阅读说明：本技术 一种SiP材料及其制备方法和应用 (SiP material and preparation method and application thereof ) 是由 王佳宏 杨环环 喻学锋 喻彬璐 于 2020-11-09 设计创作，主要内容包括：本发明公开了一种SiP材料及其制备方法和应用,本发明通过化学气相输运法(CVT法)并引入改性剂,经过高温煅烧成功将P型半导体SiP变为N型半导体SiP,大大增强了材料光催化性能的活性和稳定性,该材料在光催化领域表现出优异的性能,为开发清洁能源和保护环境助力。(The invention discloses a SiP material and a preparation method and application thereof, wherein a P-type semiconductor SiP is successfully changed into an N-type semiconductor SiP through a chemical vapor transport method (CVT method) and introduction of a modifier through high-temperature calcination, so that the activity and stability of the photocatalytic performance of the material are greatly enhanced, and the material shows excellent performance in the field of photocatalysis and is helpful for developing clean energy and protecting the environment.)

1. The SiP material is characterized in that the SiP material is an N-type SiP material.

2. The method of preparing a SiP material of claim 1, comprising the steps of:

(1) uniformly mixing silicon powder, a phosphorus source, a transport agent and a modifier;

(2) placing the reaction vessel in a reaction vessel, vacuumizing, sealing, and calcining at high temperature in a heating device to obtain a SiP material;

the modifier comprises one or a combination of several of metal sulfide, metal selenide and metal telluride.

3. The preparation method according to claim 2, wherein the mass ratio of the silicon powder, the phosphorus source, the transport agent and the modifying agent in step (1) is 1: 1: 0.001-0.5: 0.001-0.5;

preferably, the phosphorus source in step (1) is one or a combination of several of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide;

preferably, the transport agent in the step (1) is one or a combination of more of iodine and iodide; more preferably, the iodide is in the solid state and includes both metallic and nonmetallic iodides.

4. The manufacturing method according to claim 2, wherein the heating device in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (dual-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace;

preferably, the high-temperature calcination in the step (2) is carried out at a temperature of 800-1200 ℃ for 0.1-240 h.

5. A non-noble metal promoter-supported SiP material, wherein the non-noble metal promoter-supported SiP material is the SiP material of claim 1 on which a non-noble metal promoter is supported.

6. The non-noble metal promoter-supported SiP material of claim 5, wherein the non-noble metal promoter comprises one or a combination of nickel, cobalt, copper, iron;

preferably, the mass of the non-noble metal promoter is 0.1-60% of the mass of the SiP material;

preferably, the supporting manner comprises light deposition and immersion thermal reduction.

7. The method of preparing a non-noble metal promoter-supported SiP material as claimed in claim 5 or 6, wherein when the supporting means is photo-deposition, the method comprises the steps of: adding the SiP material of claim 1 into a solvent, then adding a non-noble metal-containing water-soluble inorganic salt compound, and finally performing ultraviolet light or visible light illumination for 0.5-8h in an oxygen-free environment;

or when the supporting mode is impregnation thermal reduction, the method comprises the following steps: dissolving a water-soluble inorganic salt compound containing a non-noble metal cocatalyst in deionized water, fully grinding the mixture with the SiP material of claim 1, drying the mixture, putting the dried mixture into a tubular furnace, heating the mixture at 300-600 ℃ for 1-8 hours, introducing hydrogen for reduction during the reaction, introducing argon for protection, and introducing H₂The flow rate is 10 to 100sccm, and the Ar gas flow rate is 100 to 500 sccm.

8. The preparation method of claim 7, wherein the water-soluble inorganic salt compound containing the non-noble metal promoter is one or more of a water-soluble inorganic salt compound containing nickel, a water-soluble inorganic salt compound containing cobalt, a water-soluble inorganic salt compound containing copper, and a water-soluble inorganic salt compound containing iron.

9. Use of the SiP material of claim 1, or the non-noble metal promoter supported SiP material of claim 5 or 6, as a photocatalytic material.

10. Use of the SiP material of claim 1, or the non-noble metal promoter supported SiP material of claim 5 or 6, for the production of hydrogen by the decomposition of water.

Technical Field

The invention belongs to the technical field of new energy materials, and particularly relates to a SiP material and a preparation method and application thereof.

Background

The development of semiconductor photocatalysis technology has important significance for solving the problem that fossil energy is not sustainable and protecting ecological environment, and mainly because the technology has mild reaction conditions, clean solar energy is utilized to generate chemical energy. The currently reported high-activity photocatalytic material partially supports noble metals such as Pt, Au and the like, so that the technical popularization cost is increased; meanwhile, the band gap of the materials determines that the materials can only utilize the ultraviolet band in sunlight, and the proportion of the band in the sunlight is extremely low, so that the utilization rate of the solar energy is greatly reduced.

SiP as a P-type indirect bandgap semiconductor is already a star material in the field of optical communication, and is considered as a semiconductor material with great potential for developing silicon photonics. The P-type semiconductor is conducted by the cavity, wherein if the cavity cannot be led out in time, the material can be corroded by itself, and the stability of the material is seriously affected.

Disclosure of Invention

In order to solve the technical problems in the background art, the present invention provides a SiP material, and a preparation method and an application thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

in one aspect, the invention provides a SiP material, which is an N-type SiP material.

In another aspect, the present invention provides a method for preparing the SiP material, including the following steps:

(1) uniformly mixing silicon powder, a phosphorus source, a transport agent and a modifier;

(2) placing the reaction vessel in a reaction vessel, vacuumizing, sealing, and calcining at high temperature in a heating device to obtain a SiP material;

the modifier comprises one or a combination of several of metal sulfide, metal selenide and metal telluride.

Further, the modifier is a metal sulfide.

Further, in the step (1), the mass ratio of the silicon powder, the phosphorus source, the transport agent and the modifier is 1: 1: 0.001-0.5: 0.001-0.5;

preferably, the phosphorus source in step (1) is one or a combination of several of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide;

preferably, the transport agent in the step (1) is one or a combination of more of iodine and iodide; more preferably, the iodide is in the solid state and includes both metallic and nonmetallic iodides.

Further, the heating device in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave oven or a single crystal furnace;

preferably, the temperature of the high-temperature calcination in the step (2) is 800-1200 ℃; the high-temperature calcination time is 0.1-240 h, preferably 72 h.

Further, the heating device is a double-temperature-zone tube furnace, preferably the high-temperature zone is 1100 ℃, and the low-temperature zone is 1000 DEG C

On the other hand, the invention provides a non-noble metal promoter-supported SiP material, wherein the non-noble metal promoter-supported SiP material is obtained by supporting a non-noble metal promoter on the SiP material.

Further, the non-noble metal promoter comprises one or a combination of nickel (Ni), cobalt (Co), copper (Cu) and iron (Fe), preferably nickel (Ni);

preferably, the mass of the non-noble metal promoter is 0.1-60% of the mass of the SiP material;

preferably, the supporting mode comprises light deposition and impregnation thermal reduction, and preferably the impregnation thermal reduction.

In another aspect, the present invention provides a method for preparing the non-noble metal promoter supported SiP material, where the supporting manner is photo-deposition, the method includes the following steps: adding the SiP material into a solvent, then adding a non-noble metal-containing water-soluble inorganic salt compound, and finally performing ultraviolet light or visible light illumination for 0.5-8h in an oxygen-free environment; preferably, the solvent is an aqueous organic alcohol solution, and more preferably, the aqueous organic alcohol solution is an aqueous absolute methanol solution (a mixed solution of absolute methanol and pure water) or an aqueous absolute ethanol solution (a mixed solution of absolute ethanol and pure water).

Or when the supporting mode is impregnation thermal reduction, the method comprises the following steps: dissolving a water-soluble inorganic salt compound containing a non-noble metal cocatalyst in deionized water, fully grinding the mixture with the SiP material, drying the mixture, putting the dried mixture into a tubular furnace, heating the mixture for 1 to 8 hours at 300 to 600 ℃, introducing hydrogen for reduction during the reaction, introducing argon for protection, and introducing H₂The flow rate is 10 to 100sccm, and the Ar gas flow rate is 100 to 500 sccm.

Further, the water-soluble inorganic salt compound containing the non-noble metal promoter is one or a combination of more of a water-soluble inorganic salt compound containing nickel, a water-soluble inorganic salt compound containing cobalt, a water-soluble inorganic salt compound containing copper and a water-soluble inorganic salt compound containing iron.

In another aspect, the present invention provides a use of the SiP material or the SiP material supported by any one of the non-noble metal promoters as a photocatalytic material.

In another aspect, the invention provides an application of the SiP material or the SiP material supported by any one of the non-noble metal promoters in hydrogen production by water decomposition.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, SiP is successfully modified by introducing a modifier through a chemical vapor transport method (CVT method), a P-type semiconductor is changed into an N-type semiconductor, and conduction is carried out by electrons, so that the material is prevented from being corroded by itself under illumination, the activity and stability of the photocatalytic performance of the material are greatly enhanced, and the material shows excellent performance in the field of photocatalysis and is helpful for developing clean energy and protecting the environment.

(2) The photocatalysis performance of the material can be effectively improved by loading the non-noble metal cocatalyst through a simple loading process. The photocatalytic activity of the N-type SiP material loaded with non-noble metal is better than that of the N-type SiP loaded with noble metal.

(3) The invention has the advantages of simple preparation process, cheap raw materials, wide sources and practical application value and potential.

Drawings

Fig. 1 is an XRD pattern of the N-type SiP material in example 1 of the present invention.

Fig. 2 is a mott-schottky plot of the N-type SiP material in example 1 of the present invention.

Fig. 3 is an XRD pattern of the Ni promoter-supported N-type SiP material (the mass of Ni is 30% of the mass of the SiP material) in example 2 of the present invention.

Fig. 4 is a TEM image of an N-type SiP material supporting a Ni promoter (the mass of Ni is 30% of the mass of the SiP material) in example 2 of the present invention.

FIG. 5 is a diagram of photocatalytic hydrogen production activity of N-type SiP material loaded with Ni promoters of different mass in example 3 of the present invention.

Fig. 6 is a graph showing the hydrogen production activity of the non-noble metal nickel (Ni) -supported sample in example 6 of the present invention compared with the hydrogen production activity of the noble metal (Pt) -supported sample in comparative example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.

Example 1 preparation of an N-type SiP material

0.14g of silicon powder, 0.16g of red phosphorus powder, 15mg of iodine simple substance and 3mg of sodium sulfide are respectively weighed in a glove box, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 18cm and the inner diameter of 11mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a double-temperature-zone tube furnace, setting the left temperature zone to be 1100 ℃, setting the right temperature zone to be 1000 ℃, and cooling the furnace body to obtain the N-type SiP material, wherein the reaction time is 72 hours. And finally, cleaning with acetone and ethanol, and drying in vacuum. The XRD pattern of the sample is shown in FIG. 1, which shows that SiP is prepared; the mott-schottky curve of the sample is shown in fig. 2, and the slope of the mott-schottky curve of fig. 2 is positive, which fully indicates that the material is an N-type semiconductor, unlike a P-type semiconductor reported in the literature and patents.

EXAMPLE 2 preparation of non-noble Metal Nickel (Ni) Co-catalyst Supported N-type SiP Material

50mg of the N-type SiP photocatalytic material in the embodiment 1 is weighed, and NiCl with corresponding mass is weighed according to the condition that the mass of the non-noble metal cocatalyst is 10%, 20%, 30% and 40% of the mass of the SiP material₂·6H₂And O. Mixing NiCl₂·6H₂Mixing O into deionized water, fully grinding the O and the N-type SiP photocatalytic material, drying, putting the mixture into a tubular furnace, heating the mixture for 1H at 400 ℃, introducing hydrogen for reduction all the time during the reaction, introducing argon for protection, and introducing H₂The flow rate was 10sccm and the flow rate of Ar was 100sccm, thereby obtaining an N-type SiP material loaded with a Ni promoter by Immersion thermal reduction (Immersion thermal reduction).

When the mass of the non-noble metal promoter Ni is 30% of that of the SiP material, the XRD pattern of the prepared N-type SiP material loaded with the Ni promoter is shown in figure 3, the peak of the simple substance of Ni can be obviously seen, which indicates that Ni is successfully loaded on the N-type SiP material, the TEM is shown in figure 4, and the TEM result of figure 4 also indicates that Ni is loaded on the SiP sheet material.

Example 3 determination of photocatalytic hydrogen production activity of non-noble metal nickel (Ni) cocatalyst-loaded N-type SiP material

The Ni promoter N-type SiP materials of example 2, which supported 10%, 20%, 30%, and 40% by mass of the SiP material, were measured as test samples. 25mg of the sample is added into a reactor for photocatalytic hydrogen production, and 200mL of deionized water and 50mL of ethanol are added. And (3) adding all reactants, performing ultrasonic treatment for 10min, then installing the reactor on a photocatalytic device, vacuumizing to a certain vacuum degree, then, firstly, obtaining a blank sample, and observing whether oxygen in the device is completely pumped out and whether the tightness of the device is good. And after the device is determined to be not leaked, starting a 300W xenon lamp, adding an L42 filter on a lamp source, and measuring the hydrogen production rate under visible light.

The hydrogen production activity is shown in fig. 5, the photocatalytic hydrogen production amount of 4 samples linearly increases along with the time, wherein the activity of the prepared N-type SiP material loaded with the Ni promoter is the highest when the mass of the non-noble metal promoter Ni is 30% of that of the SiP material.

Example 4 preparation of N-type SiP Material

0.14g of silicon powder, 0.16g of red phosphorus powder and 30mg of stannous iodide (SnI) are respectively weighed in a glove box₂) 10mg of tin diselenide (SnSe)₂) The raw materials are fully and uniformly ground, added into a quartz tube with the length of 12cm and the inner diameter of 18mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a box-type furnace, setting the temperature to be 1000 ℃, reacting for 120h, and cooling the furnace body to obtain the N-type SiP material. And finally, cleaning with acetone and ethanol, and drying in vacuum.

EXAMPLE 5 preparation of non-noble Metal Nickel (Ni) Co-catalyst Supported N-type SiP Material

50mg of the N-type SiP photocatalytic material obtained in example 4 was weighed, and Ni (NO) was weighed in an amount corresponding to 3% of the mass of the non-noble metal promoter (Ni)₃)₂·6H₂And O. Dispersing the N-type SiP photocatalytic material in absolute ethyl alcohol water solution, and then adding weighed Ni (NO)₃)₂·6H₂And performing light deposition on O, wherein a 300W xenon lamp is selected as a light source for light deposition, and the light irradiation time is 0.5h in an oxygen-free environment to obtain the N-type SiP material loaded with the Ni cocatalyst through light deposition.

Example 6 determination of photocatalytic hydrogen production activity of non-noble metal nickel (Ni) cocatalyst-loaded N-type SiP material

The measurements were carried out with the Ni promoter N-type SiP material of example 5 loaded with 3% of the mass of the SiP material as a test sample. 25mg of the sample is added into a reactor for photocatalytic hydrogen production, and 200mL of deionized water and 50mL of ethanol are added. And (3) adding all reactants, performing ultrasonic treatment for 10min, then installing the reactor on a photocatalytic device, vacuumizing to a certain vacuum degree, then, firstly, obtaining a blank sample, and observing whether oxygen in the device is completely pumped out and whether the tightness of the device is good. And after the device is determined to be not leaked, starting a 300W xenon lamp, adding an L42 filter on a lamp source, and measuring the hydrogen production rate under visible light.

Example 7 preparation of N-type SiP Material

0.14g of silicon powder, 0.16g of red phosphorus powder and 50mg of tellurium iodide (TeI) are respectively weighed in a glove box₄) 20mg of molybdenum telluride (MoTe)₂) The raw materials are fully and uniformly ground, added into a quartz tube with the length of 16cm and the inner diameter of 18mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a single crystal furnace, setting the temperature to be 1200 ℃, reacting for 1h, and cooling the furnace body to obtain the N-type SiP material. And finally, cleaning with acetone and ethanol, and drying in vacuum.

EXAMPLE 8 preparation of non-noble Metal cobalt (Co) Co promoter Supported N-type SiP Material

50mg of the N-type SiP photocatalytic material obtained in example 7 was weighed, and Co (NO) was weighed in an amount corresponding to 30% of the mass of the non-noble metal Co-catalyst (Co)₃)₂·6H₂And O. Mixing Co (NO)₃)₂·6H₂Mixing O into deionized water, fully grinding the O and the N-type SiP photocatalytic material, drying, putting the mixture into a tubular furnace, heating the mixture for 1H at 400 ℃, introducing hydrogen for reduction all the time during the reaction, introducing argon for protection, and introducing H₂The flow rate was 10sccm and the flow rate of Ar was 100sccm, thereby obtaining an N-type SiP material loaded with a Co promoter by Immersion thermal reduction (Immersion thermal reduction).

EXAMPLE 9 preparation of non-noble Metal copper (Cu) Co-catalyst Supported N-type SiP Material

50mg of the N-type SiP photocatalytic material obtained in example 7 was weighed, and Cu (NO) was weighed in an amount corresponding to 30% of the mass of the non-noble metal promoter (Cu)₃)₂·6H₂And O. Adding Cu (NO)₃)₂·6H₂Mixing O into deionized water, fully grinding the O and the N-type SiP photocatalytic material, drying, putting the mixture into a tubular furnace, heating the mixture for 1H at 400 ℃, introducing hydrogen for reduction all the time during the reaction, introducing argon for protection, and introducing H₂The flow rate was 10sccm and the flow rate of Ar was 100sccm, thereby obtaining an Immersion thermal reduction (Immersion thermal reduction) Cu-supported N-type SiP material.

EXAMPLE 10 preparation of non-noble Metal copper (Fe) Co-catalyst Supported N-type SiP Material

50mg of the N-type SiP photocatalytic material obtained in example 7 was weighed, and Fe (NO) was weighed in an amount corresponding to 30% of the mass of the non-noble metal promoter (Fe)₃)₂·6H₂And O. Mixing Fe (NO)₃)₂·6H₂Mixing O into deionized water, fully grinding the O and the N-type SiP photocatalytic material, drying, putting the mixture into a tubular furnace, heating the mixture for 1H at 400 ℃, introducing hydrogen for reduction all the time during the reaction, introducing argon for protection, and introducing H₂The flow rate was 10sccm and the flow rate of Ar was 100sccm, thereby obtaining an N-type SiP material supporting an Fe promoter by Immersion thermal reduction (Immersion thermal reduction).

Experiments show that the N-type SiP loaded by Co, Fe or Cu has hydrogen production activity similar to that of the N-type SiP loaded by Ni, and Ni > Co > Fe > Cu.

Comparative example 1 preparation of noble metal platinum (Pt) promoter-supported N-type SiP material and measurement of photocatalytic hydrogen production activity 50mg of the N-type SiP photocatalytic material of example 4 was weighed and subjected to the photo-deposition of noble metal platinum (Pt) in the same manner as in example 5, and since the relative atomic masses of Pt and Ni were different, the molar mass ratio of Pt and Ni supported (the ratio of the number of moles of promoter to the mass of the N-type SiP photocatalytic material) was the same, the supported mass of Pt was 10% of the mass of the SiP material, and the photo-deposited platinum (Pt) -supported SiP material was obtained.

25mg of the sample is added into a reactor for photocatalytic hydrogen production, and 200mL of deionized water and 50mL of ethanol are added. And (3) adding all reactants, performing ultrasonic treatment for 10min, then installing the reactor on a photocatalytic device, vacuumizing to a certain vacuum degree, then, firstly, obtaining a blank sample, and observing whether oxygen in the device is completely pumped out and whether the tightness of the device is good. And after the device is determined to be not leaked, starting a 300W xenon lamp, adding an L42 filter on a lamp source, and measuring the hydrogen production rate under visible light.

The comparison of hydrogen production activities of example 6 and comparative example 1 is shown in fig. 6, and it is apparent from the graph that the hydrogen production activity of the sample supporting non-noble metal nickel (Ni) is significantly higher than that of the sample supporting noble metal platinum (Pt).

The above description is only a specific embodiment of the present invention, and not all embodiments, and any equivalent modifications of the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.