CN114950295A - Preparation of Cu by gas-solid reaction 3 Method of P - Google Patents
Preparation of Cu by gas-solid reaction 3 Method of P Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/14—Production of inert gas mixtures; Use of inert gases in general
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a method for preparing Cu by gas-solid reaction 3 A method of P belongs to the technical field of semiconductor material preparation. The invention adopts a gas-solid reaction method at PH 3 Under the action of gas, the Cu is directly prepared by reaction with CuO-containing solid material 3 P, capable of realizing Cu under low temperature conditions 3 The direct synthesis of P has mild condition, and is favorable for solving the problem of the existing Cu 3 P has high synthesis conditions and complex process; meanwhile, the preparation method provided by the invention is simple and easy to operate and control, strong in stability, rapid and efficient, safe and stable in synthesis, relatively short in preparation time, easy to obtain materials, low in cost, free from the limitation of time and regions, free from solid byproducts, green and environment-friendly in process, free from complex equipment, capable of ensuring the synthesis temperature to be lower than 100 ℃, and easy to realize industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of semiconductor material preparation, in particular to a method for preparing Cu through gas-solid reaction 3 And (P) is a method.
Background
Copper phosphide (Cu) 3 P) is a P-type semiconductor material and is widely applied to the fields of photocatalysis, energy, metallurgy and the like. From research in recent decades, copper phosphide has many different phases, usually only Cu 3 P can exist stably in the air. And Cu 3 P has already been put into production in the actual industry, in the smelting industry, Cu 3 P can be used as an additive in the production of alloys or for the modification of alloys. In recent years, with the rapid development of new energy field, Cu 3 P is also used as the negative electrode material of some ion batteries. The study shows that Cu 3 P has excellent electrochemical performance, mainly represented by larger capacity and good cycle efficiency, and when the mass capacity is the same as that of graphite, the volume capacity of P is close to 4 times of that of graphite. In the scientific research field, about Cu 3 P synthetic methods are increasingly reported, and in actual industrial production, Cu 3 P is directly synthesized by solid-phase reaction at the temperature higher than 800 ℃ according to a certain proportion of simple substance phosphorus and simple substance copper. Besides, Cu can be successfully synthesized by electrochemical deposition, solvothermal method, hydrothermal synthesis method and the like 3 And P. However, the above synthesis method either requires a high reaction temperature (600-1000 ℃), or has a complicated preparation process, which is not favorable for Cu 3 And (3) industrial production of P.
Disclosure of Invention
The object of the invention isIn providing a gas-solid reaction for preparing Cu 3 P method for efficiently synthesizing Cu at low temperature by gas-solid reaction 3 And P, the method is simple and easy to implement and is beneficial to industrial production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing Cu by gas-solid reaction 3 P, comprising the steps of:
introducing the mixed gas into a CuO-containing solid material to carry out gas-solid reaction to obtain Cu 3 P；
The mixed gas comprises carrier gas and PH 3 (ii) a The temperature of the gas-solid reaction is 50-200 ℃.
Preferably, the mixed gas has a pH value of 3 The concentration of (B) is 500 to 3000 ppm.
Preferably, the mixed gas further comprises O 2 Said O is 2 The concentration of (B) is 0 to 30000 ppm.
Preferably, the CuO-containing solid material comprises CuO, carbon-doped copper oxide or a support material loaded with CuO.
Preferably, the morphology of the CuO includes hollow CuO, petal-shaped CuO, rod-shaped CuO, or layered CuO.
Preferably, in the support material loaded with CuO, the support material comprises activated carbon, metal oxide, molecular sieve or diatomite.
Preferably, the flow rate of the mixed gas is 50-300 mL/min.
Preferably, the temperature of the gas-solid reaction is 70-110 ℃.
Preferably, when the mixed gas has a pH value 3 The inlet concentration and the outlet concentration of the gas-solid reaction are the same, and the gas-solid reaction is finished.
The invention provides a method for preparing Cu by gas-solid reaction 3 P, comprising the steps of: introducing the mixed gas into a CuO-containing solid material to carry out gas-solid reaction to obtain Cu 3 P; the mixed gas comprises carrier gas and PH 3 (ii) a The temperature of the gas-solid reaction is 50-200 ℃. The invention adopts a gas-solid reaction method at PH 3 Action of gasThen directly reacting with CuO-containing solid material to prepare Cu 3 P, capable of realizing Cu under low temperature conditions 3 The direct synthesis of P has mild condition, and is favorable for solving the problem of the existing Cu 3 P has high synthesis conditions and complex process; meanwhile, the preparation method provided by the invention is simple and easy to operate and control, strong in stability, rapid and efficient, safe in synthesis, relatively short in preparation time, easy to obtain materials, low in cost, free from the limitation of time and regions, free from solid byproducts, green and environment-friendly in process, free from complex equipment, capable of ensuring the synthesis temperature to be lower than 100 ℃, and easy to realize industrial mass production.
Cu prepared by the method of the invention 3 P has good crystallinity and higher purity, no other solid by-products are generated, which shows that the synthesis process is stable, and the preparation temperature window is wide (Cu can be stably synthesized within the temperature range of 50-200℃) 3 P), wide application range and is beneficial to expanding into large-scale industrial production. The results of the examples show that the method provided by the invention can stably and efficiently synthesize high-purity and high-crystallinity Cu 3 P crystal, Cu produced 3 The P can be used for efficient photocatalytic degradation of rhodamine B pollutants in a liquid phase.
Furthermore, the CuO-containing solid material used by the invention is CuO with different shapes or a carrier material loaded with CuO, Cu 3 The morphology of P varies according to the morphology of the CuO material. Furthermore, the pH can be controlled during the preparation process 3 Concentration, reaction time and reaction temperature are controlled to increase Cu 3 Efficiency of synthesis of P.
Further, the invention controls O 2 The addition amount is controlled to control Cu in the product 3 The purity of P.
Furthermore, the method of the invention can be applied to the field of environmental protection, and when an adsorbent (namely a CuO-containing solid material) loaded with CuO active components is used for purifying and removing PH in the factory tail gas 3 When the adsorbent deactivation product is Cu 3 P, corresponding to the realization of PH in the tail gas 3 The resource utilization of the method has double meanings of environmental protection and economy.
Drawings
FIG. 1 shows 3DCuO/AC and Cu prepared in example 1 3 XRD pattern of P;
FIG. 2 is the CuO @ C and Cu prepared in example 2 3 XRD pattern of P;
FIG. 3 shows Cu prepared in example 2 3 P with commercially available g-C 3 N 4 And (3) a performance diagram of photocatalytic degradation of rhodamine B.
Detailed Description
The invention provides a method for preparing Cu by gas-solid reaction 3 P, comprising the steps of:
introducing the mixed gas into a CuO-containing solid material to carry out gas-solid reaction to obtain Cu 3 P；
The mixed gas comprises carrier gas and PH 3 (ii) a The temperature of the gas-solid reaction is 50-200 ℃.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In the present invention, the mixed gas has a pH value 3 The concentration of (b) is preferably 500 to 3000ppm, the balance is carrier gas, and more preferably 1000 to 2000 ppm. In the present invention, the carrier gas is preferably nitrogen.
In the present invention, the mixed gas preferably further comprises O 2 (ii) a Said O is 2 The concentration of (B) is preferably 0 to 30000ppm, more preferably 10000 to 20000 ppm.
In the invention, the flow rate of the mixed gas is preferably 50-300 mL/min, and more preferably 100-200 mL/min.
In the present invention, the CuO-containing solid material preferably includes CuO, carbon-doped copper oxide, or a support material loaded with CuO; the shape of the CuO preferably comprises hollow CuO, petal-shaped CuO, rod-shaped CuO or layered CuO; in the support material loaded with CuO, the support material preferably includes activated carbon, metal oxide, molecular sieve or diatomaceous earth. The sources of CuO and support materials with different morphologies are not particularly limited in the present invention, and commercially available products well known in the art are sufficient.
In the invention, when the CuO-containing solid material is a CuO-loaded carrier material, Cu-loaded carrier material is prepared 3 P as a support material.
In an embodiment of the present invention, the preparation method of the carbon-doped copper oxide comprises: grinding and mixing 2g of copper nitrate and 5g of glucose in an agate mortar to form fine sand, transferring the ground material into a tubular furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under the protection of anhydrous air atmosphere, and roasting for 2h to obtain carbon-doped CuO named CuO @ C.
The preparation method of the CuO-loaded support material and the loading amount of CuO on the prepared CuO-loaded support material are not particularly limited, and the CuO-loaded support material can be prepared by the method well known in the art. In the embodiment of the invention, the preparation method of the CuO loaded activated carbon material specifically comprises the following steps: soaking 20-40 meshes of straw activated carbon in a 50 vol% nitric acid solution for 12h, carrying out ultrasonic oscillation treatment for 30min, washing for 5 times by using ultrapure water to remove impurities and ash, transferring to a blast drying box, and drying at 90 ℃ for 12h to obtain an activated carbon carrier, wherein the activated carbon carrier is marked as AC; preparing 1.5mol/L copper nitrate solution, weighing 2g of the activated carbon carrier and 20mL of the copper nitrate solution, adding the activated carbon carrier and the copper nitrate solution into a polytetrafluoroethylene inner container, dropwise adding 0.7mL of concentrated nitric acid (the concentration is 68 vol%), transferring the concentrated nitric acid into a hydrothermal reaction kettle, sealing, carrying out hydrothermal reaction for 10 hours at 170 ℃, taking out a solid obtained in the hydrothermal reaction, cleaning the solid with ultrapure water for three times, drying the solid for 12 hours at 100 ℃ in a forced air drying oven, roasting the obtained precursor for 2 hours at 350 ℃ under the protection of nitrogen atmosphere by using a tubular furnace, and obtaining the CuO-loaded activated carbon material which is named as 3 DCuO/AC.
Before the mixed gas is introduced into the CuO-containing solid material, the CuO-containing solid material is preferably placed in a quartz tube reactor, the quartz tube is heated to 200 ℃ through a tube furnace, and nitrogen is purged for 30min to remove impurities on the surface of the CuO-containing solid material. In the present invention, the quartz tube may preferably be controlled in external temperature by a tube furnace. The quartz tube and the tube furnace are not particularly limited in the present invention, and any corresponding apparatus known in the art may be used.
The invention preferably prepares the gas containing O and taking nitrogen as carrier gas by a dynamic gas distribution method 2 And pH 3 Introducing the mixed gas into a quartz tube purged by nitrogen, and controlling the temperature of the quartz tube by a tube furnaceGas-solid reaction is carried out. In the invention, the temperature of the gas-solid reaction is 50-200 ℃, preferably 70-110 ℃, and preferably 90-100 ℃; the airspeed is 15000-20000 h -1 。
The dosage of the CuO-containing solid material in the quartz tube is not specially limited, and the CuO-containing solid material can be adjusted according to the flow of the mixed gas to ensure full reaction; in the embodiment of the invention, when the flow rate of the mixed gas is 50-300 mL/min, the mass of the CuO-containing solid material is specifically 0.1-1 g.
In the present invention, when the mixed gas has a pH value 3 The inlet concentration and the outlet concentration of the gas-solid reaction are the same, and the gas-solid reaction is finished. The invention preferably detects the PH in the gas at the outlet of the quartz tube by gas chromatography 3 And (4) concentration. The invention detects the PH in the gas at the outlet of the quartz tube by gas chromatography 3 The concentration is not particularly limited and may be carried out according to a method known in the art.
After the gas-solid reaction is finished, the obtained solid material is preferably taken out, washed for 3-6 times by deionized water, and dried to obtain Cu 3 And P. The specific process of the cleaning is not particularly limited, and the cleaning can be carried out according to the process well known in the art; the drying mode is preferably drying, and the drying is preferably carried out in an oven; the temperature of the drying is preferably 100 ℃.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Soaking 20-40-mesh straw activated carbon in a 50 vol% nitric acid solution for 12h, performing ultrasonic oscillation treatment for 30min, cleaning for 5 times by using ultrapure water to remove impurities and ash, transferring to a forced air drying oven, and drying at 90 ℃ for 12h to obtain an activated carbon carrier, wherein the label is AC;
preparing 1.5mol/L copper nitrate solution, weighing 2g of the straw activated carbon carrier and 20mL of the copper nitrate solution, adding the straw activated carbon carrier and the 20mL of the copper nitrate solution into a polytetrafluoroethylene inner container, dropwise adding 0.7mL of concentrated nitric acid (68 vol%), transferring the mixture into a hydrothermal reaction kettle for sealing, carrying out hydrothermal reaction for 10 hours at 170 ℃, taking out a solid obtained by the hydrothermal reaction, cleaning the solid with ultrapure water for three times, drying the solid for 12 hours at 100 ℃ in a forced air drying oven, roasting the obtained precursor for 2 hours at 350 ℃ under the protection of nitrogen atmosphere by using a tubular furnace to obtain an activated carbon material loaded with CuO, and naming the activated carbon material as 3 DCuO/AC;
taking nitrogen as carrier gas, mixing PH in the gas 3 Concentration 1000ppm, O 2 The concentration is 10000ppm, the rest is carrier gas, and the total flow of the mixed gas is 100 mL/min; 0.3g of the prepared 3DCuO/AC is placed in a quartz tube reactor, and the space velocity is 20000h -1 The reaction temperature was 90 ℃ and the pH in the gas at the outlet of the reactor was determined by gas chromatography 3 Concentration when pH is 3 When the inlet concentration and the outlet concentration of (2) are consistent, the gas-solid reaction is completed. At the moment, the active component CuO on the surface of the activated carbon is completely converted into Cu 3 P, taking out the obtained solid material, washing the solid material for 5 times by using deionized water, and drying the solid material in an oven at 100 ℃ to obtain the active carbon with Cu loaded on the surface 3 P is a solid material.
Example 2
Grinding and mixing 2g of copper nitrate and 5g of glucose in an agate mortar to form fine sand, transferring the ground material to a tubular furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in an anhydrous air atmosphere, and roasting for 2h to obtain carbon-doped CuO named CuO @ C;
taking nitrogen as carrier gas, mixing PH in the gas 3 Concentration 1500ppm, O 2 The concentration is 5000ppm, the balance is carrier gas, and the total flow of the mixed gas is 100 mL/min; 0.2g of prepared CuO @ C is placed in a quartz tube reactor, and the space velocity is 30000h -1 The reaction temperature was 100 ℃ and the pH in the gas at the outlet of the reactor was determined by gas chromatography 3 Concentration when pH is 3 When the inlet concentration and the outlet concentration of (2) are the same, the gas-solid reaction is completed, the obtained solid material is taken out, washed 5 times with deionized water, and put in an oven at 10 deg.fDrying at 0 ℃ to obtain Cu 3 And P material.
Characterization and Performance testing
1) For 3DCuO/AC, CuO @ C and Cu prepared in examples 1-2 3 And P is subjected to XRD characterization, the structure of a related crystal substance is determined by a D/MAX-2200 type X-ray diffractometer, CuKa rays (lambda is 0.15406nm), the voltage is 36kV, the current is 30mA, the scanning range is 20-80 degrees, the scanning speed is 5 degrees/min, and the obtained result is shown in figures 1-2.
FIG. 1 shows 3DCuO/AC and Cu prepared in example 1 3 XRD contrast pattern of P; as shown in FIG. 1, the main phase of the surface of 3DCuO/AC is CuO with high crystallinity, which passes through the reaction with PH 3 After the reaction, the characteristic peaks of XRD ascribed to CuO disappeared, and those ascribed to Cu appeared 3 The XRD characteristic diffraction peak of P shows that CuO and PH react in gas-solid reaction process 3 React to form Cu with high crystallinity 3 P, and CuO conversion is relatively thorough, Cu 3 The purity of P is higher, and no other impurity products are generated, thereby proving the superiority of the gas-solid reaction method.
FIG. 2 is the CuO @ C and Cu prepared in example 2 3 XRD contrast pattern of P; as shown in FIG. 2, the main phase of CuO @ C is highly crystalline CuO, which is in contact with pH 3 After the reaction, the characteristic peaks of XRD ascribed to CuO disappeared, and those ascribed to Cu appeared 3 The XRD characteristic diffraction peak of P shows that CuO and PH in different states 3 All the reactions can generate Cu with high crystallinity 3 And P, the universality of the method is proved.
2) Cu prepared in example 2 3 P and commercially available g-C 3 N 4 The experiment of degrading rhodamine B pollutant in liquid phase by photocatalysis is carried out by taking 20mg of Cu as a catalyst 3 P and commercially available g-C 3 N 4 Respectively adding the rhodamine B solution into 50mL (40mg/L), reaching adsorption equilibrium in a dark environment for 30min, then turning on a lamp at 25 ℃ to perform a photocatalytic experiment (visible light), measuring the concentration of the rhodamine B in the solution every 15min, and performing blank control (without adding any catalyst).
FIG. 3 shows Cu prepared in example 2 3 P andcommercial g-C 3 N 4 A performance comparison graph of photocatalytic degradation of rhodamine B is shown. As can be seen from FIG. 3, Cu 3 P and commercially available g-C 3 N 4 When the adsorption balance is reached, 18% of rhodamine B is adsorbed, the concentration of rhodamine B continues to decrease after the lamp is turned on, and finally 90% of rhodamine B is degraded, which indicates that Cu 3 P has obvious photocatalysis effect, and the result shows that the Cu prepared by the method of the invention 3 P and commercial high-performance photocatalyst g-C 3 N 4 Has similar photocatalysis effect and degradation rate and degradation time, further proves that the Cu prepared by the preparation method of the invention 3 P has better performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. Preparation of Cu by gas-solid reaction 3 P, characterized in that it comprises the following steps:
introducing the mixed gas into a CuO-containing solid material to carry out gas-solid reaction to obtain Cu 3 P；
The mixed gas comprises carrier gas and PH 3 (ii) a The temperature of the gas-solid reaction is 50-200 ℃.
2. The method of claim 1, wherein the mixed gas is at pH 3 The concentration of (A) is 500-3000 ppm; the carrier gas is nitrogen.
3. The method of claim 2, wherein the mixed gas further comprises O 2 Said O is 2 The concentration of (B) is 0 to 30000 ppm.
4. The method of claim 1, wherein the CuO-containing solid material comprises CuO, carbon-doped copper oxide, or a CuO-loaded support material.
5. The method of claim 4, wherein the CuO morphology comprises hollow CuO, petal-shaped CuO, rod-shaped CuO, or layered CuO.
6. The method of claim 4, wherein the CuO loaded support material comprises activated carbon, metal oxides, molecular sieves, or diatomaceous earth.
7. The method according to claim 1 or 2, wherein the flow rate of the mixed gas is 50 to 300 mL/min.
8. The method according to claim 1, wherein the temperature of the gas-solid reaction is 70 to 110 ℃.
9. The method as claimed in claim 1 or 8, wherein the mixed gas is pH-adjusted 3 The inlet concentration and the outlet concentration of the gas-solid reaction are the same, and the gas-solid reaction is finished.
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