CN108499585B - Phosphorus-containing compound and preparation and application thereof - Google Patents
Phosphorus-containing compound and preparation and application thereof Download PDFInfo
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- CN108499585B CN108499585B CN201810157038.8A CN201810157038A CN108499585B CN 108499585 B CN108499585 B CN 108499585B CN 201810157038 A CN201810157038 A CN 201810157038A CN 108499585 B CN108499585 B CN 108499585B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 132
- 239000011574 phosphorus Substances 0.000 title claims abstract description 131
- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000007787 solid Substances 0.000 claims description 47
- 239000002131 composite material Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 29
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 25
- 239000002073 nanorod Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 230000003197 catalytic effect Effects 0.000 claims description 18
- 238000007872 degassing Methods 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 17
- 229910052724 xenon Inorganic materials 0.000 claims description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 16
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 15
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 10
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
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- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 47
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- 239000010949 copper Substances 0.000 description 61
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 39
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 15
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 10
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- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 239000002071 nanotube Substances 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 8
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- 150000003839 salts Chemical class 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 229910002915 BiVO4 Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
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- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
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Images
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention discloses a phosphorus-containing compound and preparation and application thereof, belonging to the field of material science and technology and chemistry. The invention adopts cheap raw materials and a simple method to prepare the phosphorus-containing compound, essentially, under the condition of light irradiation of an optical active substance, metal ions and a phosphorus source generate a compound, compared with the temperature (100 ℃) of the prior method, the method adopts normal-temperature synthesis, and the crystallization degree of the obtained compound is weak. The phosphorus-containing compound of the invention is used as a conventional catalyst and a cocatalyst of a photocatalytic reaction, has higher photocatalytic activity, and has higher hydrogen production rate when being used for a photocatalytic hydrogen production reaction. The method and the phosphorus-containing compound can be used for preparing electrodes and batteries, the production cost of the electrodes and the batteries is reduced, the preparation method is simplified, and the obtained electrodes are non-noble metal catalysts, have low cost, lower overpotential and higher stability, and have certain industrial application value.
Description
Technical Field
The invention relates to a phosphorus-containing compound and a preparation method and application thereof, belonging to the field of material science and technology and chemistry.
Background
Global environmental pollution and energy crisis are becoming more serious, and development of novel sustainable energy is receiving much attention from all countries in the world. Among them, hydrogen is considered as the most ideal energy source because of its advantages of abundant source, high combustion value, clean combustion product and no pollution. Hydrogen production by splitting water is one of the important methods that make it possible to produce hydrogen on a large scale. The solar energy is utilized to decompose water to produce hydrogen, and the solar energy is converted into chemical energy stored in hydrogen energy, so that a cheap and convenient method for obtaining hydrogen is provided, and the development of a cheap and efficient photocatalyst is the key for photocatalytic decomposition of water to produce hydrogen. Solar energy, wind energy and other renewable energy sources are used for power generation, hydrogen production by water decomposition through electric energy reduction is another simple and effective mode, and efficient and cheap electrocatalyst development is the key point of hydrogen production through water electrolysis.
Noble metal catalysts, represented by platinum, are well known effective and stable photocatalysts and electrocatalysts, but their large-scale commercial application is limited by the expensive price and low abundance. Therefore, the development of non-noble metal catalysts with high activity, high abundance and good stability is particularly necessary. Over the past few years, transition metal sulfides, transition metal selenides, carbides, nitrides, and the like have been emerging as hydrogen-generating electrocatalysts. Recently, metal phosphides have been particularly attractive due to their high atomic activity sites and stability. As a novel catalyst, the high-efficiency electrocatalytic performance of the catalyst is widely researched, and the metal phosphide has been proved to be used as a high-efficiency cocatalyst in hydrogen production by photocatalytic water splitting. However, the preparation methods of metal phosphide mainly include the following methods:
the first method is the synthesis of metal phosphides under high temperature conditions (T >300 ℃) using Trioctylphosphine (TOP) as the phosphorus source, but trioctylphosphine is highly flammable and corrosive.
Second method, 300 ℃ CDecomposition of hypophosphite salts (e.g. NaH) at elevated temperatures2PO2) Generating highly toxic gas PH3，PH3And reducing the metal oxide/metal hydroxide under high temperature to generate metal phosphide.
In the third method, red phosphorus and white phosphorus are used as phosphorus sources to synthesize metal phosphide at the temperature of 140 ℃ and 200 ℃ by a solvothermal method.
The fourth method, metal phosphides are prepared by reducing orthophosphates of metals using hydrogen at high temperatures (T >600 ℃).
These methods provide for a variety of orientations for the rational design and scalable manufacturing of TMPs. It still needs to create some new synthetic methods to improve the shortcomings of the current methods.
Disclosure of Invention
In order to solve the problems, the invention adopts a simple, mild and low-cost photochemical method to prepare the phosphorus-containing compound, which can be used as a catalyst and has low cost, good performance, higher stability and use value.
The first object of the invention is to provide a method for preparing a phosphorus-containing compound, which comprises the steps of generating the phosphorus-containing compound by metal ions and a phosphorus source under the condition of light irradiation of a photoactive substance; the phosphorus-containing compound contains phosphorus and metal; in the generation reaction, necessary substances are an optical active substance, a metal source and a phosphorus source;
in the reaction for forming the phosphorus-containing compound, no other sacrificial agent is added except for the essential substances.
A photoactive material refers to a material that is capable of absorbing photon energy upon excitation by a photon.
In one embodiment, the valence state of the phosphorus in the phosphorus source may be-3 to + 5. The phosphorus source can be phosphorus sources in various forms, such as simple substance, inorganic phosphorus, organic phosphorus and the like.
In one embodiment, the phosphorus source may be an inorganic phosphorus, such as any one or combination of more of the following: hypophosphite, phosphite, or orthophosphate (H)2PO2 -,H2PO3 -，H2PO4 -)。Any one or more of the following combinations may be used: NaH2PO2、NaH2PO3、NaH2PO4。
In one embodiment, the phosphorus source may be an organic species, such as an organic phosphorus, e.g., trioctylphosphine.
In one embodiment, the phosphorus source is elemental phosphorus, such as red phosphorus, white phosphorus, and the like.
In one embodiment, the phosphorus-containing compound is a metal phosphide or a metal-phosphorus alloy.
In one embodiment, the metal In the metal ion may be a transition metal, and may be In, Pt, Pd, Rh, Re, Ir.
In one embodiment, the transition metal may be iron, cobalt, nickel, copper, manganese, zinc, aluminum, etc., and may also be chromium, molybdenum, tungsten, etc.
In one embodiment, the metal ion is provided by a metal salt.
In one embodiment, the metal salt may be a chloride salt, a bromide salt, a nitrate salt, a nitrite salt, a sulfate salt, a sulfite salt, an acetate salt, or the like.
In one embodiment, the donor of the metal ion may be dispersed in the reaction system.
In one embodiment, the light refers to light that is capable of exciting the photoactive material and is energy-level-matched to the photoactive material.
In one embodiment, the wavelength of the light is based on the requirements of the photoactive material. Generally, the light effect of the wavelength range of 200-1300nm is better, and light with corresponding wavelength can be provided as a light source, such as sunlight, and can also be an artificial light source, such as a xenon lamp, an ultraviolet lamp, an LED lamp, laser and the like. The light intensity is not specially required, the light intensity is high, and the deposition speed is high.
In one embodiment, the photoactive material may be any material that has a photoresponse, photoactive property.
In one embodiment, the photoactive material may be any one or more of the following: metal oxides, sulfides, oxyhalides, tungstates, silicon, carbon nitrides, and the like.
In one embodiment, the photoactive material may be any one or more of the following: TiO 22，BiOX(X＝Cl,Br,I)，CdX(X＝S,Se,Te)，BiWO6，BiVO4，Cu2O，Si，C3N4ZnO, ZnS, ZnSe, Zinc oxide-ruthenium oxide (ZnO-RuO)2) Copper thiogallate (CuGaS)2) Gallium phosphide (GaP), gallium arsenide (GaAs), or combinations thereof.
In one embodiment, the photoactive material may be in the form of a powder; such as nanowires, nanowire arrays, nanotubes, nanotube arrays, nanoparticles, nanostructures containing pores, or combinations thereof.
In one embodiment, the reaction system has a concentration of phosphorus and metal ions of 10-3mol L-1When the saturation range is reached, the deposition process is easily completed in a short time.
In one embodiment, the molar ratio of phosphorus to metal ion in the system of the reaction is not particularly limited. The molar ratio is 10-3Deposition is easily achieved at-1000 deg.f.
In one embodiment, the process is carried out in a low concentration oxygen or oxygen-free system. In photochemical reactions, measures are taken to reduce the oxygen concentration in the system, which helps to achieve the deposition process faster. For example, a certain inert gas may be introduced to degas, or a reducing agent may be added, or oxygen may be pumped away.
In one embodiment, the oxygen-free system is performed under the protection of an inert gas. Alternatively, the inert gas may be nitrogen, argon, or the like.
In one embodiment, the process is carried out in a solvent system; the phosphorus source and metal ion donor are dispersed, partially dissolved or completely dissolved in the solvent system.
In one embodiment, the solvent may be water, alcohols, acids, organic solvents, or a mixture thereof.
In one embodiment, the method comprises intermittent or continuous stirring.
In one embodiment, the method is: adding the photoactive material into a reaction container, then adding a metal source and a phosphorus source dispersed in a solvent, uniformly mixing, removing oxygen in a reaction system, and then placing under illumination to stir for reaction to generate a phosphorus-containing compound.
In one embodiment, the method is specifically:
(1) adding a certain amount of cadmium sulfide nano-rods into a 25mL single-neck round-bottom flask, and adding a certain amount of sodium hypophosphite (molecular formula NaH)2PO2) Mixing with a mixed aqueous solution of cobalt chloride, introducing nitrogen for 30-40min to remove oxygen in a reaction system, then placing under a xenon lamp for illumination, keeping uniform stirring during illumination, and adjusting the content of CoxP through different illumination time;
(2) and after the reaction is finished, separating the solid by centrifugal separation, centrifugally washing the solid by deionized water for 5-8 times, washing the solid by ethanol for 1-3 times, and drying the obtained solid, wherein the obtained solid is the product of the CoxP/cadmium sulfide nanorod composite catalyst.
In some embodiments, the cadmium sulfide nanorods are prepared by a hydrothermal method.
In some embodiments, the preparation of the cadmium sulfide nanorod is specifically as follows: placing a proper amount of 2.5 cadmium chloride hydrate, thiourea and a certain volume of ethylenediamine into a 100mL high-pressure reaction kettle, placing the reaction kettle into a 160 ℃ oven for hydrothermal treatment for 48h, placing the reaction kettle under natural conditions to reduce the temperature to room temperature after the reaction is finished, filtering to obtain yellow solid, washing the yellow solid with deionized water for about 10 times, washing the yellow solid with ethanol for 1-2 times, and placing the obtained solid into a 60 ℃ oven for drying overnight to obtain the yellow solid, namely the cadmium sulfide nanorod.
The second object of the present invention is to provide a phosphorus-containing compound prepared according to the above preparation method. The preparation method of the phosphorus-containing compound comprises the following steps: comprises that under the condition of light irradiation of a light active substance, metal ions and a phosphorus source generate a phosphorus-containing compound; the phosphorus-containing compound contains phosphorus and metal; in the generation reaction, necessary substances are an optical active substance, a metal source and a phosphorus source; in the formation reaction, no other sacrificial agent is added except the essential substances.
In one embodiment, the valence state of the phosphorus in the phosphorus source may be-3 to + 5. The phosphorus source may be any of various forms, such as elemental phosphorus (red phosphorus, white phosphorus, or the like), inorganic phosphorus (hypophosphite, phosphite, or orthophosphate), organic phosphorus (trioctylphosphine, or the like), or the like.
In one embodiment, the metal In the metal ion may be a transition metal, and may be In, Pt, Pd, Rh, Re, Ir. Alternatively, the transition metal may be iron, cobalt, nickel, copper, manganese, zinc, aluminum, etc., and may also be chromium, molybdenum, tungsten, etc.
In one embodiment, the metal ion is provided by a metal salt. Alternatively, chlorine salts, bromine salts, nitrate salts, nitrite salts, sulfate salts, sulfite salts, acetate salts, and the like may be used.
In one embodiment, the photoactive material may be any one or more of the following: metal oxides, sulfides, oxyhalides, tungstates, silicon, carbon nitrides, and the like. Alternatively, it may be any one or more of: TiO 22，BiOX(X＝Cl,Br,I)，CdX(X＝S,Se,Te)，BiWO6，BiVO4，Cu2O，Si，C3N4ZnO, ZnS, ZnSe, Zinc oxide-ruthenium oxide (ZnO-RuO)2) Copper thiogallate (CuGaS)2) Gallium phosphide (GaP), gallium arsenide (GaAs), or combinations thereof. Alternatively, the photoactive material can be in the form of powder; such as nanowires, nanowire arrays, nanotubes, nanotube arrays, nanoparticles, nanostructures containing pores, or combinations thereof.
A third object of the present invention is to provide a heterostructure comprising at least one substrate of a photoactive material, and a plurality of further materials formed under light conditions on the substrate of the photoactive material; preparing the other material, wherein the metal source and the phosphorus source generate the phosphorus-containing compound under the illumination condition of the photoactive material; in the other substance generation reaction, the essential substances are a photoactive substance, a metal source and a phosphorus source.
In one embodiment, the other substance is a metal phosphide or a phosphorus-containing alloy.
In one embodiment, the another substance is composed of a phosphorus element and a metal element.
In one embodiment, the valence state of the phosphorus in the phosphorus source may be-3 to + 5. The phosphorus source may be any of various forms, such as elemental phosphorus (red phosphorus, white phosphorus, or the like), inorganic phosphorus (hypophosphite, phosphite, or orthophosphate), organic phosphorus (trioctylphosphine, or the like), or the like.
In one embodiment, the metal In the metal ion may be a transition metal, and may be In, Pt, Pd, Rh, Re, Ir. Alternatively, the transition metal may be iron, cobalt, nickel, copper, manganese, zinc, aluminum, etc., and may also be chromium, molybdenum, tungsten, etc.
In one embodiment, the metal ion is provided by a metal salt. Alternatively, chlorine salts, bromine salts, nitrate salts, nitrite salts, sulfate salts, sulfite salts, acetate salts, and the like may be used.
In one embodiment, the photoactive material may be any one or more of the following: metal oxides, sulfides, oxyhalides, tungstates, silicon, carbon nitrides, and the like. Alternatively, it may be any one or more of: TiO 22，BiOX(X＝Cl,Br,I)，CdX(X＝S,Se,Te)，BiWO6，BiVO4，Cu2O，Si，C3N4ZnO, ZnS, ZnSe, Zinc oxide-ruthenium oxide (ZnO-RuO)2) Copper thiogallate (CuGaS)2) Gallium phosphide (GaP), gallium arsenide (GaAs), or combinations thereof. Alternatively, the photoactive material can be in the form of powder; such as nanowires, nanowire arrays, nanotubes, nanotube arrays, nanoparticles, nanostructures containing pores, or combinations thereof.
It is a fourth object of the present invention to provide a device comprising the phosphorus-containing composite or heterostructure of the present invention.
In one embodiment, the preparation of the phosphorus-containing compound or heterostructure comprises the steps of generating the phosphorus-containing compound by metal ions and a phosphorus source under the condition of illumination of a photoactive substance; the phosphorus-containing compound contains phosphorus and metal; in the formation reaction, the essential substances are a photoactive substance, a metal source and a phosphorus source.
In one embodiment, the device may be an electrocatalytic electrode, a fuel cell electrode, a solar cell electrode, a photoelectrocatalytic electrode, a conductive device, an electronic device, or the like.
In one embodiment, the device is obtained by first fixing or attaching a photoactive material to a corresponding substrate and then forming the phosphorus-containing complex of the present invention on the photoactive material by a photochemical deposition process.
In one embodiment, the substrate may be a substrate made of metal, metal oxide, glass, carbon, or the like.
It is a fifth object of the invention to provide a composite electrode comprising the phosphorus-containing composite of the invention or the heterostructure of the invention.
In one embodiment, the composite electrode includes a conductive substrate and a phosphorous-containing composite.
In one embodiment, the preparation of the phosphorus-containing compound comprises, in the presence of light, forming the phosphorus-containing compound of the invention from metal ions and a phosphorus source; the phosphorus-containing compound contains phosphorus and metal; in the formation reaction, the essential substances are a photoactive substance, a metal source and a phosphorus source.
In one embodiment, the composite electrode further comprises a photoactive material immobilized or attached to a corresponding conductive substrate.
In one embodiment, the conductive substrate may be one or more of nickel foam, ITO, FTO, nickel sheet, nickel mesh, titanium sheet, titanium mesh, copper sheet, copper mesh, stainless steel sheet, stainless steel mesh, carbon fiber cloth, and transparent conductive cloth.
The sixth purpose of the invention is to provide a preparation method of the composite electrode, which comprises the steps that under the condition of illumination, metal ions and a phosphorus source of a photoactive substance generate the phosphorus-containing composite; in the generation reaction, necessary substances are an optical active substance, a metal source and a phosphorus source; the photoactive material is fixed or attached to a conductive substrate.
In one embodiment, the photoactive material is immobilized or attached to a conductive substrate, and can be achieved by electrophoresis, spin coating, drop coating, hydrothermal method, electrodeposition, calcination, and the like.
In one embodiment, the photoactive material is attached to the conductive substrate by electrophoresis.
In one embodiment, the method of attaching the photoactive material to a conductive substrate is: taking 10mg of g-C3N4The yellowish white powder was placed in a 250mL beaker, 10mg of magnesium nitrate hexahydrate and 100mL of isopropanol solution were added and sonicated for 3 h. And then, carrying out electrophoresis in an electrophoresis apparatus for 10min by taking a platinum electrode as an anode, taking out the prepared electrode, washing the electrode with deionized water, and drying the electrode.
It is a seventh object of the present invention to provide a battery comprising: a positive electrode, a negative electrode, and a separator between the positive electrode and the negative electrode; wherein at least one electrode has a phosphorus-containing compound of the invention or a heterostructure of the invention.
In one embodiment, the phosphorus-containing complex is formed by metal ions and a phosphorus source under the condition that a photoactive substance is irradiated by light; in the formation reaction, the essential substances are a photoactive substance, a metal source and a phosphorus source.
In one embodiment, the valence state of the phosphorus in the phosphorus source may be-3 to + 5. The phosphorus source may be any of various forms, such as elemental phosphorus (red phosphorus, white phosphorus, or the like), inorganic phosphorus (hypophosphite, phosphite, or orthophosphate), organic phosphorus (trioctylphosphine, or the like), or the like. The metal In the metal ions may be a transition metal, In, Pt, Pd, Rh, Re, Ir. Alternatively, the transition metal may be iron, cobalt, nickel, copper, manganese, zinc, aluminum, etc., and may also be chromium, molybdenum, tungsten, etc. The metal ion may be provided by a metal salt. Alternatively, chlorine salts, bromine salts, nitrate salts, nitrite salts, sulfate salts, sulfite salts, acetate salts, and the like may be used.
In one embodiment, the photoactive material may be any one or more of the following: metal oxides, sulfides, oxyhalides, tungstates, silicon, carbon nitrides, and the like. Alternatively, it may be any one or more of: TiO 22，BiOX(X＝Cl,Br,I)，CdX(X＝S,Se,Te)，BiWO6，BiVO4，Cu2O，Si，C3N4ZnO, ZnS, ZnSe, Zinc oxide-ruthenium oxide (ZnO-RuO)2) Copper thiogallate (CuGaS)2) Gallium phosphide (GaP), gallium arsenide (GaAs), or combinations thereof. Alternatively, the photoactive material can be in the form of powder; such as nanowires, nanowire arrays, nanotubes, nanotube arrays, nanoparticles, nanostructures containing pores, or combinations thereof.
An eighth object of the present invention is to provide a fuel cell comprising the phosphorus-containing composite of the present invention or the heterostructure of the present invention.
In one embodiment, the phosphorus-containing complex is formed by metal ions and a phosphorus source under the condition that a photoactive substance is irradiated by light; in the formation reaction, the essential substances are a photoactive substance, a metal source and a phosphorus source.
In one embodiment, the fuel cell is a Proton Exchange Membrane Fuel Cell (PEMFC) or is associated with other types of fuel cells, such as Solid Oxide Fuel Cells (SOFC), Molten Carbonate Fuel Cells (MCFC), Phosphoric Acid Fuel Cells (PAFC), Alkaline Fuel Cells (AFC), and the like, with a phosphorus-containing compound as a catalyst.
In one embodiment, the membrane electrode of the fuel cell comprises a cathode catalytic layer, a proton exchange membrane and an anode catalytic layer; at least one of the cathode catalyst layer and the anode catalyst layer contains the phosphorus-containing composite.
In one embodiment, the membrane electrode of the fuel cell further comprises a cathode diffusion layer and an anode diffusion layer.
In one embodiment, the membrane electrode of the fuel cell further comprises a cathode sealing layer and an anode sealing layer.
In one embodiment, the membrane electrode of the fuel cell comprises a cathode sealing layer, a cathode diffusion layer, a cathode catalyst layer, a proton exchange membrane, an anode catalyst layer, an anode diffusion layer and an anode sealing layer in sequence.
The ninth purpose of the invention is to provide a preparation method of a fuel cell, wherein the preparation process comprises preparing a phosphorus-containing compound by adopting a photo-deposition method; the preparation of the phosphorus-containing compound is that under the condition of light irradiation of an optical active substance, metal ions and a phosphorus source generate the phosphorus-containing compound; in the formation reaction, the essential substances are a photoactive substance, a metal source and a phosphorus source.
A tenth object of the invention is to provide the use of said phosphorus-containing compound in the field of catalysis.
In one embodiment, the application may be for catalytic hydrogen production, catalytic reduction, catalytic hydrogen evolution, catalytic oxygen reduction, catalytic oxygen production, catalytic oxidation, and the like.
An eleventh object of the present invention is to provide the use of the phosphorus-containing composite of the present invention for preparing an electrode.
A twelfth object of the invention is to provide the use of the phosphorus-containing composite of the invention for the preparation of a fuel cell.
The invention has the beneficial effects that:
(1) the invention adopts cheap raw materials and a simple method, prepares the phosphorus-containing compound under the room temperature condition, and essentially, under the condition of illumination of an optical active substance, metal ions and a phosphorus source generate the compound, compared with the temperature (100 ℃) of the prior method, the method is synthesized at normal temperature, and the crystallization degree of the obtained compound is weak.
(2) The phosphorus-containing compound is dispersed on the surface of the photoactive material; CoxP is adopted as a cocatalyst for photocatalytic reaction, so that the catalytic efficiency is greatly improved, and compared with other types of cobalt catalysts, the catalyst has higher photocatalytic activity; the NixP is used as a cocatalyst for photocatalytic reaction, so that the catalytic efficiency is greatly improved, and the composite photocatalyst has higher photocatalytic activity compared with other non-noble metal modified composite photocatalysts; the phosphorus-containing compound can be used for hydrogen production reaction by photocatalytic decomposition of water, and has low cost and high hydrogen production rate.
(3) The light deposition method and the phosphorus-containing compound can be used for preparing electrodes and batteries, reduce the production cost of the electrodes and the batteries and simplify the preparation method.
(4) The inventive photochemical method successfully obtains the composite electrode, and the preparation method is simple, convenient, controllable, green and environment-friendly, and provides a new idea for preparing the electrode. By NixP and g-C3N4The composite electrode has extremely low charge transfer resistance, reduces the charge transfer resistance and enables electrons to be more easily reduced and decomposed to generate hydrogen; the electrode is a non-noble metal catalyst, so that the production cost is reduced, and the electrode has lower overpotential and higher stability and has certain industrial application value. By NixP and Cu2The composition of O not only overcomes the defect that single substance is easy to be corroded by light, but also improves Cu2The composite electrode has lower charge transfer resistance, reduces the charge transfer resistance, enables electrons to be transferred out more easily to participate in hydrogen evolution reaction, and reduces the carrier recombination; the electrode is a non-noble metal catalyst, the abundance of each element is high, the production cost is reduced, and the electrode has higher photocurrent density and good stability and has certain industrial application value.
Drawings
FIG. 1 shows the NixP @ g-C obtained in example 13N4Photographs of/NF electrodes and transmission electron micrographs;
FIG. 2 shows NixP @ g-C obtained in example 13N4Scanning electron micrographs of/NF electrodes;
FIG. 3 shows NixP @ g-C obtained in example 13N4Energy dispersion X-ray spectrum of a scanning electron microscope of the NF electrode;
FIG. 4 shows NixP @ g-C obtained in example 13N4A Fourier transform infrared spectrogram of the catalyst;
FIG. 5 shows NixP @ g-C obtained in example 13N4Linear scanning voltammogram of/NF electrode;
FIG. 6 shows NixP @ g-C obtained in example 33N4Linear scanning voltammograms of the catalyst supported on different substrates;
FIG. 7 shows NixP @ g-C obtained in example 13N4Electrochemical impedance spectrum of/NF electrode (Ni is inserted in the figure)XP@g-C3N4An enlarged view of the/NF electrode impedance spectrum);
FIG. 8 is the FTO/Cu obtained in example 52Scanning electron microscope images of O/NixP photocathodes;
FIG. 9 shows FTO/Cu data obtained in example 52X-ray diffraction pattern of O/NixP photocathode;
FIG. 10 is an X-ray photoelectron spectrum of NixP nanoparticles obtained in example 5;
FIG. 11 is the FTO/Cu obtained in example 52A photocurrent density graph of the O/NixP photocathode;
FIG. 12 is the FTO/Cu data obtained in example 52Electrochemical alternating-current impedance spectrogram of the O/NixP photocathode;
FIG. 13 is a scanning electron micrograph of the FTO/NiO/CdS/NixP electrode obtained in example 8;
FIG. 14 is the XRD pattern of the cadmium sulfide nanorods and CoxP/cadmium sulfide nanorod composite catalysis of example 9;
FIG. 15 is a transmission electron microscope image of CoxP/cadmium sulfide nanorod recombination catalysis of example 9;
FIG. 16 is a CoxP/cadmium sulfide nanorod composite catalytic scanning electron microscopy energy dispersive X-ray spectrum of example 9;
FIG. 17 is the X-ray photoelectron spectrum of CoxP/cadmium sulfide nanorod recombination catalysis of example 9;
FIG. 18 is a test chart of CoxP/cadmium sulfide nanorod composite catalytic photocatalytic hydrogen production of example 9;
FIG. 19 is an XRD pattern for the composite catalysis of the NixP/graphene-like carbonitride composite catalyst of example 11;
FIG. 20 is a TEM image of the NixP/grapheme-like carbonitride composite catalyst of example 11;
FIG. 21 is a scanning electron microscopy energy dispersive X-ray spectroscopy spectrum of a NixP/graphene-like carbon nitrogen compound composite catalyst of example 11;
FIG. 22 is an X-ray photoelectron spectrum of a NixP/graphene-like carbonitride compound composite catalyst of example 12;
FIG. 23 is a hydrogen test chart of the NixP/graphene-like carbon nitrogen compound composite catalyst photocatalytic decomposition water of example 12.
Detailed description of the preferred embodiments
The present invention will be described in detail below.
In order to illustrate the process of the invention more specifically, examples of the invention are given below, without restricting the application of the invention thereto.
Example 1: NixP @ g-C3N4Catalyst and NixP @ g-C3N4Preparation and characterization of/NF electrode
Novel NixP @ g-C3N4The preparation steps of the/NF electrode are as follows:
(1) firing of g-C3N4
Firstly weighing a certain amount of thiourea, placing the thiourea in a crucible, then placing the crucible in a muffle furnace, heating to 550 ℃ (heating rate of 2 ℃/min) and keeping for 2h, naturally cooling to room temperature, taking out the crucible, grinding the obtained yellow solid in a porcelain mortar for a certain time, pouring the yellow solid back into the crucible, placing the crucible in the muffle furnace, heating to 500 ℃ (heating rate of 2 ℃/min) and keeping for 2h, cooling to room temperature, taking out the crucible, grinding yellow-white powder for a certain time, namely g-C3N4。
(2) Pretreatment of nickel foam
Carrying out ultrasonic pretreatment on 1 × 2cm of foamed nickel in 3mol/L hydrochloric acid solution, acetone, deionized water and ethanol solution for 15min, respectively cleaning the solution for three times, and then drying the solution in an oven at 80 ℃ for later use.
(3) Electrophoresis of g-C3N4
Taking 10mg of g-C3N4Adding yellow white powderInto a 250mL beaker, 10mg of magnesium nitrate hexahydrate and 100mL of isopropanol solution were added and sonicated for 3 h. And then, carrying out electrophoresis in an electrophoresis apparatus for 10min by taking a platinum electrode as an anode, taking out the prepared electrode, washing the electrode with deionized water, and drying the electrode.
(4) Photochemical preparation of NixP/g-C3N4/NF electrode
14mL of sodium hypophosphite solution (0.2mol/L) and 4mL of nickel chloride (0.1mol/L) were added to a 25mL round-bottom flask, 2mL of deionized water was added, the flask was shaken up, the prepared electrode was placed in the flask, and then nitrogen was introduced into the sealed flask for 40min to exclude oxygen and other miscellaneous gases. The flask was placed under a 300W xenon lamp for light irradiation, and the mixture was stirred uniformly during the light irradiation. And after the reaction is finished, washing with deionized water and drying.
FIG. 1 is a photograph and a transmission electron microscope image of the prepared electrode, wherein the photograph shows that the catalyst is tightly loaded on the foamed nickel substrate, and the transmission electron microscope image shows that NixP is spherical and uniformly distributed in g-C3N4Wherein NixP is black in the figure, g-C3N4Appear in a sheet-like form.
FIG. 2 shows the preparation of NixP @ g-C3N4The scanning electron microscope image of the/NF electrode shows that the NixP nano particles are tightly loaded on g-C3N4And (4) nano-chips.
FIG. 3 shows the NixP @ g-C obtained3N4Energy dispersion X-ray spectrum of a scanning electron microscope of the NF electrode; the existence of Ni, P, C and N elements on the electrode can be visually seen from the figure, and NixP @ g-C is proved3N4The composite catalyst was successfully prepared. Wherein, the Na, Cl and O elements on the electrode are respectively caused by the impurities on the surface of the sample and the oxidation of the sample exposed in the air.
FIG. 4 shows the NixP @ g-C obtained3N4A Fourier transform infrared spectrogram of the catalyst; it can be seen from the figure that for g-C3N4The spectrum shows that the total of three characteristic absorption peaks has a wavelength of 3294cm-1,1200-1700cm-1And 810cm-1To (3). At 3294cm-1The wider peak appears at is due toNH2Or stretching vibration of the N-H bond. At 1654cm-1、1575cm-1And 1411cm-1The absorption peak at (A) is due to classical CN heterocyclic stretching vibration. At a wavelength of 810cm-1The peaks appearing there arise from out-of-plane bending of the triazine ring structure. The above results demonstrate that g-C3N4Samples were successfully prepared. From NixP@g-C3N4From the Fourier transform infrared spectrogram, the wavelength is 3450cm-1And 1635cm-1The absorption peak appeared here is due to O — H stretching vibration, corresponding to water molecules adsorbed on the sample surface. At a wavelength of 579cm-1The presence of Ni-P bonds is evidenced by the absorption peaks appearing at the sites, indicating the synthesis of NixP species.
Example 2: NixP @ g-C3N4Comparison of electrochemical Performance of the/NF electrode with other electrodes
(1) Preparation of other electrodes:
taking g-C in example 13N410mg was placed in a 250mL beaker, 10mg of magnesium nitrate hexahydrate and 100mL of isopropanol solution were added and sonicated for 3 h. Taking the solution as electrophoresis solution, foam nickel as cathode, platinum electrode as anode, performing electrophoresis in an electrophoresis apparatus for 10min, taking out the prepared electrode, washing with deionized water, and drying to obtain g-C3N4a/NF electrode.
In order to further compare the performance of the catalyst, 20 wt% of a commercial Pt/C catalyst is dispersed in a solution of ethanol and water in a volume ratio of 4:1, then 40 microliters of Nafion solution is added for 20min of ultrasonic treatment, then the mixed homogeneous catalyst is loaded on foamed nickel, and finally, a sample is placed in a 60 ℃ oven to be dried for 3h, so that the electrode loaded with the Pt/C catalyst is obtained.
(2) And (3) electrochemical performance testing:
0.5mol/L sulfuric acid (pH 0) as an electrolyte solution, g-C3N4Using a/NF electrode as a working electrode, using an Ag/AgCl electrode as a reference electrode, using a platinum net as a counter electrode, performing cyclic voltammetry circulation for 26 times in 0.5mol/L sulfuric acid solution, and performing linear scanning electrochemical performance measurement on a CHI660E electrochemical workstationTest results are shown as g-C in FIG. 53N4the/NF curve. For further comparison, 0.5mol/L sulfuric acid was used as an electrolyte solution, a Pt/C catalyst-supported electrode as a working electrode, an Ag/AgCl electrode as a reference electrode, a platinum mesh as a counter electrode, cyclic voltammetry cycles were performed 26 times in 0.5mol/L sulfuric acid solution, and then a linear scanning electrochemical performance test was performed on a CHI660E electrochemical workstation, and the test results are shown in a Pt/C curve in FIG. 5. 0.5mol/L sulfuric acid is used as an electrolyte solution, a pretreated NF electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum net is used as a counter electrode, 0.5mol/L sulfuric acid solution is subjected to cyclic voltammetry circulation for 26 times, then a linear scanning electrochemical performance test is carried out on a CHI660E electrochemical workstation, and the test result is shown as the NF curve in figure 5.
Wherein, NixP @ g-C in FIG. 53N4The linear scanning voltammogram of the/NF electrode has the following test conditions: 0.5mol/L sulfuric acid (PH ═ 0) as electrolyte solution, NixP @ g-C3N4And performing cyclic voltammetry cycling 26 times by using a/NF electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum net as a counter electrode in 0.5mol/L sulfuric acid solution, and then performing linear scanning electrochemical performance testing on a CHI660E electrochemical workstation.
Ni from FIG. 5XP@g-C3N4NF Curve, g-C3N4the/NF curve, Pt/C curve and NF curve can be visually seen: at the same current density, and g-C3N4Linear scanning voltammogram comparison of/NF, NixP@g-C3N4the/NF has a relatively low overpotential, i.e. when Ni is presentxP deposition to g-C3N4When the surface of the NF electrode is coated, the activity of the electrode hydrogen evolution reaction can be greatly improved. NixP@g-C3N4the/NF electrode only needs 126mV and 149mV overpotentials to drive 10mA cm respectively-2And 20mA cm-2Current density of (2) over potential ratio g-C3N4The overpotential of/NF and NF is much reduced. In addition to that, NixP@g-C3N4The cathodic current density of the NF electrode is increased at more negative potentialVery fast, i.e. having an efficient current response speed, and at a current density of 100mA cm-2The overpotential of time is only 217 mV.
Example 3: based on NiXP@g-C3N4Of different substrates
(1) Taking g-C in example 13N410mg was placed in a 250mL beaker, 10mg of magnesium nitrate hexahydrate and 100mL of isopropanol solution were added and sonicated for 3 h. And respectively taking the treated FTO and the copper sheet as cathodes, taking a platinum electrode as an anode, performing electrophoresis in an electrophoresis apparatus for 10min, taking out the prepared electrode, washing with deionized water, and drying. 14mL of sodium hypophosphite solution (0.2mol/L) and 4mL of nickel chloride (0.1mol/L) were added to a 25mL round-bottom flask, 2mL of deionized water was added, the flask was shaken up, the prepared electrode was placed in the flask, and then nitrogen was introduced into the sealed flask for 40min to exclude oxygen and other miscellaneous gases. The flask was placed under a 300W xenon lamp for light irradiation, and the mixture was stirred uniformly during the light irradiation. And after the reaction is finished, washing with deionized water and drying. Respectively obtain NixP @ g-C3N4FTO and NixP @ g-C3N4a/Cu plate electrode.
(2) 0.5mol/L sulfuric acid (PH ═ 0) as electrolyte solution, NixP @ g-C3N4FTO and NixP @ g-C3N4the/Cu sheet electrode is respectively used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum net is used as a counter electrode, cyclic voltammetry cycling is carried out for 26 times in 0.5mol/L sulfuric acid solution, then a linear scanning electrochemical performance test is carried out on a CHI660E electrochemical workstation, and the test results are NixP @ g-C in figure 63N4FTO and NixP @ g-C3N4Electrode curve of Cu sheet. At the same potential, the current density of the electrode is maximized when the nickel foam is used as a substrate.
As can be seen from examples 1 to 3, Ni prepared according to the inventionXP@g-C3N4the/NF electrode electrocatalytic hydrogen evolution catalyst has the best performance and low price, and is a high-efficiency and environment-friendly electrocatalytic hydrogen production catalyst.
Example 4: NixP @ g-C3N4Electrochemical impedance testing of/NF electrodes
Charge transfer resistance (Rct) in electrochemical impedance spectroscopy represents NiXP@g-C3N4The transfer resistance between the catalyst and proton can be obtained from the semi-circle diameter of the curve in the electrochemical impedance spectrogram, and the Ni can be observedXP@g-C3N4The hydrogen production mechanism of NF electrode.
0.5mol/L sulfuric acid (PH ═ 0) as electrolyte solution, NixP @ g-C3N4The method comprises the steps of taking/NF as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a platinum net as a counter electrode, carrying out cyclic voltammetry cycling for 26 times in 0.5mol/L sulfuric acid solution, then carrying out electrochemical impedance spectroscopy performance test on a CHI660E electrochemical workstation, and obtaining the test result shown in figure 7, wherein NixP @ g-C can be seen from the test result3N4The charge transfer resistance of the/NF electrode is only 3.27 ohm, and only g-C3N4The charge transfer resistance of the catalyst (approximately 150 ohms) or the nickel foam (approximately 65 ohms) is very high, indicating that Ni is presentXP@g-C3N4The transfer resistance between the catalyst and the proton is very small, and this is also NiXP and g-C3N4Results after synergy.
Example 5: FTO/Cu2Preparation and characterization of O/NixP photocathode
Novel FTO/Cu2The preparation method of the O/NixP photocathode comprises the following steps:
(1) magnetron sputtering of Cu onto FTO
Pretreating an FTO conductive substrate: the FTO glass (1 multiplied by 2cm) is sequentially placed in acetone and absolute ethyl alcohol for soaking respectively, then heated and refluxed in isopropanol solution of 2M potassium hydroxide, and finally washed by deionized water. And (2) depositing an elemental copper film on the FTO glass by adopting a domestic JGP-450B magnetron sputtering deposition system through radio frequency sputtering at room temperature, wherein the frequency of the radio frequency sputtering is 13.56HZ, and the elemental copper (99.995%) is used as a target material and is continuously sputtered for 30 min.
(2) Preparation of FTO/Cu (OH) by anodic oxidation method2Precursor body
Preparation of Cu (OH) Using anodic Oxidation2Nanowire precursors, i.e. FTO/Cu as working electrode, Pt meshAnd Ag/AgCl (3M KCl) as counter and reference electrodes, respectively, at constant current density (10 mA/cm) in potassium hydroxide (3M) electrolyte solution2) Anodic oxidation was carried out for 3 minutes. Taking out the electrode, cleaning the electrode with deionized water, and drying.
(3) Preparation of FTO/Cu by calcination method2O electrode
Mixing FTO/Cu (OH)2Placing the electrode in a porcelain boat, placing in a tube furnace, calcining at 600 deg.C for 4 hr, heating at 2 deg.C/min under Ar (99.99%) atmosphere, cooling to room temperature, and taking out to obtain the final product2And (4) O nano wires.
(4) Photochemical deposition of NixP on FTO/Cu2On the O electrode
Dual function NixP is deposited photochemically on Cu2On the O nanowire. Respectively preparing a nickel chloride solution with the concentration of 0.1M and a sodium hypophosphite solution with the concentration of 0.2M for later use. Then 0.1M nickel chloride solution (4ml), 0.2M sodium hypophosphite solution (14ml) and deionized water (2ml) are respectively transferred by a rubber head dropper and poured into a 25ml flask, and the flask is fully shaken up and sealed and then is subjected to nitrogen degassing treatment for 40min under the condition of keeping out of the light. Irradiating under UV-visible xenon lamp (300W) for 10min, washing with deionized water for several times to remove impurities on the surface of the electrode, and drying.
FIG. 8 is a scanning electron microscope image of the prepared electrode, and a is a scanning electron microscope image of the cross section of the prepared electrode, the prepared cuprous oxide nanowire has a vertical corn rod-shaped structure, and the length is about 2.3 μm. The inset portion is a top scanning electron microscope image of the electrode, with the diameter of the nanowire being approximately 750 nm. The image b is an enlarged scanning electron microscope image, from which it can be found that the corn-rod-shaped nanowires have a pore-like structure.
FIG. 9 shows the FTO/Cu is made2X-ray diffraction pattern of O/NixP photocathode, marked by the position of the heart shape of the black peach, due to Cu2Diffraction peak generated by O proves that Cu2And (4) successfully preparing O. In addition, the CuO may be present as a result of elemental copper films or Cu that is later prepared2Elemental Cu resulting from oxidation of O upon exposure to air atmosphereThe copper is caused to remain on the substrate without being completely reacted when the copper is reacted with the copper hydroxide. In sample Cu2O/NixNo corresponding Ni was detected on PxDiffraction signature peak of P, probably due to deposition on Cu2Ni on OxLess P content.
FIG. 10 is an X-ray photoelectron spectrum of the resulting NixP nanoparticles, and the Ni 2p region has three peaks at binding energies of 852.6eV, 856.3eV, and 861.3eV, respectively, which are attributed to NixIn P there are Ni respectivelyδ+Oxides of Ni and satellite peaks of Ni 2 p. For the P2P region, two peaks with binding energies at 129.5eV and 132.9eV are assigned to the reported peaks for metal phosphide and phosphorus oxide. In addition, the oxide of Ni or the oxide of p formed on NixP was caused by the exposure of the sample to air. Showing NixP was successfully prepared.
With Na2SO4And KH2PO4The mixed solution of (A) is used as an electrolyte solution, and under the condition of AM 1.5 illumination, FTO/Cu2O/NixP electrode as working electrode, Ag/AgCl electrode as reference electrode, platinum mesh as counter electrode and then performing linear scanning electrochemical performance test on CHI660E electrochemical workstation, the test results are shown as FTO/Cu in FIG. 112O/NixP curve.
Example 6: FTO/Cu2O/NixP photocathode and FTO/Cu2Comparison of electrochemical Performance of O-electrodes
FTO/Cu2Preparing an O photoelectric cathode:
(1) pretreating the FTO conductive substrate: the FTO glass (1 multiplied by 2cm) is sequentially placed in acetone and absolute ethyl alcohol for soaking respectively, then heated and refluxed in isopropanol solution of 2M potassium hydroxide, and finally washed by deionized water. And (2) depositing an elemental copper film on the FTO glass by adopting a domestic JGP-450B magnetron sputtering deposition system through radio frequency sputtering at room temperature, wherein the frequency of the radio frequency sputtering is 13.56HZ, and the elemental copper (99.995%) is used as a target material and is continuously sputtered for 30 min.
(2) Preparation of Cu (OH) Using anodic Oxidation2Nanowire precursors, i.e. using FTO/Cu asFor the working electrode, Pt mesh and Ag/AgCl (3M KCl) were used as counter and reference electrodes, respectively, in potassium hydroxide (3M) electrolyte solution at a constant current density (10 mA/cm)2) Anodic oxidation was carried out for 3 minutes. Taking out the electrode, cleaning the electrode with deionized water, and drying.
(3) Mixing FTO/Cu (OH)2Placing the electrode in a porcelain boat, placing in a tube furnace, calcining at 600 deg.C for 4 hr, heating at 2 deg.C/min under Ar (99.99%) atmosphere, cooling to room temperature, and taking out to obtain the final product2And (4) O nano wires.
FIG. 9 shows the FTO/Cu is made2X-ray diffraction pattern of O photocathode, marked by the shape of the heart of a spade, is attributed to Cu2Diffraction peak generated by O proves that Cu2And (4) successfully preparing O.
With Na2SO4And KH2PO4The mixed solution of (2) was used as an electrolyte solution (PH 5), and when AM 1.5 was irradiated with light, FTO/Cu was added2The O electrode was used as the working electrode, the Ag/AgCl electrode as the reference electrode, the platinum mesh as the counter electrode and then the linear scanning electrochemical performance test was performed on the CHI660E electrochemical workstation, the test results are shown in fig. 11. As can be seen from the figure, Cu alone2O photocathode phase, Cu2O/NixThe current density of the P photocathode is about Cu alone28 times of O. From this, it is known that Ni is photo-deposited in the photoelectrocatalytic hydrogen evolution reactionxP nanoparticles in Cu2The composite electrode material prepared on the O nanowire shows photoelectrochemical catalytic activity. Is noteworthy due to NixP to Cu2Electrons generated by O nanowire light excitation are timely transferred to participate in hydrogen evolution reaction, so that the recombination of current carriers is greatly reduced, the photoelectrocatalysis activity is improved, and the photocurrent density is remarkably increased.
Example 7: FTO/Cu2Electrochemical impedance testing of O/NixP electrodes
Charge transfer resistance (Rct) in electrochemical impedance spectroscopy represents Cu2The transfer resistance between the O/NixP catalyst and proton can be obtained from the semi-circle diameter of the curve in the electrochemical impedance spectrogram, and further obtainedTo investigate the produced FTO/Cu2The hydrogen production mechanism of the O/NixP electrode.
With Na2SO4And KH2PO4The mixed solution of (2) was used as an electrolyte solution (pH 5), FTO/Cu2O/NixP is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, a platinum net is used as a counter electrode, then electrochemical impedance spectroscopy performance test is carried out on a CHI660E electrochemical workstation, the test result is shown in figure 12, and FTO/Cu can be seen from the figure2The charge transfer resistance of the O/NixP electrode is relatively small, the transfer resistance between the catalyst and protons is very small, and the photoelectrocatalysis performance is improved.
Example 8:
(1) carrying out photochemical deposition NixP by taking CdS as a semiconductor, and specifically comprising the following steps: pretreating an FTO conductive substrate: FTO glass (1X 2cm) was placed in 2M potassium hydroxide in isopropanol and heated to reflux. And then ultrasonically washed to neutrality by deionized water to remove residual substances on the surface. Sequentially performing ultrasonic treatment for 15 minutes by using acetone, ethanol and ultrapure water respectively, and finally cleaning by using deionized water. Clean FTO glass was dipped into 0.25M Ni (NO)3)2And 0.25M hexamethylenetetramine (ensuring an immersed FTO glass area of 1 cm)2) Then heating in water bath at 100 deg.C for 12min, cooling to room temperature, taking out, cleaning with deionized water, and oven drying. Then placing the electrode in a porcelain boat, placing the porcelain boat in a muffle furnace, calcining at the constant temperature of 300 ℃ for 30min, and taking out after the temperature is reduced to room temperature to obtain the FTO/NiO electrode. CdS is prepared on the FTO/NiO electrode by adopting a simple continuous ion layer deposition method. 4.627g of Cd (NO)3)2·4H2Placing O in 50mL of ethanol solution, and uniformly mixing to obtain a cadmium source solution; 3.6027g of Na are taken2S·9H2Placing O in 50mL of ultrapure water, and uniformly mixing to obtain a sulfur source; firstly, an FTO/NiO electrode is immersed into a cadmium source solution for 5min, is taken out and then is cleaned by absolute ethyl alcohol, and then the electrode is immersed into a sulfur source solution for 5min, is taken out and is cleaned by ultrapure water (the area of immersed FTO glass is ensured to be 1 cm)2) The process is a cycle, the above process is circulated for a plurality of times, and finally, deionized water and ethanol are respectively used for washing and drying. Thus obtaining the FTO/NiO/CdS photocathode.14mL of sodium hypophosphite solution (0.2mol/L) and 4mL of nickel chloride (0.1mol/L) are added into a 25mL round-bottom flask, 2mL of deionized water is added, the mixture is shaken up, the prepared electrode is placed into the flask, and then nitrogen is introduced into the sealed flask for 40min to remove oxygen and other miscellaneous gases. The flask was placed under a 300W xenon lamp for light irradiation, and the mixture was stirred uniformly during the light irradiation. And after the reaction is finished, washing with deionized water and drying.
(2) FIG. 13 is a scanning electron microscope image of the prepared FTO/NiO/CdS/NixP electrode, from which it can be seen that NixP nanoparticles are tightly loaded on the honeycomb FTO/NiO/CdS photocathode.
Example 9: preparation of phosphorus-containing complexes
The phosphorus-containing compound was prepared as follows
(1) Placing 20.25mmol of two-point pentahydrated cadmium chloride, 40.75mmol of thiourea and 60mL of ethylenediamine in a 100mL high-pressure reaction kettle, placing the reaction kettle in a 160 ℃ oven for hydrothermal treatment for 48h, placing the reaction kettle under natural conditions after the reaction is finished, reducing the temperature to room temperature, filtering to obtain yellow solid, washing the yellow solid with deionized water for 10 times, washing the yellow solid with ethanol for 2 times, placing the obtained solid in a 60 ℃ oven, and drying the obtained solid overnight to obtain the yellow solid which is the cadmium sulfide nanorod;
(2) 50mg of cadmium sulfide nanorod is placed in a 25mL single-neck flask, and then 2mL of cobalt chloride aqueous solution (0.1M) and 7mL of sodium hypophosphite (molecular formula NaH) are added2PO2) Ultrasonic dispersion treatment is carried out on an aqueous solution (0.1mol/L) and 1mL of deionized water for 1min, and then nitrogen is used for degassing for 40min to remove oxygen in the reaction system;
(3) and after degassing is finished, placing the round-bottom flask under a 300W xenon lamp for irradiating for different time to obtain phosphorus and cobalt with different contents, centrifugally separating the obtained solid, washing with deionized water for 5 times, washing with ethanol for 2 times, drying the obtained solid by using nitrogen, and obtaining the solid which is the CoxP/cadmium sulfide nanorod composite catalyst. And the catalyst was named CoxP-T/CdS NRs (wherein T represents the light irradiation time in min).
The prepared photocatalyst was subjected to X-ray diffraction spectroscopy (shown in fig. 14), transmission electron microscopy (shown in fig. 15), energy dispersive X-ray spectroscopy (EDX) (shown in fig. 16), and X-ray photoelectron spectroscopy (XPS) (shown in fig. 17).
Example 10: catalytic activity of phosphorus-containing complex
3mg of cadmium sulfide obtained in step (1) in example 9 was placed in a 100mL photocatalytic reactor, followed by addition of 5mL of triethanolamine and 45mL of water. Ultrasonic treating for 30s, degassing with nitrogen gas for 1h to remove oxygen, irradiating round bottom flask with 300W xenon light (equipped with 420nm cut-off filter), detecting hydrogen generated in reaction by thermal conductivity-gas chromatography after reaction for 8h, wherein hydrogen production rate is 7.4 mmol/g-1h-1。
3mg of the CoxP-50/CdS NRs composite catalyst in example 9 was placed in a 100mL photocatalytic reactor, followed by 5mL triethanolamine, 45mL deionized water. Ultrasonic treating for 30s, degassing with nitrogen gas for 1h to remove oxygen, irradiating round bottom flask with 300W xenon light (equipped with 420nm cut-off filter), detecting hydrogen generated in reaction by thermal conductivity-gas chromatography after reaction for 8h, wherein hydrogen production rate is 165.8 mmol-g-1h-1And the hydrogen production rate is improved by 22 times compared with that of a pure cadmium sulfide nanorod.
1mg of the CoxP-50/CdS NRs composite catalyst in example 9 was placed in a 100mL photocatalytic reactor, followed by addition of 15g of sodium sulfide nonahydrate, 11g of anhydrous sodium sulfite, and 50mL of deionized water. Performing ultrasonic treatment for 30s, degassing for 1h by using nitrogen to remove oxygen in the system, placing the round-bottom flask under 300W xenon light (provided with a 420nm cut-off filter) for irradiation, detecting hydrogen generated in the reaction by using a thermal conductivity-gas chromatography after the reaction is finished, detecting the hydrogen generated in the reaction by using the thermal conductivity-gas chromatography every 5h, degassing once to remove the hydrogen in the reaction system, and continuing to perform light treatment, wherein the catalytic activity is not obviously reduced after the reaction is performed for 25 h.
As can be seen from the above embodiments and fig. 18, the cox p/cadmium sulfide nanorod composite catalyst prepared in this embodiment has the advantages of simple synthesis method, high photocatalytic hydrogen production rate, good stability, and low price, and can greatly save the cost when applied to industrial production, and is a novel catalytic material with a greater industrial photocatalytic hydrogen production prospect.
Example 11: preparation of phosphorus-containing complexes
The phosphorus-containing compound was prepared as follows:
(1) placing 20g of thiourea in 4 crucibles, placing the crucibles in a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃ per minute, calcining for two hours, taking out the crucibles after cooling to room temperature, grinding the solids into powder, placing the crucibles containing the solid powder in the muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃ per minute, calcining for two hours, and taking out yellow-white solid powder after cooling to room temperature to obtain the graphene-like carbon nitrogen compound;
(2) 30mg of graphene carbo-nitrogen compound was placed in a 25mL single-neck flask, followed by 4mL of aqueous nickel sulfide (0.1mol/L), 4mL of sodium hypophosphite (molecular formula NaH)2PO2) Ultrasonic dispersion treatment is carried out on an aqueous solution (0.7mol/L) and 2mL of water for 30s, and then nitrogen is used for degassing for 40min to remove oxygen in the reaction system;
(3) after degassing is finished, placing the round-bottom flask under a 300W xenon lamp for irradiating for 20min, centrifugally separating the obtained solid, washing with deionized water for 5 times, washing with ethanol for 2 times, drying the obtained solid with nitrogen, and obtaining a black substance, namely the NixP/graphene-like carbon nitrogen compound composite catalyst. The prepared NixP/graphene-like carbon nitrogen compound composite catalyst is named as NixP-20/g-C3N4。
The prepared photocatalyst was subjected to X-ray diffraction spectroscopy (shown in fig. 19), transmission electron microscopy (shown in fig. 20), energy dispersive X-ray spectroscopy (EDX) (shown in fig. 21), and X-ray photoelectron spectroscopy (shown in fig. 22).
Example 12: catalytic activity of phosphorus-containing complex
(1) 5mg of the graphene-like carbon nitrogen compound in example 11 was taken and placed in a 25mL round-bottom flask, followed by addition of 2mL of triethanolamine and 8mL of water, ultrasonic dispersion treatment for 30s, and then degassing with nitrogen for 40min to remove oxygen in the reaction system; placing the round flask under 300W xenon light (equipped with AM 1.5G filter), irradiating, detecting hydrogen generated in reaction by thermal conductivity-gas chromatography after reaction for 2 hr, wherein the hydrogen production rate is 27 μmol G-1h-1。
(2) The NixP/graphene-like carbon nitrogen compound in example 11 is subjected to composite catalysis5mg of the formulation was placed in a 25mL round bottom flask, followed by 2mL triethanolamine and 8mL water. Ultrasonic treating for 30s, degassing with nitrogen gas for 40min to remove oxygen, placing round-bottom flask under solar simulator for illumination, detecting hydrogen generated in reaction by thermal conductivity-gas chromatography after reaction for 2 hr to obtain hydrogen production rate of 8585 μmol/g-1h-1The hydrogen production rate is improved by 317 times compared with the hydrogen production rate of a pure graphene-like carbon nitrogen compound.
(3) 5mg of the NixP/graphene-like carbon nitrogen compound composite catalyst of example 11 was placed in a 25mL round bottom flask, followed by addition of 1mL of lactic acid and 9mL of water, and the pH of the mixed solution was 2. Sonication was carried out for 30s, the oxygen in the system was removed by degassing with nitrogen for 40min, and the round bottom flask was placed under a solar simulator for light. The catalyst activity did not decrease significantly after 75h of reaction (shown in figure 23).
As can be seen from the above examples and fig. 23, the prepared NixP/graphene-like carbon nitrogen compound composite catalyst has the advantages of simple synthesis method, high photocatalytic hydrogen production rate, good stability under acidic conditions, low price, substantial cost saving when applied to industrial production, no toxicity, environmental protection, and is a novel catalytic material with a great industrial photocatalytic hydrogen production prospect.
Example 13: preparation of phosphorus-containing complexes
The phosphorus-containing compound was prepared as follows:
(1) placing 50mg of cadmium sulfide nanorod into a 25mL single-neck flask, then adding 2mL of cobalt chloride aqueous solution (0.1M), 7mL of potassium phosphite aqueous solution (0.1mol/L) and 1mL of deionized water, performing ultrasonic dispersion, and removing oxygen in a reaction system by using nitrogen;
(2) and after degassing is finished, placing the round-bottom flask under a 300W xenon lamp for irradiating for different time to obtain phosphorus and cobalt with different contents, centrifugally separating the obtained solid, washing with deionized water for 5 times, washing with ethanol for 2 times, drying the obtained solid by using nitrogen, and obtaining the solid which is the CoxP/cadmium sulfide nanorod composite catalyst.
The obtained phosphorus-containing composite material has high photocatalytic hydrogen production rate through verification.
Example 14: preparation of phosphorus-containing complexes
The phosphorus-containing compound was prepared as follows:
(1) placing 50mg of cadmium sulfide nanorod into a 25mL single-neck flask, then adding 2mL of cobalt chloride aqueous solution (0.1M), trioctylphosphine solution and 1mL of deionized water, performing ultrasonic dispersion, and then removing oxygen in a reaction system by using nitrogen;
(2) and after degassing is finished, placing the round-bottom flask under a 300W xenon lamp for irradiating for different time to obtain phosphorus and cobalt with different contents, centrifugally separating the obtained solid, washing with deionized water for 5 times, washing with ethanol for 2 times, drying the obtained solid by using nitrogen, and obtaining the solid which is the CoxP/cadmium sulfide nanorod composite catalyst.
The obtained phosphorus-containing composite material has high photocatalytic hydrogen production rate through verification.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the phosphorus-containing compound is characterized in that when the phosphorus-containing compound is a cobalt phosphide/cadmium sulfide nanorod composite catalyst, the preparation method comprises the following steps: (1) placing 20.25mmol of two-point pentahydrated cadmium chloride, 40.75mmol of thiourea and 60mL of ethylenediamine in a 100mL high-pressure reaction kettle, placing the reaction kettle in a 160 ℃ oven for hydrothermal treatment for 48h, placing the reaction kettle under natural conditions after the reaction is finished, reducing the temperature to room temperature, filtering to obtain yellow solid, washing the yellow solid with deionized water for 10 times, washing the yellow solid with ethanol for 2 times, placing the obtained solid in a 60 ℃ oven, and drying the obtained solid overnight to obtain the yellow solid which is the cadmium sulfide nanorod; (2) placing 50mg of cadmium sulfide nanorod in a 25mL single-neck flask, then adding 2mL of 0.1mol/L cobalt chloride aqueous solution, 7mL of 0.1mol/L sodium hypophosphite aqueous solution and 1mL of deionized water, performing ultrasonic dispersion treatment for 1min, and degassing for 40min by using nitrogen to remove oxygen in a reaction system; (3) after degassing is finished, placing the round-bottom flask under a 300W xenon lamp for irradiating for different time to obtain phosphorus and cobalt with different contents, centrifugally separating the obtained solid, washing with deionized water for 5 times, washing with ethanol for 2 times, drying the obtained solid with nitrogen, and obtaining a solid matter, namely the cobalt phosphide/cadmium sulfide nanorod composite catalyst;
when the phosphorus-containing compound is a nickel phosphide/graphene-like carbon nitrogen compound, the preparation method comprises the following steps: (1) placing 20g of thiourea in 4 crucibles, placing the crucibles in a muffle furnace, raising the temperature to 550 ℃ at the rate of 2 ℃/min, calcining for two hours, taking out the crucibles after the crucibles are cooled to room temperature, grinding the solid into powder, placing the crucibles containing the solid powder in the muffle furnace, raising the temperature to 500 ℃ at the rate of 2 ℃/min, calcining for two hours, and taking out yellow-white solid powder after the crucibles are cooled to room temperature to obtain the graphene-like carbon nitrogen compound; (2) placing 30mg of graphene carbon nitrogen compound in a 25mL single-neck flask, then adding 4mL of nickel sulfide aqueous solution with the concentration of 0.1mol/L, 4mL of sodium hypophosphite aqueous solution with the concentration of 0.7mol/L and 2mL of water, performing ultrasonic dispersion treatment for 30s, and degassing for 40min by using nitrogen to remove oxygen in a reaction system; (3) after degassing is finished, placing the round-bottom flask under a 300W xenon lamp for irradiating for 20min, centrifugally separating the obtained solid, washing with deionized water for 5 times, washing with ethanol for 2 times, drying the obtained solid with nitrogen, and obtaining a black substance, namely the nickel phosphide/graphene-like carbon nitrogen compound composite catalyst.
2. A phosphorus-containing composite prepared by the preparation method of claim 1.
3. An electrical appliance comprising the phosphorus-containing composition of claim 2.
4. A battery, comprising: a positive electrode, a negative electrode, and a separator between the positive electrode and the negative electrode; wherein at least one electrode comprises the phosphorus-containing compound of claim 2.
5. A fuel cell comprising the phosphorus-containing compound according to claim 2.
6. Use of the process according to claim 1 or the phosphorus-containing compound according to claim 2 in catalysis.
7. Use according to claim 6, for catalytic reduction or catalytic oxidation.
8. Use according to claim 6, for the production of electrodes or for the production of fuel cells.
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