CN109943839A - A kind of preparation method based on copper-based growth cuprous sulfocyanide - Google Patents
A kind of preparation method based on copper-based growth cuprous sulfocyanide Download PDFInfo
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- CN109943839A CN109943839A CN201910167644.2A CN201910167644A CN109943839A CN 109943839 A CN109943839 A CN 109943839A CN 201910167644 A CN201910167644 A CN 201910167644A CN 109943839 A CN109943839 A CN 109943839A
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- copper
- cuprous
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- alkaline solution
- sulfocyanide
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- 239000010949 copper Substances 0.000 title claims abstract description 135
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 111
- BZWKPZBXAMTXNQ-UHFFFAOYSA-N sulfurocyanidic acid Chemical compound OS(=O)(=O)C#N BZWKPZBXAMTXNQ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 150000003567 thiocyanates Chemical class 0.000 claims abstract description 26
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 18
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 239000012670 alkaline solution Substances 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 14
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical group O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 13
- 229910017669 NH4S2O8 Inorganic materials 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 238000005242 forging Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Chemically Coating (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention proposes a kind of preparation method based on copper-based growth cuprous sulfocyanide, the good cuprous oxide of the available structure and morphology of preparation method of the invention, cuprous oxide obtained can react at normal temperature with thiocyanate salt solution generates cuprous sulfocyanide, its preparation process is simple, excellent product performance, reaction condition is simple, it is swift in response, and the cuprous sulfocyanide structural integrity as made from such method, pattern is good, it is evenly distributed, purity is high and be tightly combined with template, it is not easily to fall off, different-shape structure cuprous sulfocyanide is prepared for research to be also of great significance.And the low in raw material price that method of the invention uses, this makes it have the premise calls of industrialized production.Its preparation process is simple, produces the features such as cuprous thiocyanate membrane prepared also has high-purity, is evenly distributed.
Description
Technical field
The present invention relates to the preparation technical fields of cuprous sulfocyanide, more particularly to one kind to be based on copper-based growth cuprous sulfocyanide
Preparation method.
Background technique
Semiconductor material is as a kind of popular new material, in solar battery, photocatalysis, electronic device, sensor side
Face is all widely used.CuSCN is as a kind of typical p-type semiconductor material, electrical conductance with higher, in semiconductor
It is widely used in terms of device, CuSCN is mainly used as solid electrolyte application in solar cells at present, but it is used as one kind
Wide bandgap semiconductor, research on optical properties are also less.
There are mainly two types of crystal structure, α-CuSCN and β-CuSCN by solid CuSCN.The basic structure of CuSCN is by matching
The three-dimensional network quasi polymer stacked structure of position chemical bond, ionic bond and covalent bond composition, it is excellent that this structure has CuSCN
Photoelectric properties.In order to characterize CuSCN optical property, it is usually prepared into film, it is measured and transmits, absorbs, diffuses
Spectrum, but due to the gap of preparation process and its nanometer size effect, the forbidden bandwidth measured and block-like CuSCN have difference
It is different.From the point of view of the CuSCN film prepared at present, for transmitance in 50%-70%, there is diffusion and reflection mainly due to it in this.
It is at present the CuSCN for preparing high-volume, the uniform high-purity of particle for the application foundation of CuSCN, therefore right
The research of CuSCN preparation process is of great significance.The existing method for preparing CuSCN is divided into two classes: chemical method and electrochemistry
Method.Wherein chemical method mostly uses greatly Cu+With the SCN of solution+Complexation reaction generates CuSCN, and equipment is simple.Electrochemical process mainly may be used
To be divided into anodizing and cathode deposition method.
Summary of the invention
It is an object of the invention to propose a kind of simple process, raw material is common, the cuprous sulfocyanide prepared and copper-based company
It connects closely, structure and morphology is complete, is evenly distributed, the preparation method based on copper-based growth cuprous sulfocyanide of purity is high.
In order to achieve the above objectives, the present invention proposes a kind of based on the copper-based preparation method for growing cuprous sulfocyanide, including with
Lower step:
Step 1: configuration alkaline solution；
Step 2: metallic copper being placed in the alkaline solution, copper-based product is obtained；
Step 3: the copper-based product being placed under nitrogen and is calcined, cuprous oxide is obtained；
Step 4: the cuprous oxide being placed in thiocyanate salt solution and obtains cuprous sulfocyanide.
Preferably, in step 1, the alkaline solution according to weight percent 1%-6% NaOH, 1%-9%
NH4S2O8And 98%-85%H2O mixing match forms.
Preferably, in step 2, the copper-based product is placed in the alkaline solution and impregnates 1-3h.
Preferably, in step 3, the copper-based product is placed in Calcination: Calcination 2-5h under nitrogen, forging temperature 250
℃-600℃。
Preferably, in step 4, the thiocyanate salt solution concentration is 0.001-0.01mol/L.
Preferably, the copper-based product is Kocide SD or copper oxide.
Compared with prior art, of the invention to be advantageous in that: the available structure and morphology of preparation method of the invention
Good cuprous oxide, cuprous oxide obtained can react at normal temperature with thiocyanate salt solution generates cuprous sulfocyanide,
Preparation process is simple, and excellent product performance, reaction condition is simple, is swift in response, and the thiocyanic acid as made from such method
Cuprous structural integrity, pattern is good, be evenly distributed, purity is high and is tightly combined with template, is not easily to fall off, not for research preparation
It is also of great significance with appearance structure cuprous sulfocyanide.
And the low in raw material price that method of the invention uses, this makes it have the premise calls of industrialized production.Its
Preparation process is simple, produces the features such as cuprous thiocyanate membrane prepared also has high-purity, is evenly distributed.
Detailed description of the invention
Fig. 1 is the SEM figure that Kocide SD is generated after copper sheet corrodes in alkaline solution；
Fig. 2 is the calcined SEM figure for generating CuO；
Fig. 3 is that copper sheet reacts the SEM figure for generating cuprous sulfocyanide in thiocyanate salt solution.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be made below into
Illustrate to one step.
The present invention proposes a kind of preparation method based on copper-based growth cuprous sulfocyanide, comprising the following steps:
Step 1: configuration alkaline solution；
Step 2: metallic copper being placed in the alkaline solution, copper-based product is obtained；
Step 3: the copper-based product being placed under nitrogen and is calcined, cuprous oxide is obtained；
Step 4: the cuprous oxide being placed in thiocyanate salt solution and obtains cuprous sulfocyanide.
In the present embodiment, in step 1, the alkaline solution according to weight percent 1%-6% NaOH, 1%-
9% NH4S2O8And 98%-85%H2O mixing match forms.
In the present embodiment, in step 2, the copper-based product is placed in immersion 1-3 h in the alkaline solution.
In the present embodiment, in step 3, the copper-based product is placed in Calcination: Calcination 2-5h under nitrogen, forging temperature
It is 250 DEG C -600 DEG C.
In the present embodiment, in step 4, the thiocyanate salt solution concentration is 0.001-0.01mol/L.
In the present embodiment, the copper-based product is Kocide SD or copper oxide.
The present invention will be made by specific embodiment and be further described below:
Embodiment 1
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 1%
NH4S2O84%
H2O 95%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2It is thin
Film.
3. Cu (OH) will be grown2Copper sheet be put under 300 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper.
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 1h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 2h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.001mol/L.
Embodiment 2
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 3%
NH4S2O84%
H2O 93%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2。
3. Cu (OH) will be grown2Copper sheet be put under 300 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper.
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 2h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 2h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.001mol/L.
Embodiment 3
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 6%
NH4S2O84%
H2O 91%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2。
3. Cu (OH) will be grown2Copper sheet be put under 300 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 3h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 5h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.001mol/L.
Embodiment 4
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 6%
NH4S2O89%
H2O 85%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2。
3. Cu (OH) will be grown2Copper sheet be put under 300 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper.
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 3h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 5h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.001mol/L.
Embodiment 5
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 3%
NH4S2O81%
H2O 96%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2。
3. Cu (OH) will be grown2Copper sheet be put under 500 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper.
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 2h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 2h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.005mol/L.
Embodiment 6
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 1%
NH4S2O81%
H2O 98%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1, alkaline solution is prepared with sodium hydroxide and ammonium chloride in proportion.
2, copper sheet is put into prepared alkaline solution and is soaked for a period of time, Cu (OH) is grown on copper sheet2。
3, Cu (OH) will be grown2Copper sheet be put under 500 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper.
4, the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 2h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 2h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.01mol/L.
Embodiment 7
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 1%
NH4S2O81%
H2O 98%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2。
3. Cu (OH) will be grown2Copper sheet be put under 500 DEG C of nitrogen and calcine, it is sub- that Kocide SD is converted into red oxidation
Copper.
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 2h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 2h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.005mol/L.
Embodiment 8
One kind being based on copper-based growth cuprous sulfocyanide, and alkaline solution is prepared by weight percentage by following raw material:
NaOH 1%
NH4S2O81%
H2O 98%
It is a kind of that based on the copper-based preparation method for growing cuprous sulfocyanide, steps are as follows:
1. preparing alkaline solution with sodium hydroxide and ammonium chloride in proportion.
It is soaked for a period of time 2. copper sheet is put into prepared alkaline solution, Cu (OH) is grown on copper sheet2。
It is calcined 3. the copper sheet that grown Cu (OH) 2 is put under 500 DEG C of nitrogen, it is sub- that Kocide SD is converted into red oxidation
Copper.
4. the copper sheet that grown intermediate product cuprous oxide is put into thiocyanate salt solution, reacting can be with after a period of time
Be evenly distributed, purity is high and with being tightly combined of template, CuSCN film not easily to fall off.
In above-mentioned steps, the alkaline solution is that NaOH prepares solution.
In above-mentioned steps, it is 2h that the copper sheet, which is put into soaking time in prepared alkaline solution,.
It is described to grown Cu (OH) in above-mentioned steps2Copper sheet to be put under nitrogen calcination time be 2h.
In above-mentioned steps, the thiocyanate salt solution concentration is 0.001mol/L.
In conclusion the present invention provides a kind of methods for simply and effectively preparing sulphur hydracid copper, with copper foil or copper wire
As base material, the method for growth in situ sulphur hydracid copper, solve the problems, such as that sulphur hydracid Copper thin film falls off from substrate, and
This method is environmentally protective, and has universality.
In the above-described embodiments, Fig. 1 is the SEM figure that Kocide SD is generated after copper sheet corrodes in alkaline solution；
Fig. 2 is the calcined SEM figure for generating CuO；
Fig. 3 is that copper sheet reacts the SEM figure for generating cuprous sulfocyanide in thiocyanate salt solution.
The above is only a preferred embodiment of the present invention, does not play the role of any restrictions to the present invention.Belonging to any
Those skilled in the art, in the range of not departing from technical solution of the present invention, to the invention discloses technical solution and
Technology contents make the variation such as any type of equivalent replacement or modification, belong to the content without departing from technical solution of the present invention, still
Within belonging to the scope of protection of the present invention.
Claims (6)
1. a kind of preparation method based on copper-based growth cuprous sulfocyanide, which comprises the following steps:
Step 1: configuration alkaline solution；
Step 2: metallic copper being placed in the alkaline solution, copper-based product is obtained；
Step 3: the copper-based product being placed under nitrogen and is calcined, cuprous oxide is obtained；
Step 4: the cuprous oxide being placed in thiocyanate salt solution and obtains cuprous sulfocyanide.
2. the preparation method according to claim 1 based on copper-based growth cuprous sulfocyanide, which is characterized in that in step 1
In, the alkaline solution according to NaOH, 1%-9% of weight percent 1%-6% NH4S2O8And 98%-85%H2O mixing
It matches.
3. the preparation method according to claim 1 based on copper-based growth cuprous sulfocyanide, which is characterized in that in step 2
In, the copper-based product is placed in the alkaline solution and impregnates 1-3h.
4. the preparation method according to claim 1 based on copper-based growth cuprous sulfocyanide, which is characterized in that in step 3
In, the copper-based product is placed in Calcination: Calcination 2-5h under nitrogen, forging temperature is 250 DEG C -600 DEG C.
5. the preparation method according to claim 1 based on copper-based growth cuprous sulfocyanide, which is characterized in that in step 4
In, the thiocyanate salt solution concentration is 0.001-0.01mol/L.
6. the preparation method according to claim 1 based on copper-based growth cuprous sulfocyanide, which is characterized in that described copper-based
Product is Kocide SD or copper oxide.
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Cited By (1)
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Application publication date: 20190628 |