CN114768855A - Heterojunction composite photocatalyst with atomic-level channel, preparation method and application - Google Patents
Heterojunction composite photocatalyst with atomic-level channel, preparation method and application Download PDFInfo
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- CN114768855A CN114768855A CN202210508027.6A CN202210508027A CN114768855A CN 114768855 A CN114768855 A CN 114768855A CN 202210508027 A CN202210508027 A CN 202210508027A CN 114768855 A CN114768855 A CN 114768855A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 27
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 8
- -1 transition metal salt Chemical class 0.000 claims abstract description 5
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 29
- 239000000969 carrier Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
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- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000012688 phosphorus precursor Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- 238000001308 synthesis method 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
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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
- B01J27/24—Nitrogen compounds
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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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
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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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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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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- C01B3/042—Decomposition of water
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Abstract
The invention belongs to the technical field of photocatalysis, and particularly discloses a heterojunction composite photocatalyst with an atomic-level channel, and a preparation method and application thereof. The catalyst is made of phosphorus-doped carbon nitride P-C3N4And a loadIn P-C3N4The transition metal phosphide on the surface forms a metal-P-N bonding effect between the transition metal phosphide and the metal-P-N, and the coordination bond can provide an atomic-level charge transmission channel for photocatalytic reaction, accelerate the separation and migration of photon-generated carriers and effectively inhibit the recombination of the photon-generated carriers, thereby greatly enhancing the photocatalytic performance of the phosphorus-doped carbon nitride. The catalyst is used for preparing phosphorus-doped carbon nitride P-C by low-temperature plasma technology3N4Then P-C is added3N4Reacting with transition metal salt and phosphorus precursor in water bath, and then carrying out low-temperature plasma discharge reaction to obtain the composite photocatalyst. The catalyst shows excellent photocatalytic performance under visible light, and comprises hydrogen production by photolysis of water and photocatalytic reduction of CO2Etc. are a new type of photocatalytic material with great potential.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and relates to a preparation method and application of a heterojunction composite photocatalyst with atomic-level channels.
Background
The energy crisis and the increasingly serious environmental pollution problem are the serious challenges facing the survival and development of human beings at present, and the development and utilization of various renewable energy sources are highly regarded by the international society at the present day when fossil energy sources are increasingly exhausted. Solar energy is a new energy research and development field with high attention in academic circles and industrial circles at home and abroad due to the characteristics of inexhaustibility, no pollution, convenience and the like. The utilization of solar energy to produce clean, efficient, sustainable green energy is an important solution to achieve the "dual carbon" goal. The photocatalysis technology can directly utilize solar energy, prepare green hydrogen energy by decomposing water or convert carbon dioxide into liquid fuel, and is an ideal way for realizing solar energy conversion.
As a non-metallic photocatalyst, graphite phase carbon nitride C3N4The photocatalyst has the advantages of simple synthesis method, excellent carrier mobility, high thermal and chemical stability, planar two-dimensional layered structure and the like, so the photocatalyst is widely concerned in the field of photocatalysis. For single component C3N4In the case of the photocatalyst, although the separation of photo-generated charges can be promoted by regulating the size, dimension, crystallization degree, defects and the like of the photocatalyst, the regulation degree is still limited by the limitation of a single component, and the recombination probability of photo-generated carriers is high, so that the photocatalytic efficiency is low.
In photocatalytic reactions, the generated photogenerated electrons and photogenerated holes need to resist the coulomb force to migrate from the photocatalyst bulk to the surface active sites to participate in the catalytic reaction. However, the recombination rate of bulk charges is much faster than its separation rate, which is extremely detrimental to the photocatalytic reaction process. Therefore, there is an urgent need for an atomic-scale charge separation strategy to facilitate nanoscale photogenerated charge transfer and spatial separation processes, allowing more electrons and holes to migrate from the photocatalyst bulk to the surface.
Disclosure of Invention
One of the purposes of the invention is to provide a heterojunction composite photocatalyst with an atomic-scale channel, which can effectively promote the migration and transmission of photo-generated charges through the atomic-scale channel, reduce the recombination probability of carriers and enhance C3N4Thereby increasing C3N4The photocatalytic performance of the photocatalyst has the characteristics of wide spectral response range and high photocatalytic performance.
In order to achieve the purpose, the invention adopts the following technical scheme: a heterojunction composite photocatalyst with atomic-level channel is prepared from P-C carbon nitride doped with P3N4And loaded at P-C3N4Transition metal phosphide composition on surface, said P-C3N4And a metal-P-N bonding effect is formed between the transition metal phosphide and the transition metal phosphide, wherein the transition metal phosphide is single transition metal phosphide or phosphide of more than two transition metals.
The heterojunction composite photocatalyst with atomic scale channels is further improved:
preferably, the content of the transition metal phosphide in the photocatalyst is 0.1-20 wt%, and the phosphorus-doped carbon nitride P-C3N4The doping amount of the medium phosphorus is 0.1-10 wt%.
Preferably, the transition metal phosphide is Fe2P、Co2P、Ni2One or a combination of more than two of P, FeCoP, CoNiP and FeNiP.
The second purpose of the invention is to provide a preparation method of the heterojunction composite photocatalyst with the atomic-scale channel, which comprises the following steps: the method comprises the following steps:
(1) adding precursor powder containing phosphorus element into graphite phase carbon nitride C3N4Fully grinding the powder, carrying out discharge reaction under the action of hydrogen-containing plasma, collecting the powder after the reaction is finished, washing the powder with ethanol and deionized water, and drying to obtain phosphorus-doped carbon nitride powder, namely P-C3N4Powder;
(2) the P-C prepared in the step (1)3N4Mixing the powder with water-soluble transition metal salt and a precursor containing phosphorus, adding deionized water, fully stirring under a water bath condition, and then freeze-drying to obtain mixed powder;
(3) carrying out discharge reaction on the mixed powder in the step (2) under the action of hydrogen-containing plasma, collecting the powder after the reaction is finished, washing the powder with ethanol and deionized water, and drying to obtain transition metal phosphate @ P-C3N4A composite photocatalyst.
The preparation method of the heterojunction composite photocatalyst with atomic-scale channels is further improved:
preferably, the precursor powder containing phosphorus element in step (1) is one or a combination of two or more of orthophosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid and corresponding water-soluble salts.
Preferably, the hydrogen-containing plasma in steps (1) and (3) is pure hydrogen plasma or mixed gas plasma of hydrogen and inert gas.
Preferably, the power of the discharge reaction in the steps (1) and (3) is 50-200W, the discharge time is 10-60min, and the air pressure is 5-10 Pa.
Preferably, the water-soluble transition metal salt in step (2) is one or two or more of chloride, nitrate, sulfate and sulfite of a transition metal.
Preferably, the temperature of the water bath condition in the step (2) is 50-100 ℃, and the water bath time is 0.5-12 h.
The invention further aims to provide an application of the heterojunction composite photocatalyst with the atomic-scale channel in hydrogen production by photolysis of water.
Compared with the prior art, the invention has the beneficial effects that:
the composite photocatalyst with the heterojunction can effectively overcome the defects of narrow spectral response range and low photocatalytic efficiency of a single photocatalyst. The interface of different components in the composite photocatalyst is an important parameter for controlling the photocatalytic performance, and can influence the transfer of a photon-generated carrier in the composite material. The effective separation and migration of the photo-generated charges at the heterojunction interface are the key for constructing the high-efficiency heterojunction photocatalyst.
The invention provides a transition metal phosphate loaded phosphorus-doped carbon nitride P-C3N4The composite photocatalyst of (1). At the transition metal phosphate @ P-C3N4In the composite photocatalyst, the doping of the non-metallic element phosphorus can reduce the forbidden band width of the carbon nitride, absorb more visible light, inhibit the recombination probability of carriers and improve the photocatalytic performance of the carbon nitride. At the same time, the transition metal phosphide and P-C3N4The metal-P-N bonding effect is formed between the two, and the coordination bond can provide an atomic-scale charge transmission channel for the photocatalytic reaction. Under visible light irradiation, P-C3N4And generating photo-generated electrons and photo-generated holes, wherein photo-generated charges can be rapidly transmitted to the surface of the transition metal phosphide along an atomic-scale metal-P-N channel. Comparison of transition metal phosphide with P-C3N4The atomic-level photo-generated charge transfer channel can accelerate the separation and migration of photo-generated carriers and effectively inhibit the recombination of the photo-generated carriers, thereby greatly enhancing the photocatalytic performance of the phosphorus-doped carbon nitride.
The invention relates to a transition metal phosphate @ P-C with an atomic-scale metal-P-N channel3N4The composite photocatalyst shows excellent photocatalytic performance under visible light, and comprises hydrogen production by water photolysis and CO photocatalytic reduction2Etc. are a new type of photocatalytic material with great potential.
Drawings
FIG. 1 shows C prepared in example 13N4、P-C3N4And Fe2P@P-C3N4X-ray diffraction pattern of (a).
FIG. 2 is 1 wt% Co prepared in example 22P loaded Co2P@P-C3N4TEM pictures of the composite photocatalyst.
FIG. 3 is Co2P and 1 wt% Co2P loaded Co2P@P-C3N4XPS spectrum of Co in the composite photocatalyst.
FIG. 4 is P-C3N4And 1 wt% Co2P-loaded Co2P@P-C3N4XPS spectrum of P in the composite photocatalyst.
FIG. 5 is P-C3N4And 1 wt% Co2P-loaded Co2P@P-C3N4XPS spectrum of N in the composite photocatalyst.
FIG. 6 shows C prepared in example 23N4、P-C3N4、Pt@P-C3N4And different Co2Co of P content2P@P-C3N4The composite photocatalyst has the performance of photolyzing water to produce hydrogen under visible light.
FIG. 7 shows C prepared in example 23N4、P-C3N4And Co2P@P-C3N4Photocatalytic reduction of CO by composite photocatalyst under visible light2The performance of (c).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail with reference to the following embodiments, and all other embodiments obtained by a person of ordinary skill in the art without making creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
1) 10g of graphite-phase carbon nitride C was weighed3N4Powder and 0.46g disodium hydrogen phosphate Na2HPO4And grinding the powder for 60min, and then placing the mixed powder into a low-temperature plasma device. Introducing high-purity nitrogen gas, removing air from the device, opening the vacuum pump for pumpingEmpty to 5 Pa. Then, an alternating current power supply is turned on to generate hydrogen plasma, the discharge power is 100W, and the discharge time is 30 min. After the discharge is finished, collecting the powder, washing the powder for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying the powder to obtain 1 wt% phosphorus-doped carbon nitride P-C3N4And (3) powder.
2) Weighing 1g of P-C3N4Powder, 0.07mmol ferrous sulfate FeSO4And 0.035mmol of (NH)4)2HPO4Then, the mixture was added to 100mL of deionized water and stirred in a water bath at 80 ℃ for 2 hours. And then freeze-drying to obtain mixed powder.
3) And putting the mixed powder into a low-temperature plasma device. High-purity nitrogen is introduced, air in the device is removed, and a vacuum pump is started to pump vacuum to 5 Pa. Then, an alternating current power supply is turned on to generate hydrogen plasma (pure hydrogen), the discharge power is 150W, and the discharge time is 45 min. After discharging, collecting the powder, washing the powder for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying to obtain 5 wt% of Fe2Fe supported by P2P@P-C3N4And (3) composite photocatalyst powder.
To C3N4、P-C3N4And Fe2P@P-C3N4The crystal structure of (2) was analyzed by X-ray diffraction, and the results are shown in FIG. 1. For C3N4Diffraction peaks at 12.7 ° and 27.7 ° corresponding to graphite phase C3N4The former belongs to stacked conjugated aromatic rings, and the latter is a planar arrangement of tris-s-triazine structural units. When P is doped into C by using low-temperature plasma technology3N4In the skeleton structure, the diffraction peak of the (002) crystal plane is blue-shifted by 0.15 °, while the diffraction peak of the (100) crystal plane is weakened because the atomic radius of P is larger than that of C. When Fe2P is loaded at P-C3N4Surface, a new diffraction peak appears at 40.7 °, corresponding to Fe2The (112) crystal plane of P, which indicates Fe2P and P-C3N4The metal-P-N bonding effect can be formed between the two.
Example 2
1) Weighing 15g of graphite-phase carbon nitride powderEnd and 1.11g of ammonium dihydrogen phosphate NH4H2PO4Grinding the powder for 45min, and placing the mixed powder into a low-temperature plasma device. And introducing high-purity argon, removing air in the device, and opening a vacuum pump to vacuumize to 8 Pa. Then, the AC power supply was turned on to generate hydrogen plasma (10% H)2+ 90% Ar), a discharge power of 150W and a discharge time of 20 min. After the discharge is finished, collecting the powder, washing the powder for 4 times by using absolute ethyl alcohol and deionized water respectively, and drying the powder to obtain 2 wt% phosphorus-doped carbon nitride P-C3N4And (3) powder.
2) 0.5g of P-C was weighed3N4Powder, 0.11mmol of Co Nitrate (NO)3)2And 0.055mmol of NH4H2PO4Then, the mixture was added to 80mL of deionized water and stirred in a water bath at 70 ℃ for 3 hours. And then freeze-drying to obtain mixed powder.
3) And putting the mixed powder into a low-temperature plasma device. High-purity nitrogen is introduced, air in the device is removed, and a vacuum pump is started to vacuumize to 8 Pa. Then, the AC power supply was turned on to generate hydrogen plasma (10% H)2+ 90% Ar), discharge power 175W, discharge time 30 min. After the discharge is finished, collecting the powder, washing the powder for 4 times by using absolute ethyl alcohol and deionized water respectively, and drying the powder to obtain 1 wt% of Co2P loaded Co2P@P-C3N4And (3) composite photocatalyst powder.
By way of comparison, the inventors synthesized different Co2Co supported with P content (0.1 wt%, 0.5 wt%, 1.5 wt%, 2.0 wt%)2P@P-C3N4A composite photocatalyst. Meanwhile, Pt @ P-C loaded with 0.5 wt% Pt nanoparticles is synthesized according to a common illumination deposition method3N4A composite photocatalyst.
Evaluation of Co by photocatalytic Water decomposition2P@P-C3N4Performance under visible light. The specific reaction steps for preparing hydrogen by decomposing water through photocatalysis are as follows: (1) 10 mg of the photocatalyst powder was weighed and charged into a photocatalytic reactor containing 80ml of deionized water +20 ml of triethanolamine. The light source is PLS-SXE300D xenon lamp and UV420 filter (Beijing Pofelidae)Technical limited company); (2) after stirring uniformly, the photocatalytic reactor is sealed. The reactor was purged with high-purity nitrogen gas at a flow rate of 50 ml/min to remove oxygen remaining in the reactor. Then starting a photocatalytic reaction; (3) and (4) detecting the yield of the hydrogen in the reaction process on line by adopting a gas chromatograph at intervals.
FIG. 2 is 1 wt% Co2P-loaded Co2P@P-C3N4TEM pictures of the composite photocatalyst. As can be seen from the figure, Co having an average particle diameter of 10nm2The P nano-particles are uniformly loaded on the P-C3N4And forming a heterojunction structure on the surface. Wherein 0.22nm lattice fringes correspond to Co2The (121) plane of P. Ultrafine nano-particle Co2P loading, beneficial to enhancing Co2P and P-C3N4The interaction between them.
Fig. 3, 4 and 5 are XPS spectra of Co, P and N. FIG. 3 is Co2P and 1 wt% Co2P-loaded Co2P@P-C3N4XPS spectrum of Co in the composite photocatalyst. For Co2P, signal peaks at 782.4 and 797.7eV correspond to Co 2P3/2And 2p1/2Characteristic peaks for 793.1, 800.9 and 804.2eV are Co 2p3/2And 2p1/2And a strong peak at 778.2eV is a characteristic peak of Co-P bonds. When Co is present2P load P-C3N4After the surface, the relative intensity of the Co-P peak becomes stronger, and the characteristic peak of Co appears blue shift. FIG. 4 is P-C3N4And 1 wt% Co2P loaded Co2P@P-C3N4XPS spectrum of P in the composite photocatalyst. For P-C3N4The strong characteristic peak at 133.9eV corresponds to the P-N coordination, and no P-C coordination is observed (characteristic peak located near 131 eV), indicating that P has been incorporated into C3N4And the position of C is substituted in the framework to form a P-N coordination structure. When Co is present2P load P-C3N4After the surface, the signal peaks at 130.1 and 130.9eV correspond to Co2P2P in P2/3And 2p1/2And meanwhile, the characteristic peak of the P-N is blue-shifted. FIG. 5 is P-C3N4And 1 wt% Co2P-loaded Co2P@P-C3N4XPS spectrum of N in the composite photocatalyst. For P-C3N4The characteristic peaks at 398.8, 399.9 and 401.3eV correspond to C3N4Middle C-N, N-C3And C-N-H structural units. When Co is present2P load P-C3N4After the surface, the characteristic peak of N is red-shifted. The characteristic peaks of Co and P are blue-shifted, and the characteristic peaks of N are red-shifted, which is illustrated in Co2P and P-C3N4The Co-P-N bonding function exists between the two layers, and the bonding function is favorable for promoting the migration and the transmission of photogenerated charges at the atomic nanometer scale, thereby promoting the separation of photogenerated carriers and the enhancement of the photocatalysis performance.
FIG. 6 is C3N4、P-C3N4、Pt@P-C3N4And different Co2Co of P content2P@P-C3N4The average hydrogen production rate of the composite photocatalyst after 8-hour reaction. For graphite phase C3N4The hydrogen production rate is only 18 mu mol/h. When a non-metallic element P is incorporated into C3N4In, P-C3N4The hydrogen production rate is improved to 42.1 mu mol/h. For Pt @ P-C synthesized by illumination deposition method3N4The hydrogen production performance can be increased to 366.8 mu mol/h, which shows that the load of Pt greatly improves P-C3N4The photocatalytic hydrogen production activity of (1). For Co2P@P-C3N4Composite photocatalyst, when its surface is deposited with 0.1, 0.5, 1.0, 1.5 and 2.0 wt% of Co2After P, the hydrogen production rates respectively reach 219.6, 385.7, 542.2, 501.3 and 426.8 mu mol/h. Wherein, 1 wt% of Co2P loaded Co2P@P-C3N4Shows the best performance of photocatalytic hydrogen production, and the activity of the photocatalytic hydrogen production is C3N4、P-C3N4And Pt @ P-C3N430.1, 12.9 and 1.47 times of the total weight of the catalyst, indicating that Co with atomic scale charge transport channels is present in the photocatalytic hydrogen production reaction2P@P-C3N4The excellent photocatalytic hydrogen production performance is shown.
FIG. 7 is C3N4、P-C3N4And Co2P@P-C3N4(1wt％Co2P) composite photocatalyst for catalytic conversion of CO under visible light2The performance of (c). As shown, for C3N4Photocatalytic reduction of CO2The rates of formation of the reaction products were: c2H4＝0.4μmol/h、CO＝0.1μmol/h、CH 40 μmol/h; for P-C3N4Photocatalytic reduction of CO2The rates of formation of the reaction products were: c2H4＝1.7μmol/h、CO＝2.8μmol/h、CH40.6 mu mol/h; for Co2P@P-C3N4(0.1wt％Co2P), photocatalytic reduction of CO2The rates of formation of the reaction products were: c2H4＝8.7μmol/h、CO＝6.6μmol/h、CH42.3. mu. mol/h. In contrast, Co with atomic scale charge transport channels2P@P-C3N4Shows the highest activity, C2H4The selectivity of (a) was 49.4%.
Example 3
8g of graphite-phase carbon nitride powder and 2.68g of KH potassium hypophosphite were weighed2PO2Grinding the powder for 50min, and placing the mixed powder into a low-temperature plasma device. High-purity nitrogen is introduced, air in the device is removed, and a vacuum pump is started to pump vacuum to 10 Pa. Then, the AC power supply was turned on to generate hydrogen plasma (15% H)2+85％N2) The discharge power was 120W and the discharge time was 30 min. After the discharge is finished, collecting the powder, washing the powder for 5 times by using absolute ethyl alcohol and deionized water respectively, and drying the powder to obtain 10 wt% phosphorus-doped carbon nitride P-C3N4And (3) powder.
0.6g of P-C was weighed3N4Powder, 0.83mmol of CoCl20.83mmol of nickel chloride NiCl2And 0.83mmol of KH2PO2Then, the mixture was added to 60mL of deionized water and stirred in a water bath at 60 ℃ for 6 hours. And then freeze-drying to obtain mixed powder.
And putting the mixed powder into a low-temperature plasma device. Introducing high-purity nitrogen gas, removing air from the device, opening a vacuum pump to pump vacuum to 10Pa. Then, the AC power supply was turned on to generate hydrogen plasma (15% H)2+85％N2) The discharge power was 120W and the discharge time was 60 min. After the discharge is finished, collecting the powder, washing the powder for 5 times by using absolute ethyl alcohol and deionized water respectively, and drying the powder to obtain 20 wt% CoNiP-loaded CoNiP @ P-C3N4A composite photocatalyst powder.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (10)
1. A heterojunction composite photocatalyst with atomic level channels is characterized in that the photocatalyst is prepared from phosphorus-doped carbon nitride P-C3N4And loaded at P-C3N4Transition metal phosphide composition on surface, said P-C3N4And a metal-P-N bonding effect is formed between the metal phosphide and the transition metal phosphide, wherein the transition metal phosphide is a single transition metal phosphide or a phosphide of more than two transition metals.
2. The heterojunction composite photocatalyst with atomic scale channel of claim 1, wherein the content of the transition metal phosphide in the photocatalyst is 0.1-20 wt%, and the phosphorus-doped carbon nitride P-C3N4The doping amount of the medium phosphorus is 0.1-10 wt%.
3. The heterojunction composite photocatalyst with atomic scale channels as claimed in claim 1 or 2, wherein the transition metal phosphide is Fe2P、Co2P、Ni2One or a combination of more than two of P, FeCoP, CoNiP and FeNiP.
4. A method for preparing the heterojunction composite photocatalyst with atomic scale channels as claimed in claim 1, 2 or 3, which is characterized by comprising the following steps:
(1) adding precursor powder containing phosphorus element into graphite phase carbon nitride C3N4Fully grinding the powder, carrying out discharge reaction under the action of hydrogen-containing plasma, collecting the powder after the reaction is finished, washing the powder with ethanol and deionized water, and drying to obtain phosphorus-doped carbon nitride powder, namely P-C3N4Powder;
(2) the P-C prepared in the step (1)3N4Mixing the powder with water-soluble transition metal salt and a precursor containing phosphorus, adding deionized water, fully stirring under a water bath condition, and then freeze-drying to obtain mixed powder;
(3) carrying out discharge reaction on the mixed powder in the step (2) under the action of hydrogen-containing plasma, collecting the powder after the reaction is finished, washing the powder with ethanol and deionized water, and drying to obtain transition metal phosphate @ P-C3N4A composite photocatalyst is provided.
5. The method for preparing the heterojunction composite photocatalyst with atomic scale channels according to claim 4, wherein the precursor powder containing phosphorus element in the step (1) is one or a combination of two or more of orthophosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid and corresponding water-soluble salts.
6. The method for preparing the heterojunction composite photocatalyst with the atomic scale channel according to claim 4, wherein the hydrogen-containing plasma in the steps (1) and (3) is pure hydrogen plasma or mixed gas plasma of hydrogen and inert gas.
7. The method for preparing the heterojunction composite photocatalyst with the atomic scale channel according to claim 4 or 6, wherein the power of the discharge reaction in the steps (1) and (3) is 50-200W, the discharge time is 10-60min, and the gas pressure is 5-10 Pa.
8. The method for preparing the heterojunction composite photocatalyst with the atomic-scale channel according to claim 4, wherein in the step (2), the water-soluble transition metal salt is one or two or more of chloride, nitrate, sulfate and sulfite of a transition metal.
9. The method for preparing the heterojunction composite photocatalyst with the atomic scale channel as claimed in claim 4, wherein the temperature of the water bath condition in the step (2) is 50-100 ℃, and the water bath time is 0.5-12 h.
10. Use of the heterojunction composite photocatalyst with the atomic scale channel as defined in claim 1, 2 or 3 in hydrogen production by photolysis of water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964288A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Method for preparing mesoporous carbon nitride loaded nano nickel phosphide |
| CN107552083A (en) * | 2017-10-11 | 2018-01-09 | 肇庆市华师大光电产业研究院 | A kind of FeP/C3N4Composite photo-catalyst and its preparation method and application |
| CN107617443A (en) * | 2017-10-30 | 2018-01-23 | 吉林大学 | A kind of g C3N4The NiCoP nano particles of surface in situ growth, preparation method and applications |
| CN109746018A (en) * | 2018-12-28 | 2019-05-14 | 西安交通大学 | A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of the phosphorus doping of metal phosphide modification |
| CN113617376A (en) * | 2021-08-17 | 2021-11-09 | 青岛科技大学 | P-doped g-C3N4Catalyst for hydrogen production by water photolysis through MoP and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964288A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Method for preparing mesoporous carbon nitride loaded nano nickel phosphide |
| CN107552083A (en) * | 2017-10-11 | 2018-01-09 | 肇庆市华师大光电产业研究院 | A kind of FeP/C3N4Composite photo-catalyst and its preparation method and application |
| CN107617443A (en) * | 2017-10-30 | 2018-01-23 | 吉林大学 | A kind of g C3N4The NiCoP nano particles of surface in situ growth, preparation method and applications |
| CN109746018A (en) * | 2018-12-28 | 2019-05-14 | 西安交通大学 | A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of the phosphorus doping of metal phosphide modification |
| CN113617376A (en) * | 2021-08-17 | 2021-11-09 | 青岛科技大学 | P-doped g-C3N4Catalyst for hydrogen production by water photolysis through MoP and preparation method thereof |
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