℃ for 4-24 h, preferably at 160 ℃ for 24 h; taking out, naturally cooling to room temperature to obtain Cu2Washing O-RGO with ethanol and distilled water for 2-3 times, and vacuum drying at 60 deg.C for 24 hr to obtain Cu2O/RGO powder;
C. two 50mL portions of buffer solution were prepared, and 50mgCu was weighed2Ultrasonically dissolving O/RGO powder into one part of buffer solution, dissolving Shewanella bacteria into the other part of buffer solution, quickly mixing the two parts of solution, vacuumizing, and stirring for 20-40%min, preferably 30min, to obtain Cu2O-RGO @ SW inorganic/biological hybrid photocatalyst, wherein the Shewanella oneidensis bacterium is Shewanella oneidensis MR-1, and OD thereof600The range is 0.5 to 4.0.
In the preferred embodiment of the present invention, the buffer solution in step C is a mixture of 100mM Tris-HCl, 150mM NaCl, 5% (V/V) glycerol and 100mM ascorbic acid.
It is a further object of the present invention to disclose Cu prepared according to the above method2O/RGO @ SW inorganic/biological hybrid photocatalyst is applied to photocatalytic hydrogen production.
Photocatalytic activity test
(1) Preparing 100mL of buffer solution A (100 mM Tris-HCl, 150mM sodium chloride, 5% (V/V) glycerol and 100mM ascorbic acid), and dividing the buffer solution A into 2 parts;
(2) dissolving the prepared Shewanella bacteria in 50mL of buffer solution A in an oxygen-free operation table, and shaking to form a uniform solution;
(3) weighing 50mgCu2Dissolving O/RGO in another 50mL buffer solution A by ultrasonic for 15s, transferring the mixed solution into a reactor, and rapidly adding a bacterial solution into the reactor;
(4) the hydrogen production instrument is quickly vacuumized, and the whole system is stirred for 30min under the anaerobic condition;
(5) turning on a 300W xenon lamp provided with a 420nm optical filter, and carrying out a photocatalytic hydrogen production experiment;
(6) quantitative gas was collected every hour, and the specific hydrogen content was measured by gas chromatography (GC-7920, Zhongzhao gold source) using high-purity nitrogen as a carrier gas.
And (3) performing morphology structure analysis on the product by using instruments such as X-ray diffraction (XRD), Raman spectrum (Raman), X-ray photoelectron spectrometer (XPS) and the like, and evaluating the photocatalytic activity of the product by decomposing water to prepare hydrogen.
The invention selects Shewanella bacteria containing hydrogenase, graphene and Cu2O, the all-solid-state inorganic/biological hybrid hydrogen production photocatalyst is constructed for the first time. The graphene can be used as a current collector to effectively transfer electrons, and organic groups on the surface of the graphene canSo as to tightly adsorb Shewanella bacteria; and the Shewanella bacteria contain conductive protein which can transfer photogenerated electrons conducted by graphene from the extracellular part to the intracellular hydrogenase.
Advantageous effects
The invention relates to a preparation method of a hybrid inorganic semiconductor and biological bacteria by taking a reduced graphene oxide two-dimensional carbon material as a bridge, which is characterized in that Cu is added2O and SW bacteria are loaded on the surface of the reduced graphene oxide respectively. The composite material prepared by the method has good photocatalytic hydrogen production activity, and the highest Cu content is single Cu under the same conditions246 times of O, and Cu used2O also has the characteristics of environmental protection, low price, easy synthesis and the like.
Drawings
FIG. 1 RGO, GO, Cu2O and Cu2XRD pattern of O/RGO;
FIG. 2 different samples Cu2Raman plots of O/RGO;
FIG. 3 sample Cu2TEM image of O/RGO @ SW;
FIG. 4 shows photocatalytic hydrogen production diagrams of different samples.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
3.0Cu2The preparation method of the O/RGO @1.0SW inorganic/biological hybrid photocatalyst comprises the following steps:
firstly, 50mg of graphene oxide is added into 25mL of ethanol solution, ultrasonic treatment is carried out for 1h until the graphene oxide is dissolved in the ethanol solution,then 0.5 g of Cu (NO) is added into the graphene oxide ethanol solution3)2·3H2O and 1 mL ascorbic acid solution, and continuously stirring for 30min until the solution is uniform; graphene oxide and Cu (NO) were then adjusted3)2·3H2The pH value of the O mixed solution is 9, the O mixed solution is stirred for 30min, and finally the mixed solution is transferred to a high-temperature resistant reaction kettle and is placed in a high-temperature oven with the temperature of 160 ℃ for heating reaction for 4 h; taking out the reaction kettle, cooling to room temperature, washing with distilled water and ethanol for 2-3 times, vacuum drying at 60 deg.C for 12 hr to obtain 3.0Cu2O/RGO powder.
50mg of prepared Cu was weighed2The O/RGO powder was dissolved in 50mL of buffer solution by sonication, and 50mL of OD was added600The Shewanella bacteria solution of =2.0 is prepared by quickly vacuumizing the whole mixed solution, stirring for 30min to obtain 3.0Cu2O/RGO @1.0SW inorganic/biohybrid photocatalyst.
The obtained Cu2O/RGO @ SW inorganic/biological hybrid photocatalyst is applied to photocatalytic hydrogen production, and the hydrogen production in 4h is pure Cu246 times of O.
As shown in FIG. 1, it was confirmed that Cu of different mass ratios2O/RGO inorganic composites were successfully prepared.
As shown in fig. 2, illustrating the presence of graphene in the sample, it is demonstrated that cuprous oxide has successfully complexed with graphene.
As shown in FIG. 3, it was confirmed that Cu2The O and SW bacteria are distributed on the surface of the reduced graphene oxide in an unordered mode.
As shown in FIG. 4, sample Cu2O/RGO @ SW shows higher photocatalytic hydrogen production activity, and the hydrogen production amount in 4h is pure Cu246 times of O.
Example 2
1.8Cu2The preparation method of the O/RGO @2.0SW inorganic/biological hybrid photocatalyst comprises the following steps:
firstly, 50mg of graphene oxide is added into 25mL of ethanol solution, ultrasonic treatment is carried out for 1h until the graphene oxide is dissolved in the ethanol solution, and then 0.3 g of Cu (NO) is added into the graphene oxide ethanol solution3)2·3H2O and 0.6 mL ascorbic acid solution, with constant stirringThe solution is uniform after 30 min; graphene oxide and Cu (NO) were then adjusted3)2·3H2The pH value of the O mixed solution is 9, the O mixed solution is stirred for 30min, and finally the mixed solution is transferred to a high-temperature resistant reaction kettle and is placed in a high-temperature oven with the temperature of 160 ℃ for heating reaction for 4 h; taking out the reaction kettle, cooling to room temperature, washing with distilled water and ethanol for 2-3 times, vacuum drying at 60 deg.C for 12 hr to obtain 1.8Cu2O/RGO powder.
50mg of prepared Cu was weighed2The O/RGO powder was dissolved in 50mL of buffer solution by sonication, and 50mL of OD was added600The Shewanella bacteria solution of =4.0 is prepared by quickly vacuumizing the whole mixed solution, stirring for 30min, and finally obtaining 1.8Cu2O/RGO @2.0SW inorganic/biohybrid photocatalyst.
The obtained Cu2O/RGO @ SW inorganic/biological hybrid photocatalyst is applied to photocatalytic hydrogen production, and the hydrogen production in 4h is pure Cu 22 times of O.
Example 3
4.2Cu2The preparation method of the O/RGO @0.5SW inorganic/biological hybrid photocatalyst comprises the following steps:
firstly, 50mg of graphene oxide is added into 25mL of ethanol solution, ultrasonic treatment is carried out for 1h until the graphene oxide is dissolved in the ethanol solution, and then 0.7 g of Cu (NO) is added into the graphene oxide ethanol solution3)2·3H2O and 1.4 mL ascorbic acid solution, continuously stirring for 30min until the solution is uniform, and then adjusting graphene oxide and Cu (NO)3)2·3H2The pH value of the O mixed solution is 9, the O mixed solution is stirred for 30min, and finally the mixed solution is transferred to a high-temperature resistant reaction kettle and is placed in a high-temperature oven with the temperature of 160 ℃ for heating reaction for 4 h; taking out the reaction kettle, cooling to room temperature, washing with distilled water and ethanol for 2-3 times, vacuum drying at 60 deg.C for 12 hr to obtain 4.2Cu2O/RGO powder.
50mg of prepared Cu was weighed2The O/RGO powder was dissolved in 50mL of buffer solution by sonication, and 50mL of OD was added600The Shewanella bacteria solution of =1.0 is prepared by quickly vacuumizing the whole mixed solution, stirring for 30min, and finally obtaining 4.2Cu2O/RGO @0.5SW inorganic/biohybrid photocatalyst.
The obtained Cu2O/RGO @ SW inorganic/biological hybrid photocatalyst is applied to photocatalytic hydrogen production, and the hydrogen production in 4h is pure Cu 22 times of O.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (8)
1. Cu2The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized by comprising the following steps of:
A. ultrasonically dissolving 50mg of graphene oxide in 25mL of ethanol solution, and adding Cu (NO)3)2·3H2Continuously stirring the mixture evenly, then dropwise adding ascorbic acid solution, and stirring the mixture evenly to obtain mixed solution, wherein Cu (NO) is added3)2·3H2The mass of O is 0.2-0.7 g; the concentration of the ascorbic acid solution is 10 g/L, and the volume of the ascorbic acid solution is 0.4-1.4 mL;
B. adjusting the pH value of the mixed solution to 5-9, transferring the mixed solution to a high-temperature resistant reaction kettle, and carrying out a solvothermal reaction for 4-24 hours at 120-180 ℃; taking out, naturally cooling to room temperature to obtain Cu2Washing O-RGO with ethanol and distilled water for 2-3 times, and vacuum drying at 60 deg.C for 24 hr to obtain Cu2O-RGO powder;
C. two 50mL portions of buffer solution were prepared, and 50mgCu was weighed2Ultrasonically dissolving O/RGO powder into one part of buffer solution, dissolving Shewanella bacteria into the other part of buffer solution, quickly mixing the two parts of solution, vacuumizing, stirring for 20-40 min to obtain Cu2O-RGO @ SW inorganic/biological hybrid photocatalyst, wherein the Shewanella oneidensis bacterium is Shewanella oneidensis MR-1, OD thereof600The range is 0.5 to 4.
2. Cu according to claim 12The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized by comprising the following steps of: step A addition of Cu (NO)3)2·3H2The mass of O is 0.5 g; the above-mentionedThe concentration of the ascorbic acid solution was 10 g/L, and the volume was 1.0 mL.
3. Cu according to claim 12The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized by comprising the following steps of: and B, adjusting the pH value of the mixed solution to 9.
4. Cu according to claim 12The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized by comprising the following steps of: and (B) carrying out solvothermal reaction for 4 hours at 160 ℃.
5. Cu according to claim 12The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized by comprising the following steps of: and step C, mixing the buffer solution with 100mM Tris-HCl, 150mM sodium chloride, 5% (V/V) glycerol and 100mM ascorbic acid.
6. Cu according to claim 12The preparation method of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized by comprising the following steps of: and C, quickly mixing the two solutions, vacuumizing and stirring for 30 min.
7. Cu obtainable by a process according to any of claims 1 to 62O/RGO @ SW inorganic/biohybrid photocatalyst.
8. Cu as claimed in claim 72The application of the O/RGO @ SW inorganic/biological hybrid photocatalyst is characterized in that: the method is applied to photocatalytic hydrogen production.
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| CN117105394A (en) * | 2023-10-23 | 2023-11-24 | 江西师范大学 | Biological hybrid membrane and preparation method and application thereof |
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