CN112495379B - Cu-TiO2Composite material and application - Google Patents
Cu-TiO2Composite material and application Download PDFInfo
- Publication number
- CN112495379B CN112495379B CN202011379475.8A CN202011379475A CN112495379B CN 112495379 B CN112495379 B CN 112495379B CN 202011379475 A CN202011379475 A CN 202011379475A CN 112495379 B CN112495379 B CN 112495379B
- Authority
- CN
- China
- Prior art keywords
- tio
- composite material
- solution
- arsenic
- stirring
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
The invention discloses Cu-TiO2Composite material and application. The Cu-TiO2The preparation method of the composite material comprises the following steps: s1, mixing TiO2Dispersing in deionized water, and performing ultrasonic treatment for 30min to obtain suspension; s2, adding Cu (NO)3)2·3H2Fully dissolving O in the suspension obtained in S1, and then carrying out ultrasonic treatment for 30 min; s3, mixing KBH4Dropwise adding the solution into the solution obtained in S2, then intensively stirring at 298.15K for 20h, centrifuging the solution after stirring is completed, collecting a blue solid precipitate, washing the blue solid precipitate with sufficient deionized water, and placing the blue solid precipitate in an oven at 313.15K for drying overnight; s4, cooling the dried solid to room temperature, and fully grinding to obtain Cu-TiO2A composite material. Cu-TiO prepared by the invention2The composite material can be used as a catalyst of a sulfite system in the oxidation of trivalent arsenic, so that the oxidation efficiency of the trivalent arsenic is improved, and the pentavalent arsenic can be adsorbed at the same time.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to Cu-TiO2Composite material and application.
Background
With the rapid development of industrialization, the discharge amount of arsenic is continuously increased, so that the content of arsenic in the water environment is gradually increased, and the drinking water source is also polluted by arsenic. It has been reported that over 1.5 million people are currently exposed to unhealthy, highly toxic arsenic, and that prolonged exposure to arsenic can cause cancer and even death of the skin, nasal cavities, and internal organs. Mitigation of arsenic contamination is a very attractive challenge in today's world. Trivalent arsenic possesses higher solubility and toxicity, while most adsorbents have significantly less adsorption capacity for As (iii) than As (v). A high degree of removal of highly toxic arsenic can be more easily achieved if trivalent arsenic is oxidized to pentavalent arsenic prior to adsorption.
The advanced oxidation technology is also called as deep oxidation technology, and is characterized in that hydroxyl free radicals (OH) with strong oxidation capacity are generated, and under the reaction conditions of high temperature and high pressure, electricity, sound, light irradiation, catalysts and the like, macromolecular refractory organic matters are oxidized into low-toxicity or non-toxic micromolecular substances. Depending on the manner of generating radicals and the reaction conditions, they can be classified into photochemical oxidation, catalytic wet oxidation, sonochemical oxidation, ozone oxidation, electrochemical oxidation, Fenton oxidation, and the like. Sulfite-based advanced oxidation systems are capable of oxidizing trivalent arsenic to pentavalent arsenic, but are not capable of removing arsenic from water. After trivalent arsenic is oxidized into pentavalent arsenic, the step of arsenic adsorption is needed to be added to remove arsenic from the solution, so that the operation steps are complicated, and the cost is high. Therefore, the search of a material which can not only catalyze the sulfite, but also adsorb the arsenic becomes the key for efficiently removing the trivalent arsenic.
Cu (II) as a transition metal can catalyze a sulfite advanced oxidation system. Meanwhile, Cu (II) has high zero potential close to 9.4, and can realize the adsorption of arsenic. However, Cu (ii) is susceptible to corrosion in aqueous solutions and cannot remove arsenic, so it must be modified to meet the catalytic and adsorption requirements described above.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide Cu-TiO2The composite material solves the problem that Cu (II) is easy to corrode in aqueous solution and cannot catalyze a sulfite advanced oxidation system, and realizes arsenic removal.
The invention also provides the Cu-TiO2The application field of the composite material and a method thereof.
In order to solve the technical problem, the invention adopts the following technical scheme:
Cu-TiO2The preparation method of the composite material comprises the following steps:
s1, mixing TiO2Dispersing in deionized water, and performing ultrasonic treatment for 30min to obtain suspension, wherein the suspension contains TiO2The mass ratio of the water to the water is 1-2: 100, respectively;
s2, adding Cu (NO)3)2·3H2Fully dissolving O in the suspension obtained in the step S1, and performing ultrasonic treatment for 30min, wherein the concentration of copper ions is 4-6 mmol/L;
s3, mixing KBH4Dropwise adding the solution into the solution obtained in S2, strongly stirring at 298.15K for 20h, centrifuging the solution after stirring, collecting blue solid precipitate, washing with sufficient deionized water, and standingUntil dried overnight in a 313.15K oven, KBH4The concentration of the solution is 0.06 g/L;
s4, cooling the dried solid to room temperature, and fully grinding to obtain Cu-TiO2A composite material.
Further, the Cu (NO)3)2·3H2O、TiO2And KBH4 in a mass ratio of (10-15): (50-100): (12-20).
Further, in the above-mentioned S3, the term "vigorous stirring" means that the stirring speed is 800 rpm. The centrifugal treatment is specifically 5000-6000 rpm for 5-10 minutes.
The invention also provides Cu-TiO2Use of the composite material, the Cu-TiO2The composite material is used as a catalyst for oxidizing trivalent arsenic in a sulfite advanced oxidation system.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides Cu-TiO2The composite material has strong adsorption capacity to Cu (II) and is attached to TiO2To TiO, and2the crystal phase of the carrier has no influence, so that the carrier has the catalytic performance of Cu (II) and TiO2Rich surface hydroxyl groups, low toxicity, stable physicochemical properties and certain affinity to arsenic.
2. The invention provides Cu-TiO2The composite material realizes the high-efficiency oxidation of As (III) under the catalytic action of Cu (II), and Cu and TiO are used for preparing the catalyst2The adsorption of arsenic is jointly completed, so that the oxidation and the removal can be completed in the same reactor, the strong oxidation effect is achieved, and an independent adsorption treatment step is not needed, so that the whole treatment is more convenient and faster, and the treatment cost is lower.
3. The invention provides Cu-TiO2The composite material has the advantages of simple operation, low energy consumption and few steps. In Cu-TiO2In the preparation process of the composite material, Cu (II) is firstly reduced into Cu (I), and Cu (I) particles are smaller and are more easily adsorbed to TiO2Above. In the case of Cu (I) being adsorbed to TiO2After the above, the prepared Cu-TiO2Oxidizing the composite material in air to oxidize Cu (I) into Cu (II),and then used as a catalyst. Thus, Cu-TiO is ensured2More Cu is loaded on the composite material, and the success rate is higher.
Drawings
FIG. 1 shows Cu-TiO in example 1 of the present invention2Composite material and pure TiO2XRD diffractogram of (a).
FIG. 2 shows Cu-TiO in example 1 of the present invention2Composite material and pure TiO2XPS survey spectrum of (1).
FIG. 3 shows Cu-TiO2Composite material and pure TiO2In which (a) is TiO2(b) is Cu-TiO2Transmission electron microscopy of the composite.
FIG. 4 shows Cu-TiO2EDX map of composite.
FIG. 5 shows Cu-TiO2EDX energy spectrum of the composite.
FIG. 6 shows Cu-TiO2The material is used as a catalyst to catalyze a sulfite oxidation system.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Mono, Cu-TiO2Preparation of composite materials
Example 1
S1, mixing 5g TiO2Dispersing in 500mL of deionized water, and carrying out ultrasonic treatment for 30 min;
s2, adding 5mmol of Cu (NO)3)2·3H2Fully dissolving O in the suspension obtained in S1, and then carrying out ultrasonic treatment for 30 min;
s3, mixing 25ml KBH4The solution (0.06g/L) was added dropwise to the solution obtained in S2, followed by vigorous stirring at 298.15K for 20 h. Centrifuging the solution (6000rpm for 5min) after stirring, collecting blue solid precipitate, washing with sufficient deionized water, and drying in a 313.15K oven overnight; cooling the dried solid to room temperature, and fully grinding to obtain Cu-TiO2A composite material.
Cu-TiO prepared in this example2Composite material and pure TiO2The XRD diffraction is carried out, and the obtained product,the diffraction spectrum is shown in FIG. 1. As can be seen from FIG. 1, it is found that TiO is present in the form of pure anatase2Corresponding to these reflections, pure TiO2The diffraction peak of (A) is distinct and intense. For Cu-TiO2No obvious diffraction peak of copper compound is observed in XRD spectrum, which is probably due to low crystallinity of Cu (II) or Cu (II) in Cu-TiO2The dispersion degree of the surface is higher. Grain size and line width at 25.3 time (101), Cu-TiO calculated according to Scherrer's formula2196 grains (20.0nm) of which the size is slightly smaller than that of pure TiO2(20.5nm), which may be due to the shielding effect of the Cu (II) nanoparticles. In addition, the introduction of Cu (II) weakens the intensity of diffraction peaks, indicating that part of Cu (II) enters into the anatase enzyme structure.
For verifying Cu (II) in TiO2Surface loading of pure TiO2And Cu-TiO2The composite was analyzed by XPS, and the results are shown in FIG. 2. Full-range measurement of XPS spectrum confirms Cu (II) in TiO2Is present. The apparent C1s signal in the XPS spectra was due to the addition of carbon as a reference when the sample was transferred to the XPS apparatus. The high resolution XPS spectrum of Cu2p shows two typical peaks at 934.1eV and 954.0eV, with a binding band gap of 20.0eV, indicating the presence of Cu (II) species, rather than Cu (I) species. In addition, the strong satellite peaks associated with the Cu unfilled 3d9 shell also confirmed Cu-TiO2The presence of Cu (II) in the composite material shows that the Cu-TiO prepared in this example2The composite material successfully attaches Cu (II) to TiO2The above.
Cu-TiO2Composite material and pure TiO2FIG. 3 shows a transmission electron micrograph of (A) and (B) in FIG. 3, which shows that the loading of Cu does not affect TiO2Crystalline phase of support, TiO2The support still contains small spherical anatase TiO2Crystals with a particle size of 20-30 nm. The particle size of the CuO nanoparticles is within 25 nm.
FIG. 4 shows Cu-TiO2EDX map of the composite material, FIG. 5 is Cu-TiO2EDX energy spectrum of the composite material, and as can be seen from the figure, copper is in TiO2High dispersion of the surface. In addition, in Cu-TiO2Copper was detected in the EDX spectrum of the compositeA signal. The copper mass fraction was calculated to be 4.35 wt.% (-representing about, the same below), calculated to be (-4.1 wt.%) based on the actual copper load. Illustrating the Cu-TiO prepared in this example2The composite material successfully attaches Cu (II) to TiO2The above.
Example 2
S1, mixing 2g TiO2Dispersing in 100mL of deionized water, and carrying out ultrasonic treatment for 30 min;
s2, mixing 1mmol Cu (NO)3)2·3H2Fully dissolving O in the suspension obtained in S1, and then carrying out ultrasonic treatment for 30 min;
s3, mixing 5mlKBH4The solution (0.06g/L) was added dropwise to the solution obtained in S2, followed by vigorous stirring at 298.15K for 20 h. Centrifuging the solution (6000rpm for 5min) after stirring, collecting blue solid precipitate, washing with sufficient deionized water, and drying in a 313.15K oven overnight; cooling the dried solid to room temperature, and fully grinding to obtain Cu-TiO2A composite material.
Cu-TiO prepared in example 2 and example 12The composite material of example 2 was lighter in color than the composite material of example 1. TiO 22Since the color is white and cu (ii) is cyan, it can be inferred that the amount of cu (ii) supported is large in example 1 and small in example 2.
Example 3
S1, mixing 1g TiO2Dispersing in 100mL of deionized water, and carrying out ultrasonic treatment for 30 min;
s2, mixing 1mmol of Cu (NO)3)2·3H2Fully dissolving O in the suspension obtained in S1, and then carrying out ultrasonic treatment for 30 min;
s3, mixing 5ml KBH4The solution (0.06g/L) was added dropwise to the solution obtained in S2, and after sealing the reactor, it was stirred vigorously at 298.15K for 20 hours. After stirring, the solution was centrifuged (6000rpm for 5min) to collect a solid precipitate, which was washed with sufficient deionized water and dried overnight in a 313.15K oven. Cooling the dried solid to room temperature, and fully grinding to obtain Cu-TiO2A composite material.
The solid precipitate in this example was greenish black, the blue precipitate in example 1 could not be obtained, and the material composition was unstable and easily deteriorated.
II, mixing Cu-TiO2Composite material for removing trivalent arsenic
Effect of pH on Total arsenic removal
Into a 250mL beaker were added 200mL of distilled water, 1mL of an As (III) solution at a concentration of 100mg/L, and 50mg of Cu-TiO2Material and 1mL of Na having a concentration of 0.1mol/L2SO3The solution is prepared by using 0.2mol/L NaOH solution and 0.1mol/L H2SO4The pH value of the solution in the conical flask is adjusted to 7.5 by the solution, the solution is placed in a constant-temperature water pot, the temperature is set to 303.15K, and after 1 hour of reaction, the concentration of the residual As (V) solution is measured. And (4) carrying out parallel experiments on at least two groups, and taking the average value of the two groups of data in the case that the error of the parallel data is less than 5%. Cu-TiO prepared in example 1 and example 2 at different pH values2The removal rate of As (III) from the material is shown in Table 1. It is seen that the removal effect of arsenic is poor under acidic conditions. When the pH value is 7.5-8.5, the total arsenic removal rate is over 95 percent, and the method has good removal effect.
TABLE 1
Effect of (II) reaction time on Total arsenic removal
Cu-TiO prepared in example 1 and example 22The composite material is applied to oxidation adsorption experiments of trivalent arsenic. Into a 250mL beaker were added 200mL of distilled water, 1mL of an As (III) solution at a concentration of 100mg/L, and 50mg of Cu-TiO2The material and 1mL of Na having a concentration of 0.1mol/L2SO3The solution is prepared by using 0.2mol/L NaOH solution and 0.1mol/LH2SO4Adjusting the pH value of the solution in the conical flask to 7.5, placing the solution in a constant-temperature water kettle, setting the temperature to 303.15K, sampling at reaction time of 0, 2, 5, 10 and 20min, and determining the concentration of the residual As (V) solution. At least two groups of experiments are carried out in parallel, and the obtained experimental data are shown in the table 2.
TABLE 2
As can be seen from table 2, the removal rate of trivalent arsenic of the copper-titanium material prepared in example 2 was higher than that of the copper-titanium material prepared in example 1 in the first 20min of the reaction, but the removal rate of trivalent arsenic of the material prepared in example 2 was lower than that of the synthesized material in example 1 after 20 min. Copper (II) and TiO2The content of (b) is a main cause of the above-mentioned variation. Copper (II) is mainly involved in the catalytic cycle of sulfite in the pre-reaction stage due to the presence of sulfite, and mainly exhibits its catalytic properties, which makes the material of example 1 in the pre-reaction stage less effective in removing total arsenic than the material of example 2 containing more titanium dioxide. More copper (ii) participates in the arsenic adsorption process as sulfite is consumed in the latter stage of the reaction, so that the total arsenic removal effect of the material in example 1 is in contrast to that of the material in example 2.
Effect of sulfite content on Total arsenic removal
Into a 250mL beaker was added 200mL of distilled water, 1mL of As (III) solution at a concentration of 100mg/L, and further added 50mg of the Cu-Ti material prepared in example 1 and 0.2, 0.3, 0.6, 1, 1.6, 2mL of Na at a concentration of 0.1mol/L2SO3The solution is prepared by using 0.2mol/L NaOH solution and 0.1mol/LH2And (3) adjusting the pH value of the solution in the conical flask to 7.5 by using the S solution, placing the solution in a constant-temperature water pot, setting the temperature to 303.15K, reacting for 5min, and then measuring the concentration of the residual As (V) solution. Two sets of parallel experiments were performed. Under the condition of different S (IV) contents, Cu-TiO2As (III) removal rate of the material is shown in Table 3, it is understood that the synthetic material has the best effect of removing trivalent arsenic under the condition of 500mM sulfite.
TABLE 3
Cu-TiO2The principle of the material as a catalyst for catalyzing a sulfite oxidation system is as follows: referring to FIG. 6, Me represents a transition metal ion, and in the present invention, Me is Cu (II). The whole oxidation adsorption process occurs on the interface of the solid material and the aqueous solution, and Cu-TiO2And combining Cu (II) on the surface of the composite material with sulfite in the solution to form a Cu (II) -S (IV) composite. Subsequently, the complex decomposes to generate sulfite radicals, which under the action of oxygen and sulfate radicals generate sulfate radicals, which are released into the solution. The sulfate radical oxidizes trivalent arsenic into pentavalent arsenic, so that the arsenic is more easily absorbed on the surface of the copper-titanium material, and the aim of removing the arsenic is fulfilled.
In conclusion, the Cu-TiO provided by the invention2The composite material has strong adsorption capacity to Cu (II) and is attached to TiO2To TiO, and2the crystal phase of the carrier has no influence, so that the carrier has the catalytic performance of Cu (II) and TiO2Rich surface hydroxyl groups, low toxicity, stable physicochemical properties and certain affinity to arsenic. Cu-TiO2The composite material realizes the high-efficiency oxidation of As (III) under the catalytic action of Cu (II), and Cu and TiO are used for preparing the catalyst2The adsorption of arsenic is jointly completed, so that the oxidation and the removal can be completed in the same reactor, the strong oxidation effect is achieved, and an independent adsorption treatment step is not needed, so that the whole treatment is more convenient and faster, and the treatment cost is lower.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (4)
1. Cu-TiO2Use of a composite material, characterized in that the Cu-TiO is applied2The composite material is used for oxidizing trivalent arsenic in a sulfite advanced oxidation system; wherein, the Cu-TiO2The preparation method of the composite material comprises the following steps:
s1, mixing TiO2Dispersing in deionized water, and ultrasonic treating for 30minObtaining a suspension in which TiO2The mass ratio of the water to the water is 1-2: 100, respectively;
s2, adding Cu (NO)3)2·3H2Fully dissolving O in the suspension obtained in the step S1, and performing ultrasonic treatment for 30min, wherein the concentration of copper ions is 4-6 mmol/L;
s3, mixing KBH4Dropwise adding the solution into the solution obtained in S2, strongly stirring at 298.15K for 20h, centrifuging the solution after stirring, collecting blue solid precipitate, washing with sufficient deionized water, and oven-drying in 313.15K oven overnight4The concentration of the solution is 0.06 g/L;
s4, cooling the dried solid to room temperature, and fully grinding to obtain Cu-TiO2A composite material.
2. The Cu-TiO of claim 12Use of a composite material, characterized in that the Cu (NO) is3)2·3H2O、TiO2 And KBH4The mass ratio of (10-15): (50-100): (12-20).
3. The Cu-TiO of claim 12The application of the composite material is characterized in that in the S3, the intensive stirring is that the stirring speed is 800 rpm.
4. The Cu-TiO of claim 12The application of the composite material is characterized in that in S3, the centrifugal treatment is specifically 5000-6000 rpm for 5-10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011379475.8A CN112495379B (en) | 2020-11-30 | 2020-11-30 | Cu-TiO2Composite material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011379475.8A CN112495379B (en) | 2020-11-30 | 2020-11-30 | Cu-TiO2Composite material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112495379A CN112495379A (en) | 2021-03-16 |
| CN112495379B true CN112495379B (en) | 2022-06-24 |
Family
ID=74968581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011379475.8A Active CN112495379B (en) | 2020-11-30 | 2020-11-30 | Cu-TiO2Composite material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112495379B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113332982A (en) * | 2021-06-28 | 2021-09-03 | 苏州大学 | TiO22Preparation method and application of supported copper catalyst |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417167A (en) * | 2008-09-20 | 2009-04-29 | 大连理工大学 | Chlorinated phenol photocatalysis degradation method in water using Fe0/TiO2 |
| US20140274669A1 (en) * | 2013-03-12 | 2014-09-18 | National Yunlin University Of Science & Technology | Catalytic Article and Method for Preparing the Same |
| CN103272555A (en) * | 2013-06-09 | 2013-09-04 | 南京信息工程大学 | Adsorbing material for removing arsenic from water and preparation method of material |
| CN105253962A (en) * | 2015-10-09 | 2016-01-20 | 昆明理工大学 | Preparation method and application of arsenic removal agent |
| CN108499585B (en) * | 2017-02-27 | 2020-06-09 | 江南大学 | Phosphorus-containing compound and preparation and application thereof |
| CN108275767B (en) * | 2018-02-26 | 2020-09-11 | 宿州滋原科技咨询有限公司 | Treatment process for catalytic degradation of printing and dyeing wastewater by ozone |
| CN108452786A (en) * | 2018-03-26 | 2018-08-28 | 重庆大学 | A kind of method of permanganate regeneration Carbon Materials |
| CN108675430B (en) * | 2018-05-15 | 2021-06-25 | 吉林大学 | Catalytic process for the production of sulfate radicals and reactive oxygen species and advanced oxidation of nonbiodegradable organic pollutants |
| US11220437B2 (en) * | 2018-12-24 | 2022-01-11 | Ecometales Limited | Procedure for obtaining scorodite with a high arsenic content from acidic solutions with high content of sulfuric acid |
| CN111482172B (en) * | 2019-01-25 | 2022-08-16 | 华中师范大学 | Composite nano material of CuO/defect titanium dioxide and application thereof |
| CN110449154A (en) * | 2019-07-21 | 2019-11-15 | 内蒙古农业大学 | A kind of copper oxide and titanium dioxide heterogeneous knot composite catalyst and its preparation method and application |
-
2020
- 2020-11-30 CN CN202011379475.8A patent/CN112495379B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112495379A (en) | 2021-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111717902B (en) | Nitrogen, phosphorus and sulfur co-doped porous carbon loaded metal phosphide nano composite material and preparation method and application thereof | |
| Liang et al. | Chemically stable and reusable nano zero-valent iron/graphite-like carbon nitride nanohybrid for efficient photocatalytic treatment of Cr (VI) and rhodamine B under visible light | |
| KR101830575B1 (en) | Ag-ZnFe2O4@rGO Nanocomposite Photocatalyst for Efficient Treatment of Organic Wastes under Ultraviolet and Visible Light and the Preparation Method Thereof | |
| Jing et al. | Synthesis of Ag and AgCl co-doped ZIF-8 hybrid photocatalysts with enhanced photocatalytic activity through a synergistic effect | |
| CN112705242B (en) | Porous carbon nitride composite material modified by metal bismuth nanoparticles, preparation method thereof and application of porous carbon nitride composite material in removal of antibiotics in water | |
| CN108187687B (en) | Preparation method of photo-Fenton catalyst | |
| CN112495379B (en) | Cu-TiO2Composite material and application | |
| CN115041235A (en) | Titanium metal organic framework loaded copper sulfide composite photocatalyst and preparation method and application thereof | |
| CN114130408B (en) | Z-type alpha-Fe 2 O 3 /ZnIn 2 S 4 Preparation method and application of composite photocatalyst | |
| Khiar et al. | Ni2+ grafted Ag3PO4: enhanced photocatalytic performance under visible light | |
| CN111644188A (en) | ZnCo2O4/g-C3N4Composite material, preparation and application thereof | |
| CN113351218B (en) | Cu 2 O/BiFeO 3 Composite material and preparation method and application thereof | |
| CN112979008A (en) | Treatment method of thallium-containing wastewater | |
| CN110711598B (en) | Silver/silver phosphate/titanium carbide ternary composite material and preparation method and application thereof | |
| Baniamerian et al. | Fe2O3/TiO2/activated carbon nanocomposite with synergistic effect of adsorption and photocatalysis | |
| CN112973744A (en) | Novel photoelectric catalyst and preparation method thereof | |
| CN111617760A (en) | Mn-TiO2Composite photocatalytic material and preparation method and application thereof | |
| CN108940348B (en) | Silver chromate/sulfur-doped nitrogen carbon Z-type photocatalyst and preparation method thereof | |
| CN115814859A (en) | Novel photocatalyst, preparation method and application | |
| Kumar et al. | Photoluminescence of colloidal cadmium sulphide in the presence of aniline—study of CdS-sensitized photocatalytic reaction | |
| CN114849748A (en) | CoS/Ti 3 C 2 Preparation and application of MXene composite material | |
| CN114405506A (en) | Bi-metal PdAu auxiliary agent selectively modified bismuth vanadate photocatalyst and preparation method and application thereof | |
| CN113680374A (en) | Composite photocatalyst and preparation method and application thereof | |
| CN114534685A (en) | Silicon-aluminum-iron composite material and preparation method and application thereof | |
| CN114433020A (en) | Composite material of zero-valent iron fixed by biochar, preparation method thereof and application thereof in removing tetracycline in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |