Method for synthesizing metal element doped molybdenum-based phosphorus oxide composite material
The synthesis of molybdenum-based phosphorus-oxygen composite materials doped with metal elements through plasma discharge technology solves the problems of uneven distribution of elements and difficult to control relative content in traditional methods, and achieves the effect of small particle size, good dispersion and controllable phosphating degree, which is suitable for mass production.
Patent Information
- Application Number
- CN202411918800.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-25
- Publication Date
- 2025-03-25
AI Technical Summary
The preparation method of traditional molybdenum-based phosphorus-oxygen composite materials has problems such as uneven element distribution, difficult to control relative content, increased particle size and agglomeration, resulting in uncontrollable and unstable physical and chemical characteristics.
Plasma discharge technology is used to synthesize the molybdenum-based phosphorus-oxygen composite material doped with metal elements. By uniformly mixing metal salts and molybdenum compounds and uniformly mixing them with phosphorus elemental powder, the discharge reaction is used to generate composite materials with small particle size, good dispersion and controllable phosphation.
The metal element doped molybdenum-based phosphorus-oxygen composite material has the advantages of small particle size, high dispersion and controllable phosphating degree, simplifying the process route, simple operation, and suitable for mass production.
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Figure CN119683582A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of material science, and in particular relates to a method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material. Technical Background
[0002] Molybdenum-based phosphorus-oxygen composite materials are an important functional material with a wide range of applications in catalysis, optoelectronics, and electromagnetic devices, such as automotive radar, microwave devices, and wireless charging. The current method for synthesizing molybdenum-based phosphorus-oxygen composite materials is to prepare them by calcining metal phosphates and reducing them with high-temperature hydrogen or phosphine, but this also increases the cost of toxic gas treatment and harms health. In addition, the molybdenum-based phosphorus-oxygen composite materials prepared by this traditional method have the disadvantages of uneven element distribution, difficult to control the relative content of molybdenum-based phosphides and molybdenum-based oxides, and problems such as increased particle size and agglomeration caused by high-temperature reduction. Therefore, the traditional preparation process has an uncontrollable and uncertain influence on the physicochemical characteristics of molybdenum-based phosphorus-oxygen composite materials, resulting in instability during application. Summary of the invention
[0003] The present invention combines plasma discharge to synthesize metal-doped molybdenum-based phosphorus-oxygen composite materials. The following is the synthesis principle: Plasma is the fourth form of matter and is an excellent conductor. It is composed of a large number of high-energy particles such as free electrons and ions with energies ranging from several to tens of electron volts, which can meet the energy required for chemical reactions and are electrically neutral as a whole.
[0004] The purpose of the present invention is to provide a method for synthesizing a metal element doped molybdenum-based phosphorus-oxygen composite material. In terms of physical properties, the synthesized metal element doped molybdenum-based phosphorus-oxygen composite material has the advantages of small particle size, high dispersion, and accurate control of phosphating degree. At the same time, the synthesis process route is simple and easy to operate.
[0005] The present invention is achieved by the following technical solution: A method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material is carried out according to the following steps: Step 1, preparing a mixture A, uniformly mixing a metal salt and a molybdenum compound at a molar ratio of metal: molybdenum = 0.05-40 to obtain a mixture A; Step 2, preparing a mixture B, mixing the mixture A and phosphorus powder evenly to obtain a mixture B, wherein the molar ratio of phosphorus to molybdenum in the mixture B is 0.05-40; Step 3: Place mixture B inside the reaction tube of a plasma reactor, pass the discharge gas through the reaction tube of the plasma reactor at a flow rate of 5-2000 ml / min, the discharge frequency of the plasma reactor is 1-30 kHz, the output voltage is 2000-20000 V, and react for 5-200 minutes to obtain a metal element-doped molybdenum-based phosphorus-oxygen composite material.
[0006] The metal element as mentioned above is one of Ca, Ba, Nb, Rh, Pd, Pb, Cd, Ga, La, Zr, Ce, Zn, Mn, Cu, Fe, Cr, W, K, Na, and Ni. The metal salt is calcium sulfate, calcium nitrate, calcium chloride, barium sulfate, barium nitrate, barium chloride, niobium sulfate, niobium nitrate, niobium chloride, rhodium sulfate, rhodium nitrate, rhodium chloride, palladium sulfate, palladium nitrate, palladium chloride, platinum sulfate, platinum nitrate, platinum chloride, cadmium sulfate, cadmium nitrate, cadmium chloride, gallium sulfate, gallium nitrate, gallium chloride, lanthanum sulfate, lanthanum nitrate, lanthanum chloride, zirconium sulfate, zirconium nitrate, zirconium chloride, cerium sulfate, cerium nitrate, cerium chloride, zinc sulfate, zinc nitrate, zinc chloride, manganese sulfate, manganese nitrate, manganese chloride, copper sulfate, copper nitrate, copper chloride, iron sulfate, iron nitrate, iron chloride, chromium sulfate, chromium nitrate, chromium chloride, ammonium tungstate, potassium sulfate, potassium nitrate, potassium chloride, sodium sulfate, sodium nitrate, sodium chloride, nickel sulfate, nickel nitrate, and nickel chloride.
[0007] The molybdenum compound is one of carbonyl molybdenum, ammonium molybdate, molybdenum dioxide or molybdenum trioxide.
[0008] The phosphorus element is white phosphorus, red phosphorus, black phosphorus or purple phosphorus.
[0009] The reaction tube is one of a corundum tube, a glass tube and a ceramic tube.
[0010] The discharge gas is one of air, oxygen, H2, N2, He and Ar.
[0011] The method for preparing the metal element-doped molybdenum-based phosphorus-oxygen composite material of the present invention is convenient to operate, has a low reaction temperature, is short in time, and is expected to achieve mass production.
[0012] Plasma is used to directly excite the phosphorus phosphating agent to achieve phosphating of solid samples at low temperature. At the same time, the ratio of molybdenum and metal elements is adjusted to obtain molybdenum-based phosphorus-oxygen composite materials doped with different amounts of metal elements. The relative content of phosphorus and oxygen in the molybdenum-based phosphorus-oxygen composite materials is precisely adjusted by controlling the amount of phosphorus phosphating agent. Finally, molybdenum-based phosphorus-oxygen composite materials doped with different amounts of metal elements with uniform particles, regular structure and good repeatability are synthesized. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 This is a transmission electron micrograph of the Ni-doped molybdenum-based phosphorus-oxygen composite material in Example 26. DETAILED DESCRIPTION
[0014] The present invention is further described below in conjunction with specific implementation cases. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Various equivalent modifications of the present invention made by those skilled in the art all fall within the scope defined by the claims attached to this application. Example 1
[0015] According to the molar ratio of phosphorus: molybdenum = 5, weigh 2.5 grams of white phosphorus for use; according to the molar ratio of Ca: molybdenum = 75, weigh calcium chloride and molybdenum dioxide and mix them evenly to obtain mixture A; then further evenly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; use a gas mass flowmeter to control the air flow rate to ensure that it passes through the reaction tube at a flow rate of 10 ml / min. Connect high voltage, react for 50 minutes, discharge frequency 30 kHz, output voltage 6000 V, and finally obtain Ca-doped molybdenum-based phosphorus-oxygen composite material. Example 2
[0016] According to the molar ratio of phosphorus: molybdenum = 3, 2 grams of red phosphorus was weighed for use; according to the molar ratio of Ba: molybdenum = 1, barium nitrate and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was then placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the oxygen flow rate was controlled by a gas mass flowmeter to ensure that the oxygen flow rate passed through the reaction tube at a flow rate of 5 ml / min. The high voltage was turned on, the reaction lasted for 135 minutes, the discharge frequency was 9 kHz, and the output voltage was 18500 V, and finally a Ba-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 3
[0017] According to the molar ratio of phosphorus: molybdenum = 8, weigh 4.7 grams of black phosphorus for use; weigh zinc nitrate and carbonyl molybdenum according to the molar ratio of Zn: molybdenum = 12 and mix the two uniformly to obtain mixture A; then further uniformly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; use a gas mass flowmeter to control the H2 flow rate to ensure that it passes through the reaction tube at a flow rate of 20 ml / min. Connect high voltage, react for 15 minutes, discharge frequency 28 kHz, output voltage 2000 V, and finally obtain Zn-doped molybdenum-based phosphorus-oxygen composite material. Example 4
[0018] According to the phosphorus: molybdenum molar ratio = 33, 3.6 grams of purple phosphorus was weighed for use; potassium sulfate and ammonium molybdate were weighed according to the K: molybdenum molar ratio = 0.5 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; the N2 flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 17 ml / min. The high voltage was turned on, the reaction lasted for 155 minutes, the discharge frequency was 3 kHz, the output voltage was 7000 V, and finally a K-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 5
[0019] According to the molar ratio of phosphorus: molybdenum = 0.5, 10.6 grams of white phosphorus was weighed for use; sodium chloride and molybdenum dioxide were weighed according to the molar ratio of Na: molybdenum = 4.5 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was then placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the He flow rate was controlled by a gas mass flowmeter to ensure that the flow rate of 50 ml / min passed through the reaction tube. The high voltage was turned on, the reaction lasted for 5 minutes, the discharge frequency was 16 kHz, and the output voltage was 13000 V, and finally the Na-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 6
[0020] According to the phosphorus: molybdenum molar ratio = 36.6, 11.2 grams of red phosphorus was weighed for use; according to the Nb: molybdenum molar ratio = 8.8, niobium nitrate and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the Ar gas flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 35 ml / min. The high voltage was turned on, the reaction lasted for 8 minutes, the discharge frequency was 26 kHz, the output voltage was 14500 V, and finally the Nb-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 7
[0021] According to the molar ratio of phosphorus: molybdenum = 10, weigh 17.5 grams of black phosphorus for use; weigh sodium nitrate and carbonyl molybdenum according to the molar ratio of Na: molybdenum = 3 and mix the two uniformly to obtain mixture A; then further uniformly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; use a gas mass flowmeter to control the air flow rate to ensure that it passes through the reaction tube at a flow rate of 88 ml / min. Connect high voltage, react for 10 minutes, discharge frequency 29 kHz, output voltage 17000 V, and finally obtain Na-doped molybdenum-based phosphorus-oxygen composite material. Example 8
[0022] According to the molar ratio of phosphorus: molybdenum = 17.6, 19.7 grams of purple phosphorus was weighed for use; according to the molar ratio of Ga: molybdenum = 0.09, gallium nitrate and ammonium molybdate were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; the oxygen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 100 ml / min. The high voltage was turned on, the reaction lasted for 60 minutes, the discharge frequency was 4 kHz, and the output voltage was 19500 V, and finally a Ga-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 9
[0023] According to the molar ratio of phosphorus: molybdenum = 22, 2 grams of red phosphorus was weighed for use; according to the molar ratio of Fe: molybdenum = 33, ferric chloride and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the H2 flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 8 ml / min. The high voltage was turned on, the reaction lasted for 165 minutes, the discharge frequency was 1 kHz, and the output voltage was 8000 V, and finally the Fe-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 10
[0024] According to the molar ratio of phosphorus: molybdenum = 1, 5.5 grams of black phosphorus was weighed for use; according to the molar ratio of Zr: molybdenum = 0.8, zirconium nitrate and carbonyl molybdenum were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the nitrogen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 800 ml / min. The high voltage was turned on, the reaction lasted for 105 minutes, the discharge frequency was 14 kHz, the output voltage was 12000 V, and finally a Zr-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 11
[0025] According to the molar ratio of phosphorus: molybdenum = 23.7, 22.3 grams of purple phosphorus was weighed for use; according to the molar ratio of Ce: molybdenum = 9, cerium nitrate and ammonium molybdate were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; the He flow rate was controlled by a gas mass flowmeter to ensure that the flow rate of 75 ml / min passed through the reaction tube. The high voltage was turned on, the reaction lasted for 35 minutes, the discharge frequency was 10 kHz, the output voltage was 11500 V, and finally the Ce-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 12
[0026] According to the phosphorus: molybdenum molar ratio = 12, weigh 23.1 grams of white phosphorus for use; according to the Zn: molybdenum molar ratio = 23.38, weigh zinc sulfate and molybdenum dioxide and mix them evenly to obtain mixture A; then further evenly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; use a gas mass flowmeter to control the Ar flow rate to ensure that it passes through the reaction tube at a flow rate of 2000 ml / min. Connect high voltage, react for 180 minutes, discharge frequency 27 kHz, output voltage 17500 V, and finally obtain Zn-doped molybdenum-based phosphorus-oxygen composite material. Example 13
[0027] According to the molar ratio of phosphorus: molybdenum = 75, 5 grams of red phosphorus was weighed for use; according to the molar ratio of Mn: molybdenum = 15, manganese nitrate and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the nitrogen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 115 ml / min. The high voltage was turned on, the reaction lasted for 185 minutes, the discharge frequency was 17 kHz, the output voltage was 16000 V, and finally the Mn-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 14
[0028] According to the molar ratio of phosphorus: molybdenum = 40, weigh 24.9 grams of black phosphorus for use; weigh copper chloride and carbonyl molybdenum according to the molar ratio of Cu: molybdenum = 17.6 and mix them evenly to obtain mixture A; then further mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; use a gas mass flowmeter to control the He flow rate to ensure that it passes through the reaction tube at a flow rate of 300 ml / min. Connect high voltage, react for 90 minutes, discharge frequency 8 kHz, output voltage 10500 V, and finally obtain Cu-doped molybdenum-based phosphorus-oxygen composite material. Embodiment 15
[0029] According to the molar ratio of phosphorus: molybdenum = 4.5, 25.5 grams of purple phosphorus was weighed for use; according to the molar ratio of W: molybdenum = 8, ammonium tungstate and ammonium molybdate were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the Ar flow rate was controlled by a gas mass flowmeter to ensure that the Ar flow rate was 1350 ml / min through the reaction tube. The high voltage was turned on, the reaction lasted for 112 minutes, the discharge frequency was 15 kHz, and the output voltage was 9000 V, and finally the W-doped molybdenum-based phosphorus-oxygen composite material was obtained. Example 16
[0030] According to the molar ratio of phosphorus: molybdenum = 0.09, 2 grams of black phosphorus was weighed for use; potassium chloride and molybdenum trioxide were weighed according to the molar ratio of K: molybdenum = 7 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was then placed in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; the air flow rate was controlled by a gas mass flowmeter to ensure that the air flow rate passed through the reaction tube at 1000 ml / min. The high voltage was turned on, the reaction lasted for 190 minutes, the discharge frequency was 2 kHz, the output voltage was 18000 V, and finally a K-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 17
[0031] According to the molar ratio of phosphorus: molybdenum = 25, weigh 7 grams of white phosphorus for use; weigh sodium nitrate and carbonyl molybdenum according to the molar ratio of Na: molybdenum = 22 and mix the two uniformly to obtain mixture A; then further uniformly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; use a gas mass flowmeter to control the oxygen flow rate to ensure that it passes through the reaction tube at a flow rate of 80 ml / min. Connect high voltage, react for 110 minutes, discharge frequency 13 kHz, output voltage 8500 V, and finally obtain Na-doped molybdenum-based phosphorus-oxygen composite material. Embodiment 18
[0032] According to the molar ratio of phosphorus: molybdenum = 8.8, 6 grams of red phosphorus was weighed for use; copper nitrate and ammonium molybdate were weighed according to the molar ratio of Cu: molybdenum = 10 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; mixture B was then placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the H2 flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 175 ml / min. The high voltage was turned on, the reaction lasted for 160 minutes, the discharge frequency was 7 kHz, and the output voltage was 5000 V, and finally a Cu-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 19
[0033] According to the molar ratio of phosphorus: molybdenum = 20, 9 grams of black phosphorus was weighed for use; according to the molar ratio of Rh: molybdenum = 40, rhodium chloride and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was then placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the nitrogen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 1200 ml / min. The high voltage was turned on, the reaction lasted for 85 minutes, the discharge frequency was 22 kHz, the output voltage was 19000 V, and finally the Rh-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 20
[0034] According to the molar ratio of phosphorus: molybdenum = 38, 30 grams of purple phosphorus was weighed for use; palladium chloride and carbonyl molybdenum were weighed according to the molar ratio of Pd: molybdenum = 0.05 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the He flow rate was controlled by a gas mass flowmeter to ensure that the flow rate of He passed through the reaction tube at 220 ml / min. The high voltage was turned on, the reaction lasted for 150 minutes, the discharge frequency was 25 kHz, and the output voltage was 6500 V, and finally a Pd-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 21
[0035] According to the molar ratio of phosphorus: molybdenum = 7, weigh 29 grams of white phosphorus for use; according to the molar ratio of Cd: molybdenum = 0.83, weigh cadmium nitrate and ammonium molybdate and mix them evenly to obtain mixture A; then further evenly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; use a gas mass flowmeter to control the Ar gas flow rate to ensure that it passes through the reaction tube at a flow rate of 1500 ml / min. Connect high voltage, react for 170 minutes, discharge frequency 5 kHz, output voltage 4000 V, and finally obtain Cd-doped molybdenum-based phosphorus-oxygen composite material. Embodiment 22
[0036] According to the molar ratio of phosphorus: molybdenum = 0.8, 16 grams of red phosphorus was weighed for use; according to the molar ratio of Ga: molybdenum = 23.7, gallium chloride and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was then placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the air flow rate was controlled by a gas mass flowmeter to ensure that the air flow rate was 30 ml / min through the reaction tube. The high voltage was turned on, the reaction was carried out for 100 minutes, the discharge frequency was 21 kHz, and the output voltage was 15000 V, and finally a Ga-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 23
[0037] According to the phosphorus: molybdenum molar ratio = 0.83, 3 grams of black phosphorus was weighed for use; zinc chloride and carbonyl molybdenum were weighed according to the Zn: molybdenum molar ratio = 36.6 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; mixture B was then placed in the cavity between the high-voltage electrode of the plasma reactor and the glass reaction tube; the oxygen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 16 ml / min. The high voltage was turned on, the reaction lasted for 140 minutes, the discharge frequency was 19 kHz, and the output voltage was 2500 V, and finally a Zn-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 24
[0038] According to the molar ratio of phosphorus: molybdenum = 16, 19 grams of purple phosphorus was weighed for use; according to the molar ratio of Cr: molybdenum = 19, chromium nitrate and ammonium molybdate were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; the H2 flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 500 ml / min. The high voltage was turned on, the reaction lasted for 48 minutes, the discharge frequency was 24 kHz, the output voltage was 11000 V, and finally a Cr-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 25
[0039] According to the molar ratio of phosphorus: molybdenum = 12.2, 7.5 grams of purple phosphorus was weighed for use; copper chloride and carbonyl molybdenum were weighed according to the molar ratio of Cu: molybdenum = 0.1 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; mixture B was then placed in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; the nitrogen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 150 ml / min. The high voltage was turned on, the reaction lasted for 72 minutes, the discharge frequency was 12 kHz, the output voltage was 4500 V, and finally a Cu-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 26
[0040] According to the molar ratio of phosphorus: molybdenum = 0.05, weigh 2.5 grams of red phosphorus for use; according to the molar ratio of Ni: molybdenum = 5, weigh nickel chloride and ammonium molybdate and mix them evenly to obtain mixture A; then further evenly mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; use a gas mass flowmeter to control the He flow rate to ensure that it passes through the reaction tube at a flow rate of 1750 ml / min. Connect high voltage, react for 35 minutes, discharge frequency 23 kHz, output voltage 20000 V, and finally obtain Ni-doped molybdenum-based phosphorus-oxygen composite material. Figure 1 As shown, it can be seen that the prepared Ni-doped molybdenum-based phosphorus-oxygen composite material is small in size and the metal is in close contact with the molybdenum-based phosphorus-oxygen compound. Embodiment 27
[0041] According to the molar ratio of phosphorus: molybdenum = 23.38, 11 grams of white phosphorus was weighed for use; potassium chloride and molybdenum dioxide were weighed according to the molar ratio of K: molybdenum = 16 and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; mixture B was then placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the air flow rate was controlled by a gas mass flowmeter to ensure that the air flow rate was 276 ml / min through the reaction tube. The high voltage was turned on, the reaction was carried out for 99 minutes, the discharge frequency was 6 kHz, and the output voltage was 10000 V, and finally a K-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 28
[0042] According to the molar ratio of phosphorus: molybdenum = 0.1, 27 grams of red phosphorus was weighed for use; according to the molar ratio of Pb: molybdenum = 12.2, lead nitrate and molybdenum trioxide were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was then placed in the cavity between the high-voltage electrode of the plasma reactor and the corundum reaction tube; the H2 flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 860 ml / min. The high voltage was turned on, the reaction lasted for 78 minutes, the discharge frequency was 11 kHz, the output voltage was 14000 V, and finally a Pb-doped molybdenum-based phosphorus-oxygen composite material was obtained. Embodiment 29
[0043] According to the molar ratio of phosphorus: molybdenum = 9, weigh 18.2 grams of black phosphorus for use; according to the molar ratio of Cd: molybdenum = 38, weigh cadmium chloride and carbonyl molybdenum and mix them evenly to obtain mixture A; then further mix the above mixture A with the phosphorus powder weighed in advance to obtain mixture B; then place mixture B in the cavity between the high-voltage electrode and the ceramic reaction tube of the plasma reactor; use a gas mass flowmeter to control the H2 flow rate to ensure that it passes through the reaction tube at a flow rate of 860 ml / min. Connect high voltage, react for 78 minutes, discharge frequency 11 kHz, output voltage 14000 V, and finally obtain Cd-doped molybdenum-based phosphorus-oxygen composite material. Embodiment 30
[0044] According to the molar ratio of phosphorus: molybdenum = 15, 9.5 grams of purple phosphorus was weighed for use; according to the molar ratio of La: molybdenum = 20, lanthanum nitrate and ammonium molybdate were weighed and the two were evenly mixed to obtain mixture A; the above mixture A was further evenly mixed with the phosphorus powder weighed in advance to obtain mixture B; the mixture B was placed in the cavity between the high-voltage electrode and the glass reaction tube of the plasma reactor; the nitrogen flow rate was controlled by a gas mass flowmeter to ensure that it passed through the reaction tube at a flow rate of 900 ml / min. The high voltage was turned on, the reaction lasted for 120 minutes, the discharge frequency was 18 kHz, and the output voltage was 2000 V, and finally the La-doped molybdenum-based phosphorus-oxygen composite material was obtained.
Claims
1. A method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material, characterized in that: Follow the steps below Step 1, preparing a mixture A, uniformly mixing a metal salt and a molybdenum compound at a molar ratio of metal: molybdenum = 0.05-40 to obtain a mixture A; Step 2, preparing a mixture B, mixing the mixture A and phosphorus powder evenly to obtain a mixture B, wherein the molar ratio of phosphorus to molybdenum in the mixture B is 0.05-40; Step 3: Place mixture B inside the reaction tube of a plasma reactor, pass the discharge gas through the reaction tube of the plasma reactor at a flow rate of 5-2000 ml / min, the discharge frequency of the plasma reactor is 1-30 kHz, the output voltage is 2000-20000 V, and react for 5-200 minutes to obtain a metal element-doped molybdenum-based phosphorus-oxygen composite material.
2. The method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material according to claim 1, characterized in that: The metal salt is one of calcium sulfate, calcium nitrate, calcium chloride, barium sulfate, barium nitrate, barium chloride, niobium sulfate, niobium nitrate, niobium chloride, rhodium sulfate, rhodium nitrate, rhodium chloride, palladium sulfate, palladium nitrate, palladium chloride, platinum sulfate, platinum nitrate, platinum chloride, cadmium sulfate, cadmium nitrate, cadmium chloride, gallium sulfate, gallium nitrate, gallium chloride, lanthanum sulfate, lanthanum nitrate, lanthanum chloride, zirconium sulfate, zirconium nitrate, zirconium chloride, cerium sulfate, cerium nitrate, cerium chloride, zinc sulfate, zinc nitrate, zinc chloride, manganese sulfate, manganese nitrate, manganese chloride, copper sulfate, copper nitrate, copper chloride, iron sulfate, iron nitrate, iron chloride, chromium sulfate, chromium nitrate, chromium chloride, ammonium tungstate, potassium sulfate, potassium nitrate, potassium chloride, sodium sulfate, sodium nitrate, sodium chloride, nickel sulfate, nickel nitrate, and nickel chloride.
3. The method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material according to claim 1, characterized in that: The molybdenum compound is one of carbonyl molybdenum, ammonium molybdate, molybdenum dioxide or molybdenum trioxide.
4. The method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material according to claim 1, characterized in that: The phosphorus powder is one of white phosphorus, red phosphorus, black phosphorus or purple phosphorus.
5. The method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material according to claim 1, characterized in that: The reaction tube is one of a corundum tube, a glass tube and a ceramic tube.
6. The method for synthesizing a metal element-doped molybdenum-based phosphorus-oxygen composite material according to claim 1, characterized in that: The discharge gas is one of air, oxygen, H2, N2, He and Ar.