CN111924813A - Carbon composite metal phosphide and preparation method thereof - Google Patents
Carbon composite metal phosphide and preparation method thereof Download PDFInfo
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- CN111924813A CN111924813A CN202010838874.XA CN202010838874A CN111924813A CN 111924813 A CN111924813 A CN 111924813A CN 202010838874 A CN202010838874 A CN 202010838874A CN 111924813 A CN111924813 A CN 111924813A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 84
- 239000002184 metal Substances 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 11
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 10
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229940068041 phytic acid Drugs 0.000 claims description 4
- 235000002949 phytic acid Nutrition 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920001817 Agar Polymers 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000008272 agar Substances 0.000 claims description 3
- 235000010419 agar Nutrition 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002751 molybdenum Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000003657 tungsten Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 5
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention discloses a carbon composite metal phosphide and a preparation method thereof, belonging to the technical field of composite materials and comprising the following steps: dissolving a phosphating agent, a carbon source and soluble metal salt in water, and then removing water under the stirring condition of 50-85 ℃ to prepare colloid; drying the colloid, and then carrying out heat treatment at 600-900 ℃ in a protective atmosphere to obtain the carbon composite metal phosphide; the invention solves the problems that the existing metal phosphide preparation process generates a phosphorus-containing compound, the phosphating agent is excessively used, the preparation method is limited, and most of the metal phosphide is not suitable.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a carbon composite metal phosphide and a preparation method thereof.
Background
The metal phosphide has good stability and can be widely applied to the aspects of energy, catalysis and the like. The metal phosphide can be regarded as an alloy formed by doping phosphorus atoms into a metal lattice, and can form phosphide with various different crystal structures due to different proportions of metal elements and phosphorus atoms. The introduction of phosphorus atoms slightly increases their distance from the metal atoms, with the concomitant contraction of the d-band gap of the original metal, increasing the density of states near the fermi level, thus giving the metal phosphide noble-like properties. When the metal phosphide contains more stable metal-phosphorus (M-P) bonds, higher thermal stability and hardness are exhibited. In electrochemical applications, more metal phase phosphide is beneficial to the stability of the electrode.
In the early days, most of metal phosphide was phosphorized by high-temperature heat treatment of combustible elemental phosphorus, but a highly toxic phosphorus-containing compound was inevitably generated in the preparation process, and the generated harmful substances were difficult to treat, so that the development and application of the phosphorus-containing compound were seriously hindered for a long period of time. In order to reduce the generation of phosphorus-containing compounds, methods for preparing transition metal phosphorus by low-temperature phosphating, such as high-energy ball milling and electrodeposition, have been developed, but these methods have strong limitations for different metal phosphides and are not suitable for preparing most metal phosphides. The current strategy used is to prepare the oxide/hydroxide with a certain structure in advance, and then to react with an excessive amount of phosphating agent (such as NaH)2PO2) Co-thermal phosphating, however, involves a large number of steps and, secondly, produces large amounts of toxic, flammable pH3Gas, which in turn hinders its large-scale use.
Disclosure of Invention
Aiming at the problems of the existing method for preparing the metal phosphide, the invention provides a simple and universal method for synthesizing the metal phosphide, the metal phosphide is uniformly dispersed in a porous carbon skeleton formed by amorphous carbon by a one-step sol-gel strategy (a phosphating agent, a carbon source and soluble metal salt are prepared into colloid in one step) and heat treatment is carried out under an inert atmosphere, so that a three-dimensional porous carbon composite metal phosphide composite material is formed, the oxidation and agglomeration of metal phosphide particles are avoided, and the performance of the metal phosphide is fully exerted; the preparation process has no generation of phosphorus-containing compounds, the one-step pyrolysis strategy simplifies the phosphorization step, avoids the excessive use of a phosphorizing agent, and increases the safety and the reaction practicability; in the reaction process, the proportion or the variety of the metal elements can be adjusted according to actual needs, and the composite material of various phosphides can be obtained, so that the method is suitable for preparing different metal phosphides and has universality.
The invention is realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of carbon composite metal phosphide, which comprises the following steps:
s1, dissolving a phosphating agent, a carbon source and soluble metal salt in water, and then removing water under the stirring condition of 50-85 ℃ to prepare colloid;
and S2, drying the colloid, and performing heat treatment at 600-900 ℃ in a protective gas atmosphere to obtain the carbon composite metal phosphide.
Preferably, in S1, the soluble metal salt is one or more of a nickel salt, a copper salt, a cobalt salt, an iron salt, a manganese salt, a tin salt, a molybdenum salt and a tungsten salt.
Preferably, in S1, the carbon source is one or more of starch, gelatin, agar, carboxymethyl cellulose, polyethylene glycol and polyvinylpyrrolidone.
Preferably, in S1, the phosphating agent is hypophosphite, phytic acid, trioctylphosphine oxide, triphenylphosphine, P (Si Me)3)3Or hydroxyethylidene diphosphonic acid.
Preferably, in S1, the mass ratio of the phosphating agent, the carbon source and the soluble metal salt is 1: 0.75-1.75: 0.75-2.
Preferably, in S1, the water removal process specifically includes: stirring at 50-85 ℃ until the water is completely evaporated to obtain a transparent colloid.
Preferably, in S2, the heat treatment is specifically heat preservation at 600-900 ℃ for 3-5 h, and the heating rate is 3-10 ℃/min.
The second purpose of the invention is to provide the carbon composite metal phosphide prepared by the preparation method, which comprises an amorphous carbon framework and metal phosphide uniformly embedded in the amorphous carbon framework; wherein the particle size of the metal phosphide is 50-200 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the carbon composite metal phosphide, provided by the invention, the phosphating agent, the carbon source and the soluble metal salt are prepared into colloid in one step through a one-step strategy, namely a sol-gel method, and the carbon composite metal phosphide is obtained through heat treatment under an inert atmosphere, no phosphorus-containing compound is generated in the preparation process, the one-step pyrolysis strategy simplifies the phosphating step, avoids the excessive use of the phosphating agent, and increases the safety and the reaction practicability;
(2) in the reaction process, the proportion or the variety of the metal elements can be adjusted according to actual needs to obtain one or more metal phosphides of different types, so that the method is suitable for preparing different metal phosphides and has universality;
(3) the carbon composite metal phosphide prepared by the method has a three-dimensional porous structure, and the amorphous carbon anchors the phosphide in a porous carbon skeleton, so that the problems of oxidation and agglomeration of metal phosphide particles are effectively inhibited, and the performance of the metal phosphide is improved.
Drawings
FIG. 1 is an XRD pattern of the material obtained in example 1 of the present invention;
FIG. 2 is a TEM image of the material obtained in example 1 of the present invention;
FIG. 3 is the isotherm desorption curve and the pore size distribution diagram of the material obtained in example 1 of the present invention;
FIG. 4 shows a value of 0.5M H for the material obtained in example 1 of the present invention2A hydrogen evolution performance diagram in the SO4 electrolyte;
FIG. 5 is an XRD pattern of the material obtained in example 2 of the present invention;
FIG. 6 is an XRD pattern of the material obtained in example 3 of the present invention;
FIG. 7 is an XRD pattern of the material obtained in example 4 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the following reagents and starting materials are all commercially available unless otherwise specified.
The invention provides a preparation method of carbon composite metal phosphide, which comprises the following steps:
dissolving a phosphating agent, a carbon source and soluble metal salt in water, and then removing water under the stirring condition of 50-85 ℃ to prepare colloid; and drying the colloid, and performing heat treatment at 600-900 ℃ in a protective gas atmosphere to obtain the carbon composite metal phosphide. The phosphating agent, the carbon source and the soluble metal salt are prepared into colloid in one step by a one-step strategy, namely a sol-gel method, and are subjected to heat treatment in an inert atmosphere to obtain the carbon composite metal phosphide, the preparation process does not generate phosphorus-containing compounds, the one-step pyrolysis strategy simplifies the phosphating step, avoids the excessive use of the phosphating agent, and increases the safety and the reaction practicability; in the reaction process, the proportion or the variety of the metal elements can be adjusted according to actual needs to obtain one or more metal phosphides of different types, so that the method is suitable for preparing different metal phosphides and has universality;
wherein the soluble metal salt is one or more of nickel salt, copper salt, cobalt salt, ferric salt, manganese salt, tin salt, molybdenum salt and tungsten salt; the carbon source is one or more of starch, gelatin, agar, carboxymethyl cellulose, polyethylene glycol and polyvinylpyrrolidone; the phosphorizing agent is hypophosphite, phytic acid, trioctylphosphine oxide, triphenylphosphine, P (Si Me)3)3Or hydroxyethylidene diphosphonic acid.
The carbon composite metal phosphide prepared by the method comprises an amorphous carbon framework and metal phosphide uniformly embedded in the amorphous carbon framework, and the metal phosphide is uniformly dispersed in a porous carbon framework formed by amorphous carbon to form a three-dimensional porous composite material of the carbon composite metal phosphide, so that the oxidation and agglomeration of metal phosphide particles are avoided, and the performance of the metal phosphide is fully exerted; wherein the particle size of the metal phosphide is 50-200 nm.
The following examples are intended to illustrate the present invention.
Example 1
A preparation method of carbon composite cobalt phosphide comprises the following steps:
(1) weighing 0.5g Co (NO) in proportion3)3Dissolving 0.4g of hydroxyethylidene diphosphonic acid and 0.3g of polyvinylpyrrolidone in 50ml of deionized water, then carrying out water bath at 85 ℃ and continuously stirring until the water is completely evaporated and dried to obtain transparent colloid, and then drying the colloid at 60 ℃;
(2) and (3) placing the colloid in an Ar protective atmosphere, and keeping the temperature at 800 ℃ for 3h at the heating speed of 5 ℃/min to obtain the carbon composite cobalt phosphide material.
The XRD of the carbon composite cobalt phosphide material is shown in figure 1, and the characteristic peak of the prepared metal cobalt phosphide from figure 1 is matched with PDF #29-0497 card, wherein the mass fraction of the cobalt phosphide is 85%, and the particle size distribution is 50-100 nm. As can be seen from fig. 2, the carbon composite cobalt phosphide has a three-dimensional porous structure, and the cobalt phosphide is uniformly embedded in the carbon skeleton without agglomeration; as shown in fig. 3, by N2The specific surface area of the carbon composite cobalt phosphide is 52.29m in an adsorption and desorption isothermal test2 g-1Wherein the pore structure mainly comprises mesopores and macropores, and the pore volume is 0.1cm-3g-1(ii) a The obtained carbon composite cobalt phosphide is applied to the aspect of electrocatalytic hydrogen evolution, as shown in figure 4, and shows better catalytic activity: the current density was 10mA cm-2The overpotential was 138mV and the Tafel slope was 70.2mV/dec (whereas the Pt/C as a control was only 27.5 mV/dec).
Example 2
A preparation method of carbon composite nickel phosphide comprises the following steps:
(1) weighing 0.3g Ni (NO) in proportion3)30.2g hydroxyethylidene diphosphonic acid and 0.2g polyvinylpyrrolidone were dissolved in 50ml deionized water, then subjected to a water bath at 85 ℃ with constant stirring until the water was completely evaporated and dried to give a transparent gel, which was then dried at 70 ℃.
(2) Placing the colloid in Ar protective atmosphere, keeping the temperature at 700 ℃ for 3h, and increasing the temperature at the speed of 3 ℃/min to obtain the carbon composite nickel phosphide material, wherein XRD of the carbon composite nickel phosphide material is shown in figure 5, and the characteristic peak of the prepared metal nickel phosphide is matched with PDF #51-1367 card from figure 5. Wherein the mass fraction of the nickel phosphide is 80%, and the particle size is 80-150 nm.
Example 3
A preparation method of carbon composite copper phosphide comprises the following steps:
(1) weighing 0.8g of Cu (NO) according to the proportion3)30.4g of hydroxyethylidene diphosphonic acid and 0.7g of polyvinylpyrrolidone are dissolved in 100ml of deionized water, the mixed solution is subjected to water bath at 85 ℃ and is continuously stirred until the water is completely evaporated and dried to obtain a transparent colloid, and then the colloid is dried at 60 ℃.
(2) Placing the colloid in Ar protective atmosphere, keeping the temperature at 800 ℃ for 3h, and increasing the temperature at the speed of 3 ℃/min to obtain the carbon composite copper phosphide material, wherein XRD of the carbon composite copper phosphide material is shown in figure 6, and the characteristic peak of the prepared metal copper phosphide can be matched with PDF #02-1263 cards from figure 6. Wherein the mass fraction of the copper phosphide is 88%, and the particle size distribution is between 100 and 150 nm.
Example 4
A preparation method of carbon composite molybdenum phosphide comprises the following steps:
(1) weighing 0.3g (NH) in proportion4)2MoO4Dissolving 0.4g hydroxyethylidene diphosphonic acid and 0.5g polyvinylpyrrolidone in 60ml deionized water, water bathing the mixed solution at 75 deg.C and stirring continuously until the water is completely evaporated and dried to obtain transparent colloid, and adding the colloid into the mixtureDrying is carried out at 60 ℃.
(2) Placing the colloid in Ar protective atmosphere, keeping the temperature at 800 ℃ for 3h at the heating rate of 5 ℃/min to obtain the carbon composite molybdenum phosphide material, wherein XRD of the carbon composite molybdenum phosphide material is shown in figure 7, and the characteristic peak of the metal molybdenum phosphide prepared by figure 7 is matched with PDF #24-0771 card. Wherein the mass fraction of the molybdenum phosphide is 75%, and the particle size distribution is between 60 and 120 nm.
Example 5
The preparation method of the carbon composite cobalt phosphide is the same as the step of the example 1, except that the carbon source is starch, the phosphating agent is phytic acid, the water bath temperature is 50 ℃, and the protective atmosphere is N2The calcining temperature is 600 ℃, and the calcining time is 5 h.
Example 6
The preparation method of the carbon composite cobalt phosphide is the same as the step of the example 1, except that the calcining temperature is 900 ℃.
In conclusion, the carbon composite metal phosphide is obtained by a one-step strategy, namely a sol-gel method and heat treatment under an inert atmosphere, so that the excessive use of a phosphating agent is avoided, the safety is improved, the one-step pyrolysis strategy simplifies the phosphating step, and the reaction practicability is improved; the method can obtain one or more metal phosphides of different types, can obtain most of metal phosphides, the carbon composite metal phosphide has a three-dimensional porous structure, and the amorphous carbon anchors the phosphide in a porous carbon skeleton, so that on one hand, the conductivity of the metal phosphide can be improved, and on the other hand, the problems of oxidation and agglomeration of metal phosphide particles can be effectively inhibited, so that the carbon composite metal phosphide has wide application potential in the aspects of energy, catalysis and the like.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (9)
1. A preparation method of carbon composite metal phosphide is characterized by comprising the following steps:
s1, dissolving a phosphating agent, a carbon source and soluble metal salt in water, and then removing water under the stirring condition of 50-85 ℃ to prepare colloid;
and S2, drying the colloid, and performing heat treatment at 600-900 ℃ in a protective gas atmosphere to obtain the carbon composite metal phosphide.
2. The method according to claim 1, wherein in S1, the soluble metal salt is one or more of nickel salt, copper salt, cobalt salt, iron salt, manganese salt, tin salt, molybdenum salt and tungsten salt.
3. The method of claim 1, wherein in S1, the carbon source is one or more selected from starch, gelatin, agar, carboxymethyl cellulose, polyethylene glycol and polyvinylpyrrolidone.
4. The method according to claim 1, wherein the phosphating agent is hypophosphite, phytic acid, trioctylphosphine oxide, triphenylphosphine, P (SiMe) in S13)3Or hydroxyethylidene diphosphonic acid.
5. The method according to claim 1, wherein in S1, the mass ratio of the phosphating agent to the carbon source to the soluble metal salt is 1: 0.75-1.75: 0.75-2.
6. The method according to claim 1, wherein in step S1, the water removal process comprises: stirring at 50-85 ℃ until the water is completely evaporated to obtain a transparent colloid.
7. The method for preparing carbon composite metal phosphide according to claim 1, wherein in S2, the heat treatment is specifically performed by keeping the temperature at 600-900 ℃ for 3-5 hours at a heating rate of 3-10 ℃/min.
8. The carbon composite metal phosphide prepared by the preparation method according to any one of claims 1 to 7, wherein the carbon composite metal phosphide is characterized by comprising an amorphous carbon skeleton and metal phosphide uniformly embedded in the amorphous carbon skeleton.
9. The carbon composite metal phosphide according to claim 8, wherein the particle size of the metal phosphide is 50 to 200 nm.
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