CN107754828B - Photocatalyst with ternary composite structure and preparation method thereof - Google Patents
Photocatalyst with ternary composite structure and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 239000011206 ternary composite Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052709 silver Inorganic materials 0.000 claims abstract description 67
- 239000004332 silver Substances 0.000 claims abstract description 67
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002114 nanocomposite Substances 0.000 claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 239000002096 quantum dot Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 44
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 18
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000004044 response Effects 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000011165 3D composite Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- -1 silver amine Chemical class 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229940052810 complex b Drugs 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003378 silver Chemical class 0.000 description 6
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Materials Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a photocatalyst with a ternary composite structure and a preparation method thereof, wherein the method comprises the following steps: and reducing the silver-amine complex into silver atoms by taking the black phosphorus quantum dots as a reducing agent, simultaneously depositing the generated silver atoms on the surface of the black phosphorus quantum dots to generate a silver cluster/black phosphorus nano composite by taking the black phosphorus quantum dots as a stabilizing agent, and depositing the silver cluster/black phosphorus nano composite on the surface of two-dimensional graphene oxide to obtain the photocatalyst with a three-dimensional composite structure. According to the photocatalyst provided by the invention, through the response of the two-dimensional graphene oxide and the black phosphorus quantum dot to visible light and near infrared light, electrons generated by excitation can be transferred to the surface of a silver cluster from the black phosphorus quantum dot through the graphene oxide, so that excellent photocatalytic activity is shown.
Description
Technical Field
The invention relates to the field of photocatalysts, in particular to a photocatalyst with a ternary composite structure and a preparation method thereof.
Background
At present, solar energy is regarded as one of the most promising and valuable renewable energy sources in the 21 st century as a green, clean and inexhaustible energy source. Hydrogen is not only a clean energy source but also an excellent energy carrier with storable characteristics. The solar energy and wind energy dispersed intermittent power generation device and the peak-valley difference of the load of the power grid or a large amount of cheap electric energy can be converted into hydrogen energy for storage, and can be converted and reused by a fuel cell when needed, and the energy storage mode is dispersed flexibly.
At present, a plurality of methods for preparing hydrogen exist, wherein a photocatalytic oxidation technology for preparing hydrogen by water decomposition by using solar energy becomes one of research hotspots in the field of solar energy high-efficiency conversion, and has important research values for effectively utilizing solar energy resources and exploring clean energy. Solar energy is the ultimate source of energy on earth, and is both a primary energy source and a renewable energy source. It has rich resource, can be used freely, does not need transportation, and has no pollution to the environment. The seawater resources on the earth are very rich, the hydrogen in the seawater is released by solar energy, and water is generated after the hydrogen is utilized, so that no influence is caused on the environment. In recent years, various photocatalysts utilizing solar energy conversion have received much attention and are reported, however, the current catalysts still have a major disadvantage of low solar energy conversion efficiency due to lack of development of materials responding effectively to visible light and near infrared light. Therefore, the search for a novel catalytic material capable of responding in the visible light and near infrared light regions is an important problem which needs to be solved urgently in the field of photocatalysis at present.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a photocatalyst having a ternary composite structure and a preparation method thereof, and aims to solve the problem of low solar energy conversion efficiency caused by the fact that the existing photocatalyst cannot effectively utilize visible light and near infrared light energy.
The technical scheme of the invention is as follows:
a preparation method of a photocatalyst with a ternary composite structure comprises the following steps:
A. providing a black phosphorus quantum dot dispersion liquid and a graphene oxide dispersion liquid;
B. mixing and stirring silver nitrate and organic amine to prepare a silver-amine complex solution, adding the silver-amine complex solution and the black phosphorus quantum dot dispersion liquid into an organic solvent according to a molar ratio of 1:1-1:20, and performing ultrasonic treatment to obtain a silver cluster/black phosphorus nano-composite dispersion liquid;
C. and mixing the silver cluster/black phosphorus nano composite dispersion liquid and the graphene oxide dispersion liquid according to a preset molar ratio, and performing centrifugal washing treatment to obtain the photocatalyst with a ternary composite structure.
The preparation method of the photocatalyst with the ternary composite structure comprises the step of preparing the silver cluster/black phosphorus nano composite, wherein the size of the silver cluster is 0.5-2 nm.
The preparation method of the photocatalyst with the ternary composite structure comprises the step of preparing a photocatalyst, wherein the organic amine is one or more of tert-butylamine, n-butylamine, oleylamine, dodecylamine and octadecylamine.
The preparation method of the photocatalyst with the ternary composite structure comprises the step of B, wherein the organic solvent in the step B is one or more of cyclohexane, toluene, hexane, ethanol and N-methylpyrrolidone.
The preparation method of the photocatalyst with the ternary composite structure comprises the step of preparing the photocatalyst with the ternary composite structure, wherein the molar ratio of silver nitrate to organic amine is 1:1-1: 20.
The preparation method of the photocatalyst with the ternary composite structure comprises the step of preparing the silver cluster/black phosphorus nano composite and graphene oxide according to a molar ratio of 1:1-1: 100.
The preparation method of the photocatalyst with the ternary composite structure comprises the step of carrying out ultrasonic treatment for 2-60min in the step B.
The preparation method of the photocatalyst with the ternary composite structure comprises the following steps of A, centrifuging at a speed of 10000-20000rmp/min and centrifuging for 15-25 min.
The preparation method of the photocatalyst with the ternary composite structure comprises the following steps of:
a1, dispersing the black phosphorus crystal in an N-methyl pyrrolidone solvent, and carrying out ice-water bath ultrasonic treatment to obtain a mixed solution;
a2, centrifuging the mixed solution at a centrifugation speed of 7000r/min for 10-30min, and then taking centrifugal liquid;
and A3, centrifuging the centrifugate at the centrifugal speed of 15000r/min for 10-30min, removing the centrifugate, and dispersing the solid left after centrifugation into an N-methyl pyrrolidone solvent to obtain the black phosphorus quantum dot dispersion liquid.
A photocatalyst with a ternary composite structure is prepared by any one of the preparation methods.
Has the advantages that: the invention provides a preparation method of a photocatalyst with a ternary composite structure, wherein a black phosphorus quantum dot is used as a reducing agent to reduce a silver-amine complex into silver atoms, and is also used as a stabilizing agent to deposit the generated silver atoms on the surface of the black phosphorus quantum dot to generate a silver cluster/black phosphorus nano composite, and the silver cluster/black phosphorus nano composite is deposited on the surface of two-dimensional graphene oxide, so that the photocatalyst with the ternary composite structure is obtained.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a method for preparing a photocatalyst having a ternary composite structure according to the present invention.
Detailed Description
The invention provides a photocatalyst with a ternary composite structure and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing a photocatalyst having a ternary composite structure according to the present invention, as shown in the figure, wherein the method comprises the following steps:
s10, providing a black phosphorus quantum dot dispersion liquid and a graphene oxide dispersion liquid;
s20, mixing and stirring silver nitrate and organic amine to prepare a silver-amine complex solution, adding the silver-amine complex solution and the black phosphorus quantum dot dispersion liquid into an organic solvent according to a molar ratio of 1:1-1:20, and performing ultrasonic treatment to obtain a silver cluster/black phosphorus nano-composite dispersion liquid;
s30, mixing the silver cluster/black phosphorus nano composite dispersion liquid and the graphene oxide dispersion liquid according to a preset molar ratio, and performing centrifugal washing treatment to obtain the photocatalyst with a ternary composite structure.
In particular, the black phosphorus has the advantages of high carrier mobility, good current saturation property, plane anisotropy and the like, so the black phosphorus has good application prospect in the fields of electronics and optoelectronics. Due to the special structure of the black phosphorus quantum dot, the electronic energy band of the black phosphorus quantum dot is in the range of 0.2-2ev, so that the black phosphorus quantum dot can respond in both visible light and near infrared light regions and can be used as a near infrared photocatalytic material with huge potential.
The embodiment provides a preparation method of a black phosphorus quantum dot dispersion liquid, which specifically comprises the following steps:
s11, dispersing the black phosphorus crystal in an N-methyl pyrrolidone solvent, and carrying out ice-water bath ultrasonic treatment to obtain a mixed solution;
s12, centrifuging the mixed solution at a centrifugation speed of 7000r/min for 10-30min, and then taking centrifugal liquid;
and S13, centrifuging the centrifugate at the centrifugal speed of 15000r/min for 10-30min, removing the centrifugate, and dispersing the solid left after centrifugation into an N-methyl pyrrolidone solvent to obtain the black phosphorus quantum dot dispersion liquid.
Because the black phosphorus crystal has strong activity and certain reducibility and is very easy to oxidize when exposed in air, the black phosphorus crystal is dispersed in an N-methylpyrrolidone solvent, mixed liquid with various sizes is obtained through ice-water bath ultrasonic treatment, and then the black phosphorus quantum dot with small size is obtained through gradient centrifugation treatment.
Preferably, the black phosphorus quantum dots with the size of 1-5nm are obtained by processing at the centrifugal speed of 7000r/min for 20min and then at the centrifugal speed of 15000r/min for 20min, and phosphorus atoms on the black phosphorus quantum dots with the size are extremely active and have strong reducibility.
Further, in the step S20, a silver amine complex solution is prepared by mixing and stirring silver nitrate and organic amine, the silver amine complex solution and the black phosphorus quantum dot dispersion are added into an organic solvent according to a molar ratio of 1:1-1:20, and a silver cluster/black phosphorus nano-composite dispersion is obtained after ultrasonic treatment.
Specifically, silver mirror reaction is an ancient chemical reaction, and the main process is that silver nitrate and ammonia water are mixed to form a silver-ammonia complex, and then the silver-ammonia complex is reduced by reducing agents such as aldehydes and forms a bright silver mirror on the wall of a test tube. Therefore, the use of silver mirror reaction is mainly for preparing ultra-thin silver coatings and smooth silver surfaces, etc. In recent years, researchers report that silver nanoparticles are prepared by utilizing silver mirror reaction, however, because the silver mirror reaction is extremely fast and can be completed instantly at normal temperature, the obtained silver particles are generally large in size and very uneven in distribution, and the application of the silver particles in preparing high-quality nano materials in the nano field is limited.
According to the invention, organic amine is adopted to replace traditional ammonia water as a complexing agent, wherein the organic amine is one or more of tert-butylamine, n-butylamine, oleylamine, dodecylamine and octadecylamine; lauryl amine is preferred in the embodiment, the lauryl amine as a complexing agent can form a stable silver amine complex with silver ions, and as a surfactant can stabilize newly generated silver crystal nuclei and prevent the newly generated silver crystal nuclei from being agglomerated into nano crystals with larger sizes; in addition, the replacement of the aqueous solvent with the organic solvent enables the newly formed silver atoms and silver nuclei to be well stabilized and dispersed. Therefore, the silver mirror reaction under the organic system provided by the invention can enable the reduction reaction to be carried out in a mild and controllable manner.
In the present invention, the organic solvent is one or more of cyclohexane, toluene, hexane, ethanol, or N-methylpyrrolidone, but is not limited thereto. The silver mirror reaction in an organic system is the key for preparing the silver cluster-black phosphorus nano compound, and is different from the traditional aqueous phase silver mirror reaction in that the crystal nucleus generation and the crystal growth simultaneously occur in the aqueous phase silver mirror reaction and large-size irregular silver particles can be generated. The silver mirror reaction of the organic phase can obviously divide the reduction process into two processes of crystal nucleus generation and crystal nucleus growth. Since the nucleation is an energy-consuming process, the absorption peak grows at a lower rate in the nucleation stage, and once the nucleation has occurred, the crystal growth proceeds at a higher rate, and the corresponding absorption peak grows in a faster manner. The molar ratio of the silver nitrate to the organic amine is 1:1-1:20, and in order to ensure complete reaction of the silver nitrate and sufficient organic amine, the molar ratio of the silver nitrate to the organic amine is preferably 1: 5.
In the embodiment, the silver amine complex solution and the black phosphorus quantum dot dispersion liquid are added into an organic solvent according to the molar ratio of 1:1-1:20, and the silver cluster/black phosphorus nano-composite dispersion liquid is obtained after ultrasonic treatment.
Specifically, the black phosphorus quantum dots with the size of 1-5nm have extremely strong reducibility, and can effectively reduce silver ions in the silver-amine complex and deposit the silver ions on the surface to obtain a uniform high-activity silver cluster/black phosphorus nano complex; the small-size black phosphorus quantum dots have strong dispersibility, and can be more uniformly deposited on the surface of graphene oxide after interacting with silver clusters, so that the catalytic activity of the graphene oxide is improved. That is, the nano-composite formed by the black phosphorus quantum dots and the silver clusters exerts the unique catalytic performance of the silver clusters on one hand; on the other hand, the response of the visible and near infrared regions of the black phosphorus quantum dots is fully exerted, and the black phosphorus quantum dots can be used as a novel photocatalytic composite material.
Preferably, the size of the silver cluster on the black phosphorus quantum dot can be accurately controlled by controlling the using amount and the reaction time of the silver amine complex. When the molar ratio of the silver amine complex to the black phosphorus quantum dots is 1:1-1:20, and the ultrasonic treatment time is 2-60min, the size of the silver cluster on the black phosphorus quantum dots is 0.5-2nm, the obtained silver cluster/black phosphorus nano-composite is subjected to centrifugal treatment, the centrifugal speed is 10000-20000rmp/min, and the centrifugal time is 15-25min, so that the black phosphorus quantum dot-loaded silver cluster nano-composite has excellent photocatalytic performance.
Further, in the step S30, the silver cluster/black phosphorus nanocomposite dispersion liquid and the graphene oxide dispersion liquid are mixed according to a predetermined molar ratio, and then are centrifugally washed to obtain the photocatalyst having a ternary composite structure.
Specifically, graphene oxide is considered as an excellent solar photocatalytic material due to its response in a visible light region as a classical two-dimensional material, and can be used as an electron donor to effectively and rapidly provide electrons excited by black phosphorus quantum dots to silver clusters due to its special electronic structure, thereby more efficiently playing a catalytic role. In addition, the layered structure of the graphene oxide can stabilize the silver cluster/black phosphorus nano composite on the surface of the graphene oxide, effectively prevent the silver cluster/black phosphorus nano composite from being agglomerated and inactivated, and further improve the catalytic efficiency and catalytic stability of the photocatalyst with a ternary composite structure.
Further, the molar ratio of the silver cluster/black phosphorus nano composite to the graphene oxide is 1:1-1: 100. Specifically, in order to ensure that the silver cluster/black phosphorus nanocomposite can be completely and sufficiently loaded on the graphene oxide to form the three-way composite photocatalyst, the molar ratio of the silver cluster/black phosphorus nanocomposite to the graphene oxide is preferably 1: 50.
According to the photocatalyst, the black phosphorus quantum dots and the two-dimensional graphene oxide are effectively combined in visible and near-infrared response materials and play a synergistic role, the two-dimensional graphene oxide and the two-dimensional graphene oxide respond to visible light and near-infrared light, electrons generated by excitation can be transferred to the surfaces of silver clusters from the black phosphorus quantum dots through the graphene oxide, and excellent photocatalytic activity is further shown.
Based on the method, the invention also provides a photocatalyst with a ternary composite structure, wherein the photocatalyst is prepared by any one of the preparation methods, and the photocatalyst consists of a ternary nanocomposite formed by depositing black phosphorus quantum dots and sub-nano silver clusters embedded on the surfaces of the black phosphorus quantum dots onto the surfaces of two-dimensional graphene oxide.
The following provides a further explanation of the method for preparing a photocatalyst responsive to visible light and near-infrared light according to the present invention by way of specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Adding 40mg of black phosphorus crystals into 60mL of NMP solvent, carrying out ultrasonic treatment in ice-water bath for 3h, centrifuging 7000rmp/min of an ultrasonic sample for 20min to obtain a filtrate, centrifuging 15000rmp/min of the obtained filtrate for 20min, removing the supernatant centrifugate, and re-dispersing the obtained solid into 8mL of NMP solvent to obtain black phosphorus quantum dot dispersion A.
(2) 0.34g of silver nitrate and 1g of dodecylamine are weighed and added into 10mL of ethanol, and the mixture is fully stirred until the silver nitrate and the dodecylamine are completely dissolved, so that a silver-amine complex solution B is obtained.
(3) Adding the black phosphorus quantum dot dispersion liquid A and the silver-organic amine complex B into ethanol according to the molar ratio of 5:1, performing ultrasonic treatment for 5min, centrifuging the obtained product at 15000rmp/min for 20min after the product turns into wine red, and re-dispersing the product into an ethanol solvent to obtain the Ag/BPQDs (silver clusters/black phosphorus quantum dots) nano-composite C.
(4) And fully mixing the nano composite C and the two-dimensional graphene oxide dispersion liquid according to the molar ratio of 1:10, and then carrying out centrifugal washing to obtain the Ag/BPQDs-GO (silver cluster/black phosphorus quantum dot-graphene oxide) ternary composite photocatalyst.
Example 2
(1) Adding 25mg of black phosphorus crystals into 50mL of NMP solvent, carrying out ultrasonic treatment in ice-water bath for 2h, centrifuging 7000rmp/min of an ultrasonic sample for 20min to obtain a filtrate, centrifuging 15000rmp/min of the obtained filtrate for 20min, removing supernatant centrifugate, and re-dispersing the obtained solid into 10mL of NMP solvent to obtain a black phosphorus quantum dot dispersion A.
(2) 0.34g of silver nitrate and 1g of oleylamine were weighed into 8mL of toluene, and sufficiently stirred to be completely dissolved, thereby obtaining a silver amine complex solution B.
(3) And adding the black phosphorus quantum dot dispersion liquid A and the silver-organic amine complex B into toluene according to the molar ratio of 10:1, performing ultrasonic treatment for 10min, centrifuging the obtained product at 15000rmp/min for 20min after the product becomes wine red, and re-dispersing the product into a toluene solvent to obtain the Ag/BPQDs nano-composite C.
(4) And fully mixing the nano composite C and the two-dimensional graphene oxide dispersion liquid according to the molar ratio of 1:8, and then carrying out centrifugal washing to obtain the Ag/BPQDs-GO ternary composite photocatalyst.
Example 3
(1) Adding 22mg of black phosphorus crystals into 55mL of NMP solvent, carrying out ultrasonic treatment in ice-water bath for 4h, centrifuging 7000rmp/min of an ultrasonic sample for 20min to obtain a filtrate, centrifuging 15000rmp/min of the obtained filtrate for 20min, removing the supernatant centrifugate, and re-dispersing the obtained solid into 10mL of NMP solvent to obtain a black phosphorus quantum dot dispersion A.
(2) 0.34g of silver nitrate and 1g of n-octylamine were weighed out and added to 8mL of cyclohexane, and sufficiently stirred until completely dissolved, to obtain a silver amine complex solution B.
(3) And adding the black phosphorus quantum dot dispersion liquid A and the silver-organic amine complex B into cyclohexane according to the molar ratio of 6:1, performing ultrasonic treatment for 10min, centrifuging the obtained product at 15000rmp/min for 20min after the product becomes wine red, and re-dispersing the product in a cyclohexane solvent to obtain the Ag/BPQDs nano-composite C.
(4) And fully mixing the nano composite C and the two-dimensional graphene oxide dispersion liquid according to the molar ratio of 1:9, and then carrying out centrifugal washing to obtain the Ag/BPQDs-GO ternary composite photocatalyst.
Example 4
(1) Adding 33mg of black phosphorus crystals into 58mL of NMP solvent, carrying out ultrasonic treatment in ice-water bath for 2.6h, centrifuging 7000rmp/min of an ultrasonic sample for 20min to obtain a filtrate, centrifuging 15000rmp/min of the obtained filtrate for 20min, removing the supernatant centrifugate, and re-dispersing the obtained solid into 10mL of NMP solvent to obtain a black phosphorus quantum dot dispersion liquid A.
(2) 0.34g of silver nitrate and 1g of tert-butylamine were weighed into 8mL of ethanol, and sufficiently stirred until completely dissolved, to obtain a silver amine complex solution B.
(3) Adding the black phosphorus quantum dot dispersion liquid A and the silver-organic amine complex B into ethanol according to the molar ratio of 15:1, performing ultrasonic treatment for 10min, centrifuging the obtained product at 15000rmp/min for 20min after the product becomes wine red, and re-dispersing the product in an ethanol solvent to obtain the Ag/BPQDs nano-composite C.
(4) And fully mixing the nano composite C and the two-dimensional graphene oxide dispersion liquid according to the molar ratio of 1:15, and then carrying out centrifugal washing to obtain the Ag/BPQDs-GO ternary composite photocatalyst.
Example 5
(1) Adding 18mg of black phosphorus crystals into 30mL of NMP solvent, carrying out ultrasonic treatment in ice-water bath for 3h, centrifuging 7000rmp/min of an ultrasonic sample for 20min to obtain a filtrate, centrifuging 15000rmp/min of the obtained filtrate for 20min, removing supernatant centrifugate, and re-dispersing the obtained solid into 10mL of NMP solvent to obtain a black phosphorus quantum dot dispersion A.
(2) 0.34g of silver nitrate and 1g of octadecylamine were weighed into 11mL of ethanol, and sufficiently stirred until completely dissolved, to obtain a silver amine complex solution B.
(3) And adding the black phosphorus quantum dot dispersion liquid A and the silver-organic amine complex B into ethanol according to the molar ratio of 8:1, performing ultrasonic treatment for 10min, centrifuging the obtained product at 15000rmp/min for 20min after the product becomes wine red, and re-dispersing the product in an ethanol solvent to obtain the Ag/BPQDs nano-composite C.
(4) And fully mixing the nano composite C and the two-dimensional graphene oxide dispersion liquid according to the molar ratio of 1:8, and then carrying out centrifugal washing to obtain the Ag/BPQDs-GO ternary composite photocatalyst.
Example 6
(1) Adding 18mg of black phosphorus crystals into 40mL of NMP solvent, carrying out ultrasonic treatment in ice-water bath for 4h, centrifuging 7000rmp/min of an ultrasonic sample for 20min to obtain a filtrate, centrifuging 15000rmp/min of the obtained filtrate for 20min, removing the supernatant centrifugate, and re-dispersing the obtained solid into 10mL of NMP solvent to obtain a black phosphorus quantum dot dispersion A.
(2) 0.34g of silver nitrate and 1g of n-butylamine were weighed into 8mL of n-hexane, and sufficiently stirred until completely dissolved, to obtain a silver amine complex solution B.
(3) And adding the black phosphorus quantum dot dispersion liquid A and the silver-organic amine complex B into n-hexane according to the molar ratio of 7:1, performing ultrasonic treatment for 20min, centrifuging the obtained product at 15000rmp/min for 20min after the product becomes wine red, and re-dispersing the product in the n-hexane solvent to obtain the Ag/BPQDs nano-composite C.
(4) And fully mixing the nano composite C and the two-dimensional graphene oxide dispersion liquid according to the molar ratio of 1:12, and then carrying out centrifugal washing to obtain the Ag/BPQDs-GO ternary composite photocatalyst.
In summary, the present invention provides a preparation method of a photocatalyst with a ternary composite structure, in which black phosphorus quantum dots serve as a reducing agent to reduce a silver-amine complex to silver atoms, and simultaneously serve as a stabilizer to deposit the generated silver atoms on the surface of the black phosphorus quantum dots to generate a silver cluster/black phosphorus nanocomposite, and the silver cluster/black phosphorus nanocomposite is deposited on the surface of two-dimensional graphene oxide to obtain the photocatalyst with the ternary composite structure, and through responses of the two-dimensional graphene oxide and the black phosphorus quantum dots to visible light and near-infrared light, electrons generated by excitation can be transferred from the black phosphorus quantum dots to the surface of the silver clusters through the graphene oxide, so that excellent photocatalytic activity is exhibited.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a photocatalyst with a ternary composite structure is characterized by comprising the following steps:
A. providing a black phosphorus quantum dot dispersion liquid and a graphene oxide dispersion liquid;
B. mixing and stirring silver nitrate and organic amine to prepare a silver-amine complex solution, adding the silver-amine complex solution and the black phosphorus quantum dot dispersion liquid into an organic solvent according to a molar ratio of 1:1-1:20, and performing ultrasonic treatment to obtain a silver cluster/black phosphorus nano-composite dispersion liquid;
C. mixing the silver cluster/black phosphorus nano-composite dispersion liquid and the graphene oxide dispersion liquid according to a preset molar ratio, and then carrying out centrifugal washing treatment to obtain the photocatalyst with a ternary composite structure;
the molar ratio of the silver cluster/black phosphorus nano composite to the graphene oxide is 1:1-1: 100.
2. The method of claim 1, wherein the size of the silver cluster in the silver cluster/black phosphorus nanocomposite is 0.5 to 2 nm.
3. The method for preparing the photocatalyst having a ternary composite structure according to claim 1, wherein the organic amine is one or more of tert-butylamine, n-butylamine, oleylamine, dodecylamine, and octadecylamine.
4. The method of claim 1, wherein the organic solvent in step B is one or more selected from cyclohexane, toluene, hexane, ethanol, and N-methylpyrrolidone.
5. The method for preparing a photocatalyst having a ternary composite structure according to claim 1, wherein the molar ratio of silver nitrate to organic amine is 1:1 to 1: 20.
6. The method for preparing a photocatalyst having a ternary composite structure according to claim 1, wherein the ultrasonic treatment time in the step B is 2 to 60 min.
7. The method for preparing a photocatalyst having a ternary composite structure according to claim 1, wherein the step of preparing the black phosphorus quantum dot dispersion liquid in the step a specifically comprises:
a1, dispersing the black phosphorus crystal in an N-methyl pyrrolidone solvent, and carrying out ice-water bath ultrasonic treatment to obtain a mixed solution;
a2, centrifuging the mixed solution at a centrifugation speed of 7000r/min for 10-30min, and then taking centrifugal liquid;
and A3, centrifuging the centrifugate at the centrifugal speed of 15000r/min for 10-30min, removing the centrifugate, and dispersing the solid left after centrifugation into an N-methyl pyrrolidone solvent to obtain the black phosphorus quantum dot dispersion liquid.
8. A photocatalyst having a ternary composite structure, characterized by being prepared by the preparation method of any one of the above claims 1 to 7.
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| CN111318290A (en) * | 2019-01-28 | 2020-06-23 | 南京理工大学 | Application of black phosphorus quantum dots as photosensitizer in photocatalysis |
| CN110354873A (en) * | 2019-07-16 | 2019-10-22 | 复旦大学 | A kind of black phosphorus/ZnIn2S4Composite visible light catalyst and preparation method thereof |
| CN112675843A (en) * | 2021-01-11 | 2021-04-20 | 西部金属材料股份有限公司 | Silver quantum dot composite photocatalyst and preparation method thereof |
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