CN103964395A - Modification method for nano calcium peroxide with controllable particle size - Google Patents
Modification method for nano calcium peroxide with controllable particle size Download PDFInfo
- Publication number
- CN103964395A CN103964395A CN201410175263.6A CN201410175263A CN103964395A CN 103964395 A CN103964395 A CN 103964395A CN 201410175263 A CN201410175263 A CN 201410175263A CN 103964395 A CN103964395 A CN 103964395A
- Authority
- CN
- China
- Prior art keywords
- calcium peroxide
- reaction
- peroxide
- particle diameter
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a modification method for nano calcium peroxide with controllable particle size. The modification method comprises the following steps: adding a certain amount of a calcium salt to dispersing agent solutions of different concentrations; mixing to prepare a reaction base solution under an ultrasonic condition; slowly dripping hydrogen peroxide solution with a certain concentration to the reaction base solution at a certain rate, wherein the reaction base solution is stirred continuously; after the dripping is completed, allowing the reaction to continue for 10-20 min; after the complete reaction, the mixed solution is centrifuged to obtain precipitate; washing repeatedly with deionized water and absolute ethyl alcohol; placing in a vacuum drying box for drying for 24-48 h to obtain the nano calcium peroxide with different particle sizes. The modification method has the benefits that the process is simple; the reaction conditions are mild; the reaction time is short; the added dispersing agent in the reaction is non-toxic and harmless, low in cost and easy to obtain; no pollutants is generated in the production process; the prepared product is high in performance; nano calcium peroxide of different particle sizes can be prepared under different reaction conditions, and the average particle size is 10-200 nm. The invention provides a novel synthetic method for the nano calcium peroxide for groundwater remediation, and the particle size of the prepared calcium peroxide can be controlled.
Description
Technical field
The invention belongs to environmental technology field, relate to the recovery technique of groundwater pollution, be specially the controlled nanometer calcium peroxide method of modifying of a kind of particle diameter.
Background technology
Groundwater pollution has become the focus of concern in recent years, and according to statistics, the underground water of China nearly 90% is suffering pollution in various degree
[1].And underground water is the drinking water source in a lot of cities of northern area.Groundwater pollution serious threat arrives the mankind's health.The reason of groundwater pollution is mainly industrial pollution, and trade effluent is not treated, directly enters underground storage layer and pollutes; The surface water being polluted is immersed in underground reservoir; The agricultural of take is excessively used agricultural chemicals material as main area, through soil, oozes people in Water table.The result of polluting is to make to contain in a large number in underground water harmful composition as phenols, heavy metal, oil and petrochemicals.And these material great majority all have " three cause " (teratogenesis, carcinogenic, mutagenesis) effect, HUMAN HEALTH and industrial and agricultural production are had to irreversible harm.
The method of repairing groundwater pollution is generally divided into based technique for in-situ remediation and showering technology, showering technology because of its quantities large, processing costs is higher, and the factors such as the destruction of site environment is larger are restricted in actual applications.And based technique for in-situ remediation is less because of its ecotope disturbance to Polluted area periphery, the advantage such as processing costs is relatively low, is widely used in groundwater pollution reparation in recent years.In underground water based technique for in-situ remediation, applying maximum is permeable reactive barrier (PRB) technology and in-situ chemical recovery technique (ISCO).The features such as and in-situ chemical reparation is short because of its repairing efficiency, processing efficiency is higher, and processing costs is lower are better than permeable reactive barrier technology.In-situ chemical recovery technique is that oxygenant is imported in contaminated water layer, by redox reaction, removes the pollution substance in underground water.Using maximum oxygenants is at present permanganate, hydrogen peroxide, and persulphate, calcium peroxides etc. have the oxygenant compared with strong oxidizing property.Permanganate is being repaired during ground water chemistry that petroleum-type pollutes repairs, because of its transformation period longer, so its oxygenizement also relatively a little less than.Hydrogen peroxide generates oxygen and lose oxygenizement because disproportionation reactions can occur when the high density in a large number for it, and its pH having an effect is below 3, and the pH of environment is had relatively high expectations.Persulphate has higher oxidisability, but can produce secondary pollution in its repair process.And calcium peroxide is because of its non-secondary pollution, the advantage such as cheap, is widely used in during groundwater pollution administers in recent years.Calcium peroxide is called as " solid " hydrogen peroxide, because it reacts with water, can generate H
2o
2, its output is up to 0.47gH
2o
2/ gCaO
2 [2], and can control by controlling the solubleness of calcium peroxide the output of hydrogen peroxide.Therefore, calcium peroxide is a kind of more efficiently oxygenant in chemical recovery technique in position.
Calcium peroxide is a kind of environment-friendly material that has oxygen release and oxidisability concurrently, at first for agricultural planting, and aquaculture, food and medical industry, be also used in surrounding medium reparation in recent years.Calcium peroxide brings adverse influence can in oxidize contaminants as a kind of environmentally friendly oxygenant environment around, because reacting with water, it there is oxygen on the contrary, increased the oxygen level in surrounding medium, thereby improved the living environment of microorganism, promote in the lump the degraded of microorganism to some pollutents, improved remediation efficiency.But traditional calcium peroxide because its particle is larger, is easily reunited in some practical application embodiment, easily the down phenomenon limits such as blocking pipe its widespread use in underground water is repaired.Calcium peroxide is carried out to the particle diameter that nano modification can reduce traditional calcium peroxide, improve its specific surface area, and nano level calcium peroxide particle is difficult for reuniting, good dispersity, increase with the site that contacts of pollutent, reaction rate accelerates, shortened repairing efficiency and can reduce consumption, and then rehabilitation cost also can decrease
[3].
The particle diameter that this patent is implemented in nano level calcium peroxide building-up process is controlled research, to the preparation method who provides a kind of calcium peroxide particle diameter to control.Though the nano modification of the calcium peroxide method that provides is provided in the patent of existing announcement, but the calcium peroxide size distribution of preparation is more inhomogeneous, and all do not relate to particle diameter control problem prepared by nano level calcium peroxide, and the nano modification method that profit provides need be filtered or starting material be processed, preparation process is comparatively complicated, if be applied to, in suitability for industrialized production, will increase production cost, be not suitable for large-scale industrial production.This patent is by a series of comparative study, final definite polyvinylpyrrolidone is the excellent dispersants that a kind of building-up process is controlled nanometer calcium peroxide particle diameter, the particle diameter that generates calcium peroxide particle can be effectively controlled, and large-scale industrial production can be applied to.
[1] gold inscription. Chinese groundwater pollution crisis, the ecological economy, 2013,5 phases, 12-17;
[2] Nrthup A, Cassidy D. Calcium peroxide (CaO
2) for use in modified Fenton chemistry [J]. Journal of Hazardous Material, 2008,152: 1164-1170；
[3] Zhang Wei-xian, Bethlehem. Preparation and use of nano size peroxide particles: US 0100928 A1, 2011。
Summary of the invention
Larger to overcome traditional calcium peroxide particle diameter, the afunction of easily reuniting, easily stop up in actual applications the technical barrier of transfer canal, the object of the present invention is to provide the controlled nanometer calcium peroxide method of modifying of a kind of particle diameter, thereby optimize the performance of traditional calcium peroxide.The method preparation is simple, and cost is low, is easy to realize suitability for industrialized production, prepares gained calcium peroxide particle diameter little, has good dispersiveness, has a extensive future.
Chemical dispersant used in the present invention is nontoxic to environment and human body, has higher solubleness in water, can not produce a large amount of foams preparation feedback cannot be carried out in building-up process; And this dispersion agent is with low cost, be easier to realize suitability for industrialized production.
The controlled nanometer calcium peroxide method of modifying of a kind of particle diameter that the present invention proposes, concrete steps are as follows:
In dispersant solution, add calcium salt, be made into solution or the suspension liquid of calcium salt, through room temperature, ultrasonic and mechanical stirring 20 ~ 40min, fully mixes said mixture, forms reaction end liquid; By hydrogen peroxide, to be added drop-wise at the bottom of the reaction of continuous stirring in liquid, temperature of reaction is at room temperature carried out; Hydrogen peroxide dropwises rear continuation reaction 10 ~ 20min, and calcium salt is fully reacted with hydrogen peroxide, forms stable nano level calcium peroxide particle; The precipitation forming, after centrifugal, with deionized water, absolute ethanol washing product, after decompress filter is placed in product dry 1d ~ 2d under vacuum condition, can obtain nano level calcium peroxide powder; Wherein: the mass ratio of described calcium salt and dispersion agent is at 1:9-1:12, and the calcium salt adding and the mass ratio of hydrogen peroxide are 1:3 ~ 1:5.
In the present invention, described calcium salt is selected from the oxyhydroxide, muriate, nitrate of calcium any.
In the present invention, the massfraction of described suspension liquid is 5% ~ 10%.
In the present invention, the dispersion agent adding is polyvinylpyrrolidone;
In the present invention, polyvinylpyrrolidone (30K), its molecular-weight average is at 45,000-58, between 000;
In the present invention, centrifugal condition is 10000rmp, centrifugal 3 ~ 6min;
In the present invention, wash conditions is for using deionized water, absolute ethanol washing; Drying conditions is vacuum-drying 24 ~ 48h at 30 ℃.
The present invention be take polyvinylpyrrolidone as dispersion agent carries out modification to the calcium peroxide in building-up process, can obtain the equally distributed nano level calcium peroxide of the particle diameter particle of favorable dispersity.
Beneficial effect of the present invention:
1, cost of the present invention is low, and technological operation is simple, the material cheapness that is easy to get, and production unit is simple, is easy to realize large-scale industrial production.
2, synthetic method provided by the present invention can be controlled the particle diameter of prepared nano level calcium peroxide, is conducive to prepare for different reparation demands the calcium peroxide of different-grain diameter.
3, dispersion agent used in the present invention is nontoxic, without environmental hazard, and with low cost, be easy to get, and its performance is better than dispersion agent of the same type.
4, the preparation-obtained nano level calcium peroxide of the present invention excellent property, particle diameter is controlled, can be used as hydrogen peroxide donor and repairs underground water for chemistry, can be used as oxygen release agent simultaneously, improves the oxygen level of repairing in medium, strengthens biological restoration effect, practical.
5, the nano level calcium peroxide that the present invention prepares gained can be used for repairing and repaired by the underground water of Organic pollutants, nano level particle diameter, and reference area is larger, makes them many with the reaction site of pollutent, raising organic matter degradation efficiency; And nano level particle is owing to having larger specific surface area, thereby there is higher absorption property, also can be used for repairing the underground water be subject to heavy metal contamination, after Adsorption of Heavy Metals with its generation co-precipitation, and then change precipitation into from ionic forms, and then can from water, remove.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the synthetic nano level calcium peroxide of embodiment 1.
Fig. 2 is embodiment 1 synthesis nano calcium peroxide scanning electron microscope (SEM) photograph.
Fig. 3 is non-modified calcium peroxide scanning electron microscope (SEM) photograph.
Fig. 4 is the transmission electron microscope picture of the synthetic nano level calcium peroxide of embodiment 1.
Fig. 5,6 is the transmission electron microscope picture of embodiment 2 synthetic calcium peroxides.
Fig. 7,8 is the transmission electron microscope picture of embodiment 3 synthetic calcium peroxides.
Fig. 9,10 is the transmission electron microscope picture of embodiment 4 synthetic calcium peroxides.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) accurately take 60g polyvinylpyrrolidone (PVP), be dissolved in 120mL deionized water, ultrasonic and be stirred to it and dissolve completely.Take 6g calcium hydroxide and join in dispersant solution, mechanical stirring 20min fully mixes it at ambient temperature, forms reaction end liquid.
(2) hydrogen peroxide of 63.46mL30% is joined in homemade titration apparatus at a slow speed, drip at 20-30/min of coutroi velocity, slowly drops in end liquid, and reaction is carried out at ambient temperature, and constantly stirs.Be added dropwise to complete rear continuation reaction 15min, calcium salt is fully reacted with hydrogen peroxide, form stable nano level calcium peroxide particle.
(3) precipitation forming is through centrifugal, and with deionized water, absolute ethanol washing product, is dried 24h and obtains nano level calcium peroxide powder under 30 ℃ of vacuum conditions.
Fig. 1 spectral line is the X-ray diffractogram of the present embodiment gained nano level calcium peroxide, can find out and belong to CaO
2characteristic peak 2 θ=30.1,35.6,47.3, prove and synthesized nano level calcium peroxide.Scanning electron microscope Fig. 2 shows that the nano level calcium peroxide particle size distribution of synthesized is even, and the more unmodified calcium peroxide of agglomeration has had very large improvement.Transmission electron microscope Fig. 4 has shown CaO
2particle disperses, and particle dia is between 10nm ~ 20nm.
Embodiment 2
(1) accurately take 24g PVP, be dissolved in 120mL deionized water, ultrasonic and be stirred to it and dissolve completely.Take 6g calcium hydroxide and join in dispersant solution, mechanical stirring 20min fully mixes it at ambient temperature, forms reaction end liquid.
(2) hydrogen peroxide of 63.46mL30% is joined in homemade titration apparatus at a slow speed, drip at 20-30/min of coutroi velocity, slowly drops in end liquid, and reaction is carried out at ambient temperature, and constantly stirs.Be added dropwise to complete rear continuation reaction 15min, calcium salt is fully reacted with hydrogen peroxide, form stable nano level calcium peroxide particle.
(3) precipitation forming is through centrifugal, and with deionized water, absolute ethanol washing product, is dried 24h and obtains nano level calcium peroxide powder under 30 ℃ of vacuum conditions.
Synthesized sample carries out X-ray diffractometer sign, and the material that can prove synthesized is CaO
2.Transmission electron microscope Fig. 5 has shown when the dosage of PVP is 24g, CaO
2grain diameter is large compared with the particle diameter of the calcium peroxide particle in embodiment 1, has the phenomenon of reunion.Fig. 6 shows CaO
2particle dia is greatly about 50nm left and right, and particle diameter is large while being 60g compared with PVP dosage, and the homogeneity of size distribution weakens.
Embodiment 3
(1) accurately take 12g PVP, be dissolved in 120mL deionized water, ultrasonic and be stirred to it and dissolve completely.Take 6g calcium hydroxide and join in dispersant solution, mechanical stirring 20min fully mixes it at ambient temperature, forms reaction end liquid.
(2) hydrogen peroxide of 63.46mL30% is joined in homemade titration apparatus at a slow speed, drip at 20-30/min of coutroi velocity, slowly drops in end liquid, and reaction is carried out at ambient temperature, and constantly stirs.Be added dropwise to complete rear continuation reaction 15min, calcium salt is fully reacted with hydrogen peroxide, form stable nano level calcium peroxide particle.
(3) precipitation forming is through centrifugal, and with deionized water, absolute ethanol washing product, is dried 24h and obtains nano level calcium peroxide powder under 30 ℃ of vacuum conditions.
Synthesized sample carries out X-ray diffractometer sign, and the material that can prove synthesized is CaO
2.Transmission electron microscope Fig. 7 has shown when the dosage of PVP is 12g, CaO
2the most of one-tenth of particle agglomeration, Fig. 8 shows CaO
2particle dia is greatly about 150nm left and right, and particle diameter is large compared with the calcium peroxide particle diameter in embodiment 1 and embodiment 2, and size distribution homogeneity is relatively poor.
Embodiment 4
(1) accurately take 0.96g PVP, be dissolved in 120mL deionized water, ultrasonic and be stirred to it and dissolve completely.Take 6g calcium hydroxide and join in dispersant solution, mechanical stirring 20min fully mixes it at ambient temperature, forms reaction end liquid.
(2) hydrogen peroxide of 63.46mL30% is joined in the head space bottle of 100mL, with the sealing of gland device, insert the controlled drop-burette of flow velocity and slowly drop in end liquid, reaction is carried out at ambient temperature, and constantly stirs.Be added dropwise to complete rear continuation reaction 15min, calcium salt is fully reacted with hydrogen peroxide, form stable nano level calcium peroxide particle.
(3) precipitation forming is through centrifugal, and with deionized water, absolute ethanol washing product, is dried 24h and obtains nano level calcium peroxide powder under 30 ℃ of vacuum conditions.
Synthesized sample carries out X-ray diffractometer sign, and the material that can prove synthesized is CaO
2.Transmission electron microscope Fig. 9 has shown when the dosage of PVP is 0.96g, CaO
2particle major part is aggregating state, and Figure 10 shows CaO
2particle dia is greatly between 150 ~ 250nm, and particle diameter obviously increases.
Claims (7)
1. the controlled nanometer calcium peroxide method of modifying of particle diameter, is characterized in that concrete steps are as follows:
In dispersant solution, add calcium salt, be made into solution or the suspension liquid of calcium salt, through room temperature, ultrasonic and mechanical stirring 20 ~ 40min, fully mixes said mixture, forms reaction end liquid; By hydrogen peroxide, to be added drop-wise at the bottom of the reaction of continuous stirring in liquid, temperature of reaction is at room temperature carried out; Hydrogen peroxide dropwises rear continuation reaction 10 ~ 20min, and calcium salt is fully reacted with hydrogen peroxide, forms stable nano level calcium peroxide particle; The precipitation forming, after centrifugal, with deionized water, absolute ethanol washing product, after decompress filter is placed in product dry 1d ~ 2d under vacuum condition, can obtain nano level calcium peroxide powder; Wherein: the mass ratio of described calcium salt and dispersion agent is at 1:9-1:12, and the calcium salt adding and the mass ratio of hydrogen peroxide are 1:3 ~ 1:5.
2. the controlled nanometer calcium peroxide method of modifying of particle diameter according to claim 1, is characterized in that the dispersion agent adding is polyvinylpyrrolidone.
3. the controlled nanometer calcium peroxide method of modifying of particle diameter according to claim 1, is characterized in that the molecular-weight average of dispersion agent is between 45000 ~ 55000.
4. the controlled nanometer calcium peroxide method of modifying of particle diameter according to claim 1, the rate of addition that it is characterized in that hydrogen peroxide is 20 ~ 30/min.
5. a kind of chemical modification according to claim 1 is prepared nano level calcium peroxide method, it is characterized in that centrifugal condition is the centrifugal 3 ~ 6min of 10000rmp.
6. the controlled nanometer calcium peroxide method of modifying of particle diameter according to claim 1, is characterized in that drying conditions is vacuum-drying 1d ~ 2d at 30 ℃.
7. the controlled nanometer calcium peroxide method of modifying of particle diameter according to claim 1, it is characterized in that described calcium salt be in oxyhydroxide, muriate, nitrate any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410175263.6A CN103964395B (en) | 2014-04-29 | 2014-04-29 | A kind of nanometer calper calcium peroxide method of modifying of size tunable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410175263.6A CN103964395B (en) | 2014-04-29 | 2014-04-29 | A kind of nanometer calper calcium peroxide method of modifying of size tunable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103964395A true CN103964395A (en) | 2014-08-06 |
| CN103964395B CN103964395B (en) | 2016-06-15 |
Family
ID=51234468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410175263.6A Active CN103964395B (en) | 2014-04-29 | 2014-04-29 | A kind of nanometer calper calcium peroxide method of modifying of size tunable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103964395B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668521A (en) * | 2016-01-06 | 2016-06-15 | 华东交通大学 | Preparation method of high-purity calcium peroxide having nano particle size and smooth surface |
| WO2018203083A3 (en) * | 2017-05-04 | 2018-12-13 | University Of Ulster | Calcium peroxides nanoparticles as adjuvant therapy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601155A (en) * | 2013-11-18 | 2014-02-26 | 同济大学 | Method for preparing nano calcium peroxide by chemical modification |
-
2014
- 2014-04-29 CN CN201410175263.6A patent/CN103964395B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601155A (en) * | 2013-11-18 | 2014-02-26 | 同济大学 | Method for preparing nano calcium peroxide by chemical modification |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668521A (en) * | 2016-01-06 | 2016-06-15 | 华东交通大学 | Preparation method of high-purity calcium peroxide having nano particle size and smooth surface |
| WO2018203083A3 (en) * | 2017-05-04 | 2018-12-13 | University Of Ulster | Calcium peroxides nanoparticles as adjuvant therapy |
| US11235000B2 (en) | 2017-05-04 | 2022-02-01 | University Of Ulster | Calcium peroxides nanoparticles as adjuvant therapy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103964395B (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103934034B (en) | The preparation method of load-type iron-based metallic organic framework heterophase Fenton catalyst and application thereof | |
| CN103601155A (en) | Method for preparing nano calcium peroxide by chemical modification | |
| He et al. | Effective remediation of cadmium and zinc co-contaminated soil by electrokinetic-permeable reactive barrier with a pretreatment of complexing agent and microorganism | |
| CN104069815B (en) | Sulfur doping grapheme foam and preparation method thereof and the method for disposing of sewage | |
| CN103801284B (en) | A kind of preparation method of pucherite-graphene composite photocatalyst | |
| CN106955667A (en) | A kind of composite of activated carbon supported nano zero valence iron and silver metal cluster and preparation method thereof | |
| CN104031651A (en) | Passivation improver for heavy metal pollution farmland and using method thereof | |
| CN103170501B (en) | Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material | |
| CN105399199A (en) | Preparation method of biosurfactants-modified nano-iron/carbon composite material and application in removing nitrate nitrogen in underground water | |
| CN110759319A (en) | Slow-release nano calcium peroxide material, preparation method thereof and method for removing chlorohydrocarbon and/or benzene series in underground water by using slow-release nano calcium peroxide material | |
| CN107020144B (en) | Magnetic N doping redox graphene composite catalyst and its preparation method and application | |
| CN102266750A (en) | In situ preparation method of magnetic bio-absorbent | |
| Shi et al. | Heterogeneous photo-fenton degradation of norfloxacin with Fe 3 O 4-multiwalled carbon nanotubes in aqueous solution | |
| CN112194236A (en) | Method for treating salt-containing degradation-resistant wastewater by activating peroxymonosulfate through biochar-copper oxide composite material | |
| CN105032375A (en) | Preparation method of magnetic graphite-based heavy metal adsorbing material | |
| Agorku et al. | Fabrication of photocatalyst based on Eu3+-doped ZnS–SiO2 and sodium alginate core shell nanocomposite | |
| CN106976942A (en) | A kind of organic polymer coargulator modified Nano Zero-valent Iron and its preparation method and application | |
| Wernke et al. | Ag and CuO nanoparticles decorated on graphene oxide/activated carbon as a novel adsorbent for the removal of cephalexin from water | |
| Wu et al. | Chromium ion removal from raw water by magnetic iron composites and Shewanella oneidensis MR-1 | |
| CN109095590A (en) | LaFe1-xCuxO3The method for handling residue in water Atrazine | |
| CN109205753A (en) | Modified iron-copper bi-metal nano particle and preparation method thereof | |
| Gu et al. | Calcium oxide modification of activated sludge as a low-cost adsorbent: preparation and application in Cd (II) removal | |
| CN106583441A (en) | Method for recovery of organic chloride-polluted soil through ultrasonic intensified potassium ferrate/hydrogen peroxide | |
| CN105921763B (en) | The preparation method of sodium alginate/inorganic mineral combined loading type nano zero valence iron | |
| Sun et al. | Photocatalytic reduction performance and mechanisms of Cr (VI) by illite-g-C3N4 under visible light |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |