CN102306665A - Semiconductor film raw material slurry prepared by natural pyrite - Google Patents
Semiconductor film raw material slurry prepared by natural pyrite Download PDFInfo
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Abstract
The invention discloses semiconductor film raw material slurry prepared by natural pyrite. The raw material slurry is prepared by the following steps of: 1, mixing natural pyrite micro powder which has appropriate iron content, sulfur content and particle sizes with an organic selection agent, fully stirring, heating, and thus obtaining a solid-liquid mixture; and 2, removing easily-settled impurities from the solid-liquid mixture by a centrifugal or filtering process, and thus obtaining the semiconductor film raw material iron sulfide slurry, wherein the organic selection agent is a mixture of a particle activating agent and an organic solvent, and the particle activating agent is one or a mixture of two of a yellow catching agent, a black catching agent, alicyclic amine and benzenesulfonic acid. At least processes for decomposing a raw material of a semiconductor film from minerals and purifying the raw material in the prior art are eliminated, and an iron sulfide film and an iron sulfide film can be prepared by a relatively simple process method. The slurry has the advantages of reducing the total preparation cost of a semiconductor film. In addition, the prepared iron sulfide slurry has the advantages of simple process and convenience of operation.
Description
Technical field
The present invention relates to prepare the raw material of semiconductive thin film.
Background technology
Semiconductor iron compound film receives extensive attention in recent years, like semiconductor sulfuration iron FeS
X, semiconductor oxide iron FeO
XDeng.Different with conventional compounds, they belong to one type of special nonstoichiometric compound on chemical constitution, and promptly X can not be the ratio of simple chemical valence, even can be to be irrational number.And through changing X, property of thin film can be realized from the insulator to the semiconductor variation of conductor again.The characteristic of semiconductor that semiconductive thin film possesses can make it as the material in photovoltaic conversion and the solar cell; When X was in some special value scope, this based semiconductor film also had other characteristics such as photocatalysis.People press for the method that a kind of low energy consumption, low material consumption, structure can this based semiconductor films of freely regulated preparation.And the preparation method of existing semiconductive thin film; Comprise chemical vapour deposition technique, sol-gal process, sputtering method, pulsed laser deposition method etc.; All be to be that raw material (is also claimed " precursor ") from highly purified metal, nonmetal or their compound; Again through the chemical reaction in the above-mentioned the whole bag of tricks, on base material, generate semiconductive thin film.With semiconductor sulfuration iron thin film is example; Prior art all is from the iron sulfide composition chemical breakdown the raw material ore deposits such as troilite; And transform respectively, purify; Be prepared into highly purified Fe compound and sulphur compound, let high-purity Fe compound and high-purity sulphur compound react then, directly prepare iron sulfide film or form the former slurry body of iron sulfide film forming more earlier.Around a circle, chemical composition remains initial iron sulfide, and the Fe/S ratio has only nuance in semiconductive thin film and the raw material ore deposit.But wasted mass energy, and raw material and the time such as acid of purification process institute adapted, alkali, salt, reagent.In brief, the total cost of existing preparation semiconductor film film method is higher, has significant wastage.If can be directly prepare the former slurry body of highly purified iron sulfide, on using, obviously have huge advantage from the raw material ore deposit through conversion process non-chemically.
Summary of the invention
The objective of the invention is, a kind of former slurry body of semiconductive thin film for preparing with the natural sulphur iron ore cheaply is provided.
For realizing said goal of the invention, so former slurry body of semiconductive thin film with the preparation of natural sulphur iron ore is provided, it is characterized in that the former slurry body of this semiconductive thin film is prepared from as follows:
1. mass content＞32%, mass content＞20% of sulphur, its particle diameter with iron is the natural sulphur iron ore micro mist of 10nm～10 μ m, mixes also fully stirring with organic selected dose, is heated to 20～150 ℃ simultaneously, gets a solidliquid mixture; Wherein, natural sulphur iron ore micro mist: organic selected dose=0.05～100.0g/L;
Said organic selected dose is the mixture of particle activator and organic solvent, wherein, and particle activator: organic solvent=0.5～20.0g/L;
Said particle activator in this organic selected dose is the mixture of a kind of in xanthate class particle activator, black powder class particle activator, fatty amine particle activator and the benzene sulfonic acid class particle activator or two kinds, and the said organic solvent in this organic selected dose is that carbon number is that 5～16 hydrocarbon, carbon number are that a halogenated hydrocarbons of 1～16 and polyhalohydrocarbon, alkyl carbon atoms number are that 0～4 benzene and a halo or phenyl polyhalide, carbon number are that 2～8 nitrile, carbon number are that 1～8 alcohol, carbon number are that 3～8 ketone or carbon number are 2～10 ether;
2. with step 1. the gained solidliquid mixture remove free settling property impurity through centrifugal or filtering technique, promptly get iron sulfide slurry into the semiconductive thin film raw material.
From scheme, find out; The present invention is as the iron sulfide slurry of semiconductive thin film raw material; At the semi-finished product of the semiconductive thin film raw material that in fact is equivalent to prior art, saved at least prior art must be earlier from mineral, decompose the technical process of coming out as the metal of the pure finished product of reagent, nonmetal or their compound.Therefore; Compared with prior art; The present invention has not only saved the energy because of the technical process of having saved the required a series of complicacies of " decomposition ", especially " purification ", because of same reason has also been saved raw material and great amount of time such as a large amount of adapted acid, alkali, salt, reagent.Thereby can obtain the beneficial effect of the total cost that reduces the preparation semiconductive thin film.Checking shows, with iron sulfide slurry of the present invention, can prepare iron sulfide film and sull, and obtains the lower beneficial effect of total cost.It can also be seen that from scheme the particle size range broad of the used natural sulphur iron ore of the present invention micro mist is explained and realized that technological requirement of the present invention is not high; If because of certain needs strictly to have controlled the particle diameter of natural sulphur iron ore micro mist especially; So; Only use this method of the present invention; Just can prepare equally also and can finally prepare other glue, liquid or the disperse system of semiconductive thin film, for example, in the application of catalyst, semiconductor, photovoltaic cell, lithium ion battery etc.; Concrete specification requirement to semiconductive thin film is just the same not to the utmost; In the particle size range of natural sulphur iron ore micro mist of the present invention, require to select suitable particle diameter according to different technologies, just can prepare iron sulfide colloidal sol, iron sulfide suspension, iron sulfide emulsion, iron sulfide colloid, the thick disperse system of iron sulfide or the iron sulfide colloidal dispersion of satisfying the demand.Also, when coming, equally also possesses the beneficial effect that reduces total cost with the prepared by other semiconductive thin film promptly with the present invention's iron sulfide slurry.In addition, prepare iron sulfide slurry of the present invention itself, also have simple, the easy to operate advantage of technology.
Below in conjunction with embodiment the present invention is further described.
Embodiment
With the former slurry body of semiconductive thin film of natural sulphur iron ore preparation, the former slurry body of this semiconductive thin film is prepared from as follows:
1. mass content＞32%, mass content＞20% of sulphur, its particle diameter with iron is the natural sulphur iron ore micro mist of 10nm～10 μ m, mixes also fully stirring with organic selected dose, is heated to 20～150 ℃ simultaneously, gets a solidliquid mixture; Wherein, natural sulphur iron ore micro mist: organic selected dose=0.05～100.0g/L;
Said organic selected dose is the mixture of particle activator and organic solvent, wherein, and particle activator: organic solvent=0.5～20.0g/L;
Said particle activator in this organic selected dose is the mixture of a kind of in xanthate class particle activator, black powder class particle activator, fatty amine particle activator and the benzene sulfonic acid class particle activator or two kinds, and the said organic solvent in this organic selected dose is that carbon number is that 5～16 hydrocarbon, carbon number are that a halogenated hydrocarbons of 1～16 and polyhalohydrocarbon, alkyl carbon atoms number are that 0～4 benzene and a halo or phenyl polyhalide, carbon number are that 2～8 nitrile, carbon number are that 1～8 alcohol, carbon number are that 3～8 ketone or carbon number are 2～10 ether;
2. with step 1. the gained solidliquid mixture remove free settling property impurity through centrifugal or filtering technique, promptly get iron sulfide slurry into the semiconductive thin film raw material.
It will be apparent to those skilled in the art that said " free settling property impurity " comprises the solid impurity of unvulcanised iron such as kaolin, silicon dioxide, and granular size does not meet the iron sulfide of application requirements.Those skilled in the art are clear equally, and the removal of impurities of commute settleability impurity comprises conventional filtration technologies such as centrifugal, press filtration, vacuum filtration, sand filtration, membrane filtration.Conventional according to those skilled in the art, the filtration sieve part is close more or centrifugal rotational speed is high more, and gained iron sulfide distribution of particles is more little, and the iron sulfide yield is low more in the slurry simultaneously.
Disclose so far, to those skilled in the art, can combine the understanding of beneficial effect of the present invention has been realized the present invention.
More particularly, in the 1. said organic selected dose particle activator of step, the general formula of molecular structure of said xanthate class particle activator is:
, wherein to refer to carbon number be 2～24 alkyl to R, M refers to K
+/ Na
+
Said black powder class particle activator be cresols black powder, xylenol black powder, decyl phenol black powder, tert-butyl phenol black powder, oxidation tert-butyl phenol black powder, phenol black powder, two sec-butyl phosphordithiic acid ammoniums, two sec-butyl phosphordithiic acid sodium, diisopropyl disulfide for sodium phosphate, diisopropyl disulfide for potassium phosphate, diisopropyl disulfide for ammonium phosphate, diisoamyl phosphordithiic acid sodium, polyoxy butenol phosphordithiic acid sodium or polyoxy butenol phosphordithiic acid ammonium;
Said fatty amine particle activator is that carbon number is at substituted aliphatic amine between 2～22 or two substituted aliphatic amines and the ammonium salt thereof of carbon number between 2～5;
Said benzene sulfonamide acids particle activator is alkyl benzene sulphonate and the salt thereof of carbon number between 12～18.
Further say in order to obtain better effect, or to also have requirements at the higher level because of purity, particle size distribution to the semiconductive thin film finally prepared.Then said step 2. after, also have the following steps:
3. in the iron sulfide slurry that 2. step obtains, the adding gel breaker also mixes; Wherein, said gel breaker is that ethanol, acetone, volume ratio are that 0.5～3 ethanol and chloroform mixed solvent or volume ratio are 0.5～3 acetone and chloroform mixed solvent; Gel breaker and iron sulfide slurry volume ratio are 1: 1;
4. to step 3. the gained solidliquid mixture centrifugalize, with solid deposition (usually, be 500r/min～5000r/min at centrifuge speed, the time between 0.5～30min, get final product the solid deposition.Conventional according to those skilled in the art, centrifugal rotational speed is high more, and centrifugation time is long more, and gained iron sulfide particle size distribution is narrow more, and the iron sulfide yield is low more in the slurry simultaneously);
5. with step 4. gained solid deposition dissolve in the dispersant, and make it and be uniformly dispersed again (for example), to obtain the iron sulfide slurry of refining purifying through stirring or ultrasonic means is uniformly dispersed it again;
Said dispersant is the mixture of particle activator and organic solvent; Wherein, The particle activator: organic solvent=0～10.0g/L (those skilled in the art know that; At the particle activator: under the situation of organic solvent=0 g/L, be meant that in fact gained solid deposition only dissolves in the organic solvent that does not have the particle activator);
Said particle activator in this dispersant is the mixture of a kind of in xanthate class particle activator, black powder class particle activator, fatty amine particle activator and the benzene sulfonic acid class particle activator or two kinds, and the said organic solvent in this dispersant is that carbon number is that 6～16 hydrocarbon, carbon number are that a halogenated hydrocarbons of 1～16 and polyhalohydrocarbon, alkyl carbon atoms number are that 0～6 benzene and a halo or phenyl polyhalide, carbon number are that 2～7 nitrile, carbon number are that 1～6 alcohol, carbon number are that 3～9 ketone, carbon number are 3～10 ether.
3.～5. above-mentioned steps is a kind of processing step of heavy refining purifying, and these several steps also can repeatedly repeat.See that from technique effect the purity of the many more iron sulfide of number of repetition is high more, particle size distribution is narrow more.Number of repetition is selected according to specific requirement.
More particularly, 5. in the particle activator of said dispersant, said xanthate class particle activator is to contain alkyl xanthic acid and the salt thereof of alkyl carbon atoms number between 2～26 in step;
Said black powder class particle activator be cresols black powder, xylenol black powder, decyl phenol black powder, tert-butyl phenol black powder, oxidation tert-butyl phenol black powder, phenol black powder, two sec-butyl phosphordithiic acid ammoniums, two sec-butyl phosphordithiic acid sodium, diisopropyl disulfide for sodium phosphate, diisopropyl disulfide for potassium phosphate, diisopropyl disulfide for ammonium phosphate, diisoamyl phosphordithiic acid sodium, polyoxy butenol phosphordithiic acid sodium or polyoxy butenol phosphordithiic acid ammonium
Said fatty amine particle activator is that carbon number is at substituted aliphatic amine between 2～24 or two substituted aliphatic amines and the ammonium salt thereof of carbon number between 2～5;
Said benzene sulfonamide acids particle activator refers to that carbon number is alkyl benzene sulphonate and the salt thereof between 12～24.
The present invention has passed through verification experimental verification.Respectively according to the step of this embodiment 1.～2. with various different components and the proportioning of step in 1.～5.; After making the iron sulfide slurry of the iron sulfide slurry of different checking examples and heavily refining purifying; Be raw material with them again, make iron sulfide film and sull respectively.The step for preparing these two kinds of semiconductive thin films is following:
(1) deposition system film: said iron sulfide slurry is deposited on the base material, dry then to remove the organic solvent in the iron sulfide slurry.Wherein, used base material has metal, graphite, conductivity ceramics, conductive plastics or conductive oxide, perhaps Si, CdS, GaAs, CdTe or TiO
2, perhaps glass, SiO
2, pottery or plastics; The method of said deposition is coated with for dripping, spin coating, spraying, dipping or blade coating;
(2) heating reprocessing, optimization: the base material of the iron sulfide slurry that will deposit dry, or place sulfurous gas to heat, with the preparation iron sulfide film; Or directly place the air heat treated, to obtain transforming the rear oxidation iron thin film.Wherein, heating-up temperature is 0.1h～20h heating time between equal 100 ℃～700 ℃.
In preparation during iron sulfide film, the quality percentage composition of element sulphur is greater than 0.2% (this content in 0.0～1.0cm more than the film surface with the peak of interior real gas composition in the heating last handling process) in the used sulfurous gas.The iron sulfide film S that obtains at last and the ratio of Fe atomicity are between 0.8～6.0.
When compliance test result, the gained film is tested, so that being described, it possesses photoelectric characteristic, prove that the film that obtains belongs to semiconductive thin film, be to detect through CJ1-WSP-1 semiconductor property tester, and definite its semiconductor film film type.The gained film is tested; With proof gained film is the S/Fe ratio analysis of iron sulfide film; Or proof gained film be the O/Fe of sull than analyzing, be according to national standard " iron ore chemical analysis method barium sulfate gravimetric detemination sulfur content " (GB6730.16-1986), " iron ore chemical analysis method titanium trichloride-potassium bichromate titrimetric method is measured full iron amount " (GB6730.5-1986) with " in the metal dust can by the hydrogen-reducible oxygen Determination on content " (GB4164-84) analytical method of defined carry out.
Simultaneously, verify for the photocatalysis characteristic of the sull that makes.During checking, be simulated wastewater (dye solution of 20mg/L), utilize means analysis such as infrared, ultraviolet to verify the catalytic degradation effect of nano oxidized iron thin film waste water with the aqueous solution of reactive dye.
The checking result sees following each table.
For through the checking carried out of preparation iron sulfide film, in table ten, " organic selected agent concentration " represented particle activator quality and the ratio of organic solvent volume in its organic selected dose to table one at table one to table ten; " step is solid-to-liquid ratio 1. " expression natural sulphur iron ore micro mist and organic selected dose ratio; " dispersant concentration " represented particle activator quality and the ratio of organic solvent volume in its dispersant; Two " S/Fe than " is the ratio of S and the atomicity of Fe.
Table one
Table two
Table three
Table four
Table five
Table six
Table seven
Table eight
Table nine
Table ten
Table ten one is to table two ten checking for carrying out through the preparation sull, and 11 to table two ten, " organic selected agent concentration " represented particle activator quality and the ratio of organic solvent volume in its organic selected dose; " step (1) solid-to-liquid ratio " expression natural sulphur iron ore micro mist and organic selected dose ratio; " dispersant concentration " represented particle activator quality and the ratio of organic solvent volume in its dispersant; " S/Fe than " is S and the ratio of the atomicity of Fe; " O/Fe than " is O and the ratio of the atomicity of Fe.
Table ten one
Table ten two
Table ten three
Table ten four
Table ten five
Table ten six
Table ten seven
Table ten eight
Table ten nine
Table two ten
Visible from the foregoing description; The former slurry body of iron sulfide film is through refining purification step and comparing without refining purifying; Different at the S/Fe of the iron sulfide film that makes ratio, film thickness etc., final S/Fe at the heat treatment rear film compares, semiconductor type is also different.And behind the refining purification step of former slurry body process, film performance can obtain bigger change (the S/Fe ratio can be regulated and control in 1 ~ 6 scope) during its heat treatment, finally makes various suitable different functionalities films.
Claims (4)
1. with the former slurry body of semiconductive thin film of natural sulphur iron ore preparation, it is characterized in that the former slurry body of this semiconductive thin film is prepared from as follows:
1. mass content＞32%, mass content＞20% of sulphur, its particle diameter with iron is the natural sulphur iron ore micro mist of 10nm～10 μ m, mixes also fully stirring with organic selected dose, is heated to 20～150 ℃ simultaneously, gets a solidliquid mixture; Wherein, natural sulphur iron ore micro mist: organic selected dose=0.05～100.0g/L;
Said organic selected dose is the mixture of particle activator and organic solvent, wherein, and particle activator: organic solvent=0.5～20.0g/L;
Said particle activator in this organic selected dose is the mixture of a kind of in xanthate class particle activator, black powder class particle activator, fatty amine particle activator and the benzene sulfonic acid class particle activator or two kinds, and the said organic solvent in this organic selected dose is that carbon number is that 5～16 hydrocarbon, carbon number are that a halogenated hydrocarbons of 1～16 and polyhalohydrocarbon, alkyl carbon atoms number are that 0～4 benzene and a halo or phenyl polyhalide, carbon number are that 2～8 nitrile, carbon number are that 1～8 alcohol, carbon number are that 3～8 ketone or carbon number are 2～10 ether;
2. with step 1. the gained solidliquid mixture remove free settling property impurity through centrifugal or filtering technique, promptly get iron sulfide slurry into the semiconductive thin film raw material.
2. according to the said former slurry body of semiconductive thin film of claim 1, it is characterized in that in the 1. said organic selected dose particle activator of step, the general formula of molecular structure of said xanthate class particle activator is with the preparation of natural sulphur iron ore:
, wherein to refer to carbon number be 2～24 alkyl to R, M refers to K
+/ Na
+
Said black powder class particle activator be cresols black powder, xylenol black powder, decyl phenol black powder, tert-butyl phenol black powder, oxidation tert-butyl phenol black powder, phenol black powder, two sec-butyl phosphordithiic acid ammoniums, two sec-butyl phosphordithiic acid sodium, diisopropyl disulfide for sodium phosphate, diisopropyl disulfide for potassium phosphate, diisopropyl disulfide for ammonium phosphate, diisoamyl phosphordithiic acid sodium, polyoxy butenol phosphordithiic acid sodium or polyoxy butenol phosphordithiic acid ammonium;
Said fatty amine particle activator is that carbon number is at substituted aliphatic amine between 2～22 or two substituted aliphatic amines and the ammonium salt thereof of carbon number between 2～5;
Said benzene sulfonamide acids particle activator is alkyl benzene sulphonate and the salt thereof of carbon number between 12～18.
3. according to claim 1 or the 2 said former slurry body of semiconductive thin film, it is characterized in that with natural sulphur iron ore preparation, said step 2. after, also have the following steps:
3. in the iron sulfide slurry that 2. step obtains, the adding gel breaker also mixes; Wherein, said gel breaker is that ethanol, acetone, volume ratio are that 0.5～3 ethanol and chloroform mixed solvent or volume ratio are 0.5～3 acetone and chloroform mixed solvent; Gel breaker and iron sulfide slurry volume ratio are 1: 1;
4. to step 3. the gained solidliquid mixture centrifugalize, with solid deposition;
5. with step 4. gained solid deposition dissolve in the dispersant, and it is uniformly dispersed again, to obtain the iron sulfide slurry of refining purifying;
Said dispersant is the mixture of particle activator and organic solvent, wherein, and particle activator: organic solvent=0～10.0g/L;
Said particle activator in this dispersant is the mixture of a kind of in xanthate class particle activator, black powder class particle activator, fatty amine particle activator and the benzene sulfonic acid class particle activator or two kinds, and the said organic solvent in this dispersant is that carbon number is that 6～16 hydrocarbon, carbon number are that a halogenated hydrocarbons of 1～16 and polyhalohydrocarbon, alkyl carbon atoms number are that 0～6 benzene and a halo or phenyl polyhalide, carbon number are that 2～7 nitrile, carbon number are that 1～6 alcohol, carbon number are that 3～9 ketone, carbon number are 3～10 ether.
4. according to the said former slurry body of semiconductive thin film of claim 3 with the preparation of natural sulphur iron ore; It is characterized in that; 5. in the particle activator of said dispersant, said xanthate class particle activator is to contain the alkyl xanthic acid and the salt thereof of alkyl carbon atoms number between 2～26 in step;
Said black powder class particle activator be cresols black powder, xylenol black powder, decyl phenol black powder, tert-butyl phenol black powder, oxidation tert-butyl phenol black powder, phenol black powder, two sec-butyl phosphordithiic acid ammoniums, two sec-butyl phosphordithiic acid sodium, diisopropyl disulfide for sodium phosphate, diisopropyl disulfide for potassium phosphate, diisopropyl disulfide for ammonium phosphate, diisoamyl phosphordithiic acid sodium, polyoxy butenol phosphordithiic acid sodium or polyoxy butenol phosphordithiic acid ammonium
Said fatty amine particle activator is that carbon number is at substituted aliphatic amine between 2～24 or two substituted aliphatic amines and the ammonium salt thereof of carbon number between 2～5;
Said benzene sulfonamide acids particle activator refers to that carbon number is alkyl benzene sulphonate and the salt thereof between 12～24.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075896A (en) * | 2019-04-09 | 2019-08-02 | 重庆大学 | FeS2/g-C3N4The preparation method and applications of heterojunction material |
| CN111167496A (en) * | 2020-01-09 | 2020-05-19 | 南开大学 | Visible light catalytic material and preparation method and application thereof |
| CN112909244A (en) * | 2019-12-04 | 2021-06-04 | 中南大学 | Pyrite-based composite material and preparation method and application thereof |
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| CN1600878A (en) * | 2004-10-25 | 2005-03-30 | 昆明易明兴矿冶设备有限公司 | Method for producing cinder of sulfur iron ore in high iron and low sulfur type |
| CN1908205A (en) * | 2006-08-17 | 2007-02-07 | 周慧明 | Processing method of troilite powder material and use |
| CN101823023A (en) * | 2010-04-19 | 2010-09-08 | 深圳市中金岭南有色金属股份有限公司凡口铅锌矿 | Floatation process of high-ferrum sulfur ore concentrates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600878A (en) * | 2004-10-25 | 2005-03-30 | 昆明易明兴矿冶设备有限公司 | Method for producing cinder of sulfur iron ore in high iron and low sulfur type |
| CN1908205A (en) * | 2006-08-17 | 2007-02-07 | 周慧明 | Processing method of troilite powder material and use |
| CN101823023A (en) * | 2010-04-19 | 2010-09-08 | 深圳市中金岭南有色金属股份有限公司凡口铅锌矿 | Floatation process of high-ferrum sulfur ore concentrates |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075896A (en) * | 2019-04-09 | 2019-08-02 | 重庆大学 | FeS2/g-C3N4The preparation method and applications of heterojunction material |
| CN110075896B (en) * | 2019-04-09 | 2021-12-07 | 重庆大学 | FeS2/g-C3N4Preparation method and application of heterojunction material |
| CN112909244A (en) * | 2019-12-04 | 2021-06-04 | 中南大学 | Pyrite-based composite material and preparation method and application thereof |
| CN112909244B (en) * | 2019-12-04 | 2022-03-29 | 中南大学 | Pyrite-based composite material and preparation method and application thereof |
| CN111167496A (en) * | 2020-01-09 | 2020-05-19 | 南开大学 | Visible light catalytic material and preparation method and application thereof |
| CN111167496B (en) * | 2020-01-09 | 2020-12-25 | 南开大学 | Visible light catalytic material and preparation method and application thereof |
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