CN103894197B - One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material - Google Patents
One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material Download PDFInfo
- Publication number
- CN103894197B CN103894197B CN201410140436.0A CN201410140436A CN103894197B CN 103894197 B CN103894197 B CN 103894197B CN 201410140436 A CN201410140436 A CN 201410140436A CN 103894197 B CN103894197 B CN 103894197B
- Authority
- CN
- China
- Prior art keywords
- oyster shell
- extra large
- nano
- tio
- large oyster
- 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.)
- Expired - Fee Related
Links
Abstract
One utilizes extra large oyster shell loaded with nano Cu
2o-TiO
2the preparation method of optic catalytic composite material, relates to a kind of optic catalytic composite material.First carry out the pretreatment of extra large oyster shell; Prepare nano titanium oxide-Hai oyster shell composite again; Finally preparation utilizes extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material.Adopt sol-gel process to combine with coprecipitation and prepare extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material, sea oyster shell is by after activation, there is larger specific area and adsorption, improve the light energy absorption rate of catalysis material, enhance the adsorption capacity of extra large oyster shell, improve photocatalytic activity, solve current catalysis material and be applied to the problems such as the separation and recovery difficulty existed in wastewater treatment is large, the life-span is short, the efficiency of light energy utilization is low.In addition, the prices of raw and semifnished materials are low, significantly can reduce production cost.
Description
Technical field
The present invention relates to a kind of optic catalytic composite material, particularly relate to one and utilize extra large oyster shell loaded with nano Cu
2o-TiO
2the preparation method of optic catalytic composite material.
Background technology
Along with the raising of human living standard, the consumption of people to extra large oyster constantly increases, various seawater aquaculture industry, marine products processing market etc. be seen everywhere " extra large oyster shell rubbish ", because extra large oyster shell has natural concrete dynamic modulus surface, and containing macroelements such as Ca, Mg, K, Na, also containing trace elements such as Fe, Si, Zn, Mn, Al, how these resources effectively to be utilized, be the study hotspot of current many scholars.About the recycling of extra large oyster shell, most research at present concentrates on the extraction of calcium, extracts polypeptide or is used as filler etc.As Chinese patent CN102887824B, open is that highly purified calcium gluconae prepared by raw material with oyster shell, Chinese patent CN102993268B openly utilizes oyster shell to prepare anti-oxidation peptide, and Chinese patent ZL200510118987.8 is open is applied to nitrating aeration biofilter by shuck filling.Extra large oyster shell is applied to the load of catalysis material, still fresh is at present report.
Photocatalysis technology, in the organic-inorganic pollutant of degraded water and air, is considered to a potential technology.Particularly conductor oxidate, as Cu
2o and TiO
2, due to features such as their high photosensitivity, nontoxic, inexpensive and chemical stabilities, become one of most suitable catalysis material.Due to TiO
2greater band gap, therefore can only absorb the sub-fraction ultraviolet light in sunshine, but Cu
2the band gap of O is narrower, has certain absorption for the visible light part in sunshine, the two acting in conjunction, is conducive to improving the utilization to sunshine, enhances the efficiency of light-catalyzed reaction.At present, about the preparation method of combined type photochemical catalyst, (the Sun Jiawei such as Sun Jiawei, Liu Na, Zhai Shangru, Deng. chemical industry is in progress, 2014, 1(33)), (the He Xia such as He Xia, bang is auspicious, Dong Hailiang, Deng. Journal of Inorganic Materials, 2014, 3(29)), (the Wang Lili such as Wang Lili, Li Li, Wei Xing, Deng. chemistry circular, 2014, 1(77)) disclose the preparation method of multiple optic catalytic composite material, two class photochemical catalysts are just carried out compound by these methods usually, or the compound of adding modifier is carried out to a class photochemical catalyst, by inciting somebody to action wherein a kind of photochemical catalyst or modifier load on another photochemical catalyst, to reach the effect of compound, there is following shortcoming in this preparation method: one is that the composite prepared easily disperses, not easily reclaim, two is that combined strength bination is not high, and by long reaction, catalytic effect easily reduces, three be the modifier majority that adds for noble metal or environment is had to the element of pollution, this composite cost is high, and inevitably produces secondary pollution.Exploitation is needed easily to reclaim, pollution-free, the composite that efficiency is high.
Summary of the invention
The object of this invention is to provide that Production Time is short, cost of manufacture is low, sharpen shell surface in sea and form even Cu
2o and TiO
2photocatalysis layer, thus the one significantly improving adsorption capacity and photocatalysis performance utilizes extra large oyster shell loaded with nano Cu
2o-TiO
2the preparation method of optic catalytic composite material.
The present invention includes following steps:
1) extra large oyster shell pretreatment: by discarded extra large oyster shell salt acid soak, then use soaking with sodium hydroxide, after cleaning, first time dries, then fragmentation is sieved, and then soaks with saturated NaCl, and after ultrasonic, second time is dried, and obtains pretreated extra large oyster shells end;
2) nano titanium oxide-Hai oyster shell composite is prepared: by ethanol, acetic acid, butyl titanate mixing, obtain solution A, again the pretreated extra large oyster shells end obtained in step 1) is added in the mixed liquor of second alcohol and water, solution B is obtained after stirring, solution A is added in solution B, ageing, to forming gel, obtains nano titanium oxide-Hai oyster shell composite after oven dry, calcining;
3) preparation utilizes extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material: obtain mixed liquor by after copper acetate, ethanol, glucose, softex kw mixing, add step 2 after ultrasonic) in obtained nano titanium oxide-Hai oyster shell composite, NaOH is added again after stirring, and heat, until generate brick-red precipitation, washing post-drying, namely obtains utilizing extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material.
In step 1), described hydrochloric acid can adopt concentration to be the hydrochloric acid of 1mol/L, and the time of described salt acid soak can be 0.5h; Described NaOH can adopt concentration to be the NaOH of 1mol/L, and the time of described soaking with sodium hydroxide can be 0.5h; The temperature that described first time dries can be 105 ~ 110 DEG C, and the time that first time dries can be 2 ~ 3h; Described fragmentation is sieved broken by ball mill, screens extra large oyster shells end granularity with 100 mesh standard sieves; The described ultrasonic time can be 0.5h; The temperature that described second time is dried can be 105 ~ 110 DEG C, and the time that second time is dried can be 2 ~ 3h.
In step 2) in, in described solution A, the volume ratio of ethanol, acetic acid, butyl titanate can be (85% ~ 90%): (4% ~ 6%): (6% ~ 9%); In described solution B, the volume ratio of ethanol, water can be (90% ~ 99%): (1% ~ 10%); The time of described stirring can be 1h; The volume ratio of solution A and solution B liquid can be (4 ~ 6): 1, described pretreated extra large oyster shells end can be 1g with the proportioning of the mixed liquor of second alcohol and water: (5 ~ 10) mL, wherein, pretreated extra large oyster shells end is calculated in mass, and the mixed liquor of second alcohol and water is calculated by volume; The temperature of described ageing can be 30 DEG C; The temperature of described oven dry can be 105 ~ 110 DEG C, and the time of oven dry can be 5 ~ 8h; The temperature of described calcining can be 600 DEG C ~ 800 DEG C, and the time of calcining can be 2 ~ 3h.
In step 3), the concentration of described copper acetate, glucose, softex kw, NaOH is respectively 0.1mol/L, 0.2mol/L, 0.1mol/L, 0.3mol/L, and the volume ratio of described copper acetate, absolute ethyl alcohol, glucose, softex kw, NaOH can be (25% ~ 30%): (20% ~ 25%): (10% ~ 12%): (3% ~ 5%): (30% ~ 40%); The described ultrasonic time can be 1 ~ 2h; The proportioning of described nano titanium oxide-Hai oyster shell composite and mixed liquor can be 1g: (100 ~ 150) mL, and wherein, nano titanium oxide-Hai oyster shell composite is calculated in mass, and mixed liquor is calculated by volume; The time of described stirring can be 0.5h; The temperature of described heating can be 65 DEG C; After the available pure water of described washing 3 ~ 5 times, then use absolute ethanol washing 3 ~ 4 times; The temperature of described oven dry can be 105 ~ 110 DEG C, and the time of oven dry can be 1 ~ 2h.
The present invention adopts sol-gel process to combine with coprecipitation to prepare extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material, extra large oyster shell, by after activation, is provided with larger specific area and adsorption, and utilize butyl titanate hydrolysis condensation reaction under certain conditions, form the alcogel of network-like titanium, load extra large oyster shell surface after activation, generates TiO by drying, calcining
2the precursor of/extra large oyster shell composite, the thermokalite reducing process of recycling mantoquita, by the Cu generated
2o load, on the precursor surface of composite, can obtain extra large oyster shell loaded with nano Cu
2o-TiO
2composite.Invention increases the light energy absorption rate of catalysis material, enhance the adsorption capacity of extra large oyster shell, improve photocatalytic activity, solve current catalysis material simultaneously and be applied to the problems such as the separation and recovery difficulty existed in wastewater treatment is large, the life-span is short, the efficiency of light energy utilization is low.In addition, the method prices of raw and semifnished materials are low, significantly can reduce production cost.
Accompanying drawing explanation
Fig. 1 is the extra large oyster shell loaded with nano Cu of the embodiment of the present invention 2
2o-TiO
2optic catalytic composite material x-ray diffraction pattern, in FIG, abscissa is the angle of diffraction 2 θ (degree), and ordinate is intensity (%).
Fig. 2 is the extra large oyster shell loaded with nano Cu of the embodiment of the present invention 2
2o-TiO
2optic catalytic composite material electron-microscope scanning figure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details.
Embodiment 1:
Discarded extra large oyster shell watery hydrochloric acid is soaked 0.5h, then soaks 0.5h with low-concentration sodium hydroxide, after cleaning, drying, 100 mesh sieves are crossed in fragmentation, then soak by saturated NaCl solution, and after ultrasonic 0.5h, cleaning post-drying is for subsequent use, by ethanol, acetic acid, butyl titanate is by 85%: 6%: 9% volume ratio mixing, obtain solution A, second alcohol and water mixes by another 90%: 10% volume ratio of pressing, taking the pretreated extra large oyster shells end of 1.5g is added in the mixed liquor of 10mL second alcohol and water, stir 1h and obtain solution B, 35mL A liquid is poured in dropping funel, the piston of adjustment dropping funel, make solution with the speed of 1 ~ 2 drop/sec, slowly be added dropwise in the mixed liquid B at the uniform velocity stirred, whole dropping process control is in 15min, and after continuing to stir 0.5h, at 30 DEG C, allow its ageing to forming gel, the gel of formation is placed on 110 DEG C of baking oven inner drying 5h, dried composite is transferred in crucible, 2h is calcined under 600 DEG C of hot conditions, nano-TiO can be obtained
2/ extra large oyster shell composite.
Separately the ratio of 25%: 25%: 10%: 3%: 37% measures copper acetate, absolute ethyl alcohol, glucose, softex kw, sodium hydroxide solution respectively by volume, above-mentioned solution (except sodium hydroxide solution) is mixed, ultrasonic 1 ~ 2h, then get this mixed liquor 100mL, add the TiO prepared in 1g above-mentioned steps
2/ extra large oyster shell composite, mix and blend 0.5h, add the above-mentioned sodium hydroxide solution measured again, continue to stir, and be heated to 65 DEG C, until brick-red precipitation generates, continue to stir 0.5h, by sediment pure water 3 times, then after washing 2 times with ethanol, be transferred to 105 DEG C of baking oven inner drying 1h, namely obtain extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material.
Embodiment 2:
Discarded extra large oyster shell watery hydrochloric acid is soaked 0.5h, then soaks 0.5h with low-concentration sodium hydroxide, after cleaning, drying, 100 mesh sieves are crossed in fragmentation, then soak by saturated NaCl solution, and after ultrasonic 0.5h, cleaning post-drying is for subsequent use, by ethanol, acetic acid, butyl titanate is by 88%: 4%: 8% volume ratio mixing, obtain solution A, second alcohol and water mixes by another 95%: 5% volume ratio of pressing, taking the pretreated extra large oyster shells end of 1.5g is added in the mixed liquor of 10mL second alcohol and water, stir 1h and obtain solution B, 35mL A liquid is poured in dropping funel, the piston of adjustment dropping funel, make solution with the speed of 1 ~ 2 drop/sec, slowly be added dropwise in the mixed liquid B at the uniform velocity stirred, whole dropping process control is in 15min, and after continuing to stir 0.5h, at 30 DEG C, allow its ageing to forming gel, the gel of formation is placed on 110 DEG C of baking oven inner drying 5h, dried composite is transferred in crucible, 2h is calcined under 650 DEG C of hot conditions, nano-TiO can be obtained
2/ extra large oyster shell composite.
Separately the ratio of 27.5%: 22.5%: 11%: 4%: 35% measures copper acetate, absolute ethyl alcohol, glucose, softex kw, sodium hydroxide solution respectively by volume, above-mentioned solution (except sodium hydroxide solution) is mixed, ultrasonic 1 ~ 2h, then get this mixed liquor 125mL, add the TiO prepared in 1g above-mentioned steps
2/ extra large oyster shell composite, mix and blend 0.5h, add the above-mentioned sodium hydroxide solution measured again, continue to stir, and be heated to 65 DEG C, until brick-red precipitation generates, continue to stir 0.5h, by sediment pure water 3 times, then after washing 2 times with ethanol, be transferred to 105 DEG C of baking oven inner drying 1h, namely obtain extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material.
Embodiment 3:
Discarded extra large oyster shell watery hydrochloric acid is soaked 0.5h, then soaks 0.5h with low-concentration sodium hydroxide, after cleaning, drying, 100 mesh sieves are crossed in fragmentation, then soak by saturated NaCl solution, and after ultrasonic 0.5h, cleaning post-drying is for subsequent use, by ethanol, acetic acid, butyl titanate is by 90%: 3%: 7% volume ratio mixing, obtain solution A, second alcohol and water mixes by another 99%: 1% volume ratio of pressing, taking the pretreated extra large oyster shells end of 1.5g is added in the mixed liquor of 10mL second alcohol and water, stir 1h and obtain solution B, 35mL A liquid is poured in dropping funel, the piston of adjustment dropping funel, make solution with the speed of 1 ~ 2 drop/sec, slowly be added dropwise in the mixed liquid B at the uniform velocity stirred, whole dropping process control is in 15min, and after continuing to stir 0.5h, at 30 DEG C, allow its ageing to forming gel, the gel of formation is placed on 110 DEG C of baking oven inner drying 5h, dried composite is transferred in crucible, 2h is calcined under 700 DEG C of hot conditions, nano-TiO can be obtained
2/ extra large oyster shell composite.
Separately the ratio of 30%: 20%: 12%: 5%: 33% measures copper acetate, absolute ethyl alcohol, glucose, softex kw, sodium hydroxide solution respectively by volume, above-mentioned solution (except sodium hydroxide solution) is mixed, ultrasonic 1 ~ 2h, then get this mixed liquor 150mL, add the TiO prepared in 1g above-mentioned steps
2/ extra large oyster shell composite, mix and blend 0.5h, add the above-mentioned sodium hydroxide solution measured again, continue to stir, and be heated to 65 DEG C, until brick-red precipitation generates, continue to stir 0.5h, by sediment pure water 3 times, then after washing 2 times with ethanol, be transferred to 105 DEG C of baking oven inner drying 1h, namely obtain extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material.
Take the extra large oyster shell loaded with nano Cu of above preparation
2o-TiO
2optic catalytic composite material and extra large oyster shells end, nanoscale TiO
2, nanoscale Cu
2the each 0.2g of O, add Congo red solution that 100mL concentration is 50mg/L successively to and 100mL concentration is in the methylene blue solution of 50mg/L, under room temperature, under magnetic agitation condition respectively in the dark, sunshine and UV-irradiation centrifugal after 1 hour, get the concentration that supernatant measures remaining solution, degradation rate is as shown in table 1.Show extra large oyster shell loaded with nano Cu prepared by above each embodiment
2o-TiO
2optic catalytic composite material all has good adsorption capacity and photocatalysis performance.
Table 1 monomer and composite are at different conditions to degradation rate that is Congo red and methylene blue
Extra large oyster shell loaded with nano Cu prepared by embodiment 2
2o-TiO
2the x-ray diffraction pattern of optic catalytic composite material is as shown in Figure 1: this composite is 36.4 degree at 2 θ respectively, and 25.2 degree, there is very strong diffraction maximum at 29.4 degree of places, according to the comparison of standard spectrogram, and these diffraction maximums and Cu
2o, anatase titanium dioxide TiO
2, CaCO
3standard spectrogram is consistent, surface that the extra large oyster shells end that the present invention utilizes is described successfully load Cu
2o and anatase titanium dioxide TiO
2.
Extra large oyster shell loaded with nano Cu prepared by embodiment 2
2o-TiO
2the electron-microscope scanning figure of optic catalytic composite material is as shown in Figure 2: 1. in Fig. 2 is CuO
2, be 2. TiO
2, be 3. the surface that shell powder is sharpened in sea, as seen from the figure, the surface of shell powder is sharpened in two kinds of photochemical catalyst loads uniformly in sea.
Claims (9)
1. one kind utilizes extra large oyster shell loaded with nano Cu
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that comprising the following steps:
1) extra large oyster shell pretreatment: by discarded extra large oyster shell salt acid soak, then use soaking with sodium hydroxide, after cleaning, first time dries, then fragmentation is sieved, and then soaks with saturated NaCl, and after ultrasonic, second time is dried, and obtains pretreated extra large oyster shells end;
2) nano titanium oxide-Hai oyster shell composite is prepared: by ethanol, acetic acid, butyl titanate mixing, obtain solution A, again by step 1) in the pretreated extra large oyster shells end that obtains be added in the mixed liquor of second alcohol and water, solution B is obtained after stirring, solution A is added in solution B, ageing, to forming gel, obtains nano titanium oxide-Hai oyster shell composite after oven dry, calcining; In described solution A, the volume ratio of ethanol, acetic acid, butyl titanate is (85% ~ 90%): (4% ~ 6%): (6% ~ 9%); In described solution B, the volume ratio of ethanol, water is (90% ~ 99%): (1% ~ 10%); The volume ratio of solution A and solution B liquid is (4 ~ 6): 1, described pretreated extra large oyster shells end is 1g with the proportioning of the mixed liquor of second alcohol and water: (5 ~ 10) mL, wherein, pretreated extra large oyster shells end is calculated in mass, and the mixed liquor of second alcohol and water is calculated by volume;
3) preparation utilizes extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material: obtain mixed liquor by after copper acetate, ethanol, glucose, softex kw mixing, add step 2 after ultrasonic) in obtained nano titanium oxide-Hai oyster shell composite, NaOH is added again after stirring, and heat, until generate brick-red precipitation, washing post-drying, namely obtains utilizing extra large oyster shell loaded with nano Cu
2o-TiO
2optic catalytic composite material; The concentration of described copper acetate, glucose, softex kw, NaOH is respectively 0.1mol/L, 0.2mol/L, 0.1mol/L, 0.3mol/L, and the volume ratio of described copper acetate, absolute ethyl alcohol, glucose, softex kw, NaOH is (25% ~ 30%): (20% ~ 25%): (10% ~ 12%): (3% ~ 5%): (30% ~ 40%); The proportioning of described nano titanium oxide-Hai oyster shell composite and mixed liquor is 1g: (100 ~ 150) mL, and wherein, nano titanium oxide-Hai oyster shell composite is calculated in mass, and mixed liquor is calculated by volume.
2. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 1) in, described hydrochloric acid adopts concentration to be the hydrochloric acid of 1mol/L, and the time of described salt acid soak is 0.5h; Described NaOH adopts concentration to be the NaOH of 1mol/L, and the time of described soaking with sodium hydroxide is 0.5h.
3. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 1) in, the temperature that described first time dries is 105 ~ 110 DEG C, and the time that first time dries is 2 ~ 3h; The temperature that described second time is dried is 105 ~ 110 DEG C, and the time that second time is dried is 2 ~ 3h.
4. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 1) in, it is broken by ball mill that described fragmentation is sieved, and screens extra large oyster shells end granularity with 100 mesh standard sieves.
5. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 1) in, the described ultrasonic time is 0.5h.
6. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 2) in, the time of described stirring is 1h.
7. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 2) in, the temperature of described ageing is 30 DEG C; The temperature of described oven dry is 105 ~ 110 DEG C, and the time of oven dry is 5 ~ 8h; The temperature of described calcining is 600 DEG C ~ 800 DEG C, and the time of calcining is 2 ~ 3h.
8. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 3) in, the described ultrasonic time is 1 ~ 2h.
9. one utilizes extra large oyster shell loaded with nano Cu as claimed in claim 1
2o-TiO
2the preparation method of optic catalytic composite material, is characterized in that in step 3) in, the time of described stirring is 0.5h; The temperature of described heating is 65 DEG C; After described washing pure water 3 ~ 5 times, then use absolute ethanol washing 3 ~ 4 times; The temperature of described oven dry is 105 ~ 110 DEG C, and the time of oven dry is 1 ~ 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140436.0A CN103894197B (en) | 2014-04-09 | 2014-04-09 | One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140436.0A CN103894197B (en) | 2014-04-09 | 2014-04-09 | One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103894197A CN103894197A (en) | 2014-07-02 |
| CN103894197B true CN103894197B (en) | 2015-09-02 |
Family
ID=50985953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410140436.0A Expired - Fee Related CN103894197B (en) | 2014-04-09 | 2014-04-09 | One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103894197B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734042B (en) * | 2016-05-04 | 2020-06-16 | 厦门大学嘉庚学院 | Preparation method of photocatalytic immobilized nitrogen and phosphorus removal particles |
| CN106675524B (en) * | 2016-07-13 | 2019-05-17 | 北京化工大学 | A kind of multi-functional phase-change material micro-capsule and preparation method thereof |
| CN109529864B (en) * | 2018-11-14 | 2021-06-18 | 浙江海洋大学 | alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and preparation method thereof |
| CN115959867A (en) * | 2022-11-28 | 2023-04-14 | 河北工业大学 | Preparation method of modified oyster shell antibacterial calcium silicate board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352674A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Nano titanic oxide impregnation preparation method using shell powder as carrier |
| CN101956223A (en) * | 2010-10-27 | 2011-01-26 | 厦门大学 | Method for preparing cuprous oxide composite titanium dioxide nanotube array |
| CN102553590A (en) * | 2010-09-11 | 2012-07-11 | 中国科学院海洋研究所 | Abandoned shell/nanometer Cu2O composite photocatalyst material as well as preparation and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7927484B2 (en) * | 2008-09-11 | 2011-04-19 | University Of Central Florida Research Foundation, Inc. | Passive underground drainfield for septic tank nutrient removal using functionalized green filtration media |
-
2014
- 2014-04-09 CN CN201410140436.0A patent/CN103894197B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352674A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Nano titanic oxide impregnation preparation method using shell powder as carrier |
| CN102553590A (en) * | 2010-09-11 | 2012-07-11 | 中国科学院海洋研究所 | Abandoned shell/nanometer Cu2O composite photocatalyst material as well as preparation and application thereof |
| CN101956223A (en) * | 2010-10-27 | 2011-01-26 | 厦门大学 | Method for preparing cuprous oxide composite titanium dioxide nanotube array |
Non-Patent Citations (2)
| Title |
|---|
| 牡蛎壳粉为载体纳米TiO2催化降解甲基橙的研究;张兆霞 等;《广东化工》;20081231;第35卷(第4期);第55-57页 * |
| 纳米Cu2O/珍珠贝壳复合光催化材料的制备与表征;邹晓兰 等;《环境化学》;20110831;第30卷(第8期);第1480-1485页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103894197A (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20180291266A1 (en) | A carbon quantum dot synthesizing method and its application of modifying functional water purification material | |
| CN103894197B (en) | One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material | |
| CN104772158B (en) | Preparation method of WO3/C3N4 mixed photocatalyst | |
| CN105080526B (en) | A kind of titanium dioxide-diatom ooze composite process of indoor formaldehyde degradation by photocatalytic oxidation process prepared by biological template | |
| CN107824196B (en) | A kind of organic wastewater ozone oxidation catalyst and its preparation and application | |
| CN104289179A (en) | Method for preparing attapulgite/carbon composite adsorbent by one-step carbonization-activation | |
| CN102658111B (en) | Method for preparation of ZnO/diatomite nanoscale composite material by layer-by-layer self-assembly | |
| CN109569581B (en) | Three-dimensional composite material Bi responding to visible light2MoO6/ZnO and preparation method and application thereof | |
| CN107754797B (en) | Nano Cu2O @ porous carbon composite photocatalytic material and preparation method thereof | |
| CN106076303B (en) | Graphene oxide/nano titania needle composite material and preparation method and application | |
| CN109574333A (en) | A kind of copper modification nitrogen-doped titanium dioxide material and its preparation method and application | |
| CN103657623A (en) | Microballoon-type titanium dioxide photocatalyst and preparation method thereof | |
| CN106862585A (en) | It is a kind of to prepare CaCO by template of egg-shell meal3The method of Ag composites | |
| CN109550500A (en) | It is a kind of can Magnetic Isolation graphene-based zinc-iron mixing bimetallic oxide photochemical catalyst preparation method and applications | |
| CN102286896A (en) | Preparation method for adsorption paper with air purification function | |
| CN108993576A (en) | A kind of zinc catalyst and preparation method thereof for catalyzing acetylene hydration reaction | |
| CN107715906A (en) | A kind of preparation method of the direct Z-type heterojunction composite photocatalyst of carbonitride/zinc titanate/titanium oxide sandwich-like | |
| CN106268907B (en) | A kind of two dimension Conductive mica load carbonitride catalysis material and preparation method thereof | |
| CN110368973A (en) | A kind of khaki (BiO)2CO3The preparation method of multilevel structure microballoon | |
| CN107442153A (en) | A kind of g C based on the modification of waste paper biomass carbon3N4The Preparation method and use of composite photo-catalyst | |
| CN101857390A (en) | Composite powder with antibacterial and heat insulation functions and preparation method and purposes thereof | |
| CN106955677A (en) | It is a kind of based on ion liquid modified egg shell/acticarbon and preparation method thereof | |
| CN106111139A (en) | A kind of native protein stone and TiO2hydro-thermal complex method | |
| CN105460964A (en) | Method for preparing nano-hydroxy aluminum oxide powder | |
| CN104888701A (en) | Adsorbent capable of purifying air |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150902 Termination date: 20160409 |