CN111330603A - Novel efficient photocatalytic material and application thereof - Google Patents
Novel efficient photocatalytic material and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000000877 morphologic effect Effects 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- 239000011574 phosphorus Substances 0.000 claims description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011863 silicon-based powder Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910001511 metal iodide Inorganic materials 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- PZHNNJXWQYFUTD-UHFFFAOYSA-N phosphorus triiodide Chemical compound IP(I)I PZHNNJXWQYFUTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000010453 quartz Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical compound [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- XCOKHDCPVWVFKS-UHFFFAOYSA-N tellurium tetraiodide Chemical compound I[Te](I)(I)I XCOKHDCPVWVFKS-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 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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- A62—LIFE-SAVING; FIRE-FIGHTING
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- 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
- B01J27/182—Phosphorus; Compounds thereof with silicon
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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Abstract
The invention discloses a novel high-efficiency photocatalytic material and application thereof. The invention successfully obtains a novel high-efficiency photocatalytic material SiP through high-temperature sintering by utilizing a chemical vapor transport method, and SiP with different morphological structures can be obtained by controlling whether a regulating agent is added or not, wherein the SiP comprises powder, flocculent fibers and linear crystals. The silicon phosphide material prepared by the invention has a two-dimensional structure, large specific surface area, high crystallinity, high separation efficiency of photon-generated carriers, excellent photocatalytic performance and important assistance to energy and environmental protection industries.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a novel efficient photocatalytic material and application thereof.
Background
Rapid development of global economy is accompanied by huge consumption of fossil energy, mainly including petroleum and coal, which are mainly used for combustion to generate thermal energy for conversion into electric energy, mechanical energy, or processing into other organic chemicals. This energy consumption and conversion process is accompanied by the production of large amounts of "greenhouse gases" and the pollution of various organic compounds. Over the years, the rate of consumption of these pollutants is far from increasing, and has severely threatened human survival and health. Semiconductor photocatalysis technology is a technology for converting water, carbon dioxide or organic matters into chemical energy beneficial to human beings, such as hydrogen energy, by utilizing clean and abundant solar energy on earth through semiconductor materials. The photocatalytic technology mainly comprises photocatalytic organic matter decomposition, photocatalytic water decomposition for hydrogen production and photocatalytic carbon dioxide reduction.
SiP is a P-type direct band gap semiconductor, is already a star material in the field of optical communication, and is considered as a semiconductor material with great potential for developing silicon photonics. In the field of photocatalysis, the photocatalytic performance of the SiP material is not reported in documents.
Disclosure of Invention
The invention aims to provide a SiP material with different morphological structures prepared by a chemical vapor transport method, which has excellent performance in the field of photocatalysis and is helpful for developing clean energy and protecting the environment.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the novel high-efficiency photocatalytic material is a silicon phosphide SiP prepared by adopting a chemical vapor transport method, and silicon phosphide SiP materials with different morphological structures are obtained by adding a regulating agent or not, wherein the different morphological structures are respectively powder, flocculent fibers and linear crystals.
Further, the preparation method of the silicon phosphide SiP powder and the flocculent fiber comprises the following steps:
(1) silicon powder and a phosphorus source are weighed and uniformly mixed according to the stoichiometric ratio of SiP, and a transport agent with a certain material quantity ratio is added;
(2) the powder is placed in a reaction container and then is vacuumized and sealed, and the powder is sintered at a high temperature in a heating device for a certain time to obtain SiP powder and flocculent fibers.
Further, in the step (1), the silicon powder, the phosphorus source and the transport agent are mixed according to the mass ratio of 1: 1: 0.005-0.5 weight percent.
Further, the phosphorus source is one or a combination of several of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide; the transport agent is one or the combination of more of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide.
Further, the heating device in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave oven or a single crystal furnace; the sintering temperature is 900-1200 ℃, and the sintering time is 0.1-680 h.
Further, the preparation method of the linear silicon phosphide SiP crystal comprises the following steps:
(1) silicon powder and a phosphorus source are weighed and uniformly mixed according to the stoichiometric ratio of SiP, and a transport agent and a regulating agent with a certain material quantity ratio are added;
(2) and placing the crystal into a reaction container, vacuumizing and sealing, and sintering at a high temperature in a heating device for a certain time to obtain the SiP linear crystal.
Further, in the step (1), the silicon powder, the phosphorus source, the transport agent and the regulating agent are mixed according to the mass ratio of 1: 1: 0.005-0.5: 0.01-0.1 weight percent; the phosphorus source is one or more of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide; the transport agent is one or a combination of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide; the regulating agent is one or a combination of more of elemental sulfur, elemental selenium and elemental tellurium.
The heating device in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace; the sintering temperature is 900-1200 ℃, and the sintering time is 12-680 hours.
The SiP photocatalytic material is applied to degrading alcohol, aldehyde, acid, ketone and aromatic organic pollutants.
The SiP photocatalytic material is applied to the preparation of hydrogen through water decomposition.
The use of any of the above SiP photocatalytic materials in the reduction of carbon dioxide gas.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention is innovative, and the photocatalytic performance of the SiP material is not reported in documents. The silicon phosphide material prepared by the invention has a two-dimensional structure, large specific surface area, high carrier separation efficiency and excellent photocatalytic performance, and has important assistance to energy and environmental protection.
(2) The preparation method of the SiP material provided by the invention has the advantages of simple and mature process, wide and rich raw material sources, low price and high yield.
Drawings
FIG. 1 is a photograph of SiP powder in example 1 of the present invention.
FIG. 2 is a photograph of SiP floe fibers in example 1 of the present invention.
Fig. 3 is an XRD of SiP powder and flocculent fibers in example 1 of the present invention.
FIG. 4 is a photograph of SiP linear crystals in example 2 of the present invention.
FIG. 5 is an XRD of a SiP linear crystal in example 2 of the present invention.
Fig. 6 shows the photocatalytic degradation organic activity of three SiP materials in examples 1 and 2 of the present invention, wherein the materials are provided in examples 1 and 2.
Fig. 7 shows the photocatalytic hydrogen production activity of three SiP materials in examples 1 and 2 of the present invention, which are provided in examples 1 and 2.
Fig. 8 shows the photocatalytic carbon dioxide reduction activity of three SiP materials of examples 1 and 2 of the present invention, which are provided in examples 1 and 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the silicon phosphide photocatalytic material with different morphological structures provided by the invention comprises the following steps:
the preparation method of the SiP powder and the flocculent fiber comprises the following steps:
(1) weighing silicon powder, a phosphorus source and a transport agent in a certain proportion in a glove box, fully mixing uniformly, and transferring into a quartz tube;
(2) vacuumizing and sealing the quartz tube, and sintering the quartz tube in a heating device at a high temperature for a certain time;
(3) cooling, washing with solvent, and vacuum drying to obtain the final product.
In the step (1), the mass ratio of the Si, the phosphorus source and the transport agent in the step (1) is 1: 1: (0.005-0.5);
the phosphorus source is one or more of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide;
the transport agent is one or the combination of more of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide.
The heating equipment in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace;
the calcination condition is that the temperature is set to be 900-1200 ℃, and the sintering time is 0.1-680 h.
The solvents in the step (3) are acetone and ethanol respectively.
b. The preparation method of the linear SiP crystal comprises the following steps:
(1) weighing silicon powder, a phosphorus source, a transport agent and a regulating agent in a certain proportion in a glove box, fully mixing uniformly, and transferring into a quartz tube;
(2) vacuumizing and sealing the quartz tube, and sintering the quartz tube in a heating device at a high temperature for a certain time;
(3) cooling, washing with solvent, and vacuum drying to obtain the final product.
In the step (1), the mass ratio of the Si, the phosphorus source, the transport agent and the regulating agent in the step (1) is 1: 1: (0.005-0.5): (0.01-0.1);
the phosphorus source is one or more of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide;
the transport agent is one or a combination of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide;
the regulating agent is one or a combination of more of elemental sulfur, elemental selenium and elemental tellurium.
The heating equipment in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace;
the calcination condition is that the temperature is set to be 900-1200 ℃, and the sintering time is 12-680 h.
The solvents in the step (3) are acetone and ethanol respectively.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
Example 1
0.28g of silicon powder, 0.31g of red phosphorus powder and 128mg of iodine simple substance are respectively weighed in a glove box, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 15cm and the inner diameter of 16mm, and the quartz tube is sealed by using an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a muffle furnace, wherein the temperature is 1050 ℃, the reaction time is 120h, cooling the furnace body to obtain SiP powder and flocculent fibers simultaneously, and photographic images are respectively shown in figures 1 and 2, wherein the powder yield is 85%, the flocculent fiber yield is 11%, and the overall yield of the SiP reaches 96%. The XRD results are shown in fig. 3, indicating successful SiP acquisition. The sample is washed with acetone and ethanol and dried in vacuum.
Example 2
0.14g of silicon powder, 0.16g of red phosphorus powder, 0.64g of iodine simple substance and 40mg of simple substance selenium are respectively weighed in a glove box, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 20cm and the inner diameter of 18mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a muffle furnace, wherein the temperature is 950 ℃, the reaction time is 320h, taking out the SiP linear crystal after the furnace body is cooled, and taking out the SiP linear crystal after the furnace body is cooled, wherein a photographic image is respectively shown in figure 4, the yield is 91%, and an XRD result is shown in figure 5, which indicates that the SiP is successfully obtained. And cleaning with acetone and ethanol, and vacuum drying.
Example 3
0.28g of silicon powder, 0.32g of red phosphorus powder and 32mg of tellurium tetraiodide are respectively weighed in a glove box, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 18cm and the inner diameter of 11mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (2) placing the sealed quartz tube in a single crystal furnace, setting the furnace temperature at 1200 ℃, reacting for 0.1h, cooling the furnace body to obtain SiP powder and flocculent fibers simultaneously, cleaning the quartz tube by using acetone and ethanol, and drying in vacuum, wherein the SiP powder yield is 67%, the flocculent fibers yield is 30%, and the SiP overall yield is 97%.
Example 4
0.28g of silicon powder, 0.32g of red phosphorus powder, 32mg of tellurium tetraiodide and 3mg of sulfur powder are respectively weighed in a glove box, the raw materials are fully and uniformly ground, a quartz tube with the length of 18cm and the inner diameter of 11mm is added, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a single crystal furnace, setting the furnace temperature at 1200 ℃, reacting for 12 hours, cooling the furnace body, taking out the SiP linear crystal, wherein the yield is 95%, finally cleaning with acetone and ethanol, and drying in vacuum.
Example 5
0.14g of silicon powder, 0.16g of red phosphorus powder and 7.3mg of ammonia iodide are weighed in a glove box respectively, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 11cm and the inner diameter of 11mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a double-temperature-zone tube furnace, wherein the left end temperature is 1080 ℃, the right end temperature is 1030 ℃, the raw material is in a high-temperature section, the reaction time is 680h, finally, SiP powder is obtained in the high-temperature section, the yield is 73%, SiP flocculent fibers are obtained in the low-temperature section, the yield is 20%, and the overall yield of SiP reaches 93%. Washing the product with acetone and ethanol, and vacuum drying.
Example 6
0.14g of silicon powder, 0.16g of red phosphorus powder, 7.3mg of ammonia iodide and 32mg of tellurium powder are respectively weighed in a glove box, the raw materials are fully and uniformly ground, a quartz tube with the length of 11cm and the inner diameter of 11mm is added, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a double-temperature-zone tube furnace, wherein the left end temperature is 1080 ℃, the right end temperature is 1030 ℃, the raw material is in a high-temperature section, the reaction time is 680h, and finally, SiP linear crystals are obtained in a low-temperature section, and the yield is 93%. Washing the product with acetone and ethanol, and vacuum drying.
Example 7
50mg of the SiP powder obtained in example 1 was ground and dispersed in a circular quartz vessel having an inner diameter of 3.2cm, the quartz vessel was sealed in a 0.5L circular vessel, and the reactor was purged with artificial air for 15 mm to remove carbon dioxide from the reactor. Then injecting 600umol isopropanol, starting a 300W xenon lamp, then installing an L42 filter, extracting 0.5ml of gas from the reactor every 5min during the photoreaction period, and injecting the gas into a gas chromatograph to obtain the performance of the SiP powder for photocatalytic degradation of the isopropanol.
The photocatalytic activities of the two samples were measured by grinding 50mg of the SiP flocculent fibers of example 1 and the SiP linear crystals of example 2, respectively, and repeating the above-mentioned method, and the results are shown in FIG. 6. It can be seen from the figure that the SiP samples of three different structures all have good visible light degradation isopropyl alcohol activity, and the flocculent fibers perform best, followed by linear crystals and finally by powder samples.
Example 8
50mg of the SiP powder obtained in example 1 was ground and added to a reactor for photocatalytic hydrogen production, 220ml of deionized water and 50ml of methanol were added, and finally 100ul of 0.025mol/L chloroplatinic acid was added using a pipette. And (3) adding all reactants, performing ultrasonic treatment for 5-10min, then installing a reactor on a photocatalytic device, vacuumizing to a certain vacuum degree, then, firstly, obtaining a blank sample, and observing whether oxygen in the device is completely pumped out and whether the tightness of the device is good. And after the device is determined to be not leaked, starting a 300W xenon lamp, performing light deposition for two hours, vacuumizing the device again after the deposition is finished, adding an L42 filter on a lamp source, and measuring the hydrogen production rate under visible light.
The photocatalytic water splitting hydrogen production activity of the two samples was measured by grinding 50mg of the SiP flocculent fibers of example 1 and the SiP linear crystals of example 2, respectively, and the results are shown in FIG. 7. From the figure, it can be seen that the SiP samples with three different structures all have good hydrogen production performance by visible light dissociation water, the hydrogen production rate is linearly increased, the performance of flocculent fibers is optimal, and the next is linear crystals and the last is powder samples.
Example 9
Taking 50mg of SiP powder obtained in the example 1, grinding, adding the powder into a reactor for photocatalytic carbon dioxide reduction, adding 3ml of deionized water, installing the reactor on a photocatalytic device, sealing, vacuumizing, introducing 99.999% pure carbon dioxide gas after vacuumizing to a certain vacuum degree, and then, firstly, obtaining a blank sample, and observing whether oxygen in the device is completely pumped out and whether the tightness of the device is good. And after the device is determined to be not leaked, starting a 300W xenon lamp, extracting 0.5ml of xenon from the reactor by using a sampling needle every 1h, and injecting the xenon into the Shimadzu gas chromatograph to obtain the corresponding yield of the reduction product.
The photocatalytic carbon dioxide reduction activity of the two samples was measured by grinding 50mg of the SiP flocculent fibers of example 1 and the SiP linear crystals of example 2, respectively, and the results are shown in FIG. 8. It can be seen from the figure that the SiP samples with three different structures all have good performance of reducing carbon dioxide all at once, the reduction product is mainly carbon monoxide, the growth rate of the CO accords with linear growth, the flocculent fiber has the best performance, and the flocculent fiber is next to a linear crystal and finally to a powder sample.
Claims (10)
1. The novel high-efficiency photocatalytic material is characterized in that the photocatalytic material is silicon phosphide SiP, the silicon phosphide SiP is prepared by adopting a chemical vapor transport method, and silicon phosphide SiP materials with different morphological structures are obtained by adding a regulating agent or not, wherein the different morphological structures are respectively powder, flocculent fibers and linear crystals.
2. The novel high-efficiency photocatalytic material as set forth in claim 1, wherein the preparation method of the silicon phosphide SiP powder and the flocculent fiber comprises the following steps:
(1) silicon powder and a phosphorus source are weighed and uniformly mixed according to the stoichiometric ratio of SiP, and a transport agent with a certain material quantity ratio is added;
(2) the powder is placed in a reaction container and then is vacuumized and sealed, and the powder is sintered at a high temperature in a heating device for a certain time to obtain SiP powder and flocculent fibers.
3. The novel high-efficiency photocatalytic material according to claim 2, wherein the silicon powder, the phosphorus source and the transport agent in step (1) are mixed in a mass ratio of 1: 1: 0.005-0.5 weight percent.
4. The novel high-efficiency photocatalytic material according to claim 2, characterized in that the phosphorus source is one or a combination of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide; the transport agent is one or the combination of more of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide.
5. The novel high-efficiency photocatalytic material according to claim 2, wherein in step (2), the heating device is one of a single-temperature-zone tube furnace, a multi-temperature-zone (dual-temperature-zone and higher) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace; the sintering temperature is 900-1200 ℃, and the sintering time is 0.1-680 h.
6. The novel highly efficient photocatalytic material as set forth in claim 1, wherein said linear crystal of silicon phosphide SiP is prepared by a method comprising the steps of:
(1) silicon powder and a phosphorus source are weighed and uniformly mixed according to the stoichiometric ratio of SiP, and a transport agent and a regulating agent with a certain material quantity ratio are added;
(2) and placing the crystal into a reaction container, vacuumizing and sealing, and sintering at a high temperature in a heating device for a certain time to obtain the SiP linear crystal.
7. The novel high-efficiency photocatalytic material according to claim 6, wherein the silicon powder, the phosphorus source, the transport agent and the control agent in step (1) are mixed in a mass ratio of 1: 1: 0.005-0.5: 0.01-0.1 weight percent; the phosphorus source is one or more of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide; the transport agent is one or a combination of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide; the regulating agent is one or a combination of more of elemental sulfur, elemental selenium and elemental tellurium;
the heating device in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace; the sintering temperature is 900-1200 ℃, and the sintering time is 12-680 hours.
8. Use of the SiP photocatalytic material of any of claims 1-7 for the degradation of alcohols, aldehydes, acids, ketones and aromatic organic pollutants.
9. Use of a SiP photocatalytic material as claimed in any of claims 1-7 for the production of hydrogen by the decomposition of water.
10. Use of a SiP photocatalytic material according to any of claims 1-7 for the reduction of carbon dioxide gas.
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