CN113663703B - High-selectivity solar-driven carbon dioxide conversion composite material and preparation thereof - Google Patents
High-selectivity solar-driven carbon dioxide conversion composite material and preparation thereof Download PDFInfo
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- CN113663703B CN113663703B CN202110814197.2A CN202110814197A CN113663703B CN 113663703 B CN113663703 B CN 113663703B CN 202110814197 A CN202110814197 A CN 202110814197A CN 113663703 B CN113663703 B CN 113663703B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 62
- 239000010941 cobalt Substances 0.000 claims abstract description 61
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 49
- 239000010439 graphite Substances 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002135 nanosheet Substances 0.000 claims abstract description 30
- 239000002114 nanocomposite Substances 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- -1 carbon nitride compound Chemical class 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002064 nanoplatelet Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 18
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C01B32/40—Carbon monoxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a high-selectivity solar-driven carbon dioxide conversion composite material and a preparation method thereof, and belongs to the field of environmental and new energy materials. Firstly, stripping a block-shaped black phosphorus material into a two-dimensional black phosphorus nano sheet by a solvent stripping method; adding a precursor of cobalt phosphide into the black phosphorus nanosheet solution to be uniformly dispersed, and preparing cobalt phosphide@black phosphorus under the protection of inert gas; preparing a thin-layer graphite-phase carbon nitride nano-sheet by taking a carbon nitride compound as a precursor through a high-temperature calcination and thermal stripping method; and finally, compounding the graphite-phase carbon nitride nano sheet with a black phosphorus@cobalt phosphide sheet by adopting a self-assembly method to obtain the cobalt phosphide@black phosphorus/graphite-phase carbon nitride nano composite material. The cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite prepared by the method has good carbon dioxide reduction performance under the illumination condition; and the synthesis steps are simple, the selectivity of carbon monoxide is high, and the like, and the method has a great industrial application prospect in the aspects of carbon dioxide emission reduction and clean energy production.
Description
Technical Field
The invention relates to the technical field of environment and new energy materials, in particular to a high-selectivity solar-driven carbon dioxide conversion composite material and a preparation method thereof.
Background
Due to excessive consumption of fossil fuels, carbon dioxide (CO 2 ) The concentration of (2) is continuously increasing, and 400ppm is broken through, so that the global energy crisis and the ecological environment are caused. In order to solve the above problems, a series of countermeasures such as "carbon peak value" and "carbon neutralization" are recently proposed in China, and clean new energy is vigorously developed. Therefore, reducing the content of carbon dioxide while developing clean energy has become one of the global urgent problems to be solved. The use of solar energy based semiconductor materials to drive the conversion of carbon dioxide to high value fuels or chemicals has become a viable approach. The method has the advantages of energy conservation, environmental protection, mild reaction conditions and the like, and can effectively solve the two problems at the same time.
In the field of solar driven carbon dioxide conversion, two-dimensional materials have received much attention due to their excellent in-plane carrier mobility, sites with catalytic activity, and easier construction of interface heterojunctions. The graphite phase carbon nitride material has the advantages of higher photocatalytic activity, proper band gap (about 2.7 eV), low cost, good chemical stability, easy preparation and the like, and has been widely applied to photocatalytic carbon dioxide reduction. However, graphite-phase carbon nitride materials have many disadvantages such as rapid recombination of photo-generated carriers, poor charge transfer efficiency, and a narrow absorption range of visible light. Thus, constructing a suitable heterojunction is an effective method to overcome its limitations. Black phosphorus nanoplatelets have unique optoelectronic properties with excellent light absorption capabilities, suitable band gaps, and higher electron transfer rates. Therefore, the black phosphorus/graphite phase carbon nitride heterojunction construction can effectively improve the photocatalytic activity, but the black phosphorus nano-sheet is extremely unstable in the environment and is easy to oxidize, so that the photocatalytic activity of the black phosphorus nano-sheet is limited. In addition, the solar energy drives more products in the carbon dioxide conversion process, which is not beneficial to the industrialized application. Thus, increasing the selectivity of solar driven carbon dioxide conversion and enhancing the stability of black phosphorus based composites is a serious challenge at present.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems of overcoming the selectivity of solar-driven carbon dioxide conversion and the stability of the black phosphorus-based composite material in the prior art.
In order to solve the technical problems, the invention provides a high-selectivity solar-driven carbon dioxide conversion composite material and a preparation method thereof. The invention constructs a stable black phosphorus-based solar-driven carbon dioxide conversion material through a solvent stripping method, a hydrothermal method and a hydrothermal method. The material has excellent visible light responsiveness, high carrier mobility and good stability, and realizes high activity and high selectivity of the material in solar driven carbon dioxide conversion.
The first object of the invention is to provide a preparation method of cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite, which comprises the following steps:
(1) Stripping the blocky black phosphorus with a solvent to obtain a two-dimensional black phosphorus nano-sheet;
(2) Uniformly dispersing a precursor of cobalt phosphide and the two-dimensional black phosphorus nano-sheets in the step (1) in an organic solvent, and heating under a protective atmosphere to obtain cobalt phosphide@black phosphorus;
(3) Taking a carbon nitride compound as a precursor, and calcining and stripping to obtain graphite-phase carbon nitride nano-sheets;
(4) And (3) uniformly mixing the cobalt phosphide@black phosphorus obtained in the step (2) and the graphite phase carbon nitride nanosheets obtained in the step (3) to obtain the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite.
Further, in the step (1), the mass ratio of black phosphorus to the solvent is 1:1000-5000.
Further, in step (1), the peeling power is 10 to 200W; the stripping time is 1-5d. The two-dimensional flaky material can be obtained by adopting a simple solution stripping method, the specific surface area of the black phosphorus material can be effectively increased, the active site is increased, and the catalytic effect of the photocatalyst is enhanced.
Further, in the step (2), the mass ratio of the precursor of cobalt phosphide to the two-dimensional black phosphorus nanoplatelets is 1:20-50.
Further, in the step (2), the heating is 150-200 ℃ heating for 3-5 hours.
Further, in step (3), the carbon nitrogen compound is one or more of dicyandiamide, urea, thiourea, mono-cyanamide and tri-cyanamide.
Further, in the step (3), the calcination is carried out at 400-600 ℃ for 2-6 hours, so that the bulk graphite phase carbon nitride is obtained.
Further, in the step (3), the peeling is to peel the bulk graphite phase carbon nitride by adopting a thermal peeling method, and the peeling is to peel for 1-4 hours at 400-600 ℃ to obtain the thin layer graphite phase carbon nitride nano-sheet.
Further, in the step (4), the mass ratio of the cobalt phosphide@black phosphorus to the graphite phase carbon nitride nano-sheet is 1:1-100; the reaction time is 10-16h.
Further, after the reaction in the step (4), washing the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite material with water and ethanol for 2-5 times respectively, and then drying in vacuum at 50-70 ℃. The two-dimensional cobalt phosphide@black phosphorus is successfully modified on the surface of the graphite phase carbon nitride nanosheet, a perfect heterojunction structure is formed, and the method plays a vital role in improving the efficiency of solar driven carbon dioxide conversion.
A second object of the present invention is to provide a cobalt phosphide @ black phosphorus/graphite phase carbon nitride nanocomposite.
The third object of the invention is to provide the application of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite material in the production of clean fuel.
The fourth object of the invention is to provide the application of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite in solar-driven carbon dioxide conversion.
Further, the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite is added into a sacrificial agent solution, and carbon dioxide is introduced to carry out solar energy driven carbon dioxide conversion reaction.
Further, the temperature of the reaction is 5-20 ℃; the pressure is 60-100kPa.
The preparation method takes carbon nitrogen compound as a precursor, and prepares the thin-layer graphite-phase carbon nitride nano-sheet by calcining under the air condition; stripping the blocky black phosphorus into two-dimensional black phosphorus flakes by using a solvent stripping method, and modifying cobalt phosphide on the black phosphorus nano-flakes; finally, a self-assembly method is adopted to prepare the stable cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite. The cobalt phosphide is modified, the stability of black phosphorus and the selectivity of converting solar-driven carbon dioxide into carbon monoxide are improved, and the cobalt phosphide is introduced to ensure that the material has strong absorption capacity to visible light, and the composite material has proper band gap and good conductivity, so that the conversion performance of solar-driven carbon dioxide can be greatly improved. Therefore, the invention discloses application of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite in solar-driven carbon dioxide conversion; meanwhile, the invention also discloses application of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite in energy production, in particular application of solar energy to drive carbon dioxide to convert clean energy such as carbon monoxide.
The principle of the invention is as follows: the conduction band value of the graphite phase carbon nitride material is about-1.0V (relative to a standard hydrogen electrode), and the valence band value is about 2.0V (relative to a standard hydrogen electrode); the conduction band value of the black phosphorus material is about-0.8V (relative to the standard hydrogen electrode) and the valence band value is about-0.7V (relative to the standard hydrogen electrode). Their conduction band values are all more negative than the standard potential for carbon dioxide to carbon monoxide (-0.53V versus standard hydrogen electrode) and methane (-0.24V versus standard hydrogen electrode). Therefore, after the cobalt phosphide@black phosphorus/graphite phase carbon nitride forms a heterojunction, the heterojunction is favorable for carrying out solar-driven carbon dioxide conversion reaction.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The solar-driven carbon dioxide conversion device disclosed by the invention is clean, environment-friendly, energy-saving and efficient, and has a good large-scale industrial application prospect. The preparation method of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite is simple, raw materials are easy to obtain, the operation is simple and convenient, and the preparation method is very critical to industrial application.
(2) The graphite-phase carbon nitride has higher efficiency in solar-driven carbon dioxide conversion, but the application of the graphite-phase carbon nitride is limited by the rapid recombination of photo-generated carriers, the non-ideal sunlight absorption capacity and the poor charge transfer efficiency.
(3) The black phosphorus nano-sheet has unique photoelectric characteristics, such as strong sunlight absorption capability, adjustable band gap and high charge mobility, and is also the most suitable solar driven carbon dioxide conversion material. Therefore, a black phosphorus/graphite phase carbon nitride heterojunction is constructed, the electron transmission efficiency can be greatly improved by introducing the two-dimensional black phosphorus nano sheet, the utilization rate of the graphite phase carbon nitride to visible light can be improved, and the carbon dioxide conversion activity driven by solar energy is further improved.
(4) The cobalt-based material has high carbon monoxide selectivity, and the cobalt phosphide is used for modifying the black phosphorus material, so that the selectivity of the composite material to carbon monoxide can be greatly improved. The cobalt phosphide is modified on the surface of the black phosphorus material through cobalt-phosphorus bonds, so that lone pair electrons of the black phosphorus are occupied, the defect that the black phosphorus is easy to oxidize in the environment is overcome, the stability of the composite material in the solar-driven carbon dioxide conversion process is improved, the recycling and the reutilization of the material are facilitated, the efficiency and the selectivity of carbon monoxide production by converting solar-driven carbon dioxide can be increased, and the method has a good application prospect.
(5) The cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite disclosed by the invention is a novel composite material with high visible light absorption efficiency, good catalytic effect and stable performance, has the selectivity of generating carbon monoxide by converting solar-driven carbon dioxide up to 95%, and can be used for generating carbon monoxide in a visible light environment.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a Transmission Electron Microscope (TEM) of a two-dimensional black phosphorus nanoplatelet according to example 1 of the present invention.
FIG. 2 is a Transmission Electron Microscope (TEM) image of cobalt phosphide@black phosphorus of example 1 of the present invention.
FIG. 3 is a Transmission Electron Microscope (TEM) of graphite-phase carbon nitride of example 1 of the present invention.
FIG. 4 is a Transmission Electron Microscope (TEM) image of a cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite material according to example 1 of the present invention.
Fig. 5 is a graph showing the effect of solar energy driving carbon dioxide conversion to carbon monoxide in example 2 of the present invention.
FIG. 6 is a graph showing the effect of solar-driven carbon dioxide conversion to methane in example 2 of the present invention.
FIG. 7 is a graph showing the selective effect of solar-driven carbon dioxide conversion in example 2 of the present invention.
FIG. 8 is a graph showing the effect of solar-driven carbon dioxide conversion cycle in example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
1. Preparation of two-dimensional black phosphorus Material
20mg of the block-shaped black phosphorus material is dispersed into 25 mLN-methyl pyrrolidone, and ultrasonic crushing is carried out for 3d by using a cell crusher with power of 160W, so that a two-dimensional black phosphorus N-methyl pyrrolidone solution is obtained.
Fig. 1 is a TEM image of two-dimensional black phosphorus, which can be seen by the pictures to exhibit a thin plate-like structure.
2. Preparation of cobalt phosphide@black phosphorus nanosheets
Taking 10mL of N-methylpyrrolidone solution of two-dimensional black phosphorus, washing three times with the N, N-dimethylformamide solution to obtain 10mL of N, N-dimethylformamide solution of two-dimensional black phosphorus, adding 35.6mg of cobalt (II) acetylacetonate into the solution, dispersing uniformly, adding the solution into a reaction kettle, introducing argon into the reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 4 hours, washing the product with ethanol for 3 times after projection, and drying the product in a vacuum oven for 12 hours to obtain the cobalt phosphide@black phosphorus nano-sheet.
Fig. 2 is a TEM image of two-dimensional cobalt phosphide@black phosphorus nanoplatelets, by which it can be observed that the prepared cobalt phosphide is uniformly dispersed on the black phosphorus nanoplatelets.
3. Preparation of graphite phase carbon nitride nanosheets
Adding 3g of dicyandiamide into a crucible, putting the crucible into a muffle furnace, setting a program to heat up to 550 ℃ from 20 ℃ at a heating rate of 2.5 ℃/min, preserving heat for 4 hours, and naturally cooling to obtain a massive graphite phase carbon nitride nano-sheet; and (3) tiling the blocky graphite-phase carbon nitride at the bottom of the flat bottom porcelain boat, putting the flat bottom porcelain boat into a muffle furnace, setting the program to heat up to 550 ℃ from 20 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and naturally cooling to obtain the graphite-phase carbon nitride nanosheets. The product was added to a beaker containing a mixed solution of concentrated sulfuric acid and concentrated nitric acid, 5mL of the mixed solution of concentrated sulfuric acid and 10mL of concentrated nitric acid for every 100mg of graphite-phase carbon nitride nanoplatelets. After acidification for 10min, pouring the solution into a beaker containing 150mL of water, stirring, washing, standing for extraction, pouring out supernatant, adding 200mL of water, repeating the extraction operation for 5 times, washing the bottom turbid liquid twice with ethanol, and drying in vacuum at 60 ℃.
Fig. 3 is a TEM image of graphite-phase carbon nitride, from which it can be seen that the black phosphorus exhibits a thin plate-like structure.
4. Preparation of cobalt phosphide @ black phosphorus/graphite phase carbon nitride nanocomposite
Dispersing 10mg of black phosphorus nano-sheets and 100mg of cobalt phosphide@black phosphorus nano-sheets into 30mL of ethanol solution, carrying out ultrasonic treatment for 10min to uniformly disperse the black phosphorus nano-sheets, stirring the mixture at room temperature for 12h, centrifugally separating the product after the reaction is finished, washing the product twice with ethanol, and finally drying the product in a vacuum oven at 60 ℃ to obtain the cobalt phosphide@black phosphorus/graphite phase carbon nitride nano-composite material.
Fig. 4 is a TEM image of a cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite, from which it can be clearly and intuitively seen that the graphite phase carbon nitride nanoplatelets successfully form a perfect heterojunction structure with cobalt phosphide@black phosphorus.
Example 2
A photocatalytic reactor was used for photocatalytic reduction of carbon dioxide: uniformly mixing 10mg of the cobalt phosphide@black phosphorus/graphite phase-based carbon nitride nanocomposite prepared in the example 1 with 12mL of mixed solution (acetonitrile: deionized water: triethanolamine=3:2:1), then placing the mixture into the photocatalytic reactor, introducing condensed water to keep the temperature at 5 ℃, turning on a xenon lamp light source, introducing carbon dioxide to enable the pressure in a reaction system to reach 80kPa, and starting to perform solar-driven carbon dioxide conversion reaction; the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite has high carbon dioxide reduction efficiency and carbon monoxide generation selectivity.
FIGS. 5 and 6 are respectively cobalt phosphide @ black phosphorus/graphite phase carbon nitride nanocomposite solar driven carbon dioxide conversion to produce carbon monoxide (CO) and methane (CH) 4 ) Is a graph of the effect of (3). Fig. 7 is a graph of the selective effect of solar-driven carbon dioxide conversion, and fig. 8 is a graph of the cyclic effect of solar-driven carbon dioxide conversion. As can be seen from the figure, the main product of carbon dioxide reduction is carbon monoxide and the by-product is methane. The cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite has the solar energy driven carbon dioxide conversion efficiency obviously superior to that of a graphite phase carbon nitride material and a cobalt phosphide@black phosphorus material, wherein the yield of carbon monoxide can reach 16.21 mu mol at mostg -1 h -1 Is 5 times higher than the carbon monoxide produced by the graphite phase carbon nitride material and 4 times higher than the cobalt phosphide @ black phosphorus material. The selectivity of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite to carbon monoxide is also obviously better than that of the graphite phase carbon nitride material, and the selectivity of the composite material with the best performance to carbon monoxide reaches about 95%. Especially, the selectivity of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nano composite material to carbon monoxide increases along with the increase of the proportion of the cobalt phosphide@black phosphorus nano sheet, and the selectivity reaches the maximum when the proportion of the cobalt phosphide@black phosphorus is 10%, which indicates that the modification of the cobalt phosphide@black phosphorus can effectively improve the selectivity of the graphite phase carbon nitride to carbon monoxide. Through a circulation experiment, the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite is basically stable in solar energy driven carbon dioxide conversion efficiency after four circulation, the yield of carbon monoxide and methane is only slightly changed, the selectivity of reduced carbon dioxide is basically unchanged, and after four circulation, the selectivity of the composite to carbon monoxide can still be kept at about 95%, so that the composite is proved to have good stability and can be recycled.
Through the analysis, the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite prepared by the simple and effective method has higher solar-driven carbon dioxide conversion efficiency and selectivity; the method has the advantages of simple and convenient preparation process, easily available production raw materials and the like, and has application prospect in the aspect of solar-driven carbon dioxide conversion.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The application of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite in the production of carbon monoxide and methane by solar-driven carbon dioxide conversion is characterized in that the preparation method of the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite comprises the following steps:
(1) Stripping the blocky black phosphorus with a solvent to obtain a two-dimensional black phosphorus nano-sheet;
(2) Uniformly dispersing a precursor of cobalt phosphide and the two-dimensional black phosphorus nano-sheets in the step (1) in an organic solvent, and heating under a protective atmosphere to obtain cobalt phosphide@black phosphorus;
(3) Taking a carbon nitride compound as a precursor, and calcining and stripping to obtain graphite-phase carbon nitride nano-sheets;
(4) And (3) uniformly mixing the cobalt phosphide@black phosphorus obtained in the step (2) and the graphite phase carbon nitride nanosheets obtained in the step (3) to obtain the cobalt phosphide@black phosphorus/graphite phase carbon nitride nanocomposite.
2. The use according to claim 1, characterized in that: in the step (1), the mass ratio of black phosphorus to solvent is 1:1000-5000.
3. The use according to claim 1, characterized in that: in step (1), the stripping power is 10-200W; the stripping time is 1-5d.
4. The use according to claim 1, characterized in that: in the step (2), the mass ratio of the precursor of cobalt phosphide to the two-dimensional black phosphorus nanoplatelets is 1:20-50.
5. The use according to claim 1, characterized in that: in step (2), the heating is at 150-200 ℃ for 3-5h.
6. The use according to claim 1, characterized in that: in step (3), the carbon nitrogen compound is one or more of dicyandiamide, urea, thiourea, mono-cyanamide and tri-cyanamide.
7. The use according to claim 1, characterized in that: in step (3), the calcination is at 400-600 ℃ for 2-6 hours; the stripping is carried out at 400-600 ℃ for 1-4h.
8. The use according to claim 1, characterized in that: in the step (4), the mass ratio of the cobalt phosphide@black phosphorus to the graphite phase carbon nitride nano-sheet is 1:1-100.
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